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Oleogels containing bioactive substances such as citral (CT) are used as functional food ingredients. However, little information is available on the influence of different oleogel network structure caused by CT addition and fatty acid distribution on its digestion behavior. Coconut oil, palm oil, high oleic peanut oil, safflower seed oil, and perilla seed oil were used in this study. The results showed that perilla seed oil-CT-based oleogels had the highest oil-holding capacity (99.03 ± 0.3), whereas CT addition higher than 10 wt% could lead to the morphology collapse of oleogels. Physical and thermodynamic analyses revealed that CT could reduce oleogel hardness and higher unsaturated fatty acid content is more likely to form oleogel with stable and tight crystalline network. Moreover, the dense structure of oleogels hinders the contact between oleogels and lipase, thus weakening triglyceride digestion. These findings provide valuable insights into the design of oleogels loading with CT., Competing Interests: Declaration of competing interest The authors declare that they have no 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 ideal physicochemical properties of bigels are important for food applications. Therefore, a new bigel was prepared based on mixed beef tallow and soybean oil oleogel and deacetylated konjac glucomannan (KGM) hydrogel. The effect of the deacetylation degree of KGM on the physicochemical properties and microstructure of bigels was studied. The bigel containing moderate deacetylation degree of KGM had better rheological properties and hardness (319.84 g) than that with low and high deacetylation degrees of KGM. The interactions among the bigel components were analyzed by Fourier transform infrared spectroscopy and molecular dynamics simulation, indicating that the formation of the bigels was dominated by electrostatic interactions. Overall, the bigels containing moderate deacetylation degree of KGM had better physical properties, which may provide a theoretical foundation to develop bigels with low cholesterol, trans and saturated fats levels to replace traditional solid fats in food industry., 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.)

Oleogels have been used in the gelled surimi products to replace animal fats due to its structure characteristics. The effect of structure characteristics in fish oil oleogels on the mechanism of oil/water retention was investigated in meat emulsions. Beeswax assembly improved the oil and water retention. The unsaturation degree of fatty acids lowered the mobility of bound water, immobilized water as well as bound fat in the fish oil oleogel, but enhanced the mobility of free water and protons of unsaturated fatty acids. Beeswax addition and oil phase characteristics could enhance β-sheets, disulfide bonds and hydrophobic force to improve the viscoelasticity, gel strength and oil/water retention. Beeswax assembly facilitated the tight micro-sol network and filling effect, and high unsaturation degree promoted the emulsification effect, thus reducing phase transition temperature and juice loss. The study could lay the foundation for development of gelled shrimp meat products with EPA and DHA., Competing Interests: Declaration of competing interest The authors declare they have no conflict of interest., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Sediment-derived dissolved organic matter (SDOM) is instrumental in the cycling of nutrients and heavy metals within lakes, influencing ecological balance and contaminant distribution. Given the influence of photodegradation on the alteration and breakdown of SDOM, further understanding of this process is essential. In this research, the properties of the SDOM photodegradation process and its metal-binding reactions in Nansi Lake were analyzed using the EEM-PARAFAC and 2D-SF/FTIR-COS techniques. Our study identified three sorts of humic-like components and one protein-like component in SDOM, with the humic-like material accounting for 71.3 ± 5.19% of the fluorescence intensity (F max ). Photodegradation altered the abundance and structure of SDOM, with a 41.6 ± 5.82% decrease in a 280 and a 29.1 ± 9.31% reduction in F max after 7 days, notably reducing the protein-like component C4 by 54.0 ± 5.17% and the humic-like component C2 by 48.5 ± 2.54%, which led to SDOM being formed with lower molecular weight and aromaticity. After photodegradation, the LogK Cu values for humic-like and protein-like substances decreased (humic-like C2: LogK Cu : 1.35 ± 0.10-1.11 ± 0.15, protein-like C4: 1.49 ± 0.14-1.29 ± 0.34), yet the preferential binding sequence of protein-like materials and specific functional groups with Cu 2+ such as aliphatic C-OH, amide (I) C=O and polysaccharide C-O groups remained unaltered. Our results enhance the knowledge of light-induced SDOM alterations and offer insights into SDOM-metal interactions in aquatic ecosystems., 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.)

Soybean protein isolate (SPI) was frequently used to make edible films due to its highly degradability and excellent film forming ability. However, the limited barrier properties and low tensile strength of SPI films prevent their application in food packaging. In this study, the SPI film was modified by blending camellia oil body-based oleogel (COBO). COBO improved the mechanical properties of SPI film and increased its light-blocking, water insolubility and barrier properties. Micrograph, particle size distribution, protein conformation and crystalline structure analysis illustrated that camellia saponin in COBO formed hydrogen bonds with SPI, significantly reduced the particle size of the film-forming emulsion, and enhanced the order and uniformity of composite films structure, thus improved the overall performance of the SPI films. The SPI-COBO film packing delayed the weight loss, total soluble solids content increase, and the decrease in hardness of stored strawberries. This study puts forwards a new approach for SPI film modification by blending natural emulsified lipids, contributing to the development of sustainable packaging alternatives., 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 © 2023. Published by Elsevier Ltd.)

The deposition of biomass-burning smoke water-soluble organic matter (BBS-WSOM) significantly affects the environmental behavior of heavy metals in aqueous environments. However, the interactions between BBS-WSOM and heavy metals at the molecular level remain unknown. This study combined FT-ICR-MS, fluorescence spectrum, FTIR, and two-dimensional correlation spectroscopy to anatomize the molecular characteristics of BBS-WSOM binding with Cd(II). The results show that CHO and CHOP compounds were responsible for the fluorescence response of BBS-WSOM at Ex: 225 nm and 275 nm/Em: 325 nm, and abundant proteins or CHON compounds were responsible for the fluorescence response of BBS-WSOM at Ex: 225-250 nm/Em: 350-450 nm and Ex: 300-350 nm/Em: 350-450 nm, which was very different from the fluorescence molecules in natural organic matters. Fluorescence change after Cd(II) addition indicated that CHOP and CHOS compounds enhanced BBS-WSOM binding with Cd(II). Differently, the CHON compounds could weaken the binding of other compounds with Cd(II). Different compounds binding with Cd(II) generally followed the order: CHON/CHOS compounds>CHOP compounds>CHO compounds, and the chemical groups binding with Cd(II) generally followed the prioritization: -COO - > -NH/SO>P = O/P-O>aromatic ring>CO>C-OH of phenol/alcohol>C-O-C. This study provides a profound insight into the interaction between BBS-WSOM and Cd(II) at the molecular level., 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.)

In this study, we utilized an innovative quantitative read-across (RA) structure-activity relationship (q-RASAR) approach to predict the bioconcentration factor (BCF) values of a diverse range of organic compounds, based on a dataset of 575 compounds tested using Organisation for Economic Co-operation and Development Test Guideline 305 for bioaccumulation in fish. Initially, we constructed the q-RASAR model using the partial least squares regression method, yielding promising statistical results for the training set (R 2 =0.71, Q 2 LOO =0.68, mean absolute error [MAE] training =0.54). The model was further validated using the test set (Q 2 F1 =0.77, Q 2 F2 =0.75, MAE test =0.51). Subsequently, we explored the q-RASAR method using other regression-based supervised machine-learning algorithms, demonstrating favourable results for the training and test sets. All models exhibited R 2 and Q 2 F1 values exceeding 0.7, Q 2 LOO values greater than 0.6, and low MAE values, indicating high model quality and predictive capability for new, unidentified chemical substances. These findings represent the significance of the RASAR method in enhancing predictivity for new unknown chemicals due to the incorporation of similarity functions in the RASAR descriptors, independent of a specific algorithm., 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.)

The study aimed to develop a novel eutecto-oleogel and its characterizations. Using starch, beeswax, oil, and natural deep eutectic solvents (NADES), an oleogel with low hardness and high liquid fat was developed. The addition of starch and NADES in oleogels caused the formation of new intra or intermolecular hydrogen bonding and improved the oil binding capacity, thermal behavior, and texture of the oleogels. The oleogel with 1 % starch formed a strong gel with the most favorable functional, textural, flow properties and a high fanning factor. Complementary tests of the oleogel exhibited shear thinning and frequency-independent behavior, with zero residual effect. Non-isothermal crystallization and melting analysis of the oleogels showed noticeable differences among the various oleogels. These results contribute to a better understanding of oleo gelation in rice bran oil-based oleogels with NADES, and beeswax for formulating food, pharmaceutical, and personal care products with desired physical properties., 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.)

The ocular administration of lipophilic and labile drugs such as epalrestat, an aldose reductase inhibitor with potential for diabetic retinopathy treatment, demands the development of topical delivery systems capable of providing sufficient ocular bioavailability. The aim of this work was to develop non-aqueous oleogels based on soybean oil and gelators from natural and sustainable sources (ethyl cellulose, beeswax and cocoa butter) and to assess their reproducibility, safety and efficiency in epalrestat release and permeation both ex vivo and in vivo. Binary combinations of gelators at 10% w/w resulted in solid oleogels (oleorods), while single gelator oleogels at 5% w/w remained liquid at room temperature, with most of the oleogels displaying shear thinning behavior. The oleorods released up to 4 µg epalrestat per mg of oleorod in a sustained or burst pattern depending on the gelator (approx. 10% dose in 24 h). The HET-CAM assay indicated that oleogel formulations did not induce ocular irritation and were safe for topical ocular administration. Corneal and scleral ex vivo assays evidenced the permeation of epalrestat from the oleorods up to 4 and 2.5 µg/cm 2 after six hours, respectively. Finally, the capacity of the developed oleogels to sustain release and provide significant amounts of epalrestat to the ocular tissues was demonstrated in vivo against aqueous-based niosomes and micelles formulations loaded with the same drug concentration. Overall, the gathered information provides valuable insights into the development of oleogels for ocular drug delivery, emphasizing their safety and controlled release capabilities, which have implications for the treatment of diabetic neuropathy and other ocular conditions., (© 2024. The Author(s).)

Terrestrial dissolved organic matter (DOM) plays critical roles in many biotic and abiotic environmental reactions as well as in water treatment. Its structure is therefore of great interest. We examined dissolved Suwannee River Humic Acid (HA) to probe the potential participation of exceptionally strong, negative charge-assisted hydrogen bonds, (-)CAHB, in DOM cohesion and interaction with small weak acids using high performance size exclusion chromatography (HPSEC), transmission electron microscopy, zeta-pH curves, and pH drift experiments. The results support a previously proposed two-tier state of aggregation, in which tightly-knit primary particles (≤ ∼10 kDa) form larger secondary aggregates (up to micrometer in size). Evidence for (-)CAHB is gained through zeta potential changes and pH drift experiments. The primary particles interact with (-)CAHB-capable solutes (simple carboxylic acids and phosphate) but not (-)CAHB-incapable solutes. We identified disruption of intra-segmental and inter-molecular (-)CAHB leading to swelling and disaggregation, as well as formation of nouveau (-)CAHB with free groups on HA. The effects were solute-concentration dependent and greater at pH 5 than pH 6, consistent with CAHB theory. Phosphate induced the greatest shifts in the HPSEC molecular size distribution curves. The shifts were unaffected by prior stripping of innate polyvalent metals. We conclude that the (-)CAHB contributes to the cohesion of DOM, affecting its size and charge, and provides a means by which weak acid pollutants, nutrients, and natural compounds can interact with DOM. Such interactions have implications for the behavior of DOM in the environment, the fate and transport of anthropogenic pollutants, and the roles DOM play in water treatment technologies., 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.)

Excessive dietary salt intake leads to health issues, while reducing NaCl content compromises flavor. Therefore, identifying methods to decrease salt levels without sacrificing flavor is crucial. This study investigated the sensory interaction between the saltiness of NaCl and the pungency of Litsea oleoresin. Glyceryl monostearate (6.6%) and soy lecithin (4.4%) were used as gelling agents to create oleogels, which were then employed to immobilize NaCl nanocrystals, optimizing sensory interactions. NaCl nanocrystals (427.73 ± 61.98 nm) were encapsulated in a Litsea oleoresin-sunflower seed oleogel system with uniform distribution. Sensory evaluation indicated that the NaCl nanocrystal/Litsea oleoresin@oleogel system, with moderate pungency, significantly enhanced perceived saltiness intensity (29.00 ± 1.14, compared to the control, 18.48 ± 1.12) (P < 0.05). When applied to potato chips, this system noticeably increased saltiness perception. This research provides a promising approach for developing low-sodium yet flavorful foods., Competing Interests: Declaration of competing interest The authors have confirmed that they have no conflicts of interest associated with this publication., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The baking process has the potential to generate health-risk compounds, including products from lipid oxidation and Maillard reaction. Pre- and post-digestion levels of hydroxymethylfurfural (HMF), malondialdehyde (MDA), glyoxal (GO), and methylglyoxal (MGO) were studied in cakes formulated with hazelnut and sunflower oil, along with their oleogels as margarine substitutes. The concentration of HMF in oil and oleogel-formulated cakes increased after digestion compared to cakes formulated with margarine. The MDA values were between 82 and 120 μg/100 g in oil and oleogel formulated cakes before digestion and a decrease was observed after digestion. The substitution of margarine with oil and oleogels resulted in the production of high amounts of GO and MGO in cakes. However, the highest bioaccessibility as 318.2% was found in cakes formulated by margarine for GO. Oleogels may not pose a potential health benefit compared to margarines due to the formation of HMF, MDA, GO, and MGO., 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.)

GC-MS/MS combines the superior chromatographic resolution of GC with the specific and sensitive detection of tandem MS. On paper, it is an ideal system for the routine analyses of organic acids, yet very few studies have used and published such methods. This is likely due to several challenges highlighted in this communication. Briefly, the combination of EI ionization with MRM detection provides arguably insufficient specificity when targeting organic acids. Moreover, the narrow peaks generally produced by GC can lead to inaccurate quantification when the mass spectrometer's cycle time is too long. Potential solutions to these problems are discussed., 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.)

This study explored how co-oleogelator type, concentration, and water addition affect lipid digestion and β-carotene (βC) bioaccessibility in corn oil oleogels. Oleogels containing 0.1% βC, 20% glyceryl stearate (GS), with lecithin (L) or hydrogenated lecithin (HL) (at 0, 0.5, or 2.5%) and their water-filled counterparts (1% water) were examined. In vitro intestinal digestion revealed HL-oleogels experienced higher lipolysis due to their smaller crystal size enhancing surface area for lipase action, whereas L-oleogels presented lower digestibility, attributed to larger oil droplets and a minimized surface area. Water addition didn't significantly change lipid digestibility. βC bioaccessibility was inversely related to co-oleogelator concentration, with L-oleogels demonstrating the largest decrease, likely due to less free fatty acids released for micelle formation. However, water-filled oleogels enhanced βC bioaccessibility. These findings highlight that tailored microstructure in oleogels can control lipid digestion and βC bioaccessibility, paving the way for designing efficient delivery systems for targeted nutrient delivery., 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 Ltd.. All rights reserved.)

Biodegradability testing in soil helps to identify safe synthetic organic chemicals but is still obscured by the formation of soil-bound 'non-extractable' residues (NERs). Present-day methodologies using radiocarbon or stable ( 13 C, 15 N) isotope labeling cannot easily differentiate soil-bound parent chemicals or transformation products (xenoNERs) from harmless soil-bound biomolecules of microbial degraders (bioNERs). Hypothesizing a minimal retention of hydrogen in biomolecules, we here apply stable hydrogen isotope - deuterium (D) - labeling to unravel the origin of NERs. Soil biodegradation tests with D- and 13 C-labeled 2,4-D, glyphosate and sulfamethoxazole reveal consistently lower proportions of applied D than 13 C in total NERs and in amino acids, a quantitative biomarker for bioNERs. Soil-bound D thus mostly represents xenoNERs and not bioNERs, enabling an efficient quantification of xenoNERs by just measuring the total bound D. D or tritium (T) labeling could thus improve the value of biodegradability testing results for diverse organic chemicals forming soil-bound residues., (© 2024. The Author(s).)

In this assay, based on the terminal protection of small-molecule-linked DNA, a new ultrasensitive real-time fluorescence strategy combined with an isothermal exponential amplification reaction (IEXPAR) has been established for protein assay. By the clever design of DNA, terminal protection is combined with efficient IEXPAR. The target protein explicitly binds to small molecules attached to the template DNA, protecting the template DNA from exonuclease I (Exo I) degradation. The added DNA primer hybridizes with the protected template DNA and triggers the following IEXPAR. IEXPAR has a super amplification efficiency of 10 6 -10 9 times. The IEXPAR yields numerous double-stranded DNA (dsDNA) molecules. The fluorescence dye SYBR Green I (SG), which is sensitive to dsDNA, is used to determine the real-time fluorescence of the IEXPAR. Conversely, without the target protein, the template DNA is hydrolyzed by Exo I, failing to trigger the IEXPAR. The intriguing combination of IEXPAR and terminal protection realizes the ultrasensitive detection of protein. As low as 100 fmol L -1 SA and 200 pg mL -1 folic acid (FR) are accurately detected.

Dissolved organic matter (DOM) is ubiquitous in aquatic environments and challenging to characterize due to its heterogeneity. Optical measurements ( i.e. , absorbance and fluorescence spectroscopy) are popular characterization tools, because they are non-destructive, require small sample volumes, and are relatively inexpensive and more accessible compared to other techniques ( e.g. , high resolution mass spectrometry). To make inferences about DOM chemistry, optical surrogates have been derived from absorbance and fluorescence spectra to describe differences in spectral shape ( e.g. , E2:E3 ratio, spectral slope, fluorescence indices) or quantify carbon-normalized optical responses ( e.g. , specific absorbance (SUVA) or specific fluorescence intensity (SFI)). The most common interpretations relate these optical surrogates to DOM molecular weight or aromaticity. This critical review traces the genesis of each of these interpretations and, to the extent possible, discusses additional lines of evidence that have been developed since their inception using datasets comparing diverse DOM sources or strategic endmembers. This review draws several conclusions. More caution is needed to avoid presenting surrogates as specific to either molecular weight or aromaticity, as these physicochemical characteristics are often correlated or interdependent. Many surrogates are proposed using narrow contexts, such as fractionation of a limited number of samples or dependence on isolates. Further study is needed to determine if interpretations are generalizable to whole-waters. Lastly, there is a broad opportunity to identify why endmembers with low abundance of aromatic carbon ( e.g. , effluent organic matter, Antarctic lakes) often do not follow systematic trends with molecular weight or aromaticity as observed in endmembers from terrestrial environments with higher plant inputs.

Oleogels are semi-solid materials that consist primarily of liquid oil immobilized in a network of organized structural molecules, which provide stability and maintain the oil in the desired shape. Due to their structure, oleogels can stabilize large amounts of liquid, making them excellent carriers for active substances, both lipophilic and hydrophilic. This study presents the synthesis methodology and investigations of olive oil-based oleogels, which are among the healthiest and most valuable vegetable fats, rich in unsaturated fatty acids and antioxidants such as vitamin E. Two types of surfactants were used: TWEEN 80, which lowers surface tension and stabilizes emulsions, and SPAN 80, which acts in oil-dominated phases. The oleogels were enriched with lidocaine, an active substance commonly used as a pain reliever and local anesthetic. This research characterized the obtained oleogels regarding their medical applications, paying particular attention to the influence of surfactant type and amount as well as the active substance on their physicochemical properties. Structural analyses were also conducted using Fourier transform infrared (FTIR) spectroscopy, alongside rheological and sorption studies, and the wettability of the materials was evaluated. The stability of the obtained oleogels was verified using the MultiScan MS20 system, allowing for an assessment of their potential suitability for long-term pharmaceutical applications. The results indicated that SPAN-stabilized oleogels exhibited better stability and favorable mechanical properties, making them promising candidates for medical applications, particularly in pain relief formulations.

The excessive presence of geogenic ammonium (NH 4 + ) in groundwater poses a global environmental concern, commonly linked to the degradation of nitrogen-containing dissolved organic matter (DOM). However, there is a gap in systematic studies on the combination of soluble organic matter (SOM) in sediments and DOM in groundwater, with few indoor incubation experiments to validate their degradation pathways. This study utilized ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry to analyze the molecular characteristics of DOM and SOM in aquifer systems affected by geogenic NH 4 + . Subsequently, indoor incubation experiments spanning up to 140 d were conducted to verify the degradation pathways. The experimental results revealed a two-phase degradation process for both the DOM and SOM. The initial stage was characterized by the degradation of aliphatic compounds (ALC) with the production of polyphenols (PPE) and highly unsaturated compounds (HUC). The second stage was dominated by the degradation of PPE and HUC, accompanied by the re-consumption of some ALC, while more recalcitrant HUC persisted. Notably, the first stage of SOM degradation exceeded that of DOM degradation, indicating that SOM exhibited greater resistance to aging. This phenomenon may be attributed to a wider range of active enzymes in sediments, the rapid replenishment of SOM by organic matter in sediments, or the accelerated degradation of DOM. The experimental results aligned with the molecular characterization of DOM and SOM in actual aquifer systems. It is hypothesized that NH 4 + produced through the direct mineralization of SOM may contribute more to the enrichment of NH 4 + in groundwater than that produced through the mineralization of DOM. This study is the first to analyze DOM and SOM together in aquifer systems and validate their degradation pathways through incubation experiments, thereby providing novel insights into the enrichment of geogenic NH 4 + in groundwater., 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.)

This study reports the development of a photocatalytic electrochemical aptasensor for the purpose of detecting chloramphenicol (CAP) antibiotic residues in water by utilizing SYBR Green I (SG) and chemically exfoliated MoS 2 (ce-MoS 2 ) as synergistically signal-amplification platforms. The Au nanoparticles (AuNPs) were electrodeposited onto the surface of an indium tin oxide (ITO) electrode. After that, the thiolate-modified cDNA, also known as capture DNA, was combined with the aptamer. Subsequently, photosensitized SG molecules and ce-MoS 2 nanomaterial were inserted into the groove of the resultant double-stranded DNA (dsDNA). The activation of the photocatalytic process upon exposure to light resulted in the generation of singlet oxygen. The singlet oxygen effectively split the dsDNA, resulting in significant enhancement in the current of [Fe(CN) 6 ] 3-/4- . When the CAP was present, both SG molecules and ce-MoS 2 broke away from the dsDNA, which turned off the photosensitization response, leading to significant reduction in the current of [Fe(CN) 6 ] 3-/4- . Under the optimal conditions, the aptasensor exhibited a linear relationship between the current of [Fe(CN) 6 ] 3-/4- with logarithmic concentrations of CAP from 20 to 1000 nM, with a detection of limit (3σ) of 3.391 nM. The aptasensor also demonstrated good selectivity towards CAP in the presence of interfering antibiotics, such as tetracycline, streptomycin, levofloxacin, ciprofloxacin, and sulfadimethoxine. Additionally, the results obtained from the analysis of natural water samples using the proposed aptasensor were consistent with the findings acquired through the use of a liquid chromatograph-mass spectrometer. Therefore, with its simplicity and high selectivity, this aptasensor can potentially detect alternative antibiotics in environmental water samples by replacing the aptamers based on photosensitization., 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.)

The Glycerol monolaurate (GML) oleogel was induced using Camellia oil by slowly raising the temp to the melting point (MP) of GML. Whey protein isolate (WPI) solution with different ratios was composited with GML oleogel by emulsion template methods, forming dense spines and honeycomb-like networks and impressed with an adjustable composite structure. Textural results showed that compared with single GML-based oleogels, the GML/WPI composite oleogels had the advantages of high hardness and molding, and structural stability. The composite oleogels had moderate thermal stability and maximal oil binding (96.36%). In particular, as up to 6 wt% GML/WPI, its modulus apparent viscosity was significantly increased in rheology and similar to commercial fats. Moreover, it achieved the highest release of FFA (64.07%) and the synergy provided a lipase substrate and reduced the body's burden. The resulting composite oleogel also showed intermolecular hydrogen bonding and van der Waals force interactions. These findings further enlarge the application in the plant and animal-based combined of fat substitutes, delivery of bioactive molecules, etc., with the desired physical and functional properties according to different proportions., 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.)

Hydroxyl radical (HO • ) and chlorine atom (Cl • ) are common reactive species in aqueous environments. However, the intrinsic difference in their reactions with organic compounds has not been revealed. This study compared the reaction mechanisms of HO • and Cl • with 13 aromatic and 11 aliphatic compounds by quantum chemical calculation and laser flash photolysis. Both HO • and Cl • can spontaneously react with aromatic compounds via radical adduct formation (RAF), hydrogen atom transfer (HAT), and single electron transfer (SET) pathways. The SET reactions of Cl • were more thermodynamically favorable than HO • , but contrary results were obtained for HAT reactions. According to the free energy of activation (Δ G aq ‡ ), the dominant oxidation mechanisms of aromatic compounds were RAF and SET by HO • and SET by Cl • . The important role of SET in the HO • reactions with aromatic compounds was further verified by accurately calculating the solvation free energy of HO • /HO - and experimentally tracking the radical cations, which were generally neglected in previous studies. Meanwhile, the Δ G aq ‡ value of each reaction pathway of Cl • was lower than that of HO • , resulting in higher rate constants of Cl • with aromatic compounds than HO • . For saturated aliphatic compounds, HAT was found to be the only mechanism accounting for their transformation by HO • and Cl • . This study proposed general rules for the reaction mechanisms of HO • and Cl • and unraveled their differences in the aspects of thermodynamics and kinetics, providing fundamental information for understanding contaminant transformation in processes involving HO • and Cl • .

Nairobi River sediments from locations adjacent to the Kawangware and Kiambio slums were analyzed via Fourier transform ion cyclotron resonance mass spectrometry with atmospheric pressure photoionization (APPI-FT-ICR-MS). The data from these ultrahigh resolution, untargeted measurements provided new insights into the impacts of local anthropogenic activity, which included likely benzo- and dibenzothiophene pollution with a suspected petrogenic origin, and prominent surfactant-like compositions. Other features in the data included highly abundant tetra-oxygenated compounds, and oxygenated nitrogen compounds with sphingolipid interpretations. Most notably, several hydrocarbon and oxygenated compound classes in the sediment data featured intensity patterns consistent with steroid molecular formulas, including those associated with sewage contamination investigatory work. In support of this interpretation, standards of cholesterol, β-sitosterol, stigmasterol, coprostanol, cholestanol, and 5α-sitostanol were analyzed via APPI, to explore steroid ionization behavior. Generally, these analytes produced radical molecular ions ([M] •+ ), and water-loss pseudo molecular ion species ([M-H 2 O] •+ and [M+H-H 2 O] + ), among various other less intense contributions. The absence of pseudo molecular protonated species ([M+H] + ) was notable for these compounds, because these are often assumed to form with APPI. The standard measurements demonstrated how steroids can create the observed intensity patterns in FT-ICR-MS data, and hence these patterns have the potential to indicate sewage contamination in the analysis of other complex environmental samples. The steroid interpretation for the Kawangware and Kiambio data was further verified by subjecting the steroid standard radical molecular ions to collision-induced dissociation and comparing the detected fragments to those for the corresponding isolated ions from a Kawangware sediment sample.

This study evaluated the influence of organic matter (OM) constituents on the potential for recovery of P from wastewaters when FeCl 3 treatment is employed for P removal. The presence of OM constituents did not influence P release from Fe-P sludges when alkaline and ascorbic acid treatments were employed. However, the overall recovery of P from wastewater was impacted by the presence of selected OM constituents through the reduction of P uptake during coagulation. The presence of protein and humic matter showed remarkably low P removal values (3.0 ± 0.4% and 23 ± 1% respectively) when compared to an inorganic control recipe (62 ± 2%). Elevated soluble Fe (SFe) residuals in the presence of proteins (87 ± 5%) and humics (51 ± 1%) indicated interactions between Fe(III) cations and negatively charged functional groups like hydroxyl, carboxyl, and phenolic groups available in these organics. Significant negative correlations between P removal and residual SFe were observed suggesting Fe solubilization by OM constituents was the mechanism responsible for reduced P removal. The findings of this study identify, for the first time, the impact of OM constituents on overall P recovery when Fe(III) salts are employed and provide insights into recoveries that can be expected when Fe is added to primary, secondary treated, and industrial wastewaters. PRACTITIONER POINTS: Low P removal values were observed for protein and humic dominated wastewater recipes. Iron(III) solubilization counted for P removal reduction by proteins and humic acids. There is no effect of OM on P release from Fe-P sludge at pH 10 and ascorbic acid treatments. OM and agent employed to release P from sludges affected overall recovery of P., (© 2024 The Author(s). Water Environment Research published by Wiley Periodicals LLC on behalf of Water Environment Federation.)

Polar organic chemical integrative samplers (POCIS) are promising devices for measuring the time-weighted average concentrations of hydrophilic compounds in aquatic environments. However, the mechanisms underlying compound uptake by POCIS remain unclear. We investigated the permeation kinetics of polyethersulfone and polytetrafluoroethylene membrane filters, and the sorption kinetics of Oasis HLB (Waters), Envi-Carb (Supelco), and Oasis WAX (Waters) sorbents. The log octanol-water partition coefficient (K OW ) values of the 19 targeted compounds ranged from -0.55 to 6.0. The overall mass-transfer coefficients were negatively correlated with K OW , indicating that interactions between hydrophobic compounds and the membrane inhibit permeation. The sorption rate coefficient showed no correlation with K OW and depended on the type of sorbent used. These results imply that the uptake of highly hydrophilic compounds by POCIS is determined by both the membrane and the sorbent kinetics; however, membrane kinetics dominate the uptake of hydrophobic compounds. Environ Toxicol Chem 2024;43:2115-2121. © 2024 SETAC., (© 2024 SETAC.)

Background: The effect of oleogels prepared with peanut oil and different concentrations of γ-oryzanol and β-sitosterol mixture (γ/β; 20, 40, 60, 80 and 100 g kg -1 ) on the physicochemical and gel properties of myofibrillar protein (MP) was investigated., Results: The solubility and average particle size of MP first decreased and then increased with increasing γ/β concentration. Peanut oil or oleogels could induce the exposure of hydrophobic amino acids and the unfolding of MP, thus significantly increasing the surface hydrophobicity, sulfhydryl content and absolute value of zeta potential, which reached maximum values when the γ/β concentration was 60 g kg -1 (P < 0.05). The addition of peanut oil decreased the gel strength and water holding capacity of MP gel. However, oleogels prepared with 60 g kg -1 γ/β could significantly increase the hydrophobic interactions and disulfide bond content of MP gel (P < 0.05), which promoted the crosslinking and aggregation of MP, enhancing the gel properties. Peanut oil had no significant influence on the secondary structure of MP, while oleogels promoted the transition of MP conformation from α-helix to β-sheet structure. The results of light microscopy and confocal laser scanning microscopy indicated that oleogels prepared with 60 g kg -1 γ/β filled in the pores of MP gel network to form denser and more uniform structure., Conclusion: Oleogels prepared with 60 g kg -1 γ/β could effectively improve the quality of MP gel and have promising application prospects in surimi products. © 2024 Society of Chemical Industry., (© 2024 Society of Chemical Industry.)

Aerosol whipped cream, widely used in various foods, relies on solid fats rich in saturated fatty acids (SFAs) for stable gas entrapment. In this study, the potential of oleogels as a healthy fat substitute for formulating aerosol whipped cream was studied. The analysis focused on the effects of different types (beeswax [BW], rice bran wax [RW], and carnauba wax) and the quantities of wax on the properties of the aerosol whipped creams. The BW-oleogel-based aerosol whipped cream exhibited the highest foam ability and foam stability. The superior physical properties of the bees wax-oleogel were attributed to the higher overrun and height stability of its whipped cream compared to RW and carnauba oleogels. The 6% BW-whipped cream showed significantly higher overrun and cream stability. The 6% BW oleogel whipped cream contained 4.4 times lower SFAs than the dairy milk fat whipped cream. This study represents the first exploration into the feasibility of formulating oleogel-based aerosol whipped cream using liquid vegetable oil., (© 2024 Institute of Food Technologists.)

Oleogels have been explored as a new lipid-based delivery system, however, their insolubility and unsuitable shape severely limit their application in food systems. Herein, core-shell oleogel capsules with high monodispersity (coefficient variation (CV) < 5%)) were prepared via gravity-assisted co-flowing microfluidic device and simply air-drying. The oleogel capsules with oleogel core and ultrathin calcium-alginate shell were prepared. Oleogel capsules maintained their original shape at pH = 2.0 but swelled rapidly at pH = 6.8 and 7.4. The swelling ratio of shell can be adjusted by inner fluid flow rate (Q in ). Notably, the core with beeswax (BW) crystal network, effectively improved the stability performances and also could provide thermal response. Finally, the oleogel capsules demonstrated excellent sustained release and UV protection of lipophilic bioactives. This work sheds light on development of novel oleogel capsules, making them ideal candidates for smart food encapsulation applications., 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 substitution of margarine with candelilla wax (CW)-based oleogel is currently a prominent focus of research in the bakery industry. However, the use of CW-based oleogel in cookies increased starch digestibility, potentially posing a risk to human health. Thus, the anti-enzymatic mechanism of lipid-amylose complexes was used to evaluate the influence of olive diacylglycerol stearin (ODS) on starch digestibility in CW-based oleogel cookies. The in vitro digestibility analysis demonstrated that the DCW/ODS-35 cookie exhibited a increase of 27.72 % in slowly digestible starch (SDS) and resistant starch (RS) contents, compared to cookie formulated with margarine. The in-vivo glycemic index analysis revealed that the DCW/ODS-35 cookie had a medium glycemic index of 68. XRD pattern suggested that the presence of ODS in oleogels facilitated the formation of lipid-amylose complexes. The DSC analysis revealed that the addition of ODS resulted in the gelatinization enthalpy of DCW-based cookies increased from 389.9 to 3314.9 J/g. The FTIR spectra indicated that the combination of ODS could promote a short-range ordered structure in DCW-based cookies. Overall, these findings demonstrated that the utilization of DCW-based oleogel presented a viable alternative to commercial margarine in the development of CW-based cookies with reduced starch digestibility., 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.)

In this work, the electrospun short fiber-based oleogels (ESFO) were formed by thermal crosslinking. Gelatin and gluten nanofibers were obtained via electrospinning, then homogenized and transformed into short fiber dispersions. Through freeze-drying, electrospun short fiber-based aerogel (ESF-A) templates were obtained for oil adsorption. All ESF-A exhibited the micromorphology of loose fibrous pore structure and prominent changes of characteristic peaks in the thermal and infrared analyses. Moreover, the highly crosslinked templates owned excellent hydrophobicity and mechanical performances (elastic modulus: 0.25 kPa, yield strength: 14.56 kPa, compressive strength: 52.54 kPa, and the final compression recovery: 91.27%). Meanwhile, the oil adsorption/oil holding capacity could reach 76.56 g/g and 80.04%, respectively. Through thermal crosslinking, ESF-O presented good and controllable rheological/in vitro digestion properties, which were further confirmed by PCA analysis. According to different application conditions, ESF-O properties could be adjusted by different degrees of fiber addition or thermal crosslinking., 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.)

Background: In response to growing concerns regarding heavy metal contamination in food, particularly chromium (Cr)(VI) contamination, this study presented a simple, sensitive and practical method for Cr(VI) detection., Results: A magnetic separation-based capture-exponential enrichment ligand system evolution (SELEX) method was used to identify and characterize DNA aptamers with a high affinity for Cr(VI). An aptamer, Cr-15, with a dissociation constant (K d ) of 4.42 ± 0.44 μmol L -1 was obtained after only eight rounds of selection. Further innovative methods combining molecular docking, dynamic simulation and thermodynamic analysis revealed that CrO 4 2- could bind to the 19th and 20th guanine bases of Cr-15 via hydrogen bonds. Crucially, a label-free fluorometric aptasensor based on SYBR Green I was successfully constructed to detect CrO 4 2- , achieving a linear detection range of 60-300 nmol L -1 with a lower limit of detection of 44.31 nmol L -1 . Additionally, this aptasensor was able to quantitatively detect CrO 4 2- in grapes and broccoli within 40 min, with spike recovery rates ranging from 89.22% to 108.05%. The designed fluorometric aptasensor exhibited high selectivity and could detect CrO 4 2- in real samples without sample processing or target pre-enrichment., Conclusion: The aptasensor demonstrated its potential as a reliable tool for monitoring Cr(VI) contamination in fruit and vegetable products. © 2024 Society of Chemical Industry., (© 2024 Society of Chemical Industry.)

Algal proteins are an emerging source of functional foods. Herein, Chlorella pyrenoidosa protein (CPP)/xanthan gum-based hydrogels (HG) and beeswax-gelled oleogels (OG) are adopted to fabricate bigels. The phase inversion of bigels can be regulated by the ratio of OG and HG: As the OG increased, bigels turn from OG-in-HG (OG/HG) to a semicontinuous state and then HG-in-OG (HG/OG). In OG/HG bigels (OG ≤ 50 %), hydrophilic CPP acts as the emulsifier at the interface of OG and HG, while beeswax emulsifies the system in HG/OG bigels (OG = 80 %). A semicontinuous bigel appears during the transition between HG/OG and OG/HG. The increase of OG can enhance the viscoelasticity, hardness, adhesiveness, chewiness, and thermal stability. OG/HG bigels exhibit stronger thixotropic recovery and oil-holding capacity than HG/OG bigels. In the in-vitro digestion and food 3D printing, the high specific surface area and the highest thixotropic recovery caused by the emulsion structure of the OG/HG bigel (OG = 50 %) are conducive to the release of free fatty acids and molding of 3D-printed objects, respectively. This study provides a new approach to structure the gelled water-oil system with CPP and helps to develop edible algal proteins-based multiphase systems in food engineering or pharmacy., 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.)

Cryogel-templated oleogels (CTO) were fabricated via a facile polyphenol crosslinking strategy, where apple polyphenol was utilized to crosslink the gelatin/egg white protein conjugates without forming hydrogels. After freeze-drying, cryogel templates were obtained and used to construct CTO by oil absorption. Apple polyphenol crosslinking improved the emulsion-related properties with appearance changes on samples, and infrared spectroscopy further confirmed the interactions between proteins and apple polyphenol. The crosslinked cryogels presented porous microstructures (porosity of over 96 %), enhanced thermal/mechanical stabilities, and could absorb a high content of oil (14.41 g/g) with a considerable oil holding capacity (90.98 %). Apple polyphenol crosslinking also influenced the rheological performances of CTO, where the highly crosslinked samples owned the best thixotropic recovery of 85.88 %. Moreover, after the rapid oxidation of oleogels, the generation of oxidation products was effectively inhibited by crosslinking (POV: 0.48 nmol/g, and TBARS: 0.53 mg/L). The polyphenol crosslinking strategy successfully involved egg white protein and gelatin to fabricate CTO with desired physical/chemical properties. Apple polyphenol acted as both a crosslinker and an antioxidant, which provided a good reference for fabricating pure protein-based CTO., Competing Interests: Declaration of competing interest Authors claim that there are no conflicts to declare., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Oleogels are innovative structured fat systems that can replace detrimental lipids and saturated fats. Among the various gelators used to construct oleogels, phytosterols are regarded as potential oleogelators due to ability to lower blood cholesterol levels and protect patients from cardiovascular illnesses, although little research has been conducted on phytosterols. This article examines the formation, characterization, and application of phytosterol-based oleogels in detail. The oleogelation behaviors of phytosterol-based oleogels are affected by their formulation, which includes phytosterol type, combined oleogelator, proportion, concentration and oil type. These oleogels exhibit potential applications as solid fat substitutes without affecting the texture or sensory properties of food products or as effective delivery vehicles. To encourage the research and implementation of phytosterol-based oleogels, we will ultimately not only highlight problems related to their use in food processing, but also provide a few viewpoints, with the goal of providing fresh insights for advancing trends., 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 © 2023. Published by Elsevier Ltd.)

Constructing van der Waals (vdW) heterostructures is a prospective approach that is essential for developing a new generation of functional two-dimensional (2D) materials and designing new conceptual nanodevices. Using density-functional theory combined with a nonequilibrium Green's function approach allows for the theoretical and systematic exploration of the electronic structure, transport properties, and sensitivity of organic small molecules adsorbed on 2D C 3 B/graphene (Gra) and C 3 N/Gra vdW heterojunctions. Calculations show the metallic properties of C 3 B/Gra and C 3 N/Gra after the formation of heterojunctions. Interestingly, the heterojunctions C 3 B/Gra (C 3 N/Gra) for the adsorption of small organic molecules (C 2 H 2 , C 2 H 4 , CH 3 OH, CH 4 , and HCHO) at the C 3 B (C 3 N) side are sensitive to the chemisorption of C 2 H 2 and C 2 H 4 . Similarly, the Gra/C 3 B is chemisorbed for both C 2 H 2 and C 2 H 4 when adsorbed on Gra side, while it is only chemisorbed for C 2 H 2 in Gra/C 3 N. Interestingly, all heterojunctions on different sides are physisorbed for CH 3 OH, CH 4 , and HCHO. Furthermore, the calculated I-V curves demonstrate that the devices based on the adsorption of C 2 H 2 and C 2 H 4 at each side of the heterojunction have remarkable anisotropy, in with the current being considerably greater in the zigzag direction than in the armchair direction. More specifically, with C 2 H 2 adsorbed on the Gra side, the sensitivity along the armchair direction is up to 85.0% for Gra/C 3 B and close to 100% for Gra/C 3 N. This study reveals that C 3 B/Gra (C 3 N/Gra) heterojunctions with high selectivity, high anisotropy, and excellent sensitivity are highly prospective 2D materials for applications, which further contributes new insights into the development of future electronic nanodevices.

The study of nanomaterials' nature, function, and biocompatibility highlights their potential in drug delivery, imaging, diagnostics, and therapeutics. Advancements in nanotechnology have fostered the development and application of diverse nanomaterials. These materials facilitate drug delivery and influence the immune system directly. Yet, understanding of their impact on the immune system is incomplete, underscoring the need to select materials to achieve desired outcomes carefully. In this review, we outline and summarize the distinctive characteristics and effector functions of inorganic nanomaterials and organic materials in inducing immune responses. We highlight the role and advantages of nanomaterial-induced immune responses in the treatment of immune-related diseases. Finally, we briefly discuss the current challenges and future opportunities for disease treatment and clinical translation of these nanomaterials.

Since the discovery of the first peroxidase nanozyme (Fe 3 O 4 ), numerous nanomaterials have been reported to exhibit intrinsic enzyme-like activity toward inorganic oxygen species, such as H 2 O 2 , oxygen, and O 2 - . However, the exploration of nanozymes targeting organic compounds holds transformative potential in the realm of industrial synthesis. This review provides a comprehensive overview of the diverse types of nanozymes that catalyze reactions involving organic substrates and discusses their catalytic mechanisms, structure-activity relationships, and methodological paradigms for discovering new nanozymes. Additionally, we propose a forward-looking perspective on designing nanozyme formulations to mimic subcellular organelles, such as chloroplasts, termed "nano-organelles". Finally, we analyze the challenges encountered in nanozyme synthesis, characterization, nano-organelle construction and applications while suggesting directions to overcome these obstacles and enhance nanozyme research in the future. Through this review, our goal is to inspire further research efforts and catalyze advancements in the field of nanozymes, fostering new insights and opportunities in chemical synthesis., (© 2024 Wiley-VCH GmbH.)

Lead ions (Pb 2+ ) are a widely distributed and highly toxic heavy metal pollutant, which seriously threatens the environment, economy and human safety. Here, a label-free ratiometric fluorescent biosensor was constructed for Pb 2+ detection using DNAzyme-driven target cycling and exonuclease III (Exo III)-mediated DNA cycling as a dual signal amplification strategy. The SYBR Green I (SGI) and N -methyl mesoporphyrin IX (NMM) used in this study are characterized by low cost, storage resistance, and short preparation time compared with conventional signaling probes labeled with fluorescent groups. Unlike the single-emission fluorescence strategy, monitoring the fluorescence intensity ratio of SGI and NMM can effectively reduce external interference to achieve accurate detection of Pb 2+ . DNAzyme structures on the surface of magnetic beads (MBs) can recognize Pb 2+ and activate the target circulatory system to cleave single-stranded DNA (ssDNA). The ssDNA further initiated the Exo III-assisted DNA circulatory system to digest double-stranded DNA (dsDNA) and release guanine-rich G1. Finally, the fluorescence signals of SGI and NMM were weakened and enhanced, respectively. The sensing strategy achieved a wide linear range from 0.5 to 500 nM and a low limit of detection (LOD) of 26.4 pM. Furthermore, its anti-interference ability and potential applicability for Pb 2+ detection in actual samples were verified. This work ingeniously combines the dual signal amplification strategy with the ratiometric sensing strategy constructed by structure-specific fluorescent dyes, which provides a promising method for constructing sensitive and accurate fluorescent biosensors.

The turnover and stabilization of soil organic carbon are tightly associated with the properties of litter input. Due to the complexity of litter decomposition and the high heterogeneity of forest soils, there are considerable uncertainties about how soil minerals, microorganisms, and environmental factors jointly regulate the transformation and stability of litter-derived soil organic carbon. Here, we present an overview of the "microbial efficiency-matrix stabilization" framework centered on microbial metabolism and organic carbon transformation, as well as the new "microbial carbon pump" and "mineral carbon pump" theories in forest soil organic carbon transformation and stabilization. We specifically highlighted a differential mechanism of "organo-organic interfaces" from the "organo-mineral interfaces" in the effects on soil organic carbon accumulation. We further expounded the transformation processes and stability of soil organic carbon based on the "carbon material cycling" and "energy fluxes", aiming to provide theoretical support for the research on carbon sequestration in forest soils.

Soil organic carbon (SOC) represents the largest terrestrial organic carbon pool and plays an important role in mitigating global climate change. Warming can change the stabilization process and the balance of inputs and outputs of the SOC pool, thereby affecting the content, fraction, and chemical structure of SOC. It has become a research hotspot to reveal the mechanisms underlying the effects of warming on SOC stability by analyzing the fraction and molecular structure of C. Here, we reviewed the warming effects on the SOC pool from three aspects, e.g. , the content, fraction, and chemical structure of SOC. We also summarized the response of key ecosystem processes to warming, including plant productivity and community composition, microbial activity and community structure. We highlighted the importance of prospective and systematic research focusing on elucidating the microbial mechanism, identifying SOC source and turnover processes, establishing long-term dynamic networked experiments, and mining and optimizing key parameters in C cycle models. This would provide theoretical support for better understanding the change and mechanism of SOC under global warming and predicting the alterations of SOC pool under climate change.

This study demonstrated that NiO and Ni(OH) 2 as Ni(II) catalysts exhibited significant activity for organic oxidation in the presence of various oxyanions, such as hypochlorous acid (HOCl), peroxymonosulfate (PMS), and peroxydisulfate (PDS), which markedly contrasted with Co-based counterparts exclusively activating PMS to yield sulfate radicals. The oxidizing capacity of the Ni catalyst/oxyanion varied depending on the oxyanion type. Ni catalyst/PMS (or HOCl) degraded a broad spectrum of organics, whereas PDS enabled selective phenol oxidation. This stemmed from the differential reactivity of two high-valent Ni intermediates, Ni(III) and Ni(IV). A high similarity with Ni(III)OOH in a substrate-specific reactivity indicated the role of Ni(III) as the primary oxidant of Ni-activated PDS. With the minor progress of redox reactions with radical probes and multiple spectroscopic evidence on moderate Ni(III) accumulation, the significant elimination of non-phenolic contaminants by NiOOH/PMS (or HOCl) suggested the involvement of Ni(IV) in the substrate-insensitive treatment capability of Ni catalyst/PMS (or HOCl). Since the electron-transfer oxidation of organics by high-valent Ni species involved Ni(II) regeneration, the loss of the treatment efficiency of Ni/oxyanion was marginal over multiple catalytic cycles.

Human hair has become a promising non-invasive matrix in assessing exposure to environmental organic pollutants (OPs). However, exogenous contaminants, which were absorbed into the hair via sweat, sebum, and air particles/dust, could contribute to OP levels in hair and interfere with the precise exposure assessment. So far, the microscopic mechanisms underlying the absorption of exogenous OPs into hair remain inadequately understood. This study focused on the in-situ investigation of the diffusion processes of exogenous OPs into the hair structure using secondary ion mass spectrometry (SIMS) and isotopic tracer techniques. Results showed that the relative signal intensities of deuterium-labeled tris(1,3-dichloro-2-propyl) phosphate (TDCPP), 1-hydroxypyrene (1-OH-Pry), and bisphenol A (BPA) in the hair cortex were notably elevated after a 6-hour exposure. Diffusion coefficients of contaminants were related to their molecular weight, and absorption volumes to their water solubility and molecular structures. Exposure duration and solvent influenced the rate of diffusion and absorption volumes. The distribution of deuterium-labeled molecules in exposed hair samples after washing with two different solvents (acetone or water) was similar to that before washing. Our findings revealed the diffusion of OPs in hair cross-sections, indicating exogenous contributions to contaminants that are biologically incorporated into the hair., 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.)

The oil phase obtained by blending and oleogel methods has potential for the production of non‑hydrogenated and low-saturated puff pastry margarine, thereby reducing intakes of both types of dietary fat. The crystal form, microstructure, rheology, and baking applications of puff pastry margarines prepared with anhydrous milk fat (AMF)/palm stearin (POs), POs/palm oil (PO), beef tallow (BT)/PO, or AMF/POs/diacetyl tartaric acid ester of mono(di)glycerides (DATEM) oleogels were investigated using X-ray scattering, polarized light microscope, and rheometer, respectively. All margarines exhibited β'-form crystal and strongly viscoelastic at low strain. With the addition of DATEM oleogel, their crystal microstructure became more uniform and finer, and the croissants were less hard (1690) and chewiness (160). The chewiness of croissants produced using the margarines was significantly improved with POs content. The theoretical basis for preparation and application in non‑hydrogenated and low-saturated puff pastry margarine was provided in the present study., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In electrokinetic remediation (EKR), the sedimentary dissolved organic matter (DOM) could impede remediation by scavenging reactive species and generating unintended byproducts. Yet its transformation and mechanisms remained largely unknown. This study conducted molecular-level characterization of the water-extractable DOM (WEOM) in EKR using negative-ion electrospray ionization coupled to 21 tesla Fourier transform ion cyclotron resonance mass spectrometry (21 T FT-ICR MS). The results suggested that ∼55 % of the ∼7,000 WEOM compounds identified were reactive, and EKR lowered their diversity, molecular weight distribution, and double-bond equivalent (DBE) through a combination of electrochemical and microbial redox reactions. Heteroatom-containing WEOM (CHON and CHOS) were abundant (∼ 35% of the total WEOM), with CHOS generally being more reactive than CHON. Low electric potential (1 V/cm) promoted the growth of dealkylation and desulfurization bacteria, and led to anodic CO 2 mineralization, anodic cleavage of -SO and -SO 3 , and cathodic cleavage of -SH 2 ; high electric potential (2 V/cm) only enriched desulfurization bacteria, and differently, led to anodic oxygenation and cathodic hydrogenation of unsaturated and phenolic compounds, in addition to cathodic cleavage of -SH 2 . The long-term impact of these changes on soil quality and nitrogen-sulfur-carbon flux may be need to studied to identify unknown risks and new applications of EKR., 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 carbonyl functionality of natural organic matter (NOM) is poorly constrained. Here, we treated Suwannee River NOM (SRNOM) with ammonium acetate and sodium cyanoborohydride to convert ketone-containing compounds by reductive amination to their corresponding primary amines. The total dissolved nitrogen content increased by up to 275% after amination. Up to 30% of the molecular formulas of SRNOM contained isomers with ketone functionalities as detected by ultrahigh-resolution mass spectrometry. Most of these isomers contained one or two keto groups. At least 3.5% of the oxygen in SRNOM was bound in ketone moieties. The conversion of reacted compounds increased linearly with O/H values of molecular formulas and was predictable from the elemental composition. The mean conversion rate of reacted compounds nearly followed a log-normal distribution. This distribution and the predictability of the proportion of ketone-containing isomers solely based on the molecular formula indicated a stochastic distribution of ketones across SRNOM compounds. We obtained isotopically labeled amines by using 15 N-labeled ammonium acetate, facilitating the identification of reaction products and enabling NMR spectroscopic analysis. 1 H, 15 N HSQC NMR experiments of derivatized samples containing less than 20 μg of nitrogen confirmed the predominant formation of primary amines, as expected from the reaction pathway.

The environmental effect of biomass burning smoke-derived dissolved organic matter (BBS-DOM) has attracted growing attention due to the increasing wildfire globally. BBS-DOM eventually deposits on the water and soil environments, thus altering the environmental behaviors of pollutants (e.g., heavy metals) in the surface environments of the wildfire region. However, presently, the binding characters between heavy metals and BBS-DOM remains unknown. In this study, alfalfa, pinewood, and corn straw were burned at 300 °C and 600 °C to produce BBS-DOMs and their binding characters with Cu(II) were investigated using fluorescence excitation-emission matrix spectra coupled with parallel factor (EEM-PARAFAC), synchronous fluorescence spectra combined with two-dimensional correlation spectroscopy (2D-SFS-COS) and FTIR combined with two-dimensional correlation spectroscopy (2D-FTIR-COS). The fluorescence quenching/enhancing results after Cu(II) addition suggested that the binding capacities with Cu(II) of various organic components in BBS-DOMs followed an order of polyphenols-like matters (Ex/Em: 220 nm/310 nm) > aromatic protein-like matters (Ex/Em: 275 nm/310 nm) ≈ small humic-like matters (Ex/Em: 300 nm/380 nm) > large humic-like matters (Ex/Em: 330 nm/410 nm). Interestingly, the quenching effect of Cu(II) addition on the fluorescence intensities of polyphenols-like matters and humic-like matters decreased with their increasing abundances, which possibly depended on the proportion of organic ligands of these components. Furthermore, 2D-FTIR-COS demonstrated that the binding sequence of different functional groups followed deprotonated -COOH→deprotonated phenol-OH→-C]O of aldehydes, ketones, and lactones/aromatic rings/-NH→C-O-C/C-OH of ethers and alcohols. Another novelty was that Cu(II) binding could increase the molecular size and humification of BBS-DOMs, due to the bridge effect of Cu(II). This work provides an importantly theoretical basis for deeply understanding the mechanism of BBS-DOM binding with Cu(II) at the molecular level, which is a key for reasonably predicting the multimedia-crossing effects of BBS-DOM and the environmental behavior of heavy metals in the wildfire region., 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.)

Particulate matter from motor vehicle exhaust is a type of important atmospheric particulates, which can absorb sunlight affecting its photochemical behavior. However, the photochemical activity of water-soluble organic compounds (WSOC) in motor vehicle exhaust particulate matter has not been explored. Here, we applied WSOC in particulate matter from motor vehicle exhaust to investigate the photogenerating ability of its reactive oxygen species (ROS) and its effect based on model phenol photodegradation with the comparison between WSOC in diesel particulate matter and in gasoline particulate matter. The WSOC in diesel particulate matter indicates higher abililty to generate ROS. The main active substance produced by WSOC in the presence of light is 3 WSOC*, the secondary substance is 1 O 2 , and small amounts of ·OH and O 2 · - are also produced. Less active material was produced as WSOC photoaging time increases. Furthermore, the WSOC in diesel particulate matter is more sensitive to light exposure compared to WSOC in gasoline particulate matter. The effects of common atmospheric ionic components on model phenol photodegradation were also explored. Whether WSOC of diesel particulate matter or WSOC of gasoline particulate matter, ammonium nitrate, ammonium sulfate, and ferric chloride promote degradation of model phenol, and copper sulfate inhibited model phenol degradation. However, a different trend emerged with the addition of sodium chloride, which promoted the degradation of model phenol in WSOC of diesel particulate matter and inhibited the degradation in WSOC of gasoline particulate matter., 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.)

Organic crystals are widely used by animals to manipulate light for producing structural colors and for improving vision. To date only seven crystal types are known to be used, and among them β-guanine crystals are by far the most widespread. The fact that almost all these crystals have unusually high refractive indices (RIs) is consistent with their light manipulation function. Here, the physical, structural, and optical principles of how light interacts with the polarizable free-electron-rich environment of these quasiaromatic molecules are addressed. How the organization of these molecules into crystalline arrays introduces optical anisotropy and finally how organisms control crystal morphology and superstructural organization to optimize functions in light reflection and scattering are also discussed. Many open questions remain in this fascinating field, some of which arise out of this in-depth analysis of the interaction of light with crystal arrays. More types of organic crystals will probably be discovered, as well as other organisms that use these crystals to manipulate light. The insights gained from biological systems can also be harnessed for improving synthetic light-manipulating materials., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

The natural dual nanofibril system consisting of the rigid semicrystalline nanofibrils disintegrated from citrus fiber (CF) and soft semiflexible nanofibrils self-assembled from glycyrrhizic acid (GA) has been recently shown to be effective structural building blocks for fabrication of emulsion gels. In this work, the effect of the CF nanofibrils prepared by different mechanical disintegration approaches (i.e., high-pressure microfluidization and hydrodynamic cavitation) on the interfibrillar CF-GA interactions and the subsequent formation and properties of emulsion gels were investigated, with the aim of evaluating the potential of the dual nanofibril-stabilized emulsion gels as templates for synthesizing all-natural edible oleogels. The obtained results demonstrate that compared to the cavitation, the high-pressure microfluidization is more capable of generating CF nanofibrils with a higher degree of nanofibrillation and individualization, thus forming a denser CF-GA gel network with higher viscoelasticity and structural stability due to the stronger multiple intrafibrillar and interfibrillar interactions. The emulsion gels stabilized by the dual nanofibril system are demonstrated to be an efficient template to fabricate solid-like oleogels, and the structural properties of the oleogels can be well tuned by the mechanical disintegration of CF and the GA nanofibril concentration. The prepared oleogels possess high oil loading capacity, dense network microstructure, superior rheological and large deformation compression performances, and satisfactory thermal stability, which is attributed to the compact and ordered CF-GA dual nanofibrillar network via multiple hydrogen-bonding interactions in the continuous phase as well as at the droplet surface. This study highlights the unique use of all-natural dual nanofibrils to develop oil structured soft materials for sustainable applications., 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.)

Petrochemical wastewater (PCWW) treatment poses challenges due to its unique and complex dissolved organic matter (DOM) composition, originating from various industrial processes. Despite the addition of advanced treatment units in PCWW treatment plants to meet discharge standards, the mechanisms of molecular-level sights into DOM reactivity of the upgraded full-scale processes including multiple biological treatments and advanced treatment remain unclear. Herein, we employ water quality indexes, spectra, molecular weight (MW) distribution, and Fourier transform ion cyclotron resonance mass spectrometry to systematically characterize DOM in a typical PCWW treatment plant including influent, micro-oxygen hydrolysis acidification (MOHA), anaerobic/oxic (AO), and micro-flocculation sand filtration-catalytic ozonation (MFSF-CO). Influent DOM is dominated by tryptophan-like and soluble microbial products with MW fractions 〈 1 kDa and 〉 100 kDa, and CHO with lignin and aliphatic/protein structures. MOHA effectively degrades macromolecular CHO (10.86 %) and CHON (5.24 %) compounds via deamination and nitrogen reduction, while AO removes CHOS compounds with MW < 10 kDa by desulfurization, revealing distinct DOM conversion mechanisms. MFSF-CO transforms unsaturated components to less aromatic and more saturated DOM through oxygen addition reactions and shows high CHOS and CHONS reactivity via desulfurization and deamination reactions, respectively. Moreover, the correlation among multiple parameters suggests UV 254 combined with AI mod as a simple monitoring indicator of DOM to access the chemical composition. The study provides molecular-level insights into DOM for the contribution to the improvement and optimization of the upgraded processes in PCWW., 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.)