Sensitive fluorescent detection of phosmet and chlortetracycline in animal-derived food samples based on a water-stable Cd(II) chain-based zwitterionic metal-organic framework.

The residues of pesticides and antibiotics have always been a major concern in agriculture and food safety. In order to provide a new method for the rapid detection of organophosphorus pesticides and antibiotics, a novel Cd(II) chain-based zwitterionic metal-organic framework MOF 1 with high sensitivity fluorescence sensing performance was successfully synthesized. A series of researches showed that the water- and pH-stable bifunctional MOF 1 has a great ability to detect phosmet (PSM) and chlortetracycline (CTC) in water through fluorescence quenching effect, with high detection sensitivity, low detection limits (0.0124 µM and 0.0131 µM), short response time (40 s) and reusability. Practical application results revealed that MOF 1 could detect PSM and CTC in milk, beef, chicken and egg samples, with satisfactory recoveries (95.2%-103.7%). As a novel fluorescence probe, MOF 1, is known the first case that can detect PSM in animal-derived samples, and the first dual-function material capable of detecting PSM and CTC. Mechanism studies displayed that competitive absorption and photoinduced electron transfer clearly authenticate the high quenching performance of the material.

Strategy based on multiplexed brush architectures for regulating the spatiotemporal immobilization of biomolecules.

Functional surfaces that enable both spatial and temporal control of biomolecules immobilization have attracted enormous attention for various fields including smart biointerface materials, high-throughput bioarrays, and fundamental research in the biosciences. Here, a flexible and promising method was presented for regulating the spatiotemporal arrangement of multiple biomolecules by constructing the topographically and chemically diverse polymer brushes patterned surfaces. A series of polymer brushes patterned surfaces, including antifouling brushes patterned surface, epoxy-presenting brushes patterned surface without and with antifouling background layer, were fabricated to control the spatial distribution of protein and cell adhesion through specific and nonspecific means. The fluorescence measurements demonstrated the effectiveness of spatially regulating the density of surface-immobilized protein through controlling the areal thickness of the poly (glycidyl methacrylate) (PGMA) brush patterns, leading to various complex patterns featuring well-defined biomolecule concentration gradients. Furthermore, a multiplexed surface bearing epoxy groups and azido groups with various areal densities was fabricated for regulating the spatiotemporal arrangement of different proteins, enabling binary biomolecules patterns with higher degrees of functionality and complexity. The presented strategy for the spatiotemporal control of biomolecules immobilization would boost the development of dynamic and multifunctional biosystems.

The Establishment of Thermal Conductivity Model for Linear Low-Density Polyethylene/Alumina Composites Considering the Interface Thermal Resistance.

An optimized thermal conductivity model of spherical particle-filled polymer composites considering the influence of interface layer was established based on the classic series and parallel models. ANSYS software was used to simulate the thermal transfer process. Meanwhile, linear low-density polyethylene/alumina (LLDPE/Al2O3) composites with different volume fractions and Al2O3 particle sizes were prepared with the continuous mixer, and the effects of Al2O3 particle size and volume fraction on the thermal conductivity of the composites were discussed. Finally, the test result of the thermal conductivity was analyzed and compared with ANSYS simulations and the model prediction. The results proved that the thermal conductivity model considering the influence of the interface layer could predict the thermal conductivity of LLDPE/Al2O3 composites more precisely.

[Metabonomics research on lung tissue of rats with acute exacerbation of chronic obstructive pulmonary disease treated with mineral Chinese medicine Chloriti Lapis].

To study the effect of mineral Chloriti Lapis on pulmonary metabolites and metabolic pathways in lung tissues of rats with acute exacerbation of chronic obstructive pulmonary disease(AECOPD). The AECOPD rat model of phlegm heat syndrome was replicated by the method of smoking combined with Klebsiella pneumoniae infection. Except for using UPLC-Q-TOF-MS analysis, SPSS 18.0, SIMCA 13.0 and other software were also used for statistical analysis. Through literature search and online database comparison, the differential metabolites were identified, and the possible metabolic pathways were analyzed. After 15 days of administration, PLS-DA analysis was carried out on lung tissue samples of rats in each group. The results showed that the metabolic profiles of lung tissues of rats in each group could be well separated, which indicated that Chloriti Lapis and aminophylline had significant intervention effect on the lung metabolic profile of rats with AECOPD. Moreover, the metabolic profile of Chloriti Lapis group was closer to that of control group, and the intervention effect was better than that of aminophylline group. As a result, 15 potential differential metabolites were identified: phytosphingosine, sphinganine, tetradecanoylcarnitine, L-palmitoylcarnitine, elaidic carnitine, lysoPC[18∶2(9Z,12Z)], lysoPC(16∶0), lysoPC[18∶1(9Z)], lysoPC(18∶0), stearic acid, lysoPC(15∶0), arachidonic acid, docosapentaenoic acid, linoleic acid and palmitic acid. Among them, Chloriti Lapis could significantly improve the levels of 10 differential metabolites of phytosphingosine, tetradecanoylcarnitine, L-palmitoylcarnitine, elaidic carnitine, lysoPC[18∶2(9Z,12Z)], lysoPC(16∶0), lysoPC[18∶1(9Z)], stearic acid, lysoPC(15∶0), and palmitic acid(P<0.05). The intervention effect of Chloriti Lapis group was better than that of aminophylline group. Analysis of metabolic pathways showed that there were 8 possible metabolic pathways that could be affected, and three of the most important metabolic pathways(pathway impact>0.1) were involved: linoleic acid metabolism, arachidonic acid metabolism, and sphingolipid metabolism. Chloriti Lapis had obvious intervention effects on lung tissue-related metabolites and metabolic pathways in rats with AECOPD, and the effect was better than that of aminophyllinne.

[Effects of mineral Chinese medicine Chloriti Lapis on contents of metal elements in plasma and lung tissue of acute exacerbation of chronic obstructive pulmonary disease(AECOPD) rats].

The effects of Chloriti Lapis on metal elements in plasma and lung tissue of acute exacerbation of chronic obstructive pulmonary disease( AECOPD) rats were studied. The rat AECOPD model with phlegm heat syndrome was established by smoking combined with Klebsiella pneumoniae infection. After the rats were treated by Chloriti Lapis,the contents of metal elements in plasma and lung tissue were determined by inductively coupled plasma-optical emission spectroscopy( ICP-OES) and inductively coupled plasma mass spectrometry( ICP-MS). The changes in the contents of metal elements were analyzed by SPSS 18. 0. Further,the correlations of differential metal elements( including Cu/Zn ratio) with differential metabolites in plasma,lung tissue and urine of AECOPD rats treated with Chloriti Lapis were analyzed. The results showed that Chloriti Lapis significantly up-regulated the contents of Fe,Al,Mn,Cu,Zn,Sn( P<0. 05),V,Co( P< 0. 01) and Cu/Zn ratio( P< 0. 05),and significantly down-regulated the contents of Ti( P< 0. 05)and Pb( P<0. 05) in the model rat plasma. It significantly increased the content of Be( P<0. 05) and decreased the contents of Mg,Ti and Al( P<0. 01) in model rat lung tissue. The element profiles of normal group,model group and Chloriti Lapis group can be well separated. Chloriti Lapis group and other groups were clustered into two categories. The taurine in plasma and phytosphingosine in lung tissue had the strongest correlations with differential metal elements. The Fe,Al,Mg,Be,Ti,V,Mn,Cu,Zn,Sn,and Co in Chloriti Lapis may directly or indirectly participate in the intervention of AECOPD rats. This group of metal elements may be the material basis of Chloriti Lapis acting on AECOPD rats,and reduce the Cu/Zn value in vivo. It was further confirmed that Chloriti Lapis could interfere with the metabolic pathways of taurine and hypotaurine in plasma and urine as well as the sphingolipid metabolism pathway in lung tissue of AECOPD rats. In addition,this study confirmed that long-term smoking can cause high-concentration Cd accumulation in the lung and damage the lung tissue.

[Overview of metalomics research and its application prospect in mineral Chinese medicine research].

Metallomics is a frontier interdisciplinary subject at its vigorous development stage. Its goal is to systematically study the content, distribution, chemical species, structural characteristics and functions of metal elements in biological system. It is also a comprehensive discipline to study the existing state and function of free or complex metal elements in life. Metallomics is an ideal tool to study the biological behavior of inorganic elements, which can be used to solve many problems in the research of mineral Chinese medicine(MCM). It provides a strong theoretical basis and technical support for the research of MCM. Its theory and methods provide re-ference and enlightenment for the in-depth study of MCM, and also provide new ideas and open up new ways for the research of MCM. The application of metallomics theory and methods in the research of MCM is of great significance to reveal the material basis and mec-hanism of MCM, promote the process of basic research on MCM, fully exploit and utilize medicinal mineral resources and carry forward the traditional MCM treasure in China. In this paper, we introduced the concept, academic development, research content and research methods of metallomics, and discussed the application prospects of metallomics in the analysis of inorganic element composition characteristics and quality control, material basis and mechanism of MCM, so as to provide reference for further researches on MCM.

The Entangled Conductive Structure of CB/PA6/PP MFCs and Their Electromechanical Properties.

In this work, carbon black (CB)/polyamide 6 (PA6)/polypropylene (PP) microfibrillar composites (MFCs) were fabricated through an extrusion (hot stretching) heat treatment process. The CB-coated conductive PA6 microfibrils with high aspect ratio were in situ generated as a result of the selective accumulation of CB at the interface. At the proper temperature, a 3D entangled conductive structure was constructed in the PP matrix, due to topological entanglement between these conductive microfibrils. This unique conductive structure provided the PP composites with a low electrical conductivity percolation threshold. Moreover, the electromechanical properties of conductive MFCs were investigated for the first time. A great stability, a high sensitivity and a nice reproducibility were achieved simultaneously for CB/PA6/PP MFCs. This work provides a universal and low-cost method for the conductive polymer composites' (CPCs) fabrication as sensing materials.

Molybdenum contamination dispersion from mining site to a reservoir.

This study was conducted to assess heavy metals in the overlying water and sediments of Luhun Reservoir, Henan Province, China, which is positioned downstream from a molybdenum (Mo) mining area. The pollution indexes indicated that deposition of all metals may have been affected by the mining area. The single element pollution factor (Pi) of Mo was the highest among all heavy metals, with a mean value of 2.05. However, the sediments were subject to long-term accumulation of metals, particularly Mo, Cd, Pb, and Zn, which originated from anthropogenic sources. The mean individual element potential ecological risk index values for Cd were above 385, while the mean value comprehensive potential ecological risk index was 465, which indicates a high ecological risk. Moreover, the enriched heavy metals had different spatial distributions in the Luhun Reservoir sediments. Finally, Pearson correlation analysis indicated that the Pb was mainly affected by different anthropogenic sources and had no relationship with other metals, which suggests that the influence of mining area on heavy metal concentrations in the reservoir is difficult to disentangle.

Penisarins A and B, Sesquiterpene Coumarins Isolated from an Endophytic Penicillium sp.

Penisarins A (1) and B (2), sesquiterpene coumarins with an unusual tricyclic sesquiterpene system, were isolated from endophytic Penicillium sp. KMU18029. Their structures were elucidated on the basis of spectroscopic methods, single-crystal X-ray diffraction, and electronic circular dichroism calculations. Compound 2 showed significant cytotoxicities against two human cancer cell lines, HL-60 and SMMC-7721, with IC50 values of 3.6 ± 0.2 and 3.7 ± 0.2 µM, respectively.

Deformation-Induced Crystallization Behavior of Isotactic Polypropylene Sheets Containing a ß-Nucleating Agent under Solid-State Stretching.

The deformation-induced crystallization of an isotactic polypropylene (iPP) sheet containing a ß-nucleating agent was evaluated. The phase transformation of the ß-modifications was investigated and the crystal morphology was observed at room temperature after stretching at different temperatures. The results showed that the crystallinity increased after solid-state stretching. When the stretching temperature was below the initial crystallization temperature, stretching deformation promoted the orientation of amorphous molecular chains. When the deformation temperature exceeded the crystallization temperature, part of the ß-modifications underwent a phase transformation process and was stretched into a shish-kebab structure. However, once the stretching temperature was close to the melting point, the ß-modifications melted and recrystallized, and the shish-kebab structure underwent stress relaxation due to poor thermal stability, transforming into α-modifications. It was revealed that the crystal phase transformation mechanism of the ß-modifications was based on the orientation of the molecular chains between the adjacent lamellae. In addition, the shish-kebab cylindrite structure played an important role in modifying the tensile and impact properties of the iPP sheet. The tensile and impact strengths increased by as much as 34% and 126%, respectively.

The Formation of a Highly Oriented Structure and Improvement of Properties in PP/PA6 Polymer Blends during Extrusion-Stretching.

During the "slit die extrusion-hot stretching" process, highly oriented polyamide 6 (PA6) dispersed phase was produced and retained in the polypropylene (PP) matrix directly. By adjusting the stretching forces, the PA6 spherical phase evolved into the ellipsoid, rod-like microfibril with a decreasing average diameter; then, the PA6 microfibrils broke. Moreover, the effects of the PA6 phases formed in the process of the microfibrillation on PP's crystallization behaviors were studied systematically. As the stretching forces increased, the crystallization ability and orientation degree of PP crystals improved significantly. Differential scanning calorimetry and polarizing optical microscopy confirmed the formation of PP spherulite, fan-shaped lamellae and a transcrystalline layer under the induction of the PA6 phases with different morphology. In the PP/PA6 microfibrilar composites (MFCs), PP crystals showed smaller average size, more crystals and stronger interface adhesion due to more excellent heterogeneous nucleation ability of the PA6 microfibrils, which made contributions to the improvement of the melt elasticity responses and oxygen barrier properties of the PP/PA6 polymer blends.

Spatiotemporal control of polymer brush formation through photoinduced radical polymerization regulated by DMD light modulation.

Spatially arranged polymer brushes provide the essential capability of precisely regulating the surface physicochemical and functional properties of various substrates. A novel and flexible polymer brush patterning methodology, which is based on employing a digital mirror device (DMD)-based light modulation technique to spatiotemporally regulate a surface-initiated photoinduced atom transfer radical polymerization (photo-ATRP) process, is presented. Various characterization techniques confirm that the spatially and/or temporally controlled brush formation results in complex PEG-derived brush patterns in accordance with a customized digital image design. A series of step-and-exposure strategies, including in situ multiple exposure, dynamic multiple exposure and dynamic sequential exposure, are developed to implement spatiotemporal regulation of the photo-ATRP process, leading to complex patterned and gradient brushes featuring binary functionalities, pyramid nanostructures and radial directional chemical gradients. Moreover, tunable and radial directional concentration gradients of various biomacromolecules (e.g., streptavidin) are obtained through preparation of height gradients of azido-functionalized brushes and subsequent orthogonal chemical activation aimed at specific protein immobilization. Finally, a unidirectional concentration gradient of fibronectin, surrounded by non-fouling PEG brushes, is fabricated and applied for human umbilical vein endothelial cell (HUVEC) adhesion experiments, whose preliminary results indicate gradient-dependent cell adhesion behavior in response to the concentration gradient of fibronectin. The presented fabrication technique could be integrated with microfluidic devices for sensors and bio-reactors, paving the way for novel approaches for lab-on-a-chip technologies.

Effects of Solid-State Stretching on Microstructure Evolution and Physical Properties of Isotactic Polypropylene Sheets.

The microstructure evolution of an isotactic polypropylene (iPP) sheet during solid-state stretching was studied. The transition of the spherulites-cylindrites was evaluated using in-situ two-dimensional wide-angle and small-angle X-ray scattering methods. The crystallinity of stretched iPP sheets was characterized by differential scanning calorimetry. The crystal morphology was observed by means of scanning electron microscopy. It was found that the differences of crystal microstructure of the iPP sheet depended on the stretching strain, which promoted the orientation of molecular chains. Amorphous molecular chains in the spherulites oriented and formed into a mesophase near the yield point, and the partially ordered mesophase was further stretched to form an oriented cylindrite structure after the yield point. The highest relative content of cylindrites appeared at 15% strain. Notably, as the amorphous phase embedded into the lamellae layer, the crystal size decreased with the increase of strain, which indicated that the crystallinity of the stretched iPP sheet was much higher than that of unstretched iPP sheet. The induced cylindrites structure played a more important role in improving the mechanical properties and heat resistance of iPP sheets. Compared with the unstretched iPP sheets, the tensile strength increased by 28%, the notch impact toughness significantly increased by 78%, and the vicat softening point increased from 104 to 112 °C.

Novel Resveratrol-chalcone Derivatives: Synthesis and Biological Evaluation.

INTRODUCTION: Resveratrol and chalcones are lead compounds with good biological activities. METHOD: In this study, a series of novel derivatives (6-38) between resveratrol and chalcone possessing piperazine moiety have been synthesized, and in vitro anti-inflammatory activity in lipopolysaccharide (LPS)-stimulated RAW-264.7 macrophages and anti-proliferative effect on a panel of human tumor cell lines (Hela, A549 and SGC7901) by MTT assay were evaluated. RESULT: The results demonstrated that the substituents of the NH group of piperazine ring had an obvious influence on biological activities. Especially, compounds 13, 17, 30, 31 and 36 showed good inhibitory effect on the generation of NO compared to dexamethasone. Furthermore, analogs 20, 21, 22 and 25 were found to be the better anti-proliferative effect on 3 human tumor cell lines, which were found to be a better cytotoxic activity to positive control 5-FU. Many compounds displayed low cytotoxic effect on normal cells L02. CONCLUSION: Further FACs analysis showed that compounds 20 and 25 significantly induced apoptosis in A549 cell. These derivatives were considered as the potential anti-inflammatory and anti-tumor agents.

[Mineral composition analysis and hemostatic effect of limonitum with different mineral genesis].

Models were established in mice with warfarin sodium method, and their bleeding time and hemostasis time were measured by tail cutting method and slide method respectively. Rats were administered for 15 consecutive days to measure their recalcification time, plasma viscosity, platelet adhesion rate, platelet aggregation rate and other blood indexes. As compared with the blank group, the bleeding time was prolonged in model groupn(P<0.05). As compared with the model group, the results showed that the positive vitamin K, the leaching type water decoction and the sediment type decoction could significantly shorten the bleeding time (P<0.01); positive vitamin K significantly (P<0.01) shortened clotting time, and the leaching type water decoction, the sediment type water decoction and the sediment type powder could also shorten the clotting time (P<0.05). As compared with blank group, low dose, medium dose of leaching type water decoction, medium dose of powder, high dose of sediment type decoction and low dose of drug residues could reduce plasma viscosity (P<0.05), and high dose of leaching powder and low dose of water decoction could significantly reduce (P<0.01) plasma viscosity. As compared with blank group, Limonitum leaching type decoction high dose group could significantly reduce the platelet adhesion rate (P<0.05), while sediment type water decoction could significantly increase the platelet adhesion rate (P<0.05); the high dose of leaching type water decoction, high dose of drug residues, low dose of leaching type powder and low dose of drug residues could decrease the platelet aggregation rate (P<0.05), while high dose of leaching type water decoction and high dose of the powder could increase the platelet aggregation rate (P<0.05). Analysis of mineral compositions was conducted by polarized light microscopy and X-ray diffraction (XRD). The results of the both methods showed that Limonitum mineral compositions contained goethite, quartz, and kaolinite, and sedimentary type also contained illite and albite. Sediment type of Limonitum showed better hemostatic effect, which may be related to the high content of goethite and illite.

Beyond the Antagonism: Self-Labeled Xanthone Inhibitors as Modeled "Two-in-One" Drugs in Cancer Therapy.

Self-labeled inhibitors (SLIs) are promising for creating links, ranging from cancer therapy and metastatic pathways to mechanistic elucidation. In this study, a new category of "two-in-one" fluorescent xanthone inhibitors was developed for the systematic evaluation of anticