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In this study, a novel ordered multistage porous carbon (OMPC) with a micro-mesoporous structure was prepared and used for the removal of tylosin (TYL). The porous material, carbonized at 900 °C (OMPC-900), exhibited micro-mesoporous structures with pore sizes of 0.71 nm and 3.63 nm, while had a specific surface area of 1300.02 m 2  g -1 . OMPC-900 demonstrated a maximum adsorption capacity of 341.28 mg g -1 for TYL in water by electrostatic attraction, hydrogen bonding, π-π interactions, and pore-filling mechanisms, which is 6.41 times higher than that of activated carbon. The TYL-saturated adsorbents could be efficiently regenerated by in-situ oxidation through the activation of persulfate (PDS), achieving a regeneration rate of 94.17%, significantly higher than that of activated carbon (55.22%). The excellent regeneration performance may be attributed to the presence of -C=O and graphitic carbon in the adsorbent, which promotes the production of free radicals (•OH, SO 4 •- and •O 2 - ) and non-free radicals. Among these, the non-radical pathways ( 1 O 2 and electron transfer) played a key role in the degradation of TYL loaded on the adsorbent. OMPC-900 maintained stable regenerative adsorption performance of 80.85% after five in-situ regeneration, and the normalized adsorption capacity per unit surface area increased from 0.21 to 0.39 mg m -2 , which may be due to that the increase in oxygen-carbon ratio and surface defects improved the adsorption sites activity of the regenerated adsorbent. In comparison to conventional pyrolysis and organic solvent elution, oxidative regeneration through the activation of PDS is a more efficient and sustainable method., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Traditional fungi β-glucan commonly possesses high molecular weight with poor water solubility, which remains significant challenge in the drug development and medical application. Water-soluble β-glucan with high molecular weight (dHSCG) of 560 kDa, low molecular weight (dLSCG) of 60 kDa, and sulfated derivative (SCGS) with a molecular weight of 146 kDa and sulfate degree at 2.04 were obtained through well-controlled degradation and sulfated modification from Saccharomyces cerevisiae in this study. The structural characteristics were confirmed as β-1,3/6-glucan by FT-IR and NMR spectroscopy. Carbohydrate microarrays and surface plasmon resonance revealed distinct and contrasting binding affinities between the natural β-glucans and sulfated derivatives. SCGS exhibited strong binding to FGF and VEGF, while natural β-glucan showed no response, suggesting its potential as a novel antitumor agent. Moreover, SCGS significantly inhibited the migration rate of the highly metastatic melanoma (B16F10) cells. The lung metastasis mouse model also demonstrated that SCGS significantly reduced and eliminated the nodules, achieving an inhibition rate of 86.7% in vivo, with a dramatic improvement in IFN-α, TNF-α, and IL-1β levels. Through analysis of protein content and distribution in lung tissues, the anti-tumor and anti-metastasis mechanism of SCGS involves the regulation of degrading enzymes to protect extracellular matrix (ECM), as well as the reduction of angiogenic factor release. These findings provide a foundation for exploring the potential of SCGS in the development of new anti-tumor and anti-metastasis drugs and open up a new field in cancer research., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The marine ecosystem contains an assorted range of organisms, among which macroalgae stands out marine resources as an invaluable reservoir of structurally diverse bioactive compounds. Marine macroalgae are considered as primary consumers have gained more attention for their bioactive components. Sulfated polysaccharides (SPs) are complex polymers found in macroalgae that play a crucial role in their cell wall composition. This review consolidates high-tech methodologies employed in the extraction of macroalgal SPs, offering a valuable resource for researchers focuses in the pharmacological relevance of marine macromolecules. The pharmacological activities of SPs, focusing on their therapeutic action by encompassing diverse study models are summarized. Furthermore, in silico docking studies facilitates a comprehensive understanding of SPs interactions with their binding sites providing a valuable insight for future endeavors. The biological properties of algal SPs, along with a brief reference to mode of action based on different targets are presented. This review utilizes up-to-date research discoveries across various study models to elucidate the biological functions of SPs, focusing on their molecular-level mechanisms and offering insights for prospective investigations. Besides, the significance of SPs from seaweeds is highlighted, showcasing their potential beneficial applications in promoting human health. With promising biomedical prospects, this review explores the extensive uses and experimental evidence supporting the important roles of SPs in various fields., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Aerospace magnetic material scraps are abundant in cobalt and nickel. Sulfuric acid leaching process is an efficient method for extracting them. But it is a non-selective process, a significant amount of iron dissolves in the solution. This study focuses on the selective removal of iron from this solution using the jarosite process. E h -pH diagram of K-S-Fe-H 2 O system was established. Based on thermodynamic analysis, H 2 O 2 is used to oxidize Fe 2+ into Fe 3+ , achieving efficient and selective removal of iron from the solution containing cobalt and nickel. The optimal conditions are as follows: temperature 95°C, K 2 SO 4 dosage coefficient 1.5, seed dosage 10 g/L, time 90 min, pH 1.76, and endpoint pH controlled at approximately 3. Under these conditions, the iron removal efficiency is above 99%, while the loss ratios of cobalt and nickel are below 2%. The product is characterized by XRD and SEM-EDS. Results indicate that the product is jarosite ((K,H 3 O)Fe 3 (SO 4 ) 2 (OH) 6 ), exhibiting an ellipsoid structure with the mean particle size in the range of 0.2-5.0 μm. Temperature, pH value and seed dosage significantly affect reaction rate, particle size and crystallinity, and K 2 SO 4 dosage mainly affects reaction rate and the morphology of jarosite. The jarosite crystallization kinetics can be described by the Avrami equation, with an Avrami index (n) of approximately 2.5 and the apparent activation energy of 42.68 kJ/mol., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

A Co 3 Mn-LDHs and carbon nanotube (Co 3 Mn-LDHs/CNT) composite catalyst was constructed for permonosulfate (PMS) activation and degrading sulfamethoxazole (SMX) under Vis light irradiation. The introduction of CNTs into Co 3 Mn-LDHs facilitate the exciton dissociation and carrier migration, and the e- and h+ were readily separated from Co 3 Mn-LDHs/CNT in the photocatalysis process, which promoted the production rate of reactive oxygen species (ROS), so the Co 3 Mn-LDHs + Vis + PMS system exhibited better activity with an SMX degradation ratio of 61.25% than those of Co 3 Mn-LDHs + Vis system (42.30%) and Co 3 Mn-LDHs + PMS system (48.30%). After 10 cycles, the degradation rate of SMX only decreased by 7.16%, indicating the good reusability of the Co 3 Mn-LDHs/CNTs catalyst. The results of electron paramagnetic resonance (EPR) analysis and radical quenching experiments demonstrated that that the SO 4 •- played crucial role for SMX removal in Co 3 Mn-LDHs/CNTs + Vis + PMS system, and both e - and h + made an important contribution to activating PMS to produce ROS. Overall, this work provided an excellent catalyst for photo-assisted PMS activation and suggested the activation mechanism for organic pollutant remediation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

Sulfate fertilization has been proposed to limit arsenic (As) mobility in paddy soils and accumulation in rice grains. However, As and sulfur (S) have complex biogeochemical interactions. Besides the desired precipitation of sulfides that sorb or incorporate As, S can enhance As biotic methylation and abiotic thiolation. Incubating 50- to 2000-year-old paddy soil chronosequence samples without and with S-addition showed the highest relative increases in the formation of low-sorbing, phytotoxic methylated oxyarsenates, and low-sorbing, cyto-, and phytotoxic thioarsenates in the youngest soil. These increases were related to low soil organic carbon (SOC) and iron (Fe) availability, high pH, and As methylation driven by sulfate-reducing bacteria. In older paddy soils, higher SOC and Fe availability buffered these net increases but only in healthy soils. Two paddy soils, where microbial activity and Fe availability had been anthropogenically disturbed, lacked this buffering effect. Therefore, soil history should be considered prior to sulfate fertilization.

In this paper, the effect of zero-valent iron (Fe 0 ) activated persulfate (PDS) on the removal of enrofloxacin (ENR) was investigated, and the effect and mechanism were analyzed by exploring the effects of Fe 0 concentration, PDS concentration, pH, and the influence of anion and aqueous matrix on the removal of ENR by the Fe 0 /PDS system. The results showed that when [ENR] = 20 µmol/L, [Fe 0 ] = 0.15 g/L, [PDS] = 0.4 mmol/L, the removal rate of ENR was 85.3% at 90 min, the mainradicals were HO • , SO 4 •- and O 2 •- . At the same time, the system had a good mineralization effect (TOC removal rate > 40%), in addition, the system did not show obvious toxicity to soil microorganisms after the reaction, furthermore the Fe 0 /PDS system had a good removal effect on ENR in a wide pH range (4 ≤ pH ≤ 10). There is basically no difference in the removal rate of Fe 0 /PDS system in ultrapure water and river water. The results of this experiment could provide a reference for the removal of antibiotics based on advanced oxidation techniques based on SO 4 •- ., (© 2024. The Author(s).)

Fucoidan, a sulfated polysaccharide found primarily in brown algae, is known for exhibiting various biological activities, many of which have been attributed to its sulfate content. However, recent advancements in techniques for analyzing polysaccharide structures have highlighted that not only the sulfate groups but also the composition, molecular weight, and structures of the polysaccharides and their monomers play a crucial role in modulating biological effects. This review comprehensively provides the monosaccharide composition, degree of sulfation, molecular weight distribution, and linkage of glycosidic bonds of fucoidan, focusing on the diversity of its biological activities based on various characteristics. The implications of these findings for future applications and potential therapeutic uses of fucoidan are also discussed.

The filling substrate is one of key factors influencing effectiveness of sulfate reducing packed-bed bioreactor (SRPB) treating acid mine drainage (AMD). The effects of four substrates (i.e. quartz sand, steel residue, biochar, and peanut shell) on remediation performance and sulfur transformation of SRPB treating AMD was studied. The results showed that steel residue and biochar improved sulfate reduction efficiency (61% and 49%) compared to quartz sand (32%), whereas peanut shell inhibited sulfate reduction efficiency (19%), attributed to its decomposition process leading to a severe accumulation of acetic acid. More amounts of sulfides generated in steel residue bioreactor were converted into acid volatile sulfide and elemental sulfur, resulting in a significant decrease in dissolved sulfide in the effluent. Metals (Fe, Al, Zn, Cd and Cr) except for Mn were effectively immobilized in the bioreactors, particularly for Al and Cd. Sulfate reducing bacteria and sulfide oxidizing bacteria lived symbiotically in all bioreactors which exhibited similar heterogeneity in microbial distribution and function, i.e. bacterial sulfate reduction mainly occurring in bottom-middle layers and photoautotrophic sulfide oxidation in upper layer close to outlet. The microbial response mechanism to various substrate environments was revealed through co-occurrence networks analysis. This study suggests that attention should be paid to the inhibitory effect of acetic acid accumulation on sulfate reduction when using sole lignocellulosic waste (peanut shell), and steel residue and biochar could be utilized as filling substances to promote sulfate reduction., Competing Interests: Declaration of competing interest We declare that we have no conflict of interest., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Studies have highlighted the great potential of Oudemansiella canarii laccase in degrading synthetic dyes for reducing their toxicity. Immobilization of enzymes improves usability in degradation processes and the present work succeeded in immobilizing this laccase onto MANAE-agarose. Immobilization improved pH, thermal, and storage stabilities. Both, free and immobilized enzymes presented Michaelis-Menten kinetics with the substrate 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) with K m values of 0.056 ± 0.003 and 0.195 ± 0.022 mM, respectively. Immobilization increased V max 1.27-fold. NaCl caused incomplete (hyperbolic) inhibition, which was satisfactorily described by the one-substrate one-modifier mechanism. Immobilization reduced the maximal inhibition by NaCl from 80.2 to 55.7 %. The effect of Na 2 SO 4 was predominantly stimulation, but inhibition of the free enzyme occurred at high substrate concentrations. Stimulation of the immobilized enzyme by Na 2 SO 4 was much more pronounced. It strongly depended on the substrate concentration and was much stronger (up to 300 %) at low substrate concentrations. The combined effects of substrate and sulfate on the immobilized laccase could be satisfactorily described by the one-substrate one-modifier mechanism. The modified response of the immobilized O. canarii laccase to NaCl and Na 2 SO 4 considerably favors its use as a tool in bioremediation processes because environmental contamination by salts frequently represents a strong operational challenge., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

In cultured cells, herpes simplex virus (HSV) infectivity is successfully inhibited by sulfated polysaccharides. Herein, we utilized an amalgamated extraction-sulfation procedure to produce two xylogalactofucan sulfates (S203 and S204) from Spatoglossum asperum using ClSO 3 H.Pyr/DMF and SO 3 .Pyr/DMF reagents, respectively. Among these xylogalactofucans, the 17 ± 12 kDa polymer (S203) with 14 % sulfate exhibited activity on several HSV variants, including an acyclovir-resistant HSV-1 strain. This is the first report of the anti-HSV activity of a sulfated xylogalactofucan of S. asperum. The effective concentration 50 % (EC 50 ) value of S203 against HSV-1 strain F was 0.6 μg/mL with a selectivity index of 833. The backbone of this polymer (S203) is made up mostly of (1 → 4)-linked-α-l-Fucp units having sulfate groups typically at O-3 and sometimes at O-2 positions. Oligosaccharides containing Xyl, Gal and Fuc units confirms that they are an integral part of a single polymer, another novelty of this study. The EC 50 values of the native xylogalactofucan (S202) and the SO 3 .Pyr/DMF modified polymer (S204), containing 2 % and 6 % sulfates, were >100 and 3.3 μg/mL, respectively. Introduction of sulfate groups enhanced their capability to inhibit the infection of cells by HSV-1. These findings suggest feasibility of inhibiting HSV attachment to cells by blocking viral entry with polysaccharide having specific structure., Competing Interests: Declaration of competing interest I have nothing to declare., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Although autologous chondrocyte transplantation can be effective in articular cartilage repair, negative side effects limit the utility of the treatment, such as long recovery times, poor engraftment or chondrogenic dedifferentiation, and cell leakage. Peptide-based supramolecular polymers have emerged as promising bioactive systems to promote tissue regeneration through cell signaling and dynamic behavior. We report here on the development of a series of glycopeptide amphiphile supramolecular nanofibers with chondrogenic bioactivity. These supramolecular polymers were found to have the ability to boost TGFβ-1 signaling by displaying galactosamine moieties with differing degrees of sulfation on their surfaces. We were also able to encapsulate chondrocytes with these nanostructures as single cells without affecting viability and proliferation. Among the monomers tested, assemblies of trisulfated glycopeptides led to elevated expression of chondrogenic markers relative to those with lower degrees of sulfation that mimic chondroitin sulfate repeating units. We hypothesize the enhanced bioactivity is rooted in specific interactions of the supramolecular assemblies with TGFβ-1 and its consequence on cell signaling, which may involve elevated levels of supramolecular motion as a result of high charge in trisulfated glycopeptide amphiphiles. Our findings suggest that supramolecular polymers formed by the ultra-sulfated glycopeptide amphiphiles could provide better outcomes in chondrocyte transplantation therapies for cartilage regeneration. STATEMENT OF SIGNIFICANCE: This study prepares glycopeptide amphiphiles conjugated at their termini with chondroitin sulfate mimetic residues with varying degrees of sulfation that self-assemble into supramolecular nanofibers in aqueous solution. These supramolecular polymers encapsulate chondrocytes as single cells through intimate contact with cell surface structures, forming artificial matrix that can localize the growth factor TGFβ-1 in the intercellular environment. A high degree of sulfation on the glycopeptide amphiphile is found to be critical in elevating chondrogenic cellular responses that supersede the efficacy of natural chondroitin sulfate. This work demonstrates that supramolecular assembly of a unique molecular structure designed to mimic chondroitin sulfate successfully boosts chondrocyte bioactivity by single cell encapsulation, suggesting a new avenue implementing chondrocyte transplantation with supramolecular nanomaterials for cartilage regeneration., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Alginates are brown algal polysaccharides consisting of β-D-mannuronic (M) and α-l-guluronic acid (G) residues linked with 1→4 glycosidic bonds. To functionalize these natural resources for biomedical use, alginates can be chemically modified, including by sulfation. Here regioselective sulfation of alginates at M-2 in DMSO with Py∙SO 3 is described, by either sulfating alginates directly or through using alginates with added protecting groups (PG-s), including TBDMS-ether, Piv-, Bz-esters and intramolecular 3,6-lactone. Highest regioselectivity was found by sulfating TBDMS- and Piv-protected alginates, with over 65 % of M-residues being 2-O-sulfated. However significant reduction in molecular weight was found when alginates were sulfated in DMSO. Results from this work will allow a degree of control over substitution patterns in sulfated alginates. This will allow to more accurately determine structure-property relationships in biomedical research., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Prolonged exposure of human dermal fibroblasts (HDF) to ultraviolet (UV) radiation triggers the production of reactive oxygen species by upregulating the expression of matrix metalloproteinases (MMPs), causing type-I collagen degradation and photoaging. A sulfated (1 → 3)/(1 → 4) mannogalactan exopolysaccharide (BVP-2) characterized as [→3)-α-Galp-{(1 → 4)-α-6-O-SO 3 -Manp}-(1 → 3)-α-6-O-SO 3 -Galp-(1→] was isolated from seaweed-associated heterotrophic bacterium Bacillus velezensis MTCC13097. Whole genome analysis of B. velezensis MTCC13097 (Accession number JAKYLL000000000) revealed saccharine biosynthetic gene clusters for exopolysaccharide production. BVP-2 administered cells showed noteworthy reduction in mitochondrial superoxide (∼85 %, p < 0.05) and ROS production (62 %) than those exhibited by UV-A irradiated HDF cells. Oxidative imbalance in HDF cells (after UV-A exposure) was recovered with BVP-2 treatment by significantly downregulating nitric oxide (NO) production (98.6 μM/mL, 1.9-fold) and DNA damage (⁓67 %) in comparison with UV-A induced cells (191.8 μM/mL and 98.7 %, respectively). UV-irradiated HDF cells showed a ∼30-50 % downregulation in the expression of MMPs (1, 2, and 9) following treatment with BVP-2. Considerable amount of sulfation (18 %) along with (1 → 3)/(1 → 4) glycosidic linkages in BVP-2 could be pivotal factors for down-regulation of the intracellular MMP-1, which was further supported by molecular docking and structure-activity studies. The (1 → 3)/(1 → 4)-linked bacterial exopolysaccharide (BVP-2) might be used as prospective natural lead to attenuate and mitigate UV-A-induced photoaging., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Sulfation of polysaccharides can affect their biological activity by introducing sulfate groups. Skin burns occur regularly and have a great impact on normal survival. In this study, sulfated arabinogalactan (SAG) was prepared by sulfation, and polyvinyl alcohol (PVA) was used to prepare hydrogels for the treatment of scalded skin in mouse. The results show that the main chain of SAG consists of →3-β-D-Galactose (Gal)-(1, →3, 6)-β-D-Gal-(1 and →4)-β-d-Glucose (Glc)-(1. The chain is a neutral polysaccharide composed of T-β-L-Arabinose (Araf)-(1→, with a molecular weight of 17.9 kDa. At the same time, PVA + SAG hydrogel can promote the scald repair of mouse skin by promoting collagen deposition and angiogenesis, and regulating the TLR4/MyD88/NF-κB signaling pathway. Interestingly, the effect of SAG on promoting the repair of scald wounds is enhanced after AG is derivatized by sulfation. Therefore, the preparation of SAG by sulfation can promote scald repair, and has great application potential in the field of food and medicine., Competing Interests: Declaration of competing interest All authors declare that no conflict of interest exists., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Antrodia cinnamomea-derived sulfated polysaccharides (Ac-SPSs) have health benefits, but their yield is low. This study explores a strategy to increase Ac-SPS yield and elucidates the biofunctions of Ac-SPS. For this, A. cinnamomea mycelia were treated with zinc sulfate (ZnSO 4 ) administered at 1, 10, and 100 μM. Firstly, functional assay indicated that ZnSO 4 increases the Ac-SPS yield by 20 %-30 % compared with the control treatment. ZnSO 4 engenders a population of middle-molecular-weight (~200 kDa) Ac-SPSs. Ac-SPS (ASZ-10) from A. cinnamomea treated with 10 μM ZnSO 4 exhibits the best anti-proliferation ability against lung cancer A549 cells. Co-treatment of ASZ-10 does not inhibit lipopolysaccharide-induced inflammation but does induce M1-related markers of macrophage RAW264.7 cells. Secondly, immunomodulatory properties showed that ASZ-10 increases the expression of CD80 + and CD86 + in M-CSF-stimulated bone-marrow-derived macrophages. ASZ-10 induces M1 polarization through up-regulation of the AKT/mTOR pathway as confirmed by AKT and mTOR inhibitors eliminating ASZ-10-induced M1-like markers of macrophages. Through systemic chemical and functional analysis, this study shows that trace amounts (10 μM) of ZnSO 4 increase Ac-SPS yield and it reveals that ASZ-10 exhibits anti-cancer activity and acts as a stimulator for M1 macrophages by stimulation of AKT and mTOR., Competing Interests: Declaration of competing interest The authors declare no conflicts of interest. Content will be included as a part of Zhi-Hu Lin's doctoral thesis at the Institute of Traditional Medicine, College of Medicine, National Yang Ming Chiao Tung University., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Sulfated polysaccharides (SPSs) have excellent physicochemical properties, attracting research interest in the pharmaceutical industry. A previous study extracted SPS (named Suc40) from the edible fungus, Poria cocos and demonstrated that it exhibited anti-inflammatory and anticancer activities. In this study, three fractions of Suc40, Suc40 F1, Suc40 F2, and Suc40 F3, with different molecular weights and sulfate contents were prepared through gel-filtration column chromatography. The molecular weights of F1, F2, and F3 were approximately 616.23, 82.57, and 6.21 kDa, respectively, and their sulfate content were 0.23, 1.65, and 1.90 mmol/g, respectively. The fractions' anti-inflammatory activities were determined by assessing their ability to suppress inflammatory cytokines in lipopolysaccharide (LPS)-stimulated RAW264.7 cells. Suc40 F2 and Suc40 F3 suppressed interleukin-6 (IL-6) and tumor necrosis factor-α (TNF-α) production by 60 % and 35 %, respectively. Suc40 F2 and Suc40 F3 suppressed protein kinase B (AKT)/p38 and p38 signaling, which resulted in anti-inflammatory effects. The fractions' anti-lung cancer activity was evaluated by assessing their H1975 cell proliferation inhibition. Suc40 F3 at a concentration of 800 μg/ml exhibited maximal cell proliferation inhibition. The low molecular weight and high sulfate content of Suc40 F3 were associated with its enhanced anti-inflammatory and anti-lung cancer activities., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A polysaccharide, CZS-0-1, was obtained from the marine green algae Codium fragile using ion-exchange and size-exclusion chromatography. Composition and characteristics analyses showed CZS-0-1 was a sulfated galactoarabinan consisting of arabinose, galactose and a small amount of glucose in a ratio of 9:2:1 with 21% sulfate content and a molecular weight of 810 kDa. Structural properties were determined using desulfation and methylation analyses combined with instrument analysis. The results showed that the backbone of CZS-0-1 was (1 → 3)-β-L-Arap. Its O-4 and/or O-2 positions showed sulfate modification; additionally, it had 10% of (1 → 3)-β-D-Galp branches at the O-4 position of the (1 → 3)-β-L-Arap. The galactose side chains also had sulfate modification at the O-4 or O-6 position. The structure of CZS-0-1 was further confirmed by Top-down analysis of the oligosaccharides after oxidated hydrolysis by mass spectrometry. CZS-0-1 exhibited significant heparin-like anticoagulant activity. It exerted anticoagulant effects by inhibiting FIIa and FXa activities with the presence of heparin cofactors. The anticoagulant activity of CSZ-0-1 was closely related to the molecular weight, and the reduction of molecular weight may lead to a significant decrease in the anticoagulant activity. This study demonstrated that the green algae, Codium fragile can be considered as a useful resource for bioactive polysaccharides., Competing Interests: Declaration of competing interest We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted., (Copyright © 2024. Published by Elsevier B.V.)

The degradation kinetics, reaction pathways, and disinfection by-products formation of an organic UV filter, benzophenone - 4 (BP4) during UV/persulfate oxidation were investigated. BP4 can hardly be degraded by UV alone, but can be effectively decomposed by UV/persulfate following pseudo-first order kinetics. BP4 degradation rate was enhanced with increasing persulfate dosage and decreasing pH from 8 to 5. However, the degradation rate of BP4 at pH 9 was higher than that at pH 8 because of the presence of phenolic group in BP4 structure. and SO 4 - ⋅ were confirmed as the major contributors to BP4 decomposition in radical scavenging experiments, and the second-order rate constants between HO ⋅ and BP4 as well as those between SO 4 - ⋅ and BP4 were estimated by establishing and solving a kinetic model. The presence of B r - and humic acid inhibited the decomposition of BP4, while N O 3 - promoted it. The mineralisation of BP4 was only 9.1% at the persulfate concentration of 50 μM. Six degradation intermediates were identified for the promulgation of the reaction pathways of BP4 during UV/persulfate oxidation were proposed as a result. In addition, the formation of DBP in the sequential chlorination was evaluated at different persulfate dosages, pH values, and water matrix. The results of this study can provide essential knowledge for the effective control of DBP formation with reducing potential hazard to provide safe drinking water to the public.

Atom-dispersed low-coordinated transition metal-N x catalysts exhibit excellent efficiency in activating peroxydisulfate (PDS) for environmental remediation. However, their catalytic performance is limited due to metal-N coordination number and single-atom loading amount. In this study, low-coordinated nitrogen-doped graphene oxide (GO) confined single-atom Mn catalyst (Mn-SA/NGO) was synthesized by molten salt-assisted pyrolysis and coupled to PDS for degradation of tetracycline (TC) in water. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analysis showed the successful doping of single-atom Mn (weight percentage 1.6%) onto GO and the formation of low-coordinated Mn-N 2 sites. The optimized parameters obtained by Box-Behnken Design achieved 100% TC removal in both prediction and experimental results. The Mn-SA/NGO + PDS system had strong anti-interference ability for TC removal in the presence of anions. Besides, Mn-SA/NGO possessed good reusability and stability. O 2 •- , •OH, and 1 O 2 were the main active species for TC degradation, and the TC mineralization reached 85.1%. Density functional theory (DFT) calculations confirmed that the introduction of single atoms Mn could effectively enhance adsorption and activation of PDS. The findings provide a reference for the synthesis of high-performance single-atom catalysts for effective removal of antibiotics., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Stem cell-based therapies show promise for clinically addressing circumferential tracheal defects (CTD) through tissue engineering. However, creating a tissue-engineered tracheal tube possesses a healthy cartilage matrix and intact tube structure remains a challenge. A solution lies in the use of an injectable hydrogel with shape adaptability and chondrogenic capacity, serving as a practical and dependable platform for tubular tracheal cartilage regeneration. In this study, we developed an injectable hydrogel using modified natural polymers-hydrazide-grafted gelatin (Gelatin-ADH) and aldehyde-modified hyaluronic acid with sulfated groups (HA-CHO-SO 3 ) via Schiff Base interaction. Additionally, aldehyde-modified β-cyclodextrin (β-CD-CHO) was introduced into the network during hydrogel formation. The negative sulfated groups and hydrophobic cavities of β-cyclodextrin facilitated the efficient encapsulation and sustained release of transforming growth factor-β1 (TGF-β1) and kartogenin (KGN) within our hydrogel. This synergistically promoted the chondrogenesis of loaded bone marrow stem cells (BMSCs). Subsequently, we employed this TGF-β1, KGN, and BMSCs loaded hydrogel to form a cartilage ring. This ring was then assembled into an engineered tracheal cartilage tube using our previously reported ring-to-tube strategy. Our results demonstrated that the engineered tracheal cartilage tube effectively repaired CTD in a rabbit model. Hence, this study introduces a novel hydrogel with significant clinical application potential for tracheal tissue engineering., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Energy conservation and emission reduction are the general trend of the present world. In this study, a catalyst of 3WSH based on the waste recycle of waterworks sludge (WS) and Chinese herbs was prepared using one-step calcination treatment and then characterized by SEM, XRD, XPS, FTIR and BET. The catalytic performance of 3WSHB for activating potassium persulfate (PDS) was evaluated through the degradation of Safranine T (ST) in the presence of boron powder (B). The effects of vital parameters on ST removal were systematically studied, including PDS concentration, 3WSHB dosage, initial solution pH, B dosage, temperature and coexisting cations. The highest efficiency of ST removal was up to 93.0% under the optimal condition with 1.85 mM of PDS, 0.3 g/L of 3WSHB, 0.35g/L of B, 7 of pH. EPR and free radical quenching experiments demonstrated that • OH was the dominant reactive oxygen species for ST degradation in the PDS/3WSHB/B system. Moreover, the intermediates determined by HPLC-MS indicated that the oxidization of benzene ring substituents in ST and a hydrogen abstraction by electron transfer might occur during ST degradation. The dissatisfied reuse performance of 3WSHB might be attributed to its low Fe content and simple reusing way. The results demonstrate the effectiveness of WS recycling and reuse in the field of pollutant remediation.

Nano-zero valent iron (nZVI) was anchored and dispersed on the surface of acid-modified blast furnace slag (mBFS) through the liquid phase reduction method. The synthesized nZVI@mBFS composite exhibited remarkable ability to degrade phenol when used in conjunction with persulfate (PDS), 97.8% phenol could be eliminated in 30 min. All the anions like SO 4 2- , HCO 3 - , H 2 PO 4 - , and CO 3 2- were detrimental to the phenol degradation in nZVI@mBFS system. Moreover, electron paramagnetic resonance (EPR) analysis and radical scavenging tests confirmed that SO 4 •- , •OH and •O 2 - were the principal reactive oxygen species (ROSs) generated during the reaction process. The potential degradation pathways were also deduced based on the results obtained from gas chromatograph-mass spectrometer (GC-MS) analysis. Collectively, this study holds substantial significance in regards to recycling industrial solid wastes, devising efficient persulfate-activated materials, and treating wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Fenton-like processes using persulfate for oxidative water treatment and contaminant removal can be enhanced by the addition of redox-active biochar, which accelerates the reduction of Fe(III) to Fe(II) and increases the yield of reactive species that react with organic contaminants. However, available data on the formation of non-radical or radical species in the biochar/Fe(III)/persulfate system are inconsistent, which limits the evaluation of treatment efficiency and applicability in different water matrices. Based on competition kinetics calculations, we employed different scavengers and probe compounds to systematically evaluate the effect of chloride in presence of organic matter on the formation of major reactive species in the biochar/Fe(III)/persulfate system for the transformation of the model compound N,N‑diethyl-m-toluamide (DEET) at pH 2.5. We show that the transformation of methyl phenyl sulfoxide (PMSO) to methyl phenyl sulfone (PMSO 2 ) cannot serve as a reliable indicator for Fe(IV), as previously suggested, because sulfate radicals also induce PMSO 2 formation. Although the formation of Fe(IV) cannot be completely excluded, sulfate radicals were identified as the major reactive species in the biochar/Fe(III)/persulfate system in pure water. In the presence of dissolved organic matter, low chloride concentrations (0.1 mM) shifted the major reactive species likely to hydroxyl radicals. Higher chloride concentrations (1 mM), as present in a mining-impacted acidic surface water, resulted in the formation of another reactive species, possibly Cl 2 •- , and efficient DEET degradation. To tailor the application of this oxidation process, the water matrix must be considered as a decisive factor for reactive species formation and contaminant removal., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The activation of peroxymonosulfate (PMS) by carbon-based catalysts is deemed to be a promising method for the degradation of refractory organic contaminants in wastewater. Herein, a Cu-doping strategy in B and N co-doped carbon nanotubes with highly dispersed BOCu sites and graphite nitrogen were successfully synthesized for activating PMS to degradate tetracycline. The best removal rate of tetracycline within 60 min (97.63 %) was obtained by the 1.5 % Cu-BNC and the degradation rate was increased by 17.9 times. The enhanced catalyst activity was attributed to the promoting the cycle of the Cu(I)/Cu(II) redox pair by the formed BOCu sites, and the accelerating the electron transfer process by the adsorption of graphitic N for PMS. The non-free radical pathway including 1 O 2 and electron transfer played a dominant role in the 1.5 % Cu-BNC/PMS system. The degradation intermediates of TC were identified and three possible degradation pathways were proposed. Further toxicity analysis of the intermediates showed that the 1.5 % Cu-BNC/PMS system had a significant effect on weakening and reducing the biological toxicity and mutagenicity of TC. Moreover, it presented an excellent degradation performance in raw natural water. In general, the proposed regulation of carbon-based catalysts via the coordination-driven effect provides ideas for efficient wastewater treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Gold nanorods (GNR) produce heat upon irradiation with near-infrared light, enabling a tumor-targeted photothermal therapy. In this study, we prepared GNR coated with sulfated hyaluronic acid (sHA) with a binding affinity for CD44 via electrostatic interactions to deliver GNR to tumors efficiently and stably, and evaluated their usefulness for photothermal therapy. Cationic GNR modified with trimethylammonium groups electrostatically interacted with native HA or sHA with varying degrees of sulfation to form complexes. While GNR/HA was unstable in saline, GNR/sHA maintained the absorbance peak in the near-infrared region, particularly for GNR/sHA with higher degrees of sulfation. GNR/sHA exhibited an intense photothermal effect upon irradiation with near-infrared light. Furthermore, in vitro and in vivo studies revealed that GNR coated with sHA containing approximately 1.2 sulfated groups per HA unit could accumulate in CD44-positive tumors via an HA-specific pathway. These findings indicate the effectiveness of GNR/sHA as a tumor-targeted photothermal therapeutic agent., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Selecting a suitable pretreatment process for pharmaceutical wastewater that is difficult to treat biochemically so that it can enter the subsequent biochemical treatment. In this study, pharmaceutical wastewater consisting of 45 g/L sodium bisulfate, 9 g/L 3-hydroxyacetophenone (3-HAP), and 36.75 g/L sulfuric acids,which is a kind of typical pharmaceutical wastewater, was used for the pretreatment case study, and the process was screened by technology. A salting-out crystallization+Fenton system(SC-F) was developed for the treatment of this wastewater. The salting-out agent is formed by the pH adjustment process without additional additions and the salting-out crystallization effect is significant for the precipitation of 3-HAP from the wastewater. Subsequently, the optimal operating conditions for SC-F were derived from experiments as H 2 O 2 of 0.4692 mol/L, n(H 2 O 2 ):n(Fe2+)=30:1, pH=3. Under optimal conditions, the reaction time of 2 h achieved a COD removal rate of 90% and a BOD/COD value of 0.56, confirming the effectiveness of the technology in treating this wastewater. Additionally, it was discovered that the Fenton treatment was not significantly impacted by the inorganic components of the effluent. Analysis of effluent properties and possible effects on subsequent treatment by LC-MS and toxicity analysis. The results show that the biodegradability are enhanced by the pretreatment technology. However, the effluent still suffers from high acidity and high salt content, and this study proposes a solution to this problem. Furthermore, research on the treatment of 3-HAP wastewater has not been reported and this study provides a new case study in the field of wastewater treatment.

Alginate (Alg) polymers have received much attention due to the mild conditions required for gel formation and their good bio-acceptability. However, due to limited interactions with cells, many drugs, and biomolecules, chemically modified alginates are of great interest. Sulfated alginate (S-Alg) is a promising heparin-mimetic that continues to be investigated both as a drug molecule and as a component of biomaterials. Herein, the S-Alg literature of the past five years (2017-2023) is reviewed. Several methods used to synthesize S-Alg are described, with a focus on new advances in characterization and stereoselectivity. Material fabrication is another focus and spans bulk materials, particles, scaffolds, coatings, and part of multicomponent biomaterials. The new application of S-Alg as an antitumor agent is highlighted together with studies evaluating safety and biodistribution. The high binding affinity of S-Alg for various drugs and heparin-binding proteins is exploited extensively in biomaterial design to tune the encapsulation and release of these agents and this aspect is covered in detail. Recommondations include publishing key material properties to allow reproducibility, careful selection of appropriate sulfation strategies, the use of cross-linking strategies other than ionic cross-linking for material fabrication, and more detailed toxicity and biodistribution studies to inform future work., (© 2024 The Author(s). Macromolecular Bioscience published by Wiley‐VCH GmbH.)

Sulfide produced from dissimilatory sulfate reduction can combine with hydrogen to form hydrogen sulfide, causing odor issues and environmental pollution. To address this problem, ferrihydrite-humic acid coprecipitate was added to improve assimilatory sulfate reduction (ASR), resulting in a decrease in sulfide production (190.2 ± 14.6 mg/L in the Fh-HA group vs. 246.3 ± 8.1 mg/L in the Fh group) with high sulfate removal. Humic acid, adsorbed on the surface of ferrihydrite, delayed secondary mineralization of ferrihydrite under sulfate reduction condition. Therefore, more iron-reducing species (e.g. Trichococcus, Geobacter) were enriched with ferrihydrite-humic acid coprecipitate to transfer more electrons to other species, which led to more COD reduction, an increase in electron transfer capacity, and a decrease in the NADH/NAD + ratio. Metagenomic analysis also indicated that functional genes related to ASR was enhanced with ferrihydrite-humic acid coprecipitate. Thus, the addition of ferrihydrite-humic acid coprecipitate can be considered as a promising candidate for anaerobic sulfate wastewater treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The present study systematically investigated the elimination of benzalkonium chloride (BAC) in the zero valent iron activated persulfate (Fe 0 /PS) system. The influence of operational parameters, including PS concentration, Fe 0 dosage and pH, were investigated through a series of kinetic experiments. When the Fe 0 dosage was 5.0 mM, the initial ratio of [PS]: [BAC] was 10:1, the degradation efficiency could achieve 91.7% at pH 7.0 within 60 min. Common inorganic anions and humic acid did not significantly affect BAC degradation, implying that Fe 0 /PS system had a potential application prospect in the actual wastewater remediation. Based on the electron paramagnetic resonance test and quenching experiments, the BAC degradation was found to be contributed by •OH, SO 4 • - and Fe(IV). A total of 23 intermediates were identified by the liquid chromatography-mass spectrometry, and the degradation pathways were proposed accordingly, including dealkylation and demethylation, hydroxylation, sulfate substitution and benzyl C-N cleavage reactions. Density functional theory based calculations were conducted to realize the rationality of the proposed reaction mechanisms. The toxicity of transformation products was predicted by ECOSAR program. This work demonstrated the possibility of BAC removal in hospital and municipal wastewater by Fe 0 /PS treatment, and also provides a safe choice for deep treatment of quaternary ammonium salt wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Widely distributed in nature, sulfated glycan epitopes play important roles in diverse pathophysiological processes. However, due to their structural complexity, the preparation of glycan epitopes with structurally defined sulfation patterns is challenging, which significantly hampers the detailed elucidation of their biological functions at the molecular level. Here, we introduce a strategy for site-specific chemical sulfation of glycan epitopes, leveraging enzymatic sialylation and desialylation processes to precisely control the regio-specificity of sulfation of disaccharide or trisaccharide glycan backbones. Using this method, a sulfated glycan library covering the most common sialylated glycan epitopes was prepared in high yield and efficiency. By screening a microarray prepared with this glycan library, we systematically probed their binding specificity with human Siglecs (sialic acid-binding immunoglobulin-type lectins), many of which function as glyco-immune checkpoints to suppress immune system activation. Our investigation revealed that sulfation and sialylation patterns serve as important determinants of Siglec binding affinity and specificity. Thus, these findings offer new insights for the development of research tools and potential therapeutic agents targeting glyco-immune checkpoints by modulating the Siglec signaling pathway.

