ACS Omega
·
2026
·Vol. 11
·期 35
·53469-53476
·
IF 5.2
Lu Xin,Yuan Fangfang,Han Xiaojie,Qin Tingting,Wang Qianqian,Li Zengli,Ge Chuanjun,Shi Wenqing,Bai Haijiao,Wang Pei
Desmopressin, a synthetic
analog of vasopressin widely used in
the treatment of diabetes insipidus and bleeding disorders, is a representative
disulfide-containing peptide therapeutic prepared by Fmoc-based solid-phase
peptide synthesis (SPPS). Its unique sequence architecture, particularly
the spatial proximity between the N-terminal mercaptopropionic acid
residue Mpa(1) and the Tyr(2) residue, provides a distinct structural
environment for investigating sequence-dependent side reactions during
peptide manufacturing. The tert- butyl ( t- Bu) protecting group is widely employed for side-chain protection
in Fmoc-based solid-phase peptide synthesis (SPPS). However, under
certain reaction conditions, the highly reactive t- Bu + carbocation generated during acidic deprotection can
participate in nonspecific alkylation, leading to challenging process-related
impurities. In this study, we investigated a unique and highly site-selective
+56 Da impurity observed during side-chain deprotection. High-resolution
MS/MS analysis unambiguously identified this species as a site-selective
product arising from the migration of t- Bu from the
Tyr(2) side chain to the thiol group of Mpa(1). Based on the structural
features of desmopressin, in particular, the spatial proximity between
Tyr(2) and Mpa(1), we propose that the formation of this impurity
most plausibly proceeds via a vicinal-thiol-induced intramolecular
migration mechanism, which competes significantly with the conventional
diffusion-controlled carbocation intermediate intermolecular pathway.
Strengthening the scavenger conditions failed to eliminate this impurity,
further supporting the intramolecular migration mechanism induced
by vicinal thiol. This finding accounts for the observed site selectivity
that cannot be explained by the conventional carbocation intermediate
pathway alone. Guided by these mechanistic insights, we re-evaluated
the necessity of Tyr side-chain protection and proposed a “source-elimination”
strategy. Experimental validation demonstrated that the use of unprotected
Fmoc-Tyr-OH (free phenolic hydroxyl) completely suppressed the formation
of the t- Bu migration impurity and improved the crude
peptide purity to 93.5%. Overall, this study elucidates the formation
mechanism of t- Bu migration impurities and provides
a broadly applicable, mechanism-driven strategy for process optimization
in solid-phase peptide synthesis. While this study focuses on the
desmopressin system, the findings highlight a proximity-driven reactivity
pattern that may be relevant to other thiol-containing peptide sequences.
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ACS Applied Polymer Materials
·
2026
·
IF 5.2
Linzhu Xu,Qingyun Zhao,Birong Zeng,Jie Song,Ziyun Chen,Yilin Su,Zhenlong Luo,Yiting Xu,Conghui Yuan,Lizong Dai
Developing intelligent polyurethane elastomers with balanced high mechanical strength and rapid self-healing capability remains a critical challenge in advanced functional materials. Herein, we designed a kind of polyurethane elastomer of PU-A1D2 by incorporating the azobenzene compound of 3-(4-(p-tolyldiazenyl)phenoxy)propane-1,2-diol (Azo-2) and dimethylglyoxime into the polyurethane matrix as components of the chain extender, where the dual functional groups synergistically contribute to self-healing performance. Dynamic oxime-urethane bonds construct a covalent adaptable network, enabling excellent self-healing in PU-A1D2 via reversible dissociation-association, while light-responsive Azo-2 units undergo photoisomerization, inducing topology transition and reversible soft–hard switching. The resultant PU-A1D2 exhibited a tensile strength of 13 MPa, toughness of 50 MJ m–3, and 95% self-healing efficiency after heat treatment at 80 °C for 12 h, achieving a favorable balance between mechanical robustness and self-healing efficiency. Moreover, PU-A1D2 achieved complete scratch self-healing within 2 h under the synergistic effect of ultraviolet (UV) irradiation and 90 °C. In addition, the 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM·TFSI)-doped PU-A1D2-ET achieved almost 100% self-healing efficiency within merely 10 min under room-temperature UV irradiation. This work clarifies the regulatory mechanism of azobenzene on polyurethane self-healing and provides a promising design strategy for fabricating high-performance polymer elastomers integrated with outstanding mechanical properties and rapid light-controlled self-healing, which holds great potential in flexible electronics and smart wearable devices.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2026
·
IF 19.7
Ziqi Cai,Yangyang Zhang,Yi Liu,Hongyi Zhang,Zhenghua Zhang
An electrocatalytic Cu-GHM system with tunable nanoconfined spaces is constructed. • The electrified system enables 73%–100% degradation of 13 emerging contaminants. • 100 h of continuous operation is demonstrated without loss of structural integrity. • The electrified system also exhibits high energy efficiency (0.07 kWh/m 3 ). • DFT calculations and MD simulations elucidate the degradation mechanism. Persulfate-based advanced oxidation processes are promising for removing refractory contaminants from aquatic systems, however, their performance is often constrained by limited reactive oxygen species utilization and restricted mass transfer. Although spatial confinement engineering of electrocatalytic membranes has improved persulfate activation, the underlying structure–property–performance relationships remain insufficiently understood. Here, we report an electrochemical peroxomonosulfate activation system employing a three-dimensional graphene hydrogel-supported copper nanoparticle membrane (Cu-GHM) as the cathode. The system demonstrated broad applicability, achieving 73%–100% degradation across 13 representative emerging contaminants in real water matrices. Its long-term stability was further confirmed through a 100-h continuous operation test specifically using ranitidine as the model pollutant. By regulating pore architecture through controlled compression, the nanoconfined space was tuned from 13.5 to 5.0 nm, revealing a strong dependence of catalytic performance on confinement scale. The smallest pore size (5.0 nm) resulted in an 8.1-fold enhancement in degradation kinetics, attributed to increased local reactant concentration, improved mass transport, and facilitated interfacial electron transfer. Comprehensive spectroscopic analyses and molecular dynamics simulations elucidated the confinement-enhanced catalytic pathways and mass-transfer behavior. This study provides mechanistic insights into synergistic nanoconfinement and electric-field effects, offering a rational framework for designing energy-efficient electrified membrane systems for water treatment. Download: Download high-res image (250KB) Download: Download full-size image
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Journal of Future Foods
·
2026
·
IF 10.6
Mengdie Li,Yating Wang,Jipeng Wang,Xixian Lv,Yin Yin,Wenxuan Yan,Zepeng Chang,Minjie Gao,Zhitao Li,Yuqin Wang
2′-Fucosyllactose(2′-FL) is a key component of human milk oligosaccharides (HMOs). This study employed an in vitro spatiotemporal dynamic digestion model (BGR-7) to systematically investigate the structural changes, gut microbiota modulation, and metabolic regulatory effects of 2′-FL. 2′-FL remains structurally stable in the stomach and small intestine but undergoes significant degradation in the colon. It promotes the enrichment of beneficial bacteria such as Bifidobacterium and Bacteroides , inhibits the overgrowth of harmful bacteria including Streptococcus, Enterococcus, and Escherichia-Shigella , and exerts flexible regulatory effects on opportunistic pathogens such as Klebsiella, Citrobacter, and Enterobacter . 2′-FL increases levels of intestinal gases such as CO 2 , H 2 , VOCs and H 2 S, with VOCs and H 2 S exhibiting distinct spatiotemporal patterns. Metabolomic analysis indicates that it influences pathways including sulfur metabolism, the tricarboxylic acid cycle, and glutathione metabolism, thereby enhancing antioxidant and energy metabolism capabilities. In summary, 2′-FL promotes the establishment of a dynamically balanced intestinal microenvironment in infants by regulating microbial community structure and metabolic function. Its regulatory pattern differs from that of fructooligosaccharides (FOS), exhibiting more complex temporal and ecological characteristics. The findings of this study provide experimental evidence to elucidate the role of HMOs in infant intestinal health.
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ADVANCED MATERIALS
·
2026
·
IF 29.1
Yueyao Wang,Yuxiang Zhang,Shiqing Jia,Chun Feng,Xinfeng Tao,Binbin Xu,Shaoliang Lin
Nanosheet materials are tremendously attractive for their specific planar architecture and large surface area. However, fabricating nanosheet structures with morphological and functional control across spatial domains from the 2D to 3D scale remains a great challenge. Herein, we report a facile one-pot strategy for creating nanosheets with tunable geometries and multilevel hierarchies based on a liquid crystalline (LC) block copolymer. By finely tuning the assembly conditions, a variety of nanosheet morphologies were achieved, including multilayer leaf-like nanosheets (MLNs), multilayer rectangular nanosheets (MRNs), 3D stacked leaf-like nanosheets (SLNs), 3D stacked rectangular nanosheets (SRNs), and stacked flower-like nanosheets (SFNs). The formation of diverse nanosheet structures relies on LC ordering and the nucleation and growth tendencies of the copolymer. Particularly, we demonstrate that these hierarchical nanosheets are promising additives for polymer reinforcement. By mimicking biological reinforcing principles, SLNs integrating a large surface area with layered and anisotropic characteristics exhibit efficient toughening and strengthening effects through effective energy dissipation and crack deflection. This study not only offers a facile strategy for the design of nanosheet materials with precise control of their morphologies and dimensions but also provides new insight into using hierarchical nanosheet structures to achieve advanced polymer performance.
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JOURNAL OF SEPARATION SCIENCE
·
2026
·Vol. 49
·期 3
·e70400
·
IF 3.6
Xin Chen,Lingyun Shao,Wenping Qian,Huaijie Yao,Hongyan Mao,Wenfen Zhang,Shusheng Zhang
The synthesis of covalent organic polymers (COPs) with abundant active sites remains challenging. To address this, we developed β-cyclodextrin (β-CD) functionalized COPs through a modular synthesis strategy, which was comprehensively characterized and subsequently employed as a stationary phase for capillary electrochromatographic separations. Compared with the unmodified column, the β-CD-functionalized COP monolithic column exhibited better separation performance for analytes spanning a wide range of physicochemical properties, including monosubstituted benzenes, alkylbenzenes, phenols, isomers, and chiral compounds, achieving baseline resolution > 1.5 for all tested compounds and a maximum column efficiency of 35 013 plates m −1 for chlorobenzene. Experiments and non-covalent interaction analysis indicated that the synergistic effect between the β-CD cavity and aromatic groups enables the β-CD-functionalized COP stationary phase to exhibit multiple interaction modes (e.g., hydrophobic, π …π stacking, and hydrogen bonding), providing a theoretical foundation for the experimental data. Moreover, the column demonstrated good repeatability and stability, with relative standard deviations for intra-day, inter-day, and column-to-column repeatability all below 2.1%. The column was successfully applied to the determination of monosubstituted benzenes in wastewater samples, showing satisfactory linearity ( R 2 ≥ 0.998), which confirms its potential for complex sample analysis.
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JOURNAL OF NANOBIOTECHNOLOGY
·
2026
·
IF 15
Wei Zhang,Yanan Zhou,Zijun Li,Zhaowen Wang,Fangzheng Zhu,Yaoyu Zou,Nianshuang Li,Cong He,Nonghua Lu,Xiaolei Wang,Yin Zhu
Helicobacter pylori (H. pylori) infection has emerged as a serious risk factor for global human health. Current antibiotic-based clinical eradication therapies still have many challenges, including inadequate drug permeability across the gastric mucus barrier, H. pylori biofilm-induced antibiotic resistance and recurrent infections, as well as gut dysbacteriosis. Herein, we report a probiotic-nanozyme hybrid system (LP@FeTA/CuPt), which is formed by coupling polyphenol-coated Lactobacillus plantarum (LP@FeTA) and CuPt nanozymes. LP@FeTA effectively penetrates the gastric mucus barrier via autokinetic movement, and facilitates the targeted delivery of CuPt nanozymes within H. pylori biofilms by "eating" extracellular polymeric substances (EPS). CuPt nanozymes respond to the acidic and H 2 O 2 -rich biofilm microenvironment to generate reactive oxygen species (ROS) and release Cu ions, thereby achieving multi-target eradication of biofilms by interfering with H. pylori flagellar self-assembly, urease activity, outer membrane function and energy metabolism. Importantly, LP@FeTA/CuPt can be degraded by transferrin at the infection site, allowing the released CuPt nanozymes to reactivate the antibacterial immune functions of macrophage, thus eliminating biofilm-escaped bacterioplankton to prevent recurrent infections. Notably, LP@FeTA/CuPt also modulates gut microbiota homeostasis. This study provides a promising non-antibiotic therapeutic strategy for H. pylori infection.
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PHYTOMEDICINE
·
2026
·
IF 11.3
Rong Xu,Yingna Li,Xinyue Chen,Peiyao Gao,Chunlei Ji,Yiming Zhao,Chuang Xue,Hui Li,Changjiu Cai,Fangbing Liu,Liwei Sun
Background Sleep deprivation is closely associated with metabolic dysregulation, yet effective preventive interventions remain limited. Although Rhodiola rosea ( R. rosea ) exhibits promising sleep-modulating potential, the specific active components mediating its effects and the underlying mechanisms remain poorly elucidated. Purpose This study aimed to identify the sleep-regulatory component of R. rosea and elucidate its molecular mechanism. Methods A bioactivity-guided fractionation strategy was applied using a sleep-deprived Drosophila melanogaster model. The active fraction was purified and structurally characterized by chromatographic separation and spectroscopic analyses. Sleep behavior, circadian rhythmicity, oxidative stress indices, neurotransmitter levels, lipid metabolic parameters, and brain transcriptomic profiles were systematically evaluated. Mechanistic validation was performed using neuronal genetic manipulation and dual-luciferase reporter assays targeting lipid metabolism-related pathways. Results An acidic glycopeptide fraction derived from R. rosea (WRPA, 76 kDa) markedly increased total sleep duration by approximately 20%, reduced sleep fragmentation by approximately 20%, and improved circadian stability, locomotor activity, and cognitive performance in sleep-deprived flies. WRPA significantly alleviated oxidative stress by reducing reactive oxygen species (ROS) and malondialdehyde (MDA) levels and restoring antioxidant capacity, while normalizing gamma-aminobutyric acid (GABA) and 5-hydroxytryptamine (5-HT) levels in the brain. Transcriptomic analysis revealed lipid metabolism as the primary pathway modulated by WRPA, with acetyl-CoA carboxylase (ACC) identified as a key target. WRPA suppressed ACC expression by inhibiting sterol regulatory element-binding protein (SREBP)-mediated transcription, leading to decreased triglyceride, cholesterol, and free fatty acid accumulation. Importantly, WRPA effectively rescued sleep disturbances induced by neuronal ACC overexpression, confirming an SREBP/ACC-dependent mechanism. Conclusion WRPA is identified as a novel sleep-regulatory acidic glycopeptide derived from R. rosea , which restores sleep homeostasis by maintaining lipid metabolic stability through the SREBP-ACC signaling axis. These findings expand the pharmacological repertoire of R. rosea beyond small molecules and highlight glycopeptides as promising lead candidates for metabolic sleep disorder intervention.
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MICROCHEMICAL JOURNAL
·
2026
·
IF 5.2
Huizhen Zhao,Hui Li,Wenhui Lu,Shanchao Fu,Deyi Zhu,Shan Cao,Lingxin Chen,Jinhua Li
High concentration of surfactant, lipid, metal salts, tanning agent, dye and other leather auxiliaries contain in wet-blue, crust leather and tannery wastewater. The existence of these complicated matrices seriously affects the performance of analytical instruments and the accuracy of conventional analytical methods. In this study, to effectively avoid matrix interference of leather and tannery wastewater by simple pretreatment process, thermo-magnetic dual-template molecularly imprinted polymers (TM-dt-MIPs) were prepared and used as magnetic solid-phase extraction (MSPE) adsorbent to simultaneously selective extract ten kinds of phenols (phenol, five chlorophenols (CPs), and four alkylphenols (APs)), coupled with HPLC analysis. The TM-dt-MIPs prepared by stimuli-responsive imprinting and multi-template imprinting techniques utilized magnetic graphene oxide-multiwalled carbon nanotubes as supporting material, N-isopropyl acrylamide and methacrylamide as functional monomers, 2,4-dichlorophenol and nonylphenol as dual template, showing uniform morphology, high magnetic property and thermal stability. Crucially, the thermo-sensitivity and adsorption ability for target phenols were assessed through thermo-regulated capture/release, static, dynamic and selective adsorption studies, confirmed that the adsorption and desorption of the target analytes could be effectively controlled by external temperature regulation and magnetic manipulation. The developed TM-dt-MIPs-MSPE-HPLC method exhibited excellent analytical performance, characterized by high enrichment factors (26.63–110.4), wide linear ranges (2–200 μg L −1 ), low limits of detection (0.10–0.36 μg L −1 ), limits of quantitation (0.34–1.21 μg L −1 ) and good precision (intra-day RSD: 1.61–6.84%; inter-day RSD: 2.15–8.51%). For the analysis of ten phenols in crust leather, wet blue, and tannery wastewater samples, satisfactory recoveries were achieved ranging from 72.27 to 119.6%, demonstrating the practical application prospects for trace phenol analysis in leather industrial matrices.
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POLYMER
·
2026
·
IF 5.1
Jiapeng Ye,Deming Zhou,Lifan Li,Chenji Zhang,Leyan Li,Kun Luan,Zaixing Zhang,Lingxiao Jing,Ruizhi Xue,Tonghua Zhang
Poly(p-phenylene-2,6-benzobisoxazole) (PBO) fiber, made from a rigid-rod isotropic crystal polymer, exhibits exceptional tensile strength, thermal stability, and creep resistance, surpassing Kevlar fiber (one of high-performance bullet proof fibers) with twice the strength and modulus. However, UV exposure cleaves the oxazole rings in PBO’s molecular structure, leading to decreased crystallinity, reduced mechanical strength, and limited suitability for outdoor applications. This study introduces a novel surface enhancement method using an olefin addition reaction with an azobenzene polyepoxy (Bt-APDB-BA-GMA) coating for Ultraviolet (UV) resistance. Further combining this with nano titanium dioxide (TiO 2 ) forms an organic-inorganic layer for additional protection. Comparative studies were conducted on three samples, including original PBO fibers (PBO), PBO fibers modified with azobenzene/epoxy copolymer (PBO/azo-epoxy), and PBO fibers modified with both azobenzene/epoxy copolymer and nano TiO 2 (PBO/TiO 2 @azo-epoxy). Modified fibers showed significant improvements: PBO/TiO 2 @azo-epoxy exhibited a 63 % higher pull-out strength (34.58 MPa) and retained 78.2 % tensile strength after 288 hours of UV aging, compared to 28.2 % for unmodified fibers. This innovation enhances PBO fiber durability, UV resistance, and interfacial bonding, paving its way for broader applications in body armor, aircraft, and advanced technologies.
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GREEN CHEMISTRY
·
2026
·
IF 10.6
Jia Li,Yan-Hong Tan,Yancheng Hu,Hong-Yan Wang,Jing-Pei Cao
High-energy-density (HED) fuels can enhance the payload and range performance of aircraft, holding strategic importance in the field of air defense. However, conventional petroleum-derived HED fuels face growing challenges related to resource depletion and greenhouse gas emissions. In response to the urgent need for sustainable alternatives, we develop an efficient ring-increasing strategy using natural terpenes as feedstocks to construct polycyclic frameworks suitable for HED fuel applications. The process includes acid-catalyzed ringincreasing alkylation of renewable terpenes with phenols and subsequent hydrodeoxygenation over bifunctional Pd/C and H-Y catalyst system. Benefiting from their strained and polycyclic architectures, the eucalyptus oil-derived biofuel exhibits a density of 0.914 g/mL, combustion heat of 40.1 MJ/L, freezing point below -67 °C and viscosity of 34.5 cSt, while the turpentine oilderived fuel achieves even higher energy density. The high density and good low-temperature fluidity render these fuels as promising sustainable alternatives to conventional petroleum-based HED fuels.
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MARINE POLLUTION BULLETIN
·
2026
·
IF 4.9
Diyi Liu,Lu Liu,Ping Yin,Yan Tian,Jing Zhang
17β-Estradiol (E2), a typical endocrine-disrupting chemical, is widely detected in various aquatic environments, including rivers, lakes, groundwater, estuaries, and coastal waters, posing significant ecological and health risks. Photodegradation is a key pathway for the transformation and removal of E2 from aquatic systems. This study investigated the effects of dissolved organic matter (DOM) from different sources and common inorganic anions (Cl − and NO 3 − ) on E2 photodegradation under simulated solar irradiation. The results indicated that the excited triplet state of DOM ( 3 DOM*), generated upon light absorption, was the key reactive species driving E2 photodegradation. Among the DOM sources examined, humic acid exhibited the strongest promotive effect on E2 photodegradation. Correlation analysis confirmed that terrestrial humic-like components within seawater DOM were the primary contributors to 3 DOM* formation. Seawater DOM from nearshore areas exhibited higher steady-state concentrations of 3 DOM* owing to greater terrestrial input. Both Cl − and NO 3 − effectively accelerated E2 photodegradation, and the E2 degradation rate increased with their concentrations. In contrast, the coexistence of Cl − , NO 3 − , and DOM inhibited E2 photodegradation. In DOM-dominated systems, the main transformation pathways of E2 involved oxidation and hydrolysis reactions on the phenolic ring. This study elucidates the effects of DOM source and water chemical composition on E2 photodegradation, which is crucial for accurately predicting its environmental fate and ecological risks. Moreover, the findings provide valuable insights into the photochemical transformation of other emerging organic contaminants.
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