[Determination of twelve halobenzoquinones in drinking water by solid phase extraction-ultra-performance liquid chromatography-tandem mass spectrometry].

OBJECTIVE: To establish a method for twelve halobenzoquinones(HBQs) in drinking water by solid phase extraction-ultra-performance liquid chromatography coupled with electrospray-tandem mass spectrometry(SPE-UPLC-MS/MS). METHODS: The drinking water was acidified with formic acid and concentrated by Bond Elut Plexa solid phase extraction column. The sample solution was separated using Waters ACQUITY HSS T3 column(100 mm×2.1 mm, 1.8 µm) with gradient elution using methanol-water containing 0.1% formic acid as mobile phase. The target compouds were detected in negtive electrospray ionization(ESI~-) and multiple reaction monitoring. RESULTS: The concentration of twelve HBQs showed good linearity in the range 5.0-150.0 ng/mL, respectively, with the correlation coefficients greater than 0.999. The limits of detection(LOD) of twelve HBQs were lower than 2.0 ng/mL, and the limits of quantification(LOQ) for twelve HBQs were lower than 5.0 ng/mL, respectively. The recoveries of three levels in the matrix were 70.0%-84.0%. The matrix effffect was 0.08-0.64. CONCLUSION: The SPE-UPLC-MS/MS method has high sensitivity, good accuracy and fast analysis speed for the detection of halobenzoquinones in drinking water.

Caspase-8 dependent apoptosis contributes to dyskinesia caused by muscle defects and neurotoxicity in zebrafish exposed to zearalenone.

Zearalenone (ZEA), one of the usual mycotoxins, has been recognized in many areas and crops, posing a significant threat to the living organisms even to human beings. However, the mechanisms of locomotive defects remain unknown. Herein, zebrafish larvae was employed to investigate ZEA effects on developmental indexes, muscle and neural toxicity, apoptosis, transcriptome and motor behaviors of zebrafish larvae. Zebrafish larvae exposed to ZEA (0, 0.5, 1, 2 and 4 µM) showed no change in survival rate, but the malformation rate of zebrafish larvae increased dramatically manifesting with severe body bending and accomplished with adverse effects on hatching rate and body length. Moreover, the larvae manifested with defective muscle and abnormal neural development, resulting in decreased swimming ability, which probably due to the abnormal overactivation of apoptosis. And this was confirmed by enriched caspase 8-mediated apoptosis signaling pathway in the following transcriptome analysis. Meanwhile, there was a recovery in swimming behaviors in the larvae co-exposed in ZEA and caspase 8 inhibitor. These findings provide an important evidence for risk assessment and potential treatment target of ZEA exposure.

Urinary matrix metalloproteinase-7 is a sensitive biomarker to evaluate renal tubular injury in patients with minimal change disease and focal segmental glomerulosclerosis.

Objective: To explore the advantages of urinary matrix metalloproteinase-7 (MMP-7) in evaluating renal tubular injury in minimal change disease (MCD) and focal segmental glomerulosclerosis (FSGS) patients compared with urinary cystatin C (CysC) and retinol-binding protein (RBP). Methods: Serum and urine samples were collected from 20 healthy volunteers, and 40 MCD and 20 FSGS patients. Serum and urinary MMP-7 levels were measured by enzyme-linked immunosorbent assay. Urinary total protein, CysC and RBP levels were measured by automatic specific protein analyzer and compared with urinary creatinine level for calibration. The renal tissue serial sections were stained by MMP-7 immunohistochemistry and periodic acid-Schiff. Results: Under light microscopy, MMP-7 granular weak positive expression was showed sporadically in the cytoplasm of a few renal tubular epithelial cells without obvious morphological changes in MCD patients, and MMP-7-positive expression was observed in the cytoplasm of some renal tubular epithelial cells in FSGS patients. There was no significant difference in serum MMP-7 level among the three groups. Compared with the control group, the urinary MMP-7 level in MCD patients was higher, but urinary CysC and RBP levels were not increased significantly. Compared with the control group and MCD patients, urinary MMP-7, CysC and RBP levels in FSGS patients were upregulated significantly. Conclusions: Urinary MMP-7 could not only evaluate the mild renal tubular epithelial cells injury in MCD patients with massive proteinuria, but also evaluate the continuous renal tubular epithelial cells injury in FSGS patients.

