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Background: Patulin (PAT) is a mycotoxin, usually found in fruit and their products, that can potentially be harmful to human health. In order to achieve rapid detection of mycotoxins and ensure the safety of food. This study reported a novel ratiometric fluorescent aptasensor for PAT detection. In this study, we used aptamer as the recognition element, Hybrid double stranded modified with fluorescent substances as the fluorescent donor, and AuNCs@CGO as the fluorescent acceptor. After the addition of PAT, the ratiometric fluorescence "turn on" response was exhibited., Results: The AuNCs@CGO are obtained by amide reaction between BSA-AuNCs and carboxylated graphene oxide (CGO). The prepared AuNCs@CGO can shorten the time of FRET effect and exhibit highly efficient quenching ability by adsorption effects (π-π stacking and electrostatic gravity) on the Aptamer-modified CDs. When the target PAT bound specifically to the CDs-apt, the fluorescence of the CDs-apt would recover, while the fluorescence of ROX modified cDNA remained unchanged. This ratiometric fluorescence response improved the accuracy of PAT detection. In addition, the proposed had good linearity for PAT in the range of 0.1-50 ng/mL with a limit of detection 0.16 ng/mL. The recovery of standard addition in grapes were 95.9%-105.4 %., Significance: An effective fluorescent detection method for PAT was constructed based on aptamer and nanomaterials. This new fluorescent biosensor has the characteristics of simple synthesis, easy operation, high sensitivity, strong selectivity and a low LOD, which may be a promising idea and platform for the detection of food safety hazard factors., 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.)

One of the most promising approaches to effectively modulate the performance of immunochromatography (ICA) is the rational design of nanomaterials. It is anticipated to facilitate highly sensitive ICA analysis by introducing and controlling the internal defect structures of nanomaterials. Herein, we designed Bi 2 S 3- x @AuNPs with deep-level defect properties, revealing that these deep defects act as electron-hole nonradiative complex centers to promote phonon production, ultimately leading to photothermal analytical performance in ICA. By effectively regulating the defect density, the assay showed extraordinary colorimetric intensity, photothermal performance, and stability, which were conducive to constructing sensitive ICA. With a proof-of-concept for gentamicin (Gen), the limit of detection (LOD) was determined to be 0.0358 ng mL -1 , with overall recoveries ranging from 84.40% to 108.30% in both milk and milk powder samples. It demonstrates the importance of the rational design of internal defect structures to improve analytical performance and broaden the application of ICA.

Polymeric nanocarriers have attracted significant attention in the field of anticancer drug delivery due to their unique advantages. However, designing nanocarriers that can maintain stability in the bloodstream while achieving specific drug release within tumor cells remains a major challenge. To address this issue, constructing reversible cross-linked polymeric nanocarriers that are sensitive to the intracellular reducible glutathione (GSH) characteristic of the tumor microenvironment is a promising strategy. Based on this, we designed and synthesized two novel six-membered bicyclic carbonate monomers containing disulfide (DSBC) and trisulfide (TSBC) bonds. Through a one-step ring-opening polymerization, a series of reduction-sensitive polycarbonate copolymers (i.e., PEG-PDSBC and PEG-PTSBC) were prepared, and doxorubicin (DOX)-loaded nanoparticles were fabricated using a nanoprecipitation method. The in vitro drug release behaviors of these nanoparticles were systematically investigated. The results showed that these polymers, due to the cross-linked structure formed by the ring-opening polymerization of their bicyclic monomers, could self-assemble into stable nanoparticles. Under different concentrations of glutathione, DOX-loaded PEG-PTSBC nanoparticles demonstrated faster drug release, indicating more optimized intracellular drug release properties. Further cytotoxicity experiments revealed that both types of blank nanoparticles exhibited good biocompatibility with the 4T1 and NIH-3T3 cells. Fluorescence microscopy and flow cytometry results further indicated that DOX-loaded PEG-PTSBC nanoparticles released more drugs in 4T1 cells, significantly inhibiting tumor cell growth compared with DOX-loaded PEG-PDSBC nanoparticles, with no noticeable difference in NIH-3T3 normal cells. In conclusion, this study suggests that trisulfide cross-linked polycarbonate-based nanocarriers hold promise as an anticancer drug delivery system that combines stability in the bloodstream with specific intracellular drug release, offering new insights for the development of novel, efficient, and safe anticancer nanomedicines.

Around 40 % of patients fail to achieve primary clinical outcomes for rheumatoid arthritis (RA). The growth of lymphatic system in the synovial membrane, is a primary response during RA inflammation. It is suggested that a delivery strategy targeting immunosuppressive agents to the synovial lymph nodes and then to the immune cells is beneficial for resolving arthritis. This study introduced a synthetic polypropylene sulfide methotrexate nano-delivery system (PPS-MTX), which was prepared by covalently bonding methotrexate to polypropylene sulfide, with a diameter size range of 36 nm. It enhanced joint accumulation and retention, which can be selectively uptake by antigen-presenting cells in the synovial lymphatic system. The results indicated that PPS-MTX nanoparticles effectively improved arthritis disease progression and restored the immune tolerance microenvironment in the synovial lymphatic system, promoting peripheral tolerance in collagen-induced arthritis mice. Additionally, no systemic toxicity was observed. This study presents a promising targeted strategy for inducing immune tolerance in the treatment of rheumatoid arthritis., 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.)

Lead ions (Pb 2+ ) are heavy metal environmental pollutants that can significantly impact biological health. In this study, the synthesis of a ternary nanocomposite, ErVO 4 /P@g-C 3 N 4 /SnS 2 , was achieved using a combination of hydrothermal synthesis and mechanical grinding. The as-fabricated photoelectrochemical (PEC) sensor was found to be an ideal substrate for Pb 2+ detection with high sensitivity and reliability. The ErVO 4 /P@g-C 3 N 4 /SnS 2 /FTO was selected as the substrate because of its remarkable and reliable photocurrent response. The Pb 2+ sensor exhibited a low detection limit of 0.1 pM and a broad linear range of 0.002-0.2 nM. Moreover, the sensor exhibited outstanding stability, selectivity, and reproducibility. In real-time applications, it exhibited stable recovery and a low relative standard deviation, ensuring reliable and accurate measurements. The as-prepared PEC sensor was highly stable for the detection of Pb 2+ in different water samples. This promising characteristic highlights its significant potential for use in the detection of environmental pollutants., 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.)

Many studies show that ortho-phenylenediamine (OPD) produces an oxidized fluorescent product when exposed to an oxidizing agent that enables the direct or indirect fluorescence detection of a range chemical and biochemical analytes. However, there is no report on this unique optical behavior for other two isomers of phenylenediamine. This study demonstrates that a simple hydrothermal treatment of para-phenylenediamine (PPD) in the presence of sulfuric acid results in the formation of fluorescent N, S-doped carbon dots (CDs) with triple functionalities including the reduction of Au 3+ into gold nanoparticles (AuNPs), the stabilization of the produced AuNPs, and the determination of Au 3+ concentration through an intrinsic ratiometric fluorescence signal. In the presence of Au 3+ , the blue emission of CDs at 437 nm quenched, and a green emission at 540 nm emerged. The linear concentration range for the determination of Au 3+ was 20 nM-16 µM with a detection limit of 16 nM. Additionally, the dual emissive CDs-AuNPs hybrid probe showed potential for the indirect fluorescence ratiometric determination of cysteine and sulfide ions. The linear concentration range for cysteine and sulfide ions were 0.25-8 μM and 0.1-6 μΜ, with detection limits of 0.095 μM and 0.041 μM, respectively. Accordingly, CDs were applied to detect Au 3+ and S 2- in real water samples. Moreover, the synthesized CDs showed no cytotoxicity for HeLa cells up to 300 µg mL -1 , as determined by the MTT assay. Therefore, their potential for intracellular imaging of Au 3+ in living cells was also investigated., 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.)

