Inducing a Synergistic Effect on Ptδ+/Electron-Rich Sites via a Platinization Strategy: Generating Hyper-High Current Density in Hydrogen Evolution Reaction.

Herein, we propose a platinization strategy for the preparation of Pt/X catalysts with low Pt content on substrates possessing electron-rich sites (Pt/X: X = Co3O4, NiO, CeO2, Covalent Organic Framework (COF), etc.). In examples with inorganic and organic substrates, respectively, Pt/Co3O4 possesses remarkable catalytic ability toward HER, achieving a current density at an overpotential of 500 mV that is 3.22 times higher than that of commercial Pt/C. It was also confirmed by using operando Raman spectroscopy that the enhancement of catalytic activity was achieved after platinization of the COF, with a reduction of overpotential from 231 to 23 mV at 10 mA cm-2. Density functional theory (DFT) reveals that the improved catalytic activity of Pt/Co3O4 and Pt/COF originated from the re-modulation of Ptδ+ on the electronic structure and the synergistic effect of the interfacial Ptδ+/electron-rich sites. This work provides a rapid synthesis strategy for the synthesis of low-content Pt catalysts for electrocatalytic hydrogen production.

UV-Blocking and Light-Responsive Poly (ϵ-Caprolactone)/ZIF-8 Multifunctional Composite Films for Efficient Antibacterial Activities.

Antibacterial photodynamic therapy (APDT) has received considerable attention owing to its superiority. ZIF-8 was used to address the poor stability of the photosensitizer Rose Bengal (RB) encapsulation to synthesize RB@ZIF-8 NPs, which were doped into a composite film with poly (ϵ-caprolactone) (PCL) and polyvinyl alcohol-quaternary ammonium chitosan (PVA-QCS) as substrates to form composite films (PQZ). The composite films exhibited excellent photodynamic sterilization and good resistance to bacterial adhesion. The tensile strength of the film increased to 43.4 MPa, which was approximately 1.8 times that of the PCL film. With the addition of SiO2 and RB@ZIF-8 NPs, the film exhibited water repellency and UV-blocking properties. RAW264.7 cells were selected using the MTT method to confirm that the composite films had excellent biocompatibility and had no significant inhibitory effect on cell growth and reproduction. PQZ multifunctional composite films show potential as novel APDT antimicrobial materials for food packaging.

Preparation of Ropivacaine Encapsulated by Zeolite Imidazole Framework Microspheres as Sustained-Release System and Efficacy Evaluation.

The management of persistent postoperative pain still remains a clinical challenge currently. Although ropivacaine (RVC) is widely used for postoperative analgesia as a local anesthetic, the short half-life makes it difficult to achieve the desired duration of analgesia. Herein, a RVC sustained-release microspheres encapsulated by zeolite imidazole framework-8 (RVC@ZIF-8) was synthesized for the first time, which prolonged the sustained-release of RVC and decreased the resulting drug toxicity. RVC can continuously release in vitro for at least 96 h with high drug loading of 30.6 % and RVC@ZIF-8 had excellent biocompatibility and low cytotoxicity. In sciatic nerve block model, the sensory block time of RVC@ZIF-8 was significantly prolonged compared with RVC, achieving more than 72 h post injection and no inflammation or lesion were found. Based on high drug loading, ideal sustained-release and superior biological safety, RVC@ZIF-8 will be a novel delivery material for local anesthetic with potential application.

Unilateral Biportal Endoscopic Laminectomy for Treating Cervical Stenosis: A Technical Note and Preliminary Results.

Objective: The objective of this study was to introduce a surgical technique for the percutaneous decompression of cervical stenosis (CS) using a unilateral biportal endoscopic approach and characterize its early clinical and radiographic results. Materials and Methods: Nineteen consecutive patients with CS who needed surgical intervention were recruited. All enrolled patients underwent unilateral biportal endoscopic laminectomy (UBEL). All patients were followed postoperatively for >1 year. The preoperative and final follow-up evaluations included the Japanese Orthopedic Association (JOA) score for neurological assessment, visual analogue scale (VAS) for axial pain and C2-C7 Cobb angle for cervical sagittal alignment. The postoperative complications were analyzed. Results: Thirteen males and six females were included in the analysis. The mean follow-up period was 16.3 ± 2.6 months. The mean operative time was 82.6 ± 18.4 min. Postoperative MRI and CT revealed ideal neural decompression of the treated segments in all patients. Preoperative VAS and JOA scores improved significantly after the surgery, and cervical lordosis was preserved on the postoperative images. Conclusions: UBEL was an effective surgical method for CS, which may also minimize iatrogenic damage to the posterior tension band (PTB) and help to maximize the preservation of the cervical lordosis.

EF24 exerts cytotoxicity against NSCLC via inducing ROS accumulation.

BACKGROUND: The role of Diphenyldifluoroketone (EF24), a synthetic analogue of curcumin with noteworthy antitumor potential, remains unclear in non-small cell lung cancer (NSCLC). Herein, the inhibitory effect of EF24 on NSCLC and its mechanism were studied. METHODS: Cytotoxicity was measured by MTT assay, colony formation assay and xenograft model. Cell apoptosis and reactive oxygen species (ROS) level were quantified by flow cytometer. Protein level was detected by western blot assay. Mitochondria and autophagosomes were observed using transmission electron microscope and confocal microscopy. RESULTS: In-vitro, EF24 significantly induced proliferation inhibition, apoptosis, mitochondrial fission and autophagy of NSCLC cell lines. These cytotoxic effects were significantly attenuated by two reactive oxygen species (ROS) scavengers, indicating its anti-cancer effects largely depend on ROS accumulation. In-vivo, EF24 inhibited tumor growth in a dose-dependent manner. Moreover, no pathological changes of heart, lung, spleen, kidney and liver of mice were observed. Collectively, EF24 induced ROS accumulation, in turn activates cell apoptosis, and then exerts its cytotoxicity on NSCLC cells. CONCLUSIONS: The results showed that EF24 exerted cytotoxicity against NSCLC via ROS accumulation. Thus, EF24 might serve as a potential anti-cancer agent for the treatment of NSCLC.

Graphene Oxide-Assisted Covalent Triazine Framework for Boosting Photocatalytic H2 Evolution.

Covalent triazine frameworks (CTFs) with two-dimensional structures have exhibited promising visible-light-induced H2 evolution performance. However, it is still a challenge to improve their activity. Herein, we report π-conjugation-linked CTF-1/GO for boosting photocatalytic H2 evolution. The CTF-1/GO hybrid material was obtained by a facile low-temperature condensation of 1,4-dicyanobenzene in the presence of GO. The results of photocatalytic H2 evolution indicate that the optimum hybrid, CTF-1/GO-3.0, exhibited an H2 evolution rate of 2262.4 µmol ⋅ g-1 ⋅ h-1 under visible light irradiation, which was 9 times that of pure CTF-1. The enhanced photocatalytic performance could be attributed to the fact that GO in CTF-1/GO hybrids not only acts as an electron collector and transporter like a "bridge" to facilitate the separation and transfer of photogenerated charges but also shortens the electron migration path due to its thin sheet layer uniformly distribution over CTF-1. This work could help future development of novel conjugated CTF-based composite materials as high-efficiency photocatalyst for photocatalysis.

Curcumin exerts cytotoxicity dependent on reactive oxygen species accumulation in non-small-cell lung cancer cells.

AIM: Curcumin induces cytotoxic cell death in several human cancer cells. Here, we have investigated the effects of curcumin on non-small-cell lung cancer (NSCLC) with an aim to identify underlying mechanisms of its cytotoxic effect. MATERIALS & METHODS: The effects of various concentrations of curcumin on the NSCLC cell lines A549 and SPC-A1 were evaluated by MTT assay, colony-forming assay and flow cytometry. Additionally, protein expression associated with different signaling pathways was assessed using western blotting. RESULTS: Curcumin exhibited cytotoxicity against NSCLC, evident from the inhibition of cell proliferation, G2/M arrest, DNA damage, endoplasmic reticulum stress and mitochondrial apoptosis. The anticancer effect was related to reactive oxygen species (ROS) accumulation and could be reversed by ROS scavengers, catalase and N-acetyl-l-cysteine. Curcumin decreased mitochondrial transmembrane potential and induced ROS production, thereby activating the DNA damage/repair pathway and mitochondrial apoptosis. CONCLUSION: These results indicate that curcumin could be an effective therapeutic candidate for NSCLC.

[Effect of occupational exposure to toluene diisocyanate on workers' health].

OBJECTIVE: To investigate the effect of occupational exposure to toluene diisocyanate (TDI) on the workers' health. METHODS: A total of 76 workers exposed to TDI (exposure group) and 64 management staff members (control group) were selected from a factory as the study subjects. Area sampling was performed for the place with exposure to TDI according to the method in GBZ 159-2004 Specifications of air sampling for hazardous substances monitoring in the workplace, and gas chromatography was applied to measure the concentration of TDI in workplace air. The workers' personal information was collected with questionnaire, pulmonary ventilation function was determined with a portable spirometer, hematological parameters were analyzed by automatic blood analyzer and blood chemistry analyzer, and the indicators of oxidative damage and energy metabolism were measured by the reagent kit provided by Nanjing Jiancheng Bioengineering Institute. SPSS 17 software was applied for statistical analysis. RESULTS: The exposure group had significantly lower forced vital capacity (FVC), forced expiratory volume in 1 second(FEV1.0), and FEV1.0/FVC ratio than the control group (P <0.05). Compared with the control group, the exposure group had significantly higher red blood cell count, platelet distribution width, mean platelet volume, lymphocyte count, and neutrophil count(P<0.01), and significantly lower activities of lactate dehydrogenase(LDH), superoxide dismutase, and succinodehydrogenase (SDH)(P <0.01). In the exposure group, the length of exposure was negatively correlated with the activities of SDH and LDH in the serum (r=-0.319, P <0.05; r=-0.239, P <0.05), and the length of exposure was not found to be correlated with the activity of SOD and pulmonary function indices. CONCLUSION: TDI can induce inflammatory response and lung ventilation function impairment in workers exposed to TDI, as well as oxidative stress and imbalance of energy metabolism. Therefore, it can cause damage to workers' health, and protective measures should be enhanced.

[Response of soil microbial necromass carbon to litter and root carbon inputs in a mid-subtropical Castanopsis carlesii plantation]. / ä¸­äºšçƒ­å¸¦ç±³æ§ äººå·¥æž—åœŸå£¤å¾®ç”Ÿç‰©æ®‹ä½“ç¢³å¯¹å‡‹è½ç‰©å’Œæ ¹ç³»ç¢³è¾“å ¥çš„å“åº”.

Microbial necromass carbon (MNC) is a crucial source for stable soil carbon pool, and understanding its response to carbon inputs from both aboveground (litter) and belowground (roots) in subtropical forest soils is essential for assessing soil carbon stocks in global ecosystems. In a Castanopsis carlesii plantation at the Sanming Forest Ecosystem National Observation and Research Station in Fujian Province, we conducted an experiment with five treatments, including root removal (NR), aboveground litter removal (NL), no litter input (removals of both aboveground litter and roots, NI), double aboveground litter addition (DL), and control (CK). After seven years, we collected soil samples in the 0-10 cm soil layer to examine changes in MNC content and its contribution to soil organic carbon (SOC). Results showed that NR treatment reduced MNC, bacterial necromass carbon (BNC), and fungal necromass carbon (FNC) by 15.9%, 20.2%, and 14.5%, respectively, while other treatments did not induce significant changes. The NR, NL, NI, and DL treatments did not affect the contributions of BNC, FNC, and MNC to SOC. Correlation and path analyses revealed that litter and root carbon input treatments could alter the MNC content directly or indirectly through changing soil available substrates and microbial community structure. Our results suggested that roots exert a stronger influence on the maintenance of MNC than aboveground carbon source in the mid-subtropical plantations.