Sulfated polysaccharides SpvF1, SpvF2, SpvF3, and SpvF4 from the brown alga S. vietnamense collected north of Hon Do (Nha Trang Bay, Vietnam) were isolated and studied. The structure of the obtained polysaccharide was studied using chemical methods and NMR spectroscopy. Fucoidans were low-sulfated (SpvF1, SpvF2) and medium-sulfated (SpvF3, SpvF4) heterogeneous polysaccharides. The molecular weight of the polysaccharides obtained was in the range of 16 to 44 kDa. All investigated fucoidans until 400 µg/mL were not cytotoxic for human colon carcinoma cells DLD-1, HCT-116, and HT-29 in vitro. Fucoidans SpvF1 and SpvF2 have inhibited the colony formation and growth of investigated cells from 20 to 30%. Fucoidans SpvF3 and SpvF4 have the strongest inhibitory effect for investigated cancer cells: from 40 to 50%.

A sustainable alternative to conventional concrete involves using recycled aggregates (RA) instead of natural aggregates (NA) and incorporating wheat straw ash (WSA) as a partial replacement for Portland cement. The demand for high-performance concrete (HPC) is rising due to the need for architecturally complex structures and long-span bridges, but HPC's low ductility necessitates reinforcement. Waste tire steel fibers (WTSFs) are gaining popularity for their tensile strength. However, WSA-RA concrete's low early strength is a challenge. Chemical activators like sodium sulfate can enhance early-age strength. This study evaluated the durability and strength of fiber-reinforced concrete with both inactivated and activated WSA. Tests included compressive strength, indirect tensile strength, modulus of rupture (MOR), acid attack resistance, chloride penetration, sorptivity, and water absorption. Activated WSA-RA concrete showed significantly improved early strength. The mixture with 30% RA, 40% WSA, WTSFs, and activator exhibited the highest strength at 90 days. At 60% RA content, activated concrete with 40% WSA and 2.5% WTSFs outperformed the control. Durability was enhanced with a 14-17% reduction in water absorption and sorptivity and a 25.2% decrease in chloride penetration. Acid resistance improved by 26%. X-ray diffraction (XRD) confirmed these findings with elevated hydration product peaks. This study demonstrates that chemical activation of WSA optimizes the engineering properties of WSA-modified HPC with WTSFs and RA, providing a sustainable solution to their challenges., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Althoey et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Peptide hormones are decorated with post-translational modifications (PTMs) that are crucial for receptor recognition. Tyrosine sulfation on plant peptide hormones is, for example, essential for plant growth and development. Measuring the occurrence and position of sulfotyrosine is, however, compromised by major technical challenges during isolation and detection. Nanopores can sensitively detect protein PTMs at the single-molecule level. By translocating PTM variants of the plant pentapeptide hormone phytosulfokine (PSK) through a nanopore, we here demonstrate the accurate identification of sulfation and phosphorylation on the two tyrosine residues of PSK. Sulfation can be clearly detected and distinguished (>90%) from phosphorylation on the same residue. Moreover, the presence or absence of PTMs on the two close-by tyrosine residues can be accurately determined (>96% accuracy). Our findings demonstrate the extraordinary sensitivity of nanopore protein measurements, providing a powerful tool for identifying position-specific sulfation on peptide hormones and promising wider applications to identify protein PTMs.

Eclipta prostrata (Asteraceae) is employed as a hemostatic agent in many traditional medicines, owing to its sulfated flavonoid content. In this study, we obtained crude drug samples from three provinces collected in different years and analyzed their sulfated flavonoid contents using liquid chromatography-mass spectrometry (LC-MS) for quality evaluation. Because sulfated flavonoids are unstable and difficult to isolate from extracts, this study first synthesized a variety of sulfated flavonoids and accumulated spectral data in order to identify the compounds in E. prostrata . The LC-MS analysis of six crude drug samples revealed the presence of luteolin 7-sulfate, apigenin 7-sulfate, diosmetin 7-sulfate, and diosmetin 3'-sulfate. The samples without luteolin 3'-sulfate featured high apigenin 7-sulfate content. Although the samples were collected from the same locality, their compositions differed depending on the year of collection. Further, they were classified according to three patterns: (1) samples with luteolin 7-sulfate as the main component, (2) samples with apigenin 7-sulfate as the main component, and (3) samples with relatively high diosmetin sulfate content. Luteolin 7-sulfate typically exhibits relatively high erythrocyte aggregation efficiency and fibrinogen aggregation rate. These results demonstrate that the analysis of sulfated flavonoids is beneficial for the quality evaluation of E. prostrata for hemostatic applications.

This study focused on exploring the effect of peroxydisulfate (PDS) on the regulation of reactive species during water radiolysis process and its potential application for degrading organic pollutants. The results indicated that PDS was successfully activated by ionizing radiation for efficient removal of three typical phenolic compounds over a wide pH range (3.0∼12.0) at absorbed dose of 5 kGy. Chemical probe methods provided the evidence that the addition of PDS could introduce the sulfate radicals (SO 4 •- ) and enhance the production of hydroxyl radicals ( • OH). According to the quenching tests, • OH and SO 4 •- were the dominant reactive species responsible for the degradation of 4-NP, while hydrated electron (e aq - ) played a minor role. The regulatory effect of PDS on active species in the ionizing radiation process could divided by (i) PDS could be directly activated by ionizing radiation to produce • OH and SO 4 •- via energy transfer pathway; (ii) PDS could boost the conversion of e aq - to SO 4 •- via electron transfer pathway. Furthermore, we assessed the applicability of the IR and IR/PDS systems in treating mixed solutions containing various pollutants and actual coking wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Persulfate advanced oxidation technology is widely utilized for remediating organic-contaminated groundwater. Post-remediation by persulfate oxidation, the aromaticity of dissolved organic matter (DOM) in groundwater is significantly reduced. Nevertheless, the evolution trends of aromaticity and related structural changes in DOM remained unclear. Here, we selected eight types of DOM to analyze the variation in aromaticity, molecular weight, and fluorescence characteristics during oxidation by persulfate using optical spectroscopy and parallel faction analysis combined with two-dimensional correlation spectroscopy analysis (2D PARAFAC COS). The results showed diverse trends in the changes of aromaticity and maximum fluorescence intensity (F max ) among different types of DOM as the reaction time increases. Four types of DOM (humic acid 1S104H, fulvic acid, and natural organic matters) exhibited an initially noteworthy increase in aromaticity followed by a decrease, while others demonstrated a continuous decreasing trend (14.3%-69.4%). The overall decreasing magnitude of DOM aromaticity follows the order of natural organic matters ≈ commercial humic acid > fulvic acid > extracted humic acid. The F max of humic acid increased, exception of commercial humic acid. The F max of fulvic acid initially decreased and then increased, while that of natural organic matters exhibited a decreasing trend (86.4%). The fulvic acid-like substance is the main controlling factor for the aromaticity and molecular weight of DOM during persulfate oxidation process. The oxidation sequence of fluorophores in DOM is as follows: fulvic-like substance, microbial-derived humic-like substance, humic-like substance, and aquatic humic-like substance. The fulvic-like and microbial-derived humic-like substances at longer excitation wavelengths were more sensitive to the response of persulfate oxidation than that of shorter excitation wavelengths. This result reveals the structure evolution of DOM during persulfate oxidation process and provides further support for predicting its environmental behavior., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Methylation followed by depolymerization and gas chromatography (GC) is an effective methodology for the linkage analysis of polysaccharides, including fucoidan, a sulphated algal polysaccharide. However, this sample material demands attention to experimental details to prevent aberrations in the analytical result. The use of deficient bases for methylation, the presence of water, analyte degradation during hydrolysis, and coelution of the target analytes during gas chromatography create doubts about published results. We therefore investigated critical parameters of the method and carefully optimized the steps of the protocol to ensure the integrity of the results for the fucose monomers. Fucoidan from Cladosiphon okamuranus was used as reference sample to determine the glycosidic bonds, and sulphate positions in the monomer. Fucoidan in protonated form was methylated in a strictly water-free environment using lithium dimsyl as base and methyl iodide for methylation. The methylated polymer was isolated by solid phase extraction, which was crucial to recover also the highly sulfated fraction. Hydrolysis was conducted with trifluoroacetic acid. To separate all target analytes in GC-FID/MS, a stationary phase with high cyanopropyl content (HP-88) was required, as the commonly employed phenyl siloxane phases result in co-elution, which distorts the result severely., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The preparation of pure metabolites of bioactive compounds, particularly (poly)phenols, is essential for the accurate determination of their pharmacological profiles in vivo . Since the extraction of these metabolites from biological material is tedious and impractical, they can be synthesized enzymatically in vitro by bacterial PAPS-independent aryl sulfotransferases (ASTs). However, only a few ASTs have been studied and used for (poly)phenol sulfation. This study introduces new fully characterized recombinant ASTs selected according to their similarity to the previously characterized ASTs. These enzymes, produced in Escherichia coli , were purified, biochemically characterized, and screened for the sulfation of nine flavonoids and two phenolic acids using p- nitrophenyl sulfate. All tested compounds were proved to be substrates for the new ASTs, with kaempferol and luteolin being the best converted acceptors. ASTs from Desulfofalx alkaliphile ( Dal AST) and Campylobacter fetus ( Cf AST) showed the highest efficiency in the sulfation of tested polyphenols. To demonstrate the efficiency of the present sulfation approach, a series of new authentic metabolite standards, regioisomers of kaempferol sulfate, were enzymatically produced, isolated, and structurally characterized.

Here, we present a first investigation of the inhibition mechanism of surfactant Triton X-100 (TX-100) on the oxidation degradation of polycyclic aromatic hydrocarbons (PAHs) in site soil aggregates using sodium citrate assisted Fe 2+ -activated persulfate (SC/Fe 2+ /PS). First, TX-100 was not only competed the adsorption sites of soil aggregates with PS, but also consumed PS, which inhibit the PAHs remediation rate in the TX-100 elution followed by the SC/Fe 2+ /PS oxidation system from 55.6 % in the oxidation system to 50.3 %. Furthermore, in the oxidation followed by elution system, PAHs was adsorbed on the iron minerals produced during the oxidation, which would be form a bound PAHs that was difficult to react with PS, and then re-eluted to the soil by the TX-100. Additionally, it was found that the oxidative and the elution efficiency of PAHs exhibited negative correlations with aggregate particle sizes. Finally, soil microorganism communities were more strongly changed by SC/Fe 2+ /PS oxidation and PAHs concentration than that of TX-100 elution, with obvious alterations bacteria than fungi, the effects of SC/Fe 2+ /PS and PAHs concentration on microorganism communities were opposite. This study provided a proof of regulating mechanisms for the site soil remediation using surfactants combined with the iron-PS system., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Minor acidic glycans, such as sulfated and phosphorylated glycans, constitute only a small fraction of biological glycome, making their analysis a considerable challenge. In this study, we developed a technique to analyze minor acidic O -glycans in biological samples. First, efficient reaction conditions for the release of O -glycans from the proteins were determined. Next, a high-throughput method was established for the recovery of minor acidic glycans using NH 2 spin columns. The performance of the established method was evaluated using mucin samples, and sulfated O -glycans were successfully detected in bovine submaxillary gland mucin and porcine stomach mucin. We also analyzed the minor acidic O -glycans in cultured cancer cells. In addition to trifucosylated sulfated O -glycans and disulfated O -glycans, sulfated O -glycans with KDN were detected in LS174T cells. The relative amount of sulfated glycans in LS174T cells was almost 10-fold higher than that in the other cells. Moreover, a large polylactosamine-type sulfated O -glycan with a molecular weight >3500 was detected in MKN45 cells. Interestingly, phosphorylated ribose, possibly bound to serine/threonine, was observed in all the cells used in this study. Thus, our established analytical method allows for the analysis of minor acidic O -glycans that cannot be detected using existing glycomics methods.

Isoquinoline (IQL), as a typical nitrogen-containing heterocyclic contaminant in coking wastewater, poses a serious threat to the aquatic environment and human health. Due to its chemical stability, traditional sewage treatment technology is not highly efficient in IQL removal. Advanced oxidation processes (AOPs) driven by ultraviolet radiation could be an effective treatment method, but it could generate toxic byproducts. In this work, the removal of IQL initiated by HO•, ClO•, Cl•, and SO 4 •- in UV/chlorine and UV/persulfate (PDS) process was comprehensively investigated, clarifying the degradation mechanism, reaction kinetics, and ecological toxicity. The findings indicate that the dominant oxidation mechanism of IQL by HO•, ClO•, and Cl• is radical adduct formation (RAF), while single electron transfer (SET) is the main reaction pathway of SO 4 •- with IQL. At 298 K and 1 atm, the order of rate constants for the reactions of IQL with active radicals is Cl• (6.23 × 10 10  M -1  s -1 ) > SO 4 •- (8.81 × 10 9  M -1  s -1 ) > HO• (1.66 × 10 9  M -1  s -1 ) > ClO• (1.62 × 10 8  M -1  s -1 ). The acute and chronic toxicity of IQL and its degradation byproducts at three different trophic levels were evaluated using ECOSAR program. The byproducts produced by the oxidative degradation of IQL by HO• and SO 4 •- are mostly "not harmful", and their toxicity shows a decreasing trend compared to that of IQL. The byproducts derived from the reaction of IQL with Cl• are all "toxic" or "harmful", and the ranking of harm to three types of aquatic organisms is green algae > fish > daphnia. Hence, UV/PDS process could be more secure in pollutant disposal in wastewater. In actual water treatment process, merit attention should be paid to the potential hazards of the byproducts generated by various contaminants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The accurate and rapid detection of persulfate concentration is important for environmental decontamination and human health protection. In this work, a novel self-powered electrochemical sensor for the sensitive monitoring of persulfate was developed, which utilized cobalt tetroxide (Co 3 O 4 @CC) or tin-doped cobalt tetroxide (Sn x Co 3-x O 4 @CC) cathode as the sensing element and anode with electrogenic microorganisms as the power supplier. The Co 3 O 4 @CC and Sn x Co 3-x O 4 @CC electrodes were fabricated by in situ growing nanostructured Co 3 O 4 or Sn x Co 3-x O 4 catalysts on carbon cloth. Electrochemical tests revealed that these electrodes exhibited excellent catalytic reduction performance toward persulfate because of the synergistic catalysis by Co 3 O 4 and electrode electrons, well-exposed Co 2+ /Co 3+ catalytic sites, and high electron transfer efficiency. Tin doping could enhance the catalytic persulfate reduction by improving the conductivity and electron transfer of the Co 3 O 4 catalyst. The electrode prepared at a hydrothermal temperature of 90 °C and a tin dosage of 0.286 g·cm -2 achieved the highest persulfate reduction activity under pH 7. The sensing properties of the self-powered sensors toward persulfate were explored in detail. Results showed that under the optimal external load of 300 Ω, the proposed sensor could display a broad detection range of 0 to 1500 μmol L -1 K 2 S 2 O 8 with sensitivities of 1.13 and 0.12 μA μmol -1 L, a detection limit of 1.11 μmol L -1 (S/N = 3), and a fast response time within 30 s. The sensors also presented satisfactory reproducibility and selectivity during the detection of persulfate. The proposed sensor will provide a new approach for sensitive, on-site, and real-time monitoring of persulfate for a wide range of applications., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Soil contamination with hazardous substances like phenol poses significant environmental and health risks. In situ soil mixing can be a promising technological solution to this challenge. A persulfate and sulfidated zero-valent iron (S-ZVI bm ) system for remediating contaminated soil was developed and tested to be suited to in situ soil mixing. S-ZVI bm was synthesized using a ball mill process, and the optimal sulfur to iron molar ratio for effectively removing phenol from soil removal without pyrophoric risks was 0.12. Soil slurry experiments were performed, and the best phenol oxidation results (high stoichiometric efficiency and sustained oxidation after mixing) were achieved at a persulfate to S-ZVI bm molar ratio of 2:1 and a persulfate to phenol molar ratio of 8:1. A high organic matter content of the silty clay fraction of the soil strongly suppressed persulfate activation, so suppressed phenol removal and increased persulfate consumption. Electron spin resonance and radical scavenging tests confirmed that hydroxyl and sulfate radicals were present during the degradation of phenol. While sulfate radicals predominantly facilitated degradation in the soil, both sulfate and hydroxyl radicals were crucial in the aqueous phase in the absence of soil organic matter. In situ soil mixing simulation tests indicated that the persulfate and S-ZVI bm doses and the mixing rate and duration strongly affected the efficacy of the system, and the optimal conditions for phenol removal were determined. The results indicated that the persulfate/S-ZVI bm system could be tuned to achieve sustained persulfate activation and to remediate contaminated soil employing in situ soil mixing technique., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Inseong Hwang reports financial support was provided by Korea Environmental Industry and Technology Institute. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The degradation of micropollutants via in situ-generated reactive species from coexisting substances in water is a promising approach for advanced water treatment. However, treatment efficiency and practical applications are hindered by limited operation conditions and prohibitive costs, respectively. Herein, we report an upgraded electrochemical filtration system that is chemical-free and made efficient by achieving in situ SO 4 •- generation at enhanced flux and in complicated water matrices. The ion transport was enhanced by coupled electric and flow fields, providing an outstanding performance in removing micropollutants. At the optimized conditions, the proposed system degraded 90.5% of bisphenol A (BPA) in 40 min and its degradation kinetics was 14.7 times that of the batch mode, and the treatment efficiency of the proposed system was 2.5 times more efficient than our previous design because of the enhanced flux. Quenching experiments indicate that indirect oxidation by SO 4 • - and • OH as well as direct electron transfer play critical roles during the BPA degradation. Importantly, the proposed system does not need any added chemicals and uses only the ubiquitous SO 4 2- and electricity. From an environmental point of view, its energy conservation and the lack of additional chemicals ensure its applicability for purifying micropollutants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The efficiency and stability of the electrical activation of persulfate (PS) by transition metal-based cathode are controlled by the cycling of Fe(III)/Fe(II) and the mass transfer of PS. In this study, the mixed-valence MOFs catalyst (Fe II -MIL-53(Fe)) modified flow-through cathode was prepared for the first time. Fe II -MIL-53(Fe) was prepared by replacing part of the iron-oxygen network structure in MIL-53(Fe) with Fe(II), resulting in the formation of coordinated unsaturated iron centers (CUICs). The increase of the Fe(III) CUICs facilitated the conversion of Fe(III) to Fe(II). Furthermore, the cycling of Fe(III)/Fe(II) was further promoted by the electric field. Meanwhile, the hydrodynamic behavior of flow-through cathode was indicated by the computational fluid dynamics (CFD) simulation. The quenching experiments and electron paramagnetic resonance (EPR) results showed that several reactive specie (SO 4 ·- , ·OH, O 2 ·- and 1 O 2 ) were produce. In summary, this work provided an effective strategy for the efficient and stable electrical activation of PDS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Sodium diclofenac (DCF) widely exists in actual water matrices, which can negatively impact ecosystems and aquatic environments even at low-strength. Herein, the adsorption-concentration-mineralization process was innovatively constructed for low-strength DCF elimination by freeze-dried biocarbon and oven-dried biocarbon coupled with cobalt oxide composites derived from the same waste biomass. Surprisingly, low-strength DCF of 0.5 mg/L was adsorbed rapidly and enriched to high-strength DCF under light with a concentration efficiency of 99.67 % by freeze-dried biocarbon. Subsequently, the concentrated DCF was economically mineralized by bifunctional oven-dried biocarbon coupled with cobalt oxide composites for peroxydisulfate (PDS) activation with full PDS activation and 76.11 % mineralization efficiency. Compared with direct low-strength DCF oxidation, adsorption-concentration-mineralization consumed less energy and none PDS residues. Mechanisms confirmed that DCF was adsorbed by freeze-dried biocarbon through hydrogen bonds and π-π stacking interactions, which were switched on due to electron-induced effect by light in DCF desorption-concentration. Furthermore, nonradical pathway (electron transfer) and radical pathway (SO 4 •- ) were involved in efficient PDS activation by oven-dried biocarbon coupled with cobalt oxide composites for concentrated DCF mineralization, and the former was more prominent, in which graphitic carbon, cobalt redox cycle and carboxy groups were the main active sites. Overall, an energy-efficient strategy was proposed for elimination of low-strength DCF in real water matrices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Sulfated fucan from sea cucumber is mainly consists of L-fucose and sulfate groups. Recent studies have confirmed that the structure of sulfated fucan mainly consists of repeating units, typically tetrasaccharides. However, there is growing evidence indicating the presence of irregular domains with heterogeneous units that have not been extensively explored. Moreover, as a key contributor to the nutritional benefits of sea cucumbers, sulfated fucan demonstrates a range of biological activities, such as anti-inflammatory, anticancer, hypolipidemic, anti-hyperglycemic, antioxidant, and anticoagulant properties. These biological activities are profoundly influenced by the structural features of sulfated fucan including molecular weight and distribution patterns of sulfate groups. The latest research indicates that sulfated fucan is dispersed in the extracellular matrix of the body wall of sea cucumbers. This article aimed to review the research progress on the in-situ distribution, structures, structural elucidation strategies, functions, and structure-activity relationships of sulfated fucan, especially in the last decade. It also provided insights into the major challenges and potential solutions in the research and development of sulfated fucan. Moreover, the fucanase and carbohydrate binding modules are anticipated to play pivotal roles in advancing this field., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In situ vaccine (ISV) can provoke systemic anti-tumor immunity through the induction of immunogenic cell death (ICD). The development of ISV technology has been restricted by the limited and suboptimal ICD driven tumor antigen production which are currently relying on chemo-drugs, photo-/radio-sensitizers, oncolytic-virus and immunostimulatory agents. Herein, a sulfate radical (SO 4 ·- ) based ISV is reported that accomplishes superior tumor immunotherapy dispense from conventional approaches. The ISV denoted as P-Mn-LDH is constructed by intercalating peroxydisulfate (PDS, a precursor of SO 4 ·- ) into manganese layered double hydroxide nanoparticles (Mn-LDH). This design allows the stabilization of PDS under ambient condition, but triggers a Mn 2+ mediated PDS decomposition in acidic tumor microenvironment (TME) to generate in situ SO 4 ·- . Importantly, it is found that the SO 4 ·- radicals not only effectively kill cancer cells, but also induce a necroptotic cell death pathway, leading to robust ICD signaling for eliciting adaptive immunity. Further, the P-Mn-LDH can activate the stimulator of interferon genes (STING) pathway to further boost anti-tumor immunity. Collectively, the P-Mn-LDH based ISV exhibited potent activity in inhibiting tumor growth and lung metastasis. When combined with immune checkpoint inhibitor, significant inhibition of distant tumors is achieved. This study underpins the promise of SO 4 ·- based vaccine technology for cancer immunotherapy., (© 2024 Wiley‐VCH GmbH.)

Bipolar electrochemical microscopy (BEM), which visualizes the concentration distribution of molecular species in biological systems by electrochemiluminescence (ECL), is expected to be applied to the high-spatiotemporal-resolution imaging of biomolecules, enabling the analysis of cellular functions. In the past, the molecular species that could be imaged by BEM were generally restricted to oxidized molecules due to the limitation derived from the ECL mechanism of the luminophore. Recently, the imaging of dopamine (DA), a reduced molecule, was achieved using Ru (bpy) 3 2+ /glutathione disulfide (GSSG) as a cathodic luminophore. However, a large driving voltage was required for ECL generation, resulting in a low S/N ratio. In this study, we employed N,N'-dimethyl-3,4,9,10-perylenetetracarboxylic diimide (PDI-CH 3 )/potassium peroxodisulfate (K 2 S 2 O 8 ), which is a cathodic luminophore that can be reduced at a nobler potential to produce ECL than [Ru(bpy) 3 ] 2+ /GSSG. First, the ECL mechanism of PDI-CH 3 /K 2 S 2 O 8 was elucidated by using a PDI-CH 3 drop-cast glassy carbon electrode (GCE) immersed in K 2 S 2 O 8 solution as the working electrode in a 3-electrode system. The PDI-CH 3 drop-casted GCE, a single closed bipolar electrode (c-BPE), was used as the cathode in the successful quantification of 50-500 μmol L -1 DA in a sample chamber in which a c-BPE anode was immersed, resulting in a high S/N. The selective detection of DA in the presence of ascorbic acid was achieved by modifying the anode with Nafion. Finally, DA imaging was demonstrated using a commercially available anisotropic conducting film with PDI-CH 3 coating on the cathode surface as a c-BPE array. The change in the concentration distribution in the inflow of DA was successfully imaged based on the change in the ECL intensity at the c-BPE cathode. This BEM system is expected to be useful for DA imaging of the brain., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)