[Determination of beauvercin and enniatins in rice flour and wheat flour by solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry].

OBJECTIVE: To develop a method for the determination of beauvercin(BEA), enniatin A(ENNA), enniatin A1(ENNA1), enniatin B(ENNB) and enniatin B1(ENNB1) in rice flour and wheat flour by ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS). METHODS: Samples were extracted by acetonitrile-water, purified by Oasis Prime HLB solid-phase extraction column. The sample solution was separated by waters BEH C_(18) column(2.1 mm×100 mm, 1.8 µm). The detection was performed in the electrospray positive ionization(ESI+) under multiple reaction monitoring(MRM) mode. The internal standard method and the matrix-matched calibrations were used for quantification. RESULTS: The linear relationships of BEA and 4 kinds of enniatins(ENNs) were good in the range of 0.1-50.0 ng/mL(r>0.999). The average recoveries of BEA and ENNs in rice flour and wheat flour were 96.4%-105.4% and 99.1%-109.2%, with the relative standard deviations(RSD) of 1.01%-7.42% and 1.09%-9.69%(n=6). The detection limits(LOD) of BEA and ENNs were 0.03 µg/kg. The quantitative limits(LOQ) of BEA and ENNs were 0.1µg/kg. The matrix induced suppression or enhancement effect were 72.7%-99.3% and 60.8%-100.4%, respectively. The levels of emerging BEA and ENNs in wheat flour were higher than rice flour. The detection rate of enniatin B was highest in wheat flour and rice flour, the contents were 0.03-9.57 µg/kg and 0.03-0.56 µg/kg, the positive percentage were 98.5% and 36.4%. CONCLUSION: The method is quick, easy, accurate and sensitive, which is suitable for the determination of BEA and 4 kinds of ENNs in rice flour and wheat flour.

Efficacy of pericapsular nerve group block vs. fascia iliaca compartment block for Hip surgeries: A systematic review and meta-analysis.

Objective: The review aimed to compare outcomes of pericapsular nerve group block (PENG) vs. fascia iliaca compartment block (FICB) for patients undergoing hip surgeries. Methods: Randomized controlled trials (RCTs) published in the databases of PubMed, CENTRAL, Embase, and Web of Science comparing PENG vs. FICB for pain control after hip surgeries were included in the review. Results: Six RCTs were included. 133 patients received PENG block and were compared with 125 patients receiving FICB. Our analysis showed no difference in 6 h (MD: -0.19 95% CI: -1.18, 0.79 I 2 = 97% p = 0.70), 12 h (MD: 0.04 95% CI: -0.44, 0.52 I 2 = 72% p = 0.88) and 24 h (MD: 0.09 95% CI: -1.03, 1.21 I 2 = 97% p = 0.87) pain scores between PENG and FICB groups. Pooled analysis showed that mean opioid consumption in morphine equivalents was significantly less with PENG as compared to FICB (MD: -8.63 95% CI: -14.45, -2.82 I 2 = 84% p = 0.004). Meta-analysis of three RCTs showed no variation in the risk of postoperative nausea and vomiting in the two groups. The quality of evidence on GRADE was mostly moderate. Conclusion: Moderate quality of evidence suggests that PENG may result in better analgesia than FICB in patients undergoing hip surgeries. Data on motor-sparing ability and complications are scarce to draw conclusions. Further large-scale and high-quality RCTs should be conducted to supplement current findings. Systematic Review Registration: https://www.crd.york.ac.uk/prospero/, identifier CRD42022350342.

17beta-estradiol alleviates contusion-induced skeletal muscle injury by decreasing oxidative stress via SIRT1/PGC-1α/Nrf2 pathway.

PURPOSE: This study aimed to investigate the role of 17ß-estradiol (E2) in the repair of contusion-induced myoinjury in mice and to identify the underlying molecular mechanisms. METHODS: In vivo, contusion protocol was performed for preparing mice myoinjury model, and Injection (i.p.) of 17ß-estradiol (E2) or estrogen receptor antagonist ICI 182,780, or ovariectomy (OVX), was used to alter estrogen level of animal models. In vitro, C2C12 myoblasts were treated with H2O2 (oxidative stress inducer), SIRT1 inhibitor EX527, or aromatase inhibitor anastrozole. Serum E2 level was assessed by enzyme-linked immunosorbent assay (ELISA). Muscle damage repair was evaluated by H&E staining and the activities of serum creatine kinase (CK) and lactate dehydrogenase (LDH). The oxidative stress was estimated by the levels of catalase (CAT), superoxide dismutase (SOD), and malondialdehyde (MDA). Western blot was performed to measure the protein expressions of SIRT1, PGC-1α, Nrf2, and HO-1. RESULTS: We observed the elevated serum E2 levels and the upregulated oxidative stress in damaged muscle in female mice after contusion-induction. The E2 administration in vivo alleviated contusion-induced myoinjury in OVX mice by reducing CK and LDH activities, suppressing oxidative stress, and enhancing the expression levels of SIRT1, PGC-1α, Nrf2, and HO-1. These effects were inhibited by treatment with an ERα/ß antagonist. Moreover, EX527 or anastrozole treatment exacerbated H2O2-induced growth inhibition and oxidative stress, and expression downregulation of SIRT1, PGC-1α, Nrf2, and HO-1 in C2C12 cells in vitro. CONCLUSION: Our results suggest that E2 is a positive intervention factor for muscle repair followed contusion-induced myoinjury, through its effects on suppressing oxidative stress via activating the SIRT1/PGC-1α/Nrf2 pathway.

Four novel mutations identification in 17 beta-hydroxysteroid dehydrogenase-3 deficiency and our clinical experience: possible benefits of early treatment.

Introduction: Individuals with 17-beta-hydroxysteroid dehydrogenase type 3 (17ß-HSD3) deficiency face a multitude of challenges, primarily concerning genital appearance, potential malignancy risks, and fertility issues. This study reports our findings from an investigation involving five individuals affected by 17ß-HSD3 deficiency, ranging in age from pre-adolescence to adolescence. Notably, we identified four previously unreported mutations in these subjects. Methods: Our study included a comprehensive evaluation to determine the potential occurrence of testicular tumors. The methods involved clinical examinations, genetic testing, hormone profiling, and patient history assessments. We closely monitored the progress of the study subjects throughout their treatment. Results: The results of this evaluation conclusively ruled out the presence of testicular tumors among our study subjects. Moreover, four of these individuals successfully underwent gender transition. Furthermore, we observed significant improvements in genital appearance following testosterone treatment, particularly among patients in the younger age groups who received appropriate treatment interventions. Discussion: These findings underscore the critical importance of early intervention in addressing concerns related to genital appearance, based on our extensive clinical experience and assessments. In summary, our study provides insights into the clinical aspects of 17ß-HSD3 deficiency, emphasizing the vital significance of early intervention in addressing genital appearance concerns. This recommendation is supported by our comprehensive clinical assessments and experience.

[Determination of vitamin A, vitamin E isomers and cholesterol in foods by reversed-phase high-performance liquid chromatography].

OBJECTIVE: To establish a method for simultaneous analysis of vitamin A, three vitamin E isomers and cholesterol in meat products by reversed-phase high-performance liquid chromatography. This method is used to determine the contents of the corresponding nutrients in several meat products. METHODS: The sample was pretreated with saponification and liquid-liquid extraction, then separated on Waters Symmetry C_(18) column(4.6 mm×250 mm, 5 µm). The mobile phase consisted of methanol(98%) and water(2%). The analytes were detected by photo-diode array(PDA)detector. 325 nm, 294 nm, and 210 nm were selected as the characteristic absorption wavelengths of vitamin A, vitamin E, and cholesterol, respectively by scanning in the range of 190-350 nm in 3 D mode. Benzo[e]pyrene was internal standard for vitamin A and E. Cholesterol was quantified by external standard curve method. RESULTS: The concentration of vitamin A, three vitamin E isomers and cholesterol showed good linearity in the range of 0.18-9.00 µg/mL、0.76-5.2 µg/mL and 0.11-5.50 mg/mL, respectively, with the correlation coefficients greater than 0.995.The limits of detections(LODs) were 5、20 and 330 µg/100 g and the limits of quantification(LOQs) for vitamin A, three vitamin E isomers and cholesterol were 15、60 and 990 µg/100 g, respectively. The recoveries at three levels in the matrix were 86.3%-105.6%, and the relative standard deviations(RSDs) were all less than 7.0%(n=6). CONCLUSION: The method is sensitive, accurate and suitable for analysis of vitamin A, three vitamin E isomers and cholesterol in meat products.

[Nutritional composition in different processed wheats from Shaanxi Province].

OBJECTIVE: To study the content of nutritive ingredients of 11 kinds of different processed wheats planted in Shaanxi Province, and assess their nutritional value. METHODS: The macronutrients, moisture, ash and vitamins in 11 different wheat were determined. The index of nutritional quality(INQ) method was used to evaluate the different nutrients in 11 kinds of wheat and the fuzzy membership function method was used to evaluate the nutritional value comprehensively. RESULTS: The contents of water and carbohydrate in 11 kinds of whole wheat flour were lower than those of special flour and wheat core flour. The contents of ash, fat, protein and total dietary fiber were significantly higher than those of special flour and wheat core flour. The wheat flour contained high levels of vitamin B_1, certain vitamin B_2 and trace amount of ß-carotene. Under the parameters selected in this article, the comprehensive evaluation shows that Jinmai 54 had the highest nutritive value among 11 kinds of wheat, while Zhoumai 26 had the lowest nutritive value. CONCLUSION: 11 kinds of wheat is rich in protein, vitamins and other nutrients, peeling can cause a large loss of vitamin B and vitamin E in wheat flour. The comprehensive nutritional value of whole wheat flour is higher than the special flour and wheat core powder.

[Determination of vitamin A and vitamin E in human serum by high performance liquid chromatography with fluorescence detection].

OBJECTIVE: To establish a method for the simultaneous and rapid determination of vitamin A and vitamin E of different configurations in human serum by high performance liquid chromatography(HPLC) with multi-wavelength fluorescence detector. METHODS: The serum was mixed after adding internal standard, and acetonitrile was added for protein precipitation. The mixture was centrifuged after extraction with n-hexane. The n-hexane layer was dried by N_2 flow, the residue was dissolved with methanol. The HPLC system was consisted of WATERS Symmetry C_(18) column(4. 6 mm × 250 mm, 5 µm) and the mobile phase was methanol. The column temperature was 30 ℃ and fluorescence detector with online wavelength conversion method was carried out for the quantitative detection. RESULTS: The liner range of determination of vitamin A, α-vitamin E, ß-vitamin E and δ-vitamin E were 0. 050-2. 0 µg/mL, 0. 50-50 µg/mL, 0. 050-5. 0 µg/mL and 0. 050-5. 0 µg/mL, respectively(r≥0. 996). The minimum detection limits of the method for vitamin A and vitamin E were all 0. 02 µg/mL. The intraday and interday relative standard deviations(RSDs) were less than 3% at high, medium and low concentrations. The recoveries of the samples at the three concentrations were 91. 2%-107. 5%, and the RSDs were less than 10%. CONCLUSION: This method is simple and accurate, with higher sensitivity than using UV detector and can be used for the simultaneous determination of vitamin A and vitamin E of different configurations in serum, and is suitable for rapid detection of batch serum samples.

[Simultaneous determination of 25-hydroxyvitamin D and vitamin K_1 in serum by ultra-performance liquid chromatography-tandem mass spectrometry].

OBJECTIVE: To establish a method for analysis of 25-hydroxylvitamin D_2(25(OH)D_2), 25-hydroxylvitamin D_3(25(OH)D_3)and vitamin K_1 in serum by ultra-performance liquid chromatography tandem mass spectrometry(UPLC-MS/MS), which can be applied in diagnosis of vitamin deficiency and estimation on the nutritional status of people. METHODS: Serum samples mixed with d_6-25(OH)D_3, d_7-vitamin K_1(internal standard)were precipitated with acetonitrile and extracted with n-hexane. The sample solution was separated using BEH C_(18) column(2. 1 mm×100 mm, 1. 7 µm) with gradient elution using methanol-water containing 0. 1% formic acid as mobile phase. The target molecule was detected in positive electrospray ionization(ESI~+) and multiple reaction monitoring. RESULTS: The concentration of 25(OH)D_2, 25(OH)D_3 and vitamin K_1 showed good linearity in the range 5. 0-75. 0 ng/mL, 2. 0-81. 5 ng/mL and 0. 3-12. 0 ng/mL, respectively, with the correlation coefficients greater than 0. 995. The limits of detection(LOD) of 25(OH)D_2, 25(OH)D_3 and vitamin K_1 were 1, 0. 25 and 0. 1 ng/mL, and the limits of quantification(LOQ) for 25(OH)D_2, 25(OH)D_3 and vitamin K_1were 3, 0. 75 and 0. 3 ng/mL, respectively. The recoveries of three levels in the matrix were 98. 5%-104. 3%, the relative standard deviation(RSD) were all less than 5. 0%(n=6). CONCLUSION: An UPLC-MS/MS method for analysis of 25(OH)D_2, 25(OH)D_3 and vitamin K_1 in serum is sensitive, rapid, accurate and suitable for the nutritional surveillance of vitamin D and K_1 in the population.

ATG5 and ATG7 induced autophagy interplays with UPR via PERK signaling.

BACKGROUND: Autophagy and ER stress are involved in maintaining some well-orchestrated mechanisms aimed at either restoring cellular homeostasis or performing cell death. Autophagy is a well-defined process which governs overall cellular stress outcomes. Selective degradation of the ER mediated by autophagy occurs through a specific type of autophagy called ER-phagy, which ensures ER protein homeostasis. METHODS: Immunoblotting and RT-PCR were used to evaluate the expression of ATG5 and ATG7 in chondrocyte. Western blotting, Flow cytometry,immunofluorescence cell staining and confocal microscope were used to examine the effect of ATG5 and ATG7 on autophagy, ER stress, cell apoptosis and cell proliferation. Transmission electron microscope and confocal microscope were performed to visualize the autophagy flux and autolysosome formation. The role of ATG5 and ATG7 overexpression on the PERK pathway inhibitor were detected by immunoblotting and treatment with inhibitors. RESULTS: In current study, we demonstrated that Tm-induced ER stress can activate autophagy while Rapamycin-induced autophagy can inhibit ER stress in chondrocyte. Autophagy related protein ATG5 or ATG7 can promote autophagy and inhibit ER stress individually, and their combined effect can further improve the autophagy enhancement and the ER stress repression. Moreover, ATG5, ATG7 and ATG5 + ATG7 lead cells into more S phase, increase the number of S phase and inhibit apoptosis as well. ATG5, ATG7 and ATG5 + ATG7 regulate autophagy, ER stress, apoptosis and cell cycle through PERK signaling, a vital UPR branch pathway. CONCLUSIONS: ATG5 and ATG7 connect autophagy with ER stress through PERK signaling. The protective effect of ATG5/7 overexpression on chondrocyte survival relys on PERK signaling. The effect of siPERK and siNrf2 on the cytoprotective effect of ATG5/7 are of synergism, while the effect of siPERK and siATF4 are of antagonism. PERK signal may be the pivot for autophagy, ER homeostasis and ER-phagy in chondrocyte.

[Targeted binding of estradiol with ESR1 promotes proliferation of human chondrocytes in vitro by inhibiting activation of ERK signaling pathway].

OBJECTIVE: To investigate the effect of estradiol (E2)/estrogen receptor 1 (ESR1) on the proliferation of human chondrocytes in vitro and explore the molecular mechanism. METHODS: The Ad-Easy adenovirus packaging system was used to construct and package the ESR1-overexpressing adenovirus Ad-ESR1. Western blotting and qPCR were used to detect the expression of ESR1 protein and mRNA in human chondrocyte C28I2 cells. In the cells treated with different adenoviruses, the effects of E2 were tested on the expressions of proteins related with cell autophagy and apoptosis and the phosphorylation of ERK signaling pathway using Western blotting. Immunofluorescence assay was used to observe the intracellular autophagic flow, flow cytometry was performed to analyze the cell apoptosis rate and the cell cycle changes, and qPCR was used to detect the expressions of PCNA, cyclin B1 and cyclin D1 mRNAs. The inhibitory effect of the specific inhibitor of ERK on the expressions of autophagy- and apoptosis-related genes at both the protein and mRNA levels were detected using Western blotting and qPCR. RESULTS: Transfection with the recombinant adenovirus overexpressing ESR1 and E2 treatment of C28I2 cells significantly enhanced the expressions of autophagy-related proteins LC3, ATG7, promoted the colocalization of LC3 and LAMP1 in the cytoplasm, increased the expressions of the proliferation-related marker genes PCNA, cyclin B1 and cyclin D1, and supressed the expressions of cleaved caspase-3, caspase-12 and pERK. RNA interference of ESR1 obviously lowered the expression levels of autophagy-related proteins in C28I2 cells, causing also suppression of the autophagic flow, increments of the expressions of apoptosis-related proteins and pERK, and down-regulated the expressions of the proliferation marker genes. Blocking ERK activation with the ERK inhibitor obviously inhibited the effects of E2/ESR1 on autophagy, proliferationrelated gene expressions and cell apoptosis. CONCLUSIONS: The targeted binding of E2 with ESR1 promotes the proliferation of human chondrocytes in vitro possibly by inhibiting the activation of ERK signaling pathway to promote cell autophagy and induce cell apoptosis.

Rhodamine B in spices determined by a sensitive UPLC-MS/MS method.

Rhodamine B (RhB) is a banned food additive and has been classified as illegal colourant. Therefore, the risk of RhB contamination should be strictly monitored. In this study, a sensitive UPLC-MS/MS method was applied to monitor RhB in 292 various spices such as chilli, pepper and tomato products. The results showed 22.7% of chilli powder samples, 18.5% of pepper powder samples, 11.1% of chilli oil samples and 9.1% of pepper oil samples were contaminated with RhB. Chilli powder contained RhB up to 44,935 µg/kg with an average of 743 µg/kg, pepper powder up to 65.9 µg/kg with an average of 4.1 µg/kg, chilli oil up to 14.6 µg/kg with an average of 1.0 µg/kg and pepper oil up to 1.1 µg/kg with an average of 0.2 µg/kg, respectively. Considering the common consumption of chilli products and pepper products by so many consumers, RhB exposure is significant and should be decreased.

[Simultaneous determination of 6 cyclohexanedione herbicides residues in potatoes by ultra-performance liquid chromatography-tandem mass spectrometry].

OBJECTIVE: To establish a method for analysis of 6 cyclohexanedione herbicides residues in potatoes by ultra-performance liquid chromatography coupled with electrospray tandem mass spectrometry( UPLC-MS/MS). METHODS: The target compounds in samples were extracted ultrasonically with acetonitrile. After centrifugation, the supernatant was cleaned up with Envi-carb column. The sample solution was separated on an Dionex C_(18) column( 2. 1 mm × 100 mm, 2. 2 µm) with gradient elution using acetonitrile -5 mmol/L ammonium acetate and 0. 1% formic acid in water as mobile phase. The identification was performed with tandem mass spectrometer, with electrospray ionization( ESI) in positive mode under multiple reaction monitoring. The quantification was based on external standard curves. RESULTS: The method showed good linearity in the range of 2-100 µg/L( r ≥ 0. 9923). The limit of quantitation were 2. 0 µg/kg. The detection limits of the method were 0. 6 µg/kg. The recoveries were within 67. 5%-95. 8% at the spiked levels of 2. 0-10. 0 µg/kg, and the relative standard deviations were all less than 8. 5%. Six cyclohexanedione herbicides residues were detected in 6. 7% of 30 potatoes samples which was determined by the method. CONCLUSION: The method is rapid, specific, accurate, and it is suitable for detection of quinolone and tetracycline residues.

A comparative study on chitosan/gelatin composite films with conjugated or incorporated gallic acid.

Gallic acid-grafted-chitosan (GA-g-CS) was synthesized in the presence of 1-ethyl-3-(3'-dimethylaminopropyl) carbodiimide and hydroxybenzotriazole under room temperature. To develop a kind of newly functional film, CS, gelatin, glycerol and Tween 20 were utilized to prepare CS-based composite films with incorporated GA (GA-CS) or conjugated GA (GA-g-CS), and the films were characterized in aspects of physical and functional properties, as well as microstructures. With the increasing of GA concentration, there was a reduction in transmittance, elongation at break and water vapor permeability (WVP) for GA-CS film. For GA-CS films, the higher tensile strength and lower WVP could be obtained when GA was evenly distributed across the films. Different from the GA-CS films, water solubility, swelling ratio, water vapor permeability and scavenging activities on 2,2-Diphenyl-1-picrylhydrazyl/2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid) radicals were enhanced for GA-g-CS films, which could be ascribed to the rough surface morphology. The GA-g-CS films exhibited enhanced water vapor permeability when the substitution degree of GA increased. Also, the antimicrobial activities of GA-g-CS films were superior to those of GA-CS films. Our present work developed a way to prepare GA-g-CS films that owned many desirable properties and could be explored as promising biomaterials in food packaging.

Targeted cancer imaging and photothermal therapy via monosaccharide-imprinted gold nanorods.

Plasmonic nanomaterials have been widely used for photothermal therapy (PTT) of cancer, but their recognition specificity remains challenging. We prepared monosaccharide-imprinted gold nanorods (AuNRs) for targeted cancer PTT, using sialic acid (SA) as a representative monosaccharide. The SA-imprinted AuNRs exhibited good specificity, enabling the killing of cancer cells without damaging healthy cells.

Coupling of metal-organic frameworks-containing monolithic capillary-based selective enrichment with matrix-assisted laser desorption ionization-time-of-flight mass spectrometry for efficient analysis of protein phosphorylation.

Protein phosphorylation is a major post-translational modification, which plays a vital role in cellular signaling of numerous biological processes. Mass spectrometry (MS) has been an essential tool for the analysis of protein phosphorylation, for which it is a key step to selectively enrich phosphopeptides from complex biological samples. In this study, metal-organic frameworks (MOFs)-based monolithic capillary has been successfully prepared as an effective sorbent for the selective enrichment of phosphopeptides and has been off-line coupled with matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) for efficient analysis of phosphopeptides. Using s-casein as a representative phosphoprotein, efficient phosphorylation analysis by this off-line platform was verified. Phosphorylation analysis of a nonfat milk sample was also demonstrated. Through introducing large surface areas and highly ordered pores of MOFs into monolithic column, the MOFs-based monolithic capillary exhibited several significant advantages, such as excellent selectivity toward phosphopeptides, superb tolerance to interference and simple operation procedure. Because of these highly desirable properties, the MOFs-based monolithic capillary could be a useful tool for protein phosphorylation analysis.

Sorption and degradation of phthalate esters by a novel functional hyper-cross-linked polymer.

A novel functional hyper-cross-linked polymer (NFHP) modified with trimethylamine was prepared. NFHP was characterized by FTIR, XPS, XRD, SEM and Micromeritics ASAP-2010 automatic surface area analysis instrument. Adsorption and hydrolysis degradation of phthalate acid esters (PAEs) by NFHP were also investigated as a function of temperature, equilibrium concentration and PAEs types. Results indicated that NFHP could adsorb and catalyze hydrolysis of PAEs simultaneously. There was a positive relationship between the removal capacity and temperature, equilibrium concentration, and PAEs hydrophobicity. However, the increase of PAEs equilibrium concentration and hydrophobicity resulted in the decreased level of their hydrolysis, while high temperature promoted the hydrolysis of PAEs. Film diffusion was the rate controlling step of the removal process. The apparent removal rate of PAEs increased as temperature increased due to the higher diffusion coefficient at higher temperature. The results of continuous fixed-bed runs demonstrated that NFHP was capable of synchronously removing PAEs and their hydrolysis products from tap water. In the effluent solution, the PAEs concentration was below the detection limit (0.01 mg/L) of HPLC within 1400 BVs. Moreover, the exhausted NFHP beads can be completely regenerated for repeated use. Physical adsorption, hydrolysis degradation and ion-exchange played significant roles in removing of PAEs and their hydrolysis products. The analysis of hydrolysis products, FTIR and XPS spectra proved that physical adsorption, hydrolysis and ion-exchange were the main removal mechanism. The results reported herein suggested that this novel material has a great potential in efficient removal of PAEs from wastewater.

Probing Low-Copy-Number Proteins in a Single Living Cell.

Single-cell analysis techniques are essential for understanding the microheterogeneity and functions of cells. Low-copy-number proteins play important roles in cell functioning, but their measurement in single cells remains challenging. Herein, we report an approach, called plasmonic immunosandwich assay (PISA), for probing low-copy-number proteins in single cells. This approach combined in vivo immunoaffinity extraction and plasmon-enhanced Raman scattering (PERS). Target proteins were specifically extracted from the cells by microprobes modified with monoclonal antibody or molecularly-imprinted polymer (MIP), followed by labeling with Raman-active nanotags. The PERS detection, with Raman intensity enhanced by 9 orders of magnitude, provided ultrasensitive detection at the single-molecule level. Using this approach, we found that alkaline phosphatase and survivin were expressed in distinct levels in cancer and normal cells, and that extended culture passage resulted in reduced expression of survivin. We further developed acupuncture needle-based PISA for probing low-copy-number proteins in living bodies.