Fabrication of ternary composited photocatalytic nanomaterials with strong interaction is vital to deriving the fast charge separation for efficient photodegradation of organic contaminants in wastewater under visible light. In this work, novel ternary 2D/3D/2D MoS 2 -In 2 O 3 -WS 2 multi-nanostructures were synthesized using facile hydrothermal processes. XRD, FTIR, and XPS results confirmed the phase, functional groups, and element composition of pure MoS 2 , MoS 2 -In 2 O 3, and MoS 2 -In 2 O 3 -WS 2 hybrids. UV-DRS spectra of the MoS 2 -In 2 O 3 -WS 2 ternary hybrid indicate maximum absorption in the visible light range with a band-gap energy value of 2.4 eV. The surface of the 2D WS 2 nanosheet structure tightly blends and densely disperses 2D MoS 2 nanosheets and 3D In 2 O 3 nanocubes. This confirmed the formation of the MoS 2 -In 2 O 3 -WS 2 ternary hybrid in the form of 2D/3D/2D multi-nanostructures, which is also indicated from SEM and HR-TEM images. The synthesized MoS 2 -In 2 O 3 -WS 2 ternary hybrid showed maximum photocatalytic activity under visible-light for antimicrobial agents such as triclosan (TCS) and trichlorocarban (TCC). The photocatalytic activity of TCS was revealed to be 95% at 90 min, while that of TCC was 93% at 100 min. The reusability and stability tests of the prepared MoS 2 -In 2 O 3 -WS 2 ternary hybrid after four consecutive photocatalytic cycles were analyzed by FTIR and SEM, which indicated that the prepared ternary hybrid was very stable. Overall results suggested that the developed MoS 2 -In 2 O 3 -WS 2 (2D/3D/2D) multi-nanostructures are environmentally friendly and low-cost nanocomposites as a potential photocatalyst for the removal of antimicrobial agents from 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.)

Hydrogen polysulfide (H 2 S n , n≥2), as a kind of active sulfur species (RSS), has become a hot topic in RSS. It can regulate the biological activity of many proteins through S-sulfhydrylation of cysteine residues (protein Cys-SSH), and has a protective effect on cells. Although there have been some studies on hydrogen polysulfide, its production, degradation pathway and regulation mechanism still need further be researched. In presented study, an original lysosome-localized fluorescent probe for determining H 2 S n was developed utilizing rhodamine as the fluorogen. The probe used morpholine as the locating unit of lysosomes and chose 2-fluoro-5-nitrobenzoate as the recognizing group. Before adding H 2 S n , the proposed probe displayed a spironolactone structure and emitted very weak fluorescence. After adding H 2 S n , a conjugated xanthene was formed and the probe demonstrated green fluorescence. When the H 2 S n concentration was varied from 6.0×10 -7 mol·L -1 to 10.0×10 -5 mol·L -1 , the fluorescence intensity of the probe was linearly dependent on the H 2 S n concentration. And the detection limit was 1.5×10 -7 mol·L -1 . The presented probe owned a fast response speed, good selectivity, excellent sensitivity and broad pH work scope. In addition, the probe had been well utilized to sense endogenic and exogenic H 2 S n in lysosomes., 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.)

Hypoxia is one of the most typical features among various types of solid tumors, which creates an immunosuppressive tumor microenvironment (TME) and limits the efficacy of cancer treatment. Alleviating hypoxia becomes a key strategy to reshape hypoxic TME which improves cancer immunotherapy. However, it remains challenging to perform tumor precision therapy with controllable switches through hypoxia-activated gene editing and prodrugs to alleviate hypoxia. In this study, silica-coated second near-infrared window (NIR-II) emitting silver sulfide quantum dots are used as the carrier to load the Clustered Regularly Interspaced Short Palindromic Repeats/Cas9 (CRISPR/Cas9) system to target hypoxia-inducible factor-1 (HIF-1α) and guide tumor-targeted imaging. To reduce the off-target effects in nontumor cells and better control safety risks, a TME-triggered cascade-activation nanodiagnostic and therapeutic platform (AA@Cas-H@HTS) is designed, which achieves the hypoxia activation of prodrug tirapazamine (TPZ) and spatiotemporal release of CRISPR/Cas9 ribonucleoprotein. Tumor hypoxia is greatly alleviated by the synergistic function of HIF-1α depletion by gene editing and TPZ activation. Importantly, targeting HIF-1α disrupts the programmed cell death 1/programmed cell death ligand 1 (PD-1/PD-L1) signaling pathway, which effectively reshapes the immune-suppressive TME and activates T cell-mediated antitumor immunity. Taken together, we have provided a TME-triggered cascade-activation nanoplatform to alleviate hypoxia for improved cancer immunotherapy.

The sulfane sulfur pool, comprised of persulfide (RS-SH) and polysulfide (RS-S n H) derived from hydrogen sulfide (H 2 S), has emerged as a major player in redox biochemistry. Mitochondria, besides energy generation, serve as significant cellular redox hubs, mediate stress response and cellular health. However, the effects of endogenous mitochondrial sulfane sulfur (MSS) remain largely uncharacterized as compared with their cytosolic counterparts, cytosolic sulfane sulfur (CSS). To investigate this, we designed a novel artificial substrate for mitochondrial 3-mercaptopyruvate sulfurtransferase (3-MST), a key enzyme involved in MSS biosynthesis. Using cells expressing a mitochondrion-localized persulfide biosensor, we demonstrate this tool's ability to selectively enhance MSS. While H 2 S was previously known to suppress human immunodeficiency virus (HIV-1), we found that MSS profoundly affected the HIV-1 life cycle, mediating viral reactivation from latency. Additionally, we provide evidence for the role of the host's mitochondrial redox state, membrane potential, apoptosis, and respiration rates in managing HIV-1 latency and reactivation. Together, dynamic fluctuations in the MSS pool have a significant and possibly conflicting effect on HIV-1 viral latency. The precision tools developed herein allow for orthogonal generation of persulfide within both mitochondria and the cytosol and will be useful in interrogating disease biology., (© 2024 Wiley-VCH GmbH.)

The resource utilization of natural pyrite not only reduces secondary pollution but also brings certain environmental benefits. However, the green and efficient use of pyrite presents certain challenges. In this study, a novel electro-Fenton (EF) system was constructed utilizing copper modified graphite felt (GF/Cu) as cathode and natural pyrite (com-FeS 2 ) as catalyst. The results demonstrated that the system exhibited a remarkable stability over an extensive pH range (3.0-10.0) and remained effective even under adverse environmental conditions, such as high salinity or elevated antibiotic concentration. After optimizing the reaction conditions, 0.2 mM sulfamerazine (SMZ) was almost completely degraded within 1.5 h. The results highlighted the catalytic role of Fe(II) on the com-FeS 2 surface. Combined with quenching experiments and quantitative analysis of reactive oxygen species (ROS), the removal of SMZ was primarily attributed to the generation of •OH, ordered by 1 O 2  > •O 2 -  > •OH ads , a possible degradation pathway was proposed by HR-LC-MS. The biological toxicity after the reaction was detected, and the introduction of polyvinylpyrrolidone (PVP) was beneficial to reduce the biological toxicity of iron dissolution. This work provides new insights into the green and efficient resource utilization of natural pyrite and significantly expands the pH applicability range of the Fenton process, demonstrating the large-scale industrial application potential of pyrite., 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.)

As one of the most harmful pathogenic bacteria in shrimp aquaculture, Vibrio parahaemolyticus often causes massive mortality in shrimp. Accurate and rapid detection of V. parahaemolyticus in shrimp farming is essential for avoiding huge economic losses caused by related diseases. In this study, we designed a dual-recognition platform for efficient identification and quantification of V. parahaemolyticus. First, the target bacterium was captured with magnetic beads functionalized by aptamers (Apt-MBs), and then, the broad-spectrum fluorescent probe FcMBL@CdSe-ZnS was used to detect the bacterium based on the interactions between fragment crystallizable mannose-binding lectin (FcMBL) and pathogenic bacteria. The proposed dual-recognition strategy centered around aptamers and FcMBL@CdSe-ZnS was applied to definite quantification of V. parahaemolyticus over a wide range of 10-10 8 CFU/mL with a limit of detection of 4 CFU/mL within 55 min. The feasibility was demonstrated by using the platform to detect V. parahaemolyticus from shrimp intestine, aquaculture water, and seawater., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

A highly sensitive and selective label-free impedimetric immunosensor based on AuNPs@pDA@NiCo 2 S 4 @MoS 2 nanocomposite modified on the surface of a screen-printed electrode (SPE) was designed for the detection of interleukin-6 (IL-6). The distribution of NiCo 2 S 4 nanoparticles on MoS 2 nanosheets was able to prevent them from agglomerating. The polydopamine (pDA) layer was coated on the surface of NiCo 2 S 4 @MoS 2 nanosheets by self-polymerization, which improved the stability and biocompatibility of the nanomaterial. The excellent reduction ability of pDA promoted the synthesis of gold nanoparticles (AuNPs), which increased the amount of antibody adsorption and the conductivity of the material. Finally, the antibody (Ab) of IL-6 was immobilized on the surface of AuNPs@pDA@NiCo 2 S 4 @MoS 2 nanocomposite. Electrochemical impedance spectroscopy (EIS) was used to detect the change of impedance before and after the immune response between Ab and IL-6 antigen (IL-6). Under the optimal experimental conditions, the relative change in impedance and the logarithmic concentration of IL-6 showed a good linear relationship in the range 1.00 to 1.00 × 10 6  pg/mL, with a low detection limit of 0.97 pg/mL. In addition, the proposed immunosensor performed with good reproducibility, stability, and specificity. It was successfully applied to the determination of IL-6 in patient's serum samples of head and neck carcinoma with recoveries of 98.40% to 106.5%. To sum up, the proposed label-free impedimetric immunosensor was successfully constructed for IL-6 detection in real samples., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Hydrogen persulfide (H 2 S 2 ) is an important sulfur-containing signaling molecule that plays a crucial role in the homeostasis of various organ systems, such as the renal, cardiovascular, liver, and gastrointestinal systems. However, research on H 2 S 2 in biological settings is still challenging due to its instability and high reactivity. Compounds that can controllably release H 2 S 2 (also known as donors) are thus crucial research tools. Currently, available H 2 S 2 donors are still very limited, with most of them relying on modified disulfide templates. These templates possess an unavoidable limitation of being susceptible to cellular disulfide exchange which can compromise their efficacy. In this work, we explored nondisulfide-based and nonoxidation-dependent templates for the design of H 2 S 2 donors. We found that tertiary naphthacyl thiols could undergo phototriggered C-S homolytic cleavage to form H 2 S 2 via hydrosulfide (HS) radicals. In addition, the release of H 2 S 2 was associated with the formation of a product with strong blue fluorescence, which allowed for real-time monitoring of the release process. This reaction was demonstrated to proceed effectively in both buffers and cells, with the ability to enhance intracellular production of persulfides, including GSSH, CysSSH, H 2 S 2 , H 2 S 3 , etc. It provides a unique photocontrolled H 2 S 2 donor system with distinct advantages compared to known H 2 S 2 donors due to its good stability and spatiotemporal control ability.

Reactive sulfur species (RSS) including persulfides (RSSHs), biothiols, and hydrogen sulfide (H 2 S) are key regulators in various physiological processes. To better understand the symbiotic relationship and interconversion of these RSS, it is highly desirable but challenging to develop analytical techniques that are capable of detecting and quantifying them. Herein, we report the rational design and synthesis of novel trityl-radical-based electron paramagnetic resonance (EPR) probes dubbed CT02-TNB and OX-TNB. CT02-TNB underwent fast sulfur exchange reactions with two reactive RSSHs (PS1 and PS2) which were released from their corresponding donors PSD1 and PSD2 to afford the specific conjugates. The resulting conjugates exhibit characteristic EPR spectra, thus enabling discriminative detection and quantitation of the two RSSHs. Moreover, CT02-TNB showed good response toward other RSS including glutathione (GSH), cysteine (Cys), H 2 S, and sulfite as well. Importantly, based on the updated EPR spectral simulation program, simultaneous quantitation of multiple RSS (e.g., PS1/GSH/Cys or PS1/GSH/H 2 S) by CT02-TNB was also achieved. Finally, the levels of released PS1 from PSD1 and endogenous GSH in isolated mouse livers were measured by the hydrophilic OX-TNB. This work represents the first study achieving discriminative and quantitative detection of different persulfides and other RSS by a spectroscopic method.

We propose a novel approach to identify the origin of pyrite grains and distinguish biologically influenced sedimentary pyrite using combined in situ sulfur isotope (δ 34 S) and trace element (TE) analyses. To classify and predict the origin of individual pyrite grains, we applied multiple machine-learning algorithms to coupled δ 34 S and TE data from pyrite grains formed from diverse sedimentary, hydrothermal, and metasomatic processes across geologic time. Our unsupervised classification algorithm, K-means++ cluster analysis, yielded six classes based on the formation environment of the pyrite: sedimentary, low temperature hydrothermal, medium temperature, polymetallic hydrothermal, high temperature, and large euhedral. We tested three supervised models (random forest [RF], Naïve Bayes, k-nearest neighbors), and RF outperformed the others in predicting pyrite formation type, achieving a precision (area under the ROC curve) of 0.979 ± 0.005 and an overall average class accuracy of 0.878 ± 0.005. Moreover, we found that coupling TE and δ 34 S data significantly improved the performance of the RF model compared with using either TE or δ 34 S data alone. Our data provide a novel framework for exploring sedimentary rocks that have undergone multiple hydrothermal, magmatic, and metamorphic alterations. Most significant, however, is the demonstrated potential for distinguishing between biogenic and abiotic pyrite in samples from early Earth. This approach could also be applied to the search for potential biosignatures in samples returned from Mars.

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.)

Sulfide ZnS-SiO 2 composite photocatalysts with biogenic silica matrix were prepared by sol-gel method based on wet gel and xerogel. FT-IR, SEM, XRD, EDXRF, UV-Vis, and XPS methods were systematically used to characterize the obtained materials. The use of support allowed to obtain stable porous (S BET  = 79-105 m 2  g -1 ; V pore  = 0.25-0.17 cm 3 ·g -1 ) ZnS-SiO 2 photocatalysts in aqueous solutions. Zn 2+ content in methyl orange solution after its degradation was 0.4 MPC. ZnS-SiO 2 composites had 3.68-3.70 eV band gap. The obtained materials were photoactive under different irradiation conditions (sunlight, UV-light, Xenon light, visible light) due to effective separation of charge carriers (e - and h + ). Methyl orange degradation degree under UV light excitation was 35-88%, under sunlight - 11-30%. ZnS-SiO 2 composite synthesized using silica xerogel showed a greater photoactivity due to a presence of cone-shaped or cylindrical pores with one open end in its structure and a higher content of ZnS photoactive component. A comparative study of photocatalytic performance of methyl orange degradation by ZnS-SiO 2 under UV irradiation was investigated using radical scavengers. • O 2 - was main active species during MO degradation under UV irradiation, and electrons played additional role during the photocatalytic process., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

A ratiometric electrochemiluminescence (ECL) aptamer-based sensing platform was fabricated for prostate-specific antigen (PSA) determination. Activated CdS nanocrystals/multi-walled carbon nanotubes (CdS/MCNTs) and luminol-Pt/PAMAM nanocomposites (L-Pt/PAMAM NCs) were synthesized and used as cathodic and anodic ECL emitters, respectively. Amino group-modified aptamers were assembled on carboxylated magnetic beads, followed by hybridization with probe DNA functionalized L-Pt/PAMAM NCs. In the presence of PSA, the aptamer would bind specifically to the target PSA, thereby releasing L-Pt/PAMAM NCs. After magnetic separation, the separated L-Pt/PAMAM NCs would hybridize with capture DNA on CdS/MCNTs coated on glassy carbon electrode. This binding would lead to a decrease in cathodic ECL signal of CdS/MCNTs, due to the efficient energy transfer from CdS/MCNTs to L-Pt/PAMAM NCs. Meanwhile, L-Pt/PAMAM brought the anodic ECL signal from luminol. With the increase of PSA concentration, the ECL emission from luminol increased and the ECL emission from CdS/MCNTs decreased. The ratio of ECL intensity of luminol at 0.55 V and CdS/MCNTs at - 1.25 V could be used to quantify the concentration of PSA. This method enables sensitive and reliable detection of PSA over a wide range from 0.05 to 200 ng mL -1 , and the detection limit is 0.02 ng mL -1 ., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

In this work, Bi 2 S 3 nanoflowers were in situ anchored on the surface of Ti 3 C 2 via a hydrothermal process to obtain MXene-supported Ti 3 C 2 /Bi 2 S 3 nanocomposite, then incorporated inside in sodium alginate polymer to prepared hydrogel materials (Ti 3 C 2 /Bi 2 S 3 @SA-H) which outperforms and have an excellent capability for the removal of pollutants like disinfected byproducts. The synthesized hydrogel material Ti 3 C 2 /Bi 2 S 3 @SA-H may be utilized for a variety of functional materials in environmental applications. Furthermore, the Ti 3 C 2 /Bi 2 S 3 @SA-H was characterized by SEM, EDX, XRD, BET, AFM, FTIR, Zeta potential, XPS, Raman and TGA. Remarkably, Ti 3 C 2 /Bi 2 S 3 @SA-H hydrogel 0.007 cm 3  g -1 , 159.5 nm and 0.0017 cm 3  g -1 , 160.5 nm materials exhibited the highest average pore diameter. The research focused on evaluating the adsorption capability of Ti 3 C 2 /Bi 2 S 3 @SA-H hydrogel materials for 2,6-dibromo-4-nitrophenol (DBNP), 2,4,6-triiodophenol (TIP), 2,4,6-Trichlorophenol (TCP) and 2,6-dichloro-4-nitrophenol (DCNP). The findings indicated that the material exhibited the eradication efficiency of about 662, 657, 647 and 617 mg/g from DBNP, TIP, TCP and DCNP respectively. Several adsorption isotherms were extensively examined, encompassing the Temkin, Langmuir and Freundlich models, alongside pseudo-first and second-order models. The Langmuir and pseudo-second-order models showed the highest degree of consistency with the observed data. Concerning regeneration and reusability, the materials demonstrated easy regeneration and effective recyclability over the course of 10 cycles. The notable adsorption capacity, coupled with the innovative combination of Ti 3 C 2 /Bi 2 S 3 and polymer hydrogel, along with its recyclability, positions our material Ti 3 C 2 /Bi 2 S 3 @SA-H as a highly prospective competitors for wastewater treatment and other critical areas in water 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 B.V. All rights reserved.)

Numerous microbial species have caused infectious diseases worldwide, which have become a social burden and a menace to the community. So, there is a need to develop antimicrobial materials and specialized materials for biomedical applications. In the present investigation, we report the simple synthesis, the physicochemical, and antibacterial activity of Silver doped zinc sulfide (ZnS: Ag) capped with Chitosan (CS) to produce ZnS: Ag/CS bionanocomposites (BNCs). The prepared BNCs was evaluated by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) mapping, and UV-Vis spectroscopy. According to the XRD results, ZnS: Ag/CS particles with semicrystalline chitosan/hexagonal ZnS phase structures and an average crystallite size in the range of 30-40 nm was formed. According to FESEM images, a spherical/hexagonal shape of ZnS: Ag particles embedded in the polymeric chitosan matrix. The colony counting method was employed to investigate the antibacterial activity on Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria. The results revealed that ZnS: Ag particles and ZnS: Ag/CS BNCs have stronger antibacterial activities than pure CS and ZnS. The reduction percentage of ZnS: Ag/CS BNCs against S. aureus and E. coli after 6 h of treatment was >99.9 % and 70 % respectively. These findings suggest that ZnS: Ag/CS BCs not only offer superior antimicrobial properties compared to individual ZnS and CS but also have great potential for advancing biomedical applications due to their enhanced antibacterial performance. The simplicity of the synthesis method and the use of non-toxic materials like chitosan make this a sustainable approach for developing antimicrobial agents, which is a key advantage of this study., 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.)

Fluorescence imaging (FI) employing near-infrared (NIR) light within the range of ~750-1350 nm enables biomedical imaging several millimeters beneath the tissue surface. More recent investigations into the short-wave IR (SWIR) transparency windows between ~1550-1870 and 2100-2300 nm highlight their superior capabilities. This research presents a comparison of IR-FI of PbS quantum dots, emitting at 990, 1310, and 1580 nm, through the mouse scalp skin, skull, and brain. The SWIR fluorescence is the most effectively transmitted signal, showing particularly significant enhancement when passing through the skull, which causes high light scattering. For the analysis of the imaging results and light propagation through the organs, their spectra of attenuation, absorption, and scattering coefficients are measured. In view of biomedical imaging, attenuation due to light scattering is a more destructive factor. Hence, the spatial resolution and imaging contrast can be improved by operating in SWIR due to decreased light scattering., (© 2024 Wiley‐VCH GmbH.)

Herein, a novel acylhydrazone biosorbent (GSL) with abundant three-dimensional porous structure was successfully prepared by using low-cost starch as raw material for water pollution remediation applications. Various analytical techniques were applied to characterize the morphological structure and chemical composition. Interestingly, the adsorption efficiency of the adsorbent towards Malachite green (MG), Safranin O (SO), Cu 2+ , and sulfide in the static adsorption experiment was extremely high due to presence of ample functional groups. Additionally, the adsorption isotherm and kinetic experiments revealed that the adsorption processes were based on monolayer chemisorption. The maximum sorption amounts were 2237.4961 mg/g for SO, 2101.6610 mg/g for MG, 410.7019 mg/g for Cu 2+ , and 483.0194 mg/g for sulfides at 298.15 k. The thermodynamic analysis also demonstrated that all adsorption processes were spontaneous heat processes. The adsorption mechanism was analyzed by FTIR, SEM-EDAX and XPS. The adsorption of SO onto GSL reached 1025.8617 mg/g in continuous adsorption experiments, and the experimental data were fitted through the Thomas model and Yoon-Nelson model. Furthermore, the GSL showed good reusability and salt resistance. Importantly, starch-based acylhydrazone as the adsorbent for the simultaneous removal of hazardous dyes, heavy metal ions and sulfhides has not yet been seen reported., 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.)

Addressing the inefficiency of current therapeutic approaches for hepatocellular carcinoma is an urgent and pressing challenge. PANoptosis, a form of inflammatory programmed cell death, presents a dependable strategy for combating cancer by engaging multiple cell death pathways (apoptosis, pyroptosis, and necroptosis). In this study, an ultrasmall Bi 2 Sn 2 O 7 nanozyme with ultrasound-magnified multienzyme-mimicking properties is designed and engineered as a PANoptosis inducer through destroying the mitochondrial function of tumor cells and enhancing the intracellular accumulation of toxic reactive oxygen species, finally triggering the activation of PANoptosis process. The role of PANoptosis inducer has been verified by the expression of related proteins, including cleaved Caspase 3, NLRP3, N-GSDMD, cleaved Caspase 1, p-MLKL, and RIPK3. The inclusion of external ultrasonic irradiation significantly augments the enzyodynamic therapeutic efficiency. In vitro and in vivo antineoplastic efficacy, along with inhibition of lung metastasis, validate the benefits of the Bi 2 Sn 2 O 7 -mediated PANoptosis pathway. This study not only elucidates the intricate mechanisms underlying Bi 2 Sn 2 O 7 as a PANoptosis inducer, but also offers a novel perspective for the treatment of hepatocellular carcinoma., (© 2024 Wiley‐VCH GmbH.)