Portable SERS-Based POCT Kit for Ultrafast and Sensitive Determining Paraquat in Human Gastric Juice and Urine.

Paraquat (PQ) poisoning poses a significant public health concern. Unfortunately, point-of-care testing (POCT) of PQ in biofluids remains challenging. This study developed a portable kit that enables swift and reliable identification and quantification of PQ in human urine and gastric juice. The approach employed the surface-enhanced Raman scattering (SERS) technique, leveraging gold-silver core-shell nanoparticles (Au@Ag NPs) as the substrate. The kit comprised a portable Raman spectrometer and three sealed tubes containing Au@Ag NPs colloid, KI solution, and MgSO4 solution. A discernible correlation was observed between signal intensity and the logarithmic concentration, spanning from 5 to 500 µg/L in urine and 10 µg/L to 1 mg/L in gastric juice. The detection limits, calculated from the characteristic peak at 1648 cm -1, were 1.36 and 4.05 µg/L in human urine and gastric juice, respectively. Notably, this POCT kit obviated the need for pretreatment procedures, and the detection process was accomplished within 1 min, yielding satisfactory recoveries. This expeditious time frame is crucial for clinical diagnosis and rescue operations. Compared to conventional methods, this kit demonstrated real-time determinations in nonlaboratory settings. The simplicity and practicality of this POCT assay suggest its significant potential as an innovative alternative for poisoning detection applications.

Point-of-Use SERS Approach for Efficient Determination and Removal of Phthalic Acid Esters Based on a Metal-Organic Framework-Coated Melamine Sponge.

Phthalic acid esters (PAEs) are ubiquitous environmental contaminants, and their real-time monitoring and removal remain challenging. Herein, a point-of-use (POU) device integrating adsorption, surface-enhanced Raman spectroscopy (SERS), and removal strategy was developed and realized ultrafast on-site determination of PAEs and cleanup of them from water. A piece of flexible melamine sponge (MS) was coated with gold nanostars (AuNSs) and metal-organic frameworks (MOFs), thus obtaining SERS activity and adsorption capacity. Based on this multifunctional AuNSs@MOFs/MS composite, clear trends were observed between SERS signal intensity and concentration of di(2-ethylhexyl)phthalate (DEHP) and dibutyl phthalate (DBP). The method detection limits of DEHP and DBP were calculated to be 0.75 × 10-7 and 0.67 × 10-7 M in water, respectively, proving good sensitivity. Furthermore, this POU device exhibited satisfactory adsorption capacity (∼82.3 g/g for DBP and ∼90.0 g/g for DEHP), high adsorption efficiency (equilibrium in 100 s), and good regeneration capability (removal efficiency >70% after 5 cycles). The applicability of this device was verified by its good determination and removal performance in real environmental water matrices. The whole process could be completed within 5 min. This approach provides a new POU alternative for real-time monitoring and removal of PAEs in water.

A SERS-based point-of-care testing approach for efficient determination of diquat and paraquat residues using a flexible silver flower-coated melamine sponge.

Diquat (DQ) and paraquat (PQ) residues in food are potential hazards to consumers' health. Point-of-care testing (POCT) of them remains challenging. Based on surface-enhanced Raman spectroscopy (SERS) technology, we developed a POCT strategy for DQ and PQ on apple surface and in apple juice. A point-of-use composite was fabricated using a piece of porous melamine sponge (MS) modified with silver nanoflowers (AgNFs), combining the specificity of the SERS fingerprint and the excellent adsorption capacity of MS. Using this dual-functional AgNFs@MS, the on-site determination of the DQ and PQ residues was completed within 3 min without pretreatment. Clear trends were observed between SERS intensity and logarithmic concentrations, with r values from 0.962 to 0.984. The limit of detection of DQ and PQ were 0.14-0.70 ppb in apple juice and on apple surface. This study provides a new point-of-use alternative for rapidly detecting DQ and PQ residues in nonlaboratory settings.

New nervogenic acid derivatives from Liparis nervosa.

Ten new nervogenic acid derivatives (1-4, 6-11) and one known compound (5) have been isolated from Liparis nervosa. Their structures were determined using extensive spectroscopic analysis, including 1D and 2D NMR experiments. Compounds 3, 4, 9, 10, and 11 were evaluated for their cytotoxicity against A549, H460, Hela, MCF-7, Caco2, and HepG2 human cancer cell lines.

Rapid and Robust Analysis of Coumatetralyl in Environmental Water and Human Urine Using a Portable Raman Spectrometer.

The widespread use and exposure of coumatetralyl (CMTT) has led to its accumulation in the environment and organisms, causing damage to ecosystems and adverse health effects in humans. Unfortunately, achieving fast detection of CMTT remains challenging. Herein, a rapid and robust surface-enhanced Raman spectroscopy (SERS) method was developed for rapid on-site detection of CMTT in environmental water and human urine. Clear trends were observed between the signal intensity and the logarithmic concentration of CMTT, ranging from 0.025 to 5.0 µg/mL with high reproducibility. The detection limits in water and human urine were as low as 1.53 and 13.71 ng/mL, respectively. The recoveries of CMTT for environmental water and urine samples were 90.2-98.2 and 82.0-87.5%, respectively, satisfactory for practical applications. The quantitative results of this approach were highly comparable to those obtained by high-performance liquid chromatography. Most importantly, it is cost-effective, operationally simple, and without a complicated sample preparation step. Detecting CMTT in water samples took only 5 min, and the detection of urine samples was completed within 8 min. This simple yet practical SERS approach offers a reliable application prospect for on-site CMTT detection in environmental water and point-of-care monitoring of poisoned patients.

Rapid identification and quantification of diquat in biological fluids within 30 s using a portable Raman spectrometer.

Rapid detection of diquat (DQ) is essential in clinical diagnosis and rescue. Here, we developed a fast, simple-yet-practical detection strategy for the reliable identification and quantification of DQ in biological fluids. Based on surface-enhanced Raman spectroscopy (SERS), point-of-care detection was realized under the acidic condition with gold nanoparticles as the substrate. Under optimal experimental conditions, the detection limits of the strategy were 17.5 ppb and 1.99 ppm in human urine and gastric juice, respectively. High specificity and selectivity of the SERS strategy were demonstrated using common pesticides and coexisting biological substances. The method was also used to detect biofluids from 5 patients and urine samples from 10 healthy volunteers. The results were in high agreement with spectrophotometric and clinical liquid chromatography-mass spectrometry methods. The volume of urine samples required for this technique is merely 20 µL, and no preparation of the samples is required. Compared to traditional methods used in clinical settings, SERS-based methods are capable of real-time measurements that accurately provide rapid detection and response in non-laboratory settings, with great potential for on-site and point-of-care testing.

Integration of solid-phase microextraction and surface-enhanced Raman spectroscopy for in-vivo screening of polybrominated diphenyl ether.

The monitoring of polybrominated diphenyl ethers (PBDEs) is of great significance owing to their high persistence, bioaccumulation, and toxicity to humans and animals. In this study, a sensitive and reproducible probe that integrates solid-phase microextraction and surface-enhanced Raman spectroscopy (SPME-SERS) was developed for screening PBDEs in multiphase specimens, including live fish, water, and electrical products. A roughed Cu fiber with an Ag layer was fabricated with dual functions. BDE-15 was readily extracted and detected on the SPME-SERS probe consisting of propanethiol-modified Ag nanoplates on a Cu wire. A clear linear relationship (R2 = 0.988) was established between the SERS intensity at 782 cm-1 and the logarithmic concentrations (from 100 ppb to 100 ppm), with a detection limit of 15 ppb. This proposed method enables continuous in vivo monitoring in fish without complicated pretreatments. The results obtained by this SPME-SERS approach were validated by high-performance liquid chromatography and showed good agreement. This "extracting and detecting" SPME-SERS method provides a potential tool to monitor the occurrence, formation, and migration of PBDEs.

Rapid and robust analysis of aristolochic acid I in Chinese medicinal herbal preparations by surface-enhanced Raman spectroscopy.

The use of Chinese herbs containing aristolochic acid can induce the exchange of adenine and thymine in gene mutations and even cause liver cancer. To eliminate the harm of aristolochic acids (AAs) to humans, a rapid and robust method of AAs screening is a prerequisite. In this work, a facile and robust Surface-enhanced Raman spectroscopy (SERS) method was used for the qualitative and quantitative detection of AAs in Chinese medicinal herbal preparations based on the mandelic acid modified Ag nanoparticles SERS substrate. Qualitative and quantitative SERS detection of Aristolochic acid I (AAI) was achieved with a good linear relationship ranging from 0.2 - 120.0 µM and a limit of detection (LOD) of 0.06 µM. The proposed method demonstrates a refined strategy for sensitivity analysis of AAs with the advantages of easy operation, time-saving, high sensitivity, and molecular specificity, making it a preferred platform for the screening of AAI in regular inspections of herbal products and regulatory supervision of the supply chain.

Diaqua-bis-{3-[4-(1H-imidazol-1-yl)phenyl]-5-(pyridin-2-yl-κN)-1H-1,2,4-triazol-1-ido-κN(1)}zinc.

The centrosymmetric mol-ecule of the title compound, [Zn(C(16)H(11)N(6))(2)(H(2)O)(2)], contains one Zn(2+) ion located on a center of symmetry, two 3-[4-(1H-imidazol-1-yl)phen-yl]-5-(pyridin-2-yl)-1H-1,2,4-triazol-1-ide (Ippyt) ligands and two coordinating water mol-ecules. The Zn(II) ion is six-coordinated in a distorted octa-hedral coordination geometry by four N atoms from two Ippyt ligands and by two O atoms from two water mol-ecules. Adjacent units are inter-connected though O-H⋯N hydrogen bonds, forming a three-dimensional network.

New tannin-related compounds from Tagetes erecta.

A mixture of two new anomers: 3,4-di-O-[syringate]-alpha-D-glucopyranose (1) and 3,4-di-O-[syringate]-beta-D-glucopyranose (2), together with syringic acid (3), were isolated from the alcohol extract of Tagetes erecta. The structures of these compounds were elucidated by various spectroscopic methods, including intensive 1D, 2D NMR and HR-ESI-MS studies. The structural assignment was further supported by HPLC-ESI-MS with compound 1 at t(R) = 3.22 min (m/z 538.9 [M-H](-)) and compound 2 at 3.25 min (m/z 538.9 [M-H](-)) in the mixture.

Chemical constituents of Rhododendron lepidotum.

An unusual natural product named 2,4,6-trihydroxacetophenone-3, 5-di-C-beta-D-glucoside (18) were isolated from aerial parts of Rhododendron lepidotum grows in Tibet, along with other 17 known compounds: hopenol-B (1), lupeol (2), ursolic acid (3), avicularin (4), quercetin (5), myricetin (6), hyperoside (7), myricetin-3'-O-beta-D-xyloside (8), (+)-taxifolin-3-O-alpha-L-arabinopyranoside (9), (+)-taxifolin-3-O-beta-D-glucopyranoside (10), lyoniside (11), confluentin (12), 2-(4-hydroxyphenyl)-ethyltriacontanoate (13), 2, 6-dimethoxy-4-hydroxyphenyl-1-O-beta-D-glucopyranoside (14), (-)-2-hydroxy-5-(2-hydroxyethyl) phenyl-O-beta-D-glucopyranoside (15), (-)-isola-riciresinol (16) and isofraxoside (17). All the compounds were firstly isolated from this plant as well as compounds 1, 13-18 were reported occurrence in R. spp. for the first time. The structures were identified based on analyses of spectroscopic data and physico-chemical evidences.