Utilizing inexhaustible solar energy for water purification represents a green and sustainable solution to water scarcity. However, the developments of efficient, inexpensive, convenient and reliable photothermal materials remain a major challenge. Herein, a facile and versatile preparation strategy of sodium alginate (SA)-CuS composite coating with superior adhesion and stability has been proposed toward high-efficiency solar-driven interfacial evaporation. The fabrication process can be quickly completed in aqueous solution with cheap reagents. The SA-CuS coating can be firmly adhered on different substrates, which can withstand rinsing treatment, iterative freeze-thaw cycles as well as high and low pH environments. The SA-CuS coating can convert various substrates into photothermal materials with broad light absorption for desirable solar evaporation because of high CuS loading and rough surface. As a proof of concept, a wood evaporator covered with the SA-CuS coating can achieve a water evaporation rate of ∼2.2 kg m -2  h - 1 under one sun illumination, which is superior to most reported wood-based solar evaporators., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Mine environments in boreal and sub-boreal zones are expected to experience extreme weather events, increases in temperature, and shifts in precipitation patterns. Climate change impacts on geochemical stability of tailings contaminants and reclamation structures have been identified as important climate-related challenges to Canadian mining sector. Adapting current reclamation strategies for climate change will improve long-term efficiency and viability of mine tailings remediation/restoration strategies under a changing climate. Accordingly, mesocosm experiments were conducted to investigate associations of climate-driven shifts in microbial communities and functions with changes in the geochemistry of organic covers and underlying tailings. Our results show that warming appears to significantly reduce C:N of organic cover and promote infiltration of nitrogen into deeper, unoxidized strata of underlying tailings. We also observed an increase in the abundance of some nitrate reducers and sulfide oxidizers in microbial communities in underlying tailings. These results raise the concern that warming might trigger oxidation of sulfide minerals (linked to nitrate reduction) in deeper unoxidized strata where the oxygen has been eliminated. Therefore, it would be necessary to have monitoring programs to track functionality of covers in response to climate change conditions. These findings have implications for development of climate resilient mine tailings remediation/restoration strategies., Competing Interests: The authors declare no competing interests.

Carbon nanotubes supported cobalt nickel sulphide nanoparticles (nano-NiCo 2 S 4 @CNTs) were successfully prepared by a hydrothermal method as heterogeneous catalyst which can be used as an activator of peroxymonosulphate (PMS) for the degradation of chloroquine phosphate (CQP). Based on characterisation techniques, the prepared catalyst has excellent surface properties and structural stability. When different concentrations of CQP were treated with 0.2 g/L nano-NiCo 2 S 4 @CNTs and 1.0 mM PMS, the highest degradation rate could reach 99.86% after 30 min. Under the interference of pH, common anions and humic acid in the water environment, the reaction system can still achieve high degradation efficiency, showing excellent anti-interference ability and practical applicability. Furthermore, in the nano-NiCo 2 S 4 @CNTs/PMS system, according to the identification results of reactive oxygen species, the free radical and non-free radical pathway are responsible for the degradation of CQP, and the PMS mechanism activation was comprehensively proposed. Twelve intermediate products were detected in the degradation process, and the possible degradation pathways of CQP were proposed. This toxicity analysis demonstrates that the intermediate products formed during CQP degradation pose lower environmental risks compared to the original pollutant. In addition, after using the catalyst four cycles, the removal efficiency of CQP remains above 80%, indicating the excellent reusability and low metal ion leaching characteristics. Therefore, the nano-NiCo 2 S 4 @CNTs synthesised in this research has broad application prospects in activating PMS for wastewater treatment.

Effective identification of sulfur ions (S 2- ) in foodstuff is crucial for food safety and human health, but it remains challenging. Traditional single-mode colorimetric sensing methods are simple and sensitive, but are prone to interference from colored substances which can lead to false positives or negatives results. Herein, we develop a novel "mix-response" biosensor for colorimetric and photothermal dual-mode detection of S 2- with good simplicity, sensitivity and portability. In this biosensor, silver-doping Prussian blue nanoparticle (SPB NPs) was used as signal output component, which not only exhibits blue color characteristics, but also has photothermal conversion properties activated by near-infrared (NIR) laser. Upon increasing the S 2- concentration, the prepared SPB NPs undergo etching, leading to the formation of new silver sulfide precipitation (Ag 2 S), along with different colorimetric and photothermal response signals. For the portable visualization of S 2- , the color information was recorded by a smartphone in combination with RGB (red channel) analysis and the evolution of the photothermal signal was documented by a thermal imager. The introduction of smartphone and handheld thermal imager in this "mix-response" biosensor makes it suitable for on-site quantitative detection of S 2- without sophisticated instrument. Moreover, the development of this "mix-response" biosensor does not need the use of recognition probes (e.g. aptamers and reaction intermediates), thereby simplifying the construct procedures of sensing strategies and improving the economic efficiency of detection. More importantly, the photothermal response signals can overcome the interference of colored substances in foods, thereby reducing the false positives or negatives of the detection results., 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.)

To provide the necessary nitrite for the Anaerobic Ammonium Oxidation (ANAMMOX) process, the effect of nitrite accumulation in the partial sulfide autotrophic denitrification (PSAD) process was investigated using an SBR reactor. The results revealed that the effectiveness of nitrate removal was unsatisfactory when the S/N ratio (mol/mol) fell below 0.6. The optimal conditions for nitrate removal and nitrite accumulation were achieved within the S/N ratio range of 0.7-0.8, resulting in an average Nitrate Removal Efficiency (NRE) of 95.84%±4.89% and a Nitrite Accumulation Rate (NAR) of 75.31%±6.61%, respectively. It was observed that the nitrate reduction rate was three times faster than that of nitrite reduction during a typical cycle test. Furthermore, batch tests were conducted to assess the influence of pH and temperature conditions. In the pH tests, it became evident that the PSAD process performed more effectively in alkaline environment. The highest levels of nitrate removal and nitrite accumulation were achieved at an initial pH of 8.5, resulting in a NRE of 98.30%±1.93% and a NAR of 85.83%±0.47%, respectively. In the temperature tests, the most favourable outcomes for nitrate removal and nitrite accumulation were observed at 22±1 ℃, with a NRE of 100.00% and a NAR of 81.03%±1.64%, respectively. Moreover, a comparative analysis of 16S rRNA sequencing results between the raw sludge and the sulfide-enriched culture sludge sample showed that Proteobacteria (49.51%) remained the dominant phylum, with Thiobacillus (24.72%), Prosthecobacter (2.55%), Brevundimonas (2.31%) and Ignavibacterium (2.04%) emerging as the dominant genera, assuming the good nitrogen performance of the system.

Charge variants are one of the most important quality attributes for protein therapeutics, including antibody drug conjugates (ADCs). ADCs are conjugation products between monoclonal antibodies (mAbs) and highly potent payloads. After attaching a payload, the charge profile of a mAb can be modified due to the change in net charge or surface charge. In this study, we present a unique challenge of charge assay development that arises from a desirable engineering of ADCs that incorporates the hydrolysis-prone succinimide-thioether conjugation chemistry. This engineered hydrolysis at conjugation sites is usually not complete during conjugation process and continuously progressing during mild stress. This hydrolysis also creates a carboxylic functional group, which manifests as acidic peaks in the ADC charge profiles. As a result, ion exchange chromatograms become sensitive measurements of this hydrolysis, which often masks the charge profile change due to other important post-translational modifications. In this study, two approaches were explored to address this unique challenge: to remove the hydrolysis heterogeneity by incubating ADCs under high pH conditions to drive complete hydrolysis; and to analyze charge variants at the subunit level after IdeS digestion. Acceptable charge profiles and quantitative integration results were successfully obtained by both approaches., Competing Interests: Declaration of competing interest All authors are employees of AstraZeneca and may hold stock and/or stock options., (Copyright © 2024 American Pharmacists Association. Published by Elsevier Inc. All rights reserved.)

Florfenicol (F), an antimicrobial agent exclusive to veterinary use within the chloramphenicol class, is extensively applied as a broad-spectrum remedy for animal diseases. Despite its efficacy, concerns arise over potential deleterious residues in animal-derived edibles, posing threats to human health. This study pioneers an innovative approach, introducing a quantum dot fluorescence-based immunoassay (FLISA) for the meticulous detection of F residues in animal-derived foods and feeds. This method demonstrates heightened sensitivity, with a detection limit of 0.3 ng/mL and a quantitative detection range of 0.6-30.4 ng/mL. Method validation, applied to diverse food sources, yields recoveries from 90.4 % to 109.7 %, featuring RSDs within 1.3 % to 8.7 %, the results showed high consistency with the national standard HPLC-MS/MS detection method. These findings underscore the method's accuracy and precision, positioning it as a promising tool for swift and reliable F residue detection, with substantial implications for fortifying food safety monitoring., 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 intended to divulge the potential role of garlic-derived organosulfur compounds (OSCs) in targeting PCSK-9 and averting its interaction with the EGF-A portion of LDL-R via in-vitro and in-silico analysis. Our in-silico screening data showed that 3-(Propylsulfinyl)-L-alanine (PSA), S -Ethyl-L-cysteine (SEC), alliin, and S -Allyl-L-cysteine (SAC) exhibited higher binding energy (-7.05, -7.00, -6.65, and -6.31 Kcal/mol, respectively) against PCSK-9, among other selected OSCs. Further, the protein-protein interaction study of PCSK-9-OSCs-complex with EGF-A demonstrated a similar binding pattern with E-total values ranging from -430.01 to -405.6 Kcal/mol. These results were further validated via in-vitro analysis which showed that SEC, SAC, and diallyl trisulphide (DAT) exhibited the lowest IC 50 values of 4.70, 5.26, and 5.29 µg/mL, respectively. In conclusion, the presented data illustrated that SEC, SAC, and DAT were the best inhibitors of PCSK-9 activity and may have the potential to improve the LDL-R function and lower the circulatory LDL-C level.

Chemotherapy (CT) can significantly inhibit tumor growth, metastasis, and recurrence during cancer therapy. People have widely used platinum drugs in cancer treatment. However, as most chemotherapeutic drugs, platinum drugs still have shortcomings such as poor solubility, low cell uptake, nonspecific distribution, multidrug resistance, and adverse side effects. Therefore, we synthesized hollow copper sulfide (CuS) nanocubes with photothermal and photodynamic properties as carriers for Pt(IV) drugs. Hollow CuS nanocubes have attracted considerable interest in the field of cancer photothermal therapy (PTT) using multiple biological windows. Under near-infrared (NIR) laser irradiation, Cu 2+ can be reduced into Cu + in the presence of hydrogen peroxide in the tumor microenvironment. The resulting Cu + can be used for photodynamic therapy (PDT), which can perform a Fenton-like reaction under acidic conditions (pH 5.5-6.5) and catalyze hydrogen peroxide to produce ·OH in the tumor microenvironment. In addition, compared with Pt(II) drugs, Pt(IV) drugs not only have lower systemic toxicity but also consume glutathione (GSH), thereby increasing reactive oxygen species (ROS) levels in tumor cells and effectively promoting PDT. In this study, we oxidized ethylenediamine platinum chloride to its tetravalent state, loaded the Pt(IV) complexes using hollow CuS nanocubes, and modified the surfaces of the nanoparticles with PEG to improve the EPR effect. The Pt(IV)-loaded hollow CuS nanocubes modified with PEG (Pt(IV)-CuS@PEG) are expected to be used for tumor chemo/photothermal/photodynamic therapy.

The high prevalence of catheter-associated urinary tract infections (CAUTIs) is causing significant concern in healthcare systems. Antibacterial urinary catheters have been developed to prevent CAUTIs in clinical application. In this work, a copper sulfide nanorod (CuS NR)-embedded urinary catheter (CuS/UC) was designed as an antibacterial urinary catheter with photothermal sterilization. The CuS NRs with low cytotoxicity were synthesized via the hydrothermal method. The CuS NRs were embedded into urinary catheters at different weight percentages. The CuS/UC exhibited homogenous surface roughness, low wettability, hydrophobicity, and low adhesiveness, promoting minimal interaction with bacteria and healthy cells. Under near-infrared (NIR) laser irradiation, the 0.8 weight percentage of CuS NRs in the urinary catheter (0.8CuS/UC) reached a temperature of 67.4 °C, demonstrating its photothermal antibacterial activity and suitability for catheter sterilization. Agar plate test verified that CuS/UCs exhibited a superior photothermal antibacterial activity against both Gram-negative Escherichia coli ( E. coli ) and Gram-positive Streptococcus aureus ( S. aureus ). Moreover, the 0.8CuS/UC exhibited excellent biocompatibility and anti-cell adhesion properties. The 0.8CuS/UC with photothermal performance, excellent biocompatibility, and anti-cell adhesion properties demonstrated its potential as a photothermal antibacterial catheter for clinical applications.

Since the sensitivity and accuracy of traditional detection for early gastric cancer diagnosis are still insufficient, it is significant to continuously optimize the optical molecular imaging detection technology based on an endoscopic platform. The signal intensity and stability of traditional chemical fluorescent dyes are low, which hinders the clinical application of molecular imaging detection technology. This work developed a probe based on perovskite quantum dots (PQDs) and peptide ligands. By utilizing CsPbBr 3 perovskite PQDs modified by azithromycin (AZI), combined with the specific polypeptide ligand of CD44v6, a gastric cancer biomarker, the perovskite-based probe (AZI-PQDs probe) which can specifically identify gastric cancer tumor was prepared. Owing to the high photoluminescence quantum yield of CsPbBr 3 PQDs, the naked eye can observe the imaging under the excitation of the hand-held ultraviolet light source. AZI-PQDs probe can accurately identify gastric cancer cells, tissues, and xenograft models with experiments of ex vivo and in vivo fluorescence imaging detection. It also exhibited low toxicity and immunogenicity, indicating the safety of the probe. This work provides a probe combined with cancer specificity and a reliable fluorescent signal that has the potential for application in gastric cancer optical molecular imaging., (© 2024 IOP Publishing Ltd. All rights, including for text and data mining, AI training, and similar technologies, are reserved.)

Inherently limited by poor bioavailability, antiviral agent tenofovir (TFV) is administered to people living with HIV in prodrug form. However, current prodrugs are prematurely metabolized, compromising access to HIV-infected cells and inducing toxicity. Inspired by lipid conjugate TFV exalidex (TXL), we recently disclosed TXL analogs with potent activity and robust hepatic stability in vitro, as well as attractive oral PK profiles in vivo. In parallel, we discovered the equipotent and equally stable hexadecylthiopropyl (HTP) derivative of TXL ( 2a ). Reported herein are the synthetic and bioanalytic efforts that led to potent, safe, and hepatically stable HTP derivatives. While HTP analog 16h showed the most attractive PK profile in mice (55% F) discrepancies in translating in vitro cell-based results to in vivo PK data, for certain prodrugs, indicated that further in vitro/in vivo optimization is required for continued advancement of this program.

The photochemical generation of nicotinamide cofactor 1,4-NADH, facilitated by inorganic photosensitizers, emerges as a promising model system for investigating charge transfer phenomena at the interface of semiconductors and bacteria, with implications for enhancing photosynthetic biohybrid systems (PBSs). However, extant semiconductor nanocrystal model systems suffer from achieving optimal conversion efficiency under visible light. This study investigates quasi-one-dimensional CdS nanorods as superior light absorbers, surface modified with catalyst Cp*Rh(4,4'-COOH-bpy)Cl 2 to produce enzymatically active NADH. This model subsystem facilitates easy product isolation and achieves a turnover frequency (TOF) of 175 h -1 , one of the highest efficiencies reported for inorganic photosensitizer-based nicotinamide cofactor generation. Charge transfer kinetics, fundamental for catalytic solar energy conversion, range from 10 6 to 10 8 s -1 for this system highlighting the superior electron transfer capabilities of NRs. This model ensures efficient cofactor production and offers critical insights into advancing systems that mimic natural photosynthesis for sustainable solar-to-chemical synthesis.

SufU, a component of the SufCDSUB Fe-S cluster biosynthetic system, serves as a Zn-dependent sulfur-carrying protein that delivers inorganic sulfur in the form of cysteine persulfide from SufS to SufBCD. To understand this sulfur delivery mechanism, we studied the X-ray crystal structure of SufU and its sulfur-carrying state (persulfurated SufU) and performed functional analysis of the conserved amino acid residues around the Zn sites. Interestingly, sulfur-carrying SufU with Cys41-persulfide (Cys41-S γ -S δ - ) exhibited a unique Zn coordination structure, in which electrophilic S γ is ligated to Zn and nucleophilic/anionic S δ is bound to distally conserved Arg125. This structure is distinct from those of other Cys-persulfide-S δ -ligated metals of metalloproteins, such as hybrid cluster proteins and SoxAX. Functional analysis of SufU variants with Zn-ligand and Arg125 substitutions revealed that both Zn and Arg125 are critical for the function of SufU with SufS. The Zn-persulfide structure of SufU provides insight into the sulfur-transfer process, suggesting that persulfide-S δ - is stabilized via bridging by Zn and Arg125 of SufU.

Multiplexed fluorescence in vivo imaging remains challenging due to the attenuation and scattering of visible and traditional near infrared (NIR-I, 650-950 nm) wavelengths. Fluorescence imaging using shortwave infrared (SWIR, 1000-1700 nm, a.k.a. NIR-II) light enables deeper tissue penetration due to reduced tissue scattering as well as minimal background autofluorescence. SWIR-emitting semiconductor quantum dots (QDs) with tunable emission peaks and optical stability are powerful contrast agents, yet few imaging demonstrations exclusively use SWIR emission beyond two-color imaging schemes. In this study, we engineered three high quality lead sulfide/cadmium sulfide (PbS/CdS) core/shell QDs with distinct SWIR emission peaks ranging from 1100-1550 nm for simultaneous three-color imaging in mice. We first use the exceptional photostability of QDs to non-invasively track lymphatic drainage with longitudinal imaging, highlighting the detailed networks of lymphatic vessels with widefield imaging over a 2 hr period. We then perform multiplexed imaging with all three QDs to distinctly visualize the lymphatic system and spatially overlapping vasculature networks, including clearly distinguishing the liver and spleen. This work establishes optimized SWIR QDs for next generation multiplexed and longitudinal preclinical imaging, unlocking numerous opportunities for preclinical studies of disease progression, drug biodistribution, and cell trafficking dynamics in living organisms., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Background: Phototherapy based on photocatalytic semiconductor nanomaterials has received considerable attention for the cancer treatment. Nonetheless, intense efficacy for in vivo treatment is restricted by inadequate photocatalytic activity and visible light response., Methods: In this study, we designed a photocatalytic heterostructure using graphitic carbon nitride (g-C 3 N 4 ) and tin disulfide (SnS 2 ) to synthesize g-C 3 N 4 /SnS 2 heterostructure through hydrothermal process. Furthermore, Au nanoparticles were decorated in situ deposition on the surface of the g-C 3 N 4 /SnS 2 heterostructure to form g-C 3 N 4 /SnS 2 @Au nanoparticles., Results: The g-C 3 N 4 /SnS 2 @Au nanoparticles generated intense reactive oxygen species radicals under near-infrared (NIR) laser irradiation through photodynamic therapy (PDT) pathways (Type-I and Type-II). These nanoparticles exhibited enhanced photothermal therapy (PTT) efficacy with high photothermal conversion efficiency (41%) when subjected to 808 nm laser light, owing to the presence of Au nanoparticles. The in vitro studies have indicated that these nanoparticles can induce human liver carcinoma cancer cell (HepG2) apoptosis (approximately 80% cell death) through the synergistic therapeutic effects of PDT and PTT. The in vivo results demonstrated that these nanoparticles exhibited enhanced efficient antitumor effects based on the combined effects of PDT and PTT., Conclusion: The g-C 3 N 4 /SnS 2 @Au nanoparticles possessed enhanced photothermal properties and PDT effect, good biocompatibility and intense antitumor efficacy. Therefore, these nanoparticles could be considered promising candidates through synergistic PDT/PTT effects upon irradiation with NIR laser for cancer treatment., Competing Interests: The authors declare no known competing financial interests or personal relationships that could have influenced the work reported in this paper., (© 2024 Dash et al.)

In the food industry, sulfides are commonly used as preservatives and flavor regulators. However, long-term excessive intake of sulfides can lead to serious health problems. Therefore, developing efficient sulfide detection methods is particularly important. Here, we have effectively synthesized a novel bifunctional copper hydroxide nitrate (Cu 2 (OH) 3 NO 3 ) nanozyme with outstanding peroxidase-like and laccase-like behaviors in basic deep eutectic solvents (DES). Because the various types of sulfides have diverse regulatory effects on the two catalytic behaviors of Cu 2 (OH) 3 NO 3 , a two channel nanozyme sensor array based on the peroxidase-like and laccase-like behaviors of Cu 2 (OH) 3 NO 3 was constructed and successfully used for the identification of six kinds of sulfides (Na 2 S, Na 2 S 2 O 3 , Na 2 SO 3 , Na 2 SO 4 , NaHSO 3 , and Na 2 S 2 O 8 ). Remarkably, the sensor array has achieved successful discrimination among six sulfides present in wine, egg, and milk samples. Finally, the sensor array has successfully distinguished and differentiated three actual samples (wine, egg, and milk). This study is of great significance in promoting the efficient construction of array units and improving the effective identification of sulfides in complex food samples., 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.)

This study presents a novel blend of synthesis techniques for shape-controlled ZnS nanoparticles. Zinc sulfide (ZnS) nanoparticles with distinct morphologies cauliflower-like microstructures (∼4.5 μm) and uniform nanospheres (200-700 nm) were synthesized through an innovative blend of precipitation and hydrothermal techniques. Capping with polyvinylpyrrolidone (PVP) significantly decreased crystallite size (3.93 nm-2.36 nm), modulated the band gap (3.57 eV-3.71 eV), and dramatically influenced morphology, highlighting the novelty of shape-controlled synthesis and its impact on optoelectronic and functional properties. X-ray diffraction confirmed crystallinity and revealed the size-controlling influence of PVP. UV-vis spectroscopy suggested potential tuning of optical properties due to band gap widening upon PVP capping. Field-emission scanning electron microscopy (FESEM) unveiled distinct morphologies: cauliflower-like microstructures for ZnS and uniform nanospheres (200-700 nm) for PVP-ZnS. Both structures were composed of smaller spherical nanoparticles, demonstrating the role of PVP in promoting controlled growth and preventing agglomeration. High-resolution transmission electron microscope (HRTEM) images depicted that the majority of nanoparticles maintain a spherical shape, though slight deviations from perfect sphericity can be discerned. Fourier-transform infrared (FTIR) spectroscopy confirmed that successful PVP encapsulation is crucial for shaping nanospheres and minimizing aggregation through steric hindrance. Photocatalytic activity evaluation using methylene blue (MB) dye degradation revealed significantly faster degradation by PVP-ZnS under ultraviolet (UV) irradiation (within 60 min as compared to 120 min for ZnS), showcasing its superior performance. This improvement can be attributed to the smaller size, higher surface area, and potentially optimized band gap of PVP-ZnS. Additionally, PVP-ZnS exhibited promising antibacterial activity against S. aureus and P. aeruginosa, with increased activity at higher nanoparticle concentrations., 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.)

The photo-activation and photo-dissolution processes of pyrite (FeS 2 ) can affect the environmental behavior of the co-existing hexavalent chromium (Cr(VI)). But the photochemical performance of FeS 2 is intimately dependent on its exposed facets. Herein, FeS 2 nanosheets (FeS 2 NS) and FeS 2 nanocubes (FeS 2 NC) with the dominant exposed facets of (001) and (210)/(100) respectively are prepared. The more Fe 3+ , Fe 2+ , and SO 4 2- are released in the FeS 2 NS system than the other system due to its more excellent generation ability of photogenerated electrons and reactive oxygen species. The higher surface energy on (001) facet leads to the faster dissolution rate of FeS 2 NS. Due to the optimal production ability of photogenerated electrons and Fe 2+ of (001) facet, the much higher Cr(VI) elimination efficiency in the FeS 2 NS system is observed than that in the FeS 2 NC (72.8%) system within 120 min. This work could help to unveil the influence of FeS 2 on the fate of Cr(VI) in surface environment, and offer a theoretical support to clarify the influence of heavy metal ions on the iron sulfide minerals., 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 spatial-resolved and self-calibrated photoelectrochemical (PEC) biosensor has been fabricated by a multifunctional CeO 2 /CdS heterostructure, achieving portable and sensitive detection of carcinoembryonic antigen (CEA) using a homemade 3D printing device. The CeO 2 /CdS heterostructure with matched band structure is prepared to construct the dual-photoelectrodes to improve the PEC response of CeO 2 . In particular, as the photoactive nanomaterial, the CeO 2 also plays the role of peroxidase mimetic nanozymes. Therefore, the catalytic performance of CeO 2 with different morphologies (e.g., nano-cubes, nano-rods and nano-octahedra) have been studied, and CeO 2 nano-cubes (c-CeO 2 ) achieve the optimal catalytic activity. Upon introducing CEA, the sandwich-type immunocomplex is formed in the microplate using GOx-AuNPs-labeled second antibody as detection antibody. As a result, H 2 O 2 can be produced from the catalytic oxidization of glucose substrate by GOx, which is further catalyzed by CeO 2 to form •OH, thus in situ etching CdS and decreasing the photocurrents. The self-calibration is achieved by the dual-channel photoelectrodes on the homemade 3D printing device to obtain the photocurrents ratio, thus effectively normalizing the fluctuations of external factors to enhance the accuracy. This integrated biosensor with a detection limit as low as 0.057 ng mL -1 provides a promising way for ultrasensitive immunoassay in clinic application in complex environments., 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.)

This study investigates the utilization of carbon dots (CDs) from neem leaves (Azadirachta indica) decorated onto cadmium sulfide (CdS) for the photocatalytic degradation of ciprofloxacin. A comparative study of ciprofloxacin degradation with pristine CdS and CD decorated CdS demonstrated high degradation of ∼ 75 % with CD/CdS when compared to bare CdS (∼68 %). Process optimization studies were further carried out with CD/CdS catalysts at different solution pH (4-10), feed concentrations (10-50 mg/L), catalyst loadings (25-125 mg/L), temperatures (10 - 30 °C), and lamp power (25, 50, 250 W and sunlight). Higher temperatures, combined with a solution pH of 7 and catalyst loading of 100 mg/L favored the enhanced degradation of 20 mg/L of ciprofloxacin. The ciprofloxacin degradation rate increased linearly with temperature with an apparent activation energy of 27 kJ mol -1 . The CD/CdS photocatalyst demonstrated maximum degradation rates with higher lamp powers while it also showed remarkable performance under natural sunlight achieving the same degradation within 3 h., 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.)

While treating zinc-containing wastewater, recovering zinc for reuse as a secondary resource has significant environmental and economic benefits. Herein, based on the alkali-activated tourmaline tailings geopolymers (TTG) after adsorption of zinc ions (Zn (II)), a series of new composites with in-situ construction ZnS nanoparticles on TTG (ZnS/TTG) were synthesized, and used as photocatalysts for the photodegradation of tetracycline hydrochloride (TCH) in solution. Specifically, ZnS nanoparticles were uniformly and stably distributed in the layered structure of TTG, interweaving with each other to generate an interfacial electric field, which could induce more photocarrier generation. Meanwhile, TTG acted as an electron acceptor to accelerate the electron transfer at the interface, thus enhancing the photodegradation activity for TCH. The active radical quenching experiments combined with the ESR indicated that the active species produced during the photocatalytic degradation of TCH by ZnS/TTG composites were •O 2 - and photogenerated h + . When the initial concentration of Zn (II) was 60 mg/L, the synthesized 60-ZnS/TTG composites (0.5 g/L) reached 91.53% degradation efficiency of TCH (10 mg/L) at pH = 6. Furthermore, the possible pathways and mechanism of 60-ZnS/TTG composites photodegraded TCH were revealed with the aid of degraded intermediates. This report not only proposed valuable references for reusing heavy metal ions and removing TCH from wastewater, but also provided promising ideas for realizing the conversion of used adsorbents into high-efficiency photocatalysts., 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.)

To control acid mine drainage (AMD) from the source, a new environmentally and green passivator (biochar) has been introduced to passivate pyrite. To reduce the difficulty of biochar preparation and cost, and improve its production scale, in-situ pyrolysis of applewood by smoldering to produce biochar. Here, particle size, moisture content and gas flow rate were selected to prepare biochar by smoldering through orthogonal combination, and the pyrite was passivated with different conditions and biochar concentrations (2 g/L, 3 g/L, 4 g/L). The results revealed that when the particle size is 200 mm×200 mm×20 mm, the water content is 20-30%, and the gas flow rate is 0.4 L/m 3 , the biochar yield is the highest. Biochar promotes the formation of passivating layer (jarosite), inhibits the release of metal ions. Increasing biochar concentration can promote the formation of jarosite and enhance the passivation effect on pyrite., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

In this work, we report a study of a zinc sulfide (ZnS) nanocrystal and reduced graphene oxide (RGO) nanocomposite-based non-enzymatic uric acid biosensor. ZnS nanocrystals with different morphologies were synthesized through a hydrothermal method, and both pure nanocrystals and related ZnS/RGO were characterized with SEM, XRD and an absorption spectrum and resistance test. It was found that compared to ZnS nanoparticles, the ZnS nanoflakes had stronger UV light absorption ability at the wavelength of 280 nm of UV light. The RGO significantly enhanced the electron transfer efficiency of the ZnS nanoflakes, which further led to a better photoelectrochemical property of the ZnS/RGO nanocomposites. The ZnS nanoflake/RGO nanocomposite-based biosensor showed an excellent uric acid detecting sensitivity of 534.5 μA·cm -2 ·mM -1 in the linear range of 0.01 to 2 mM and a detection limit of 0.048 μM. These results will help to improve non-enzymatic biosensor properties for the rapid and accurate clinical detection of uric acid.

The present study focuses on the green synthesis of a novel Z-scheme SnS₂/HAp photocatalyst using Ocimum tenuiflorum (tulsi) leaf extract as a stabilizing agent. This approach not only emphasizes sustainability but also adds value to waste by extracting hydroxyapatite (HAp) from Labeo rohita fish scales, addressing the challenge of their disposal. The synthesized photocatalyst was thoroughly characterized using a range of analytical techniques to evaluate its crystal structure, optical properties, morphology, and elemental composition. The photocatalytic activity of the SnS₂/HAp composite was assessed through the degradation of gentian violet (GV) dye, a representative organic pollutant. Various reaction parameters were optimized to enhance the degradation efficiency, and the photocatalyst's performance was further tested across different water matrices. Under optimal conditions, the SnS₂/HAp photocatalyst achieved a maximum photodegradation efficiency of 97.49% with a rate constant of 0.0494 min - 1 for GV dye. Additionally, it exhibited an efficiency greater than 70% against other emerging pollutants via advanced oxidation processes (AOP). The enhanced photocatalytic activity was attributed to the formation of a Z-Scheme heterojunction between SnS 2 and HAp, which enhanced the charge separation efficiency and delayed the charge recombination. The study also demonstrated the photocatalyst's remarkable reusability, maintaining high performance over five cycles and across various water environments. This highlights its potential as a sustainable solution for the removal of organic pollutants from aqueous streams. Finally, a Z-scheme electron transport mechanism is proposed to explain the photodegradation process of GV dye using the SnS₂/HAp photocatalyst., (© 2024. The Author(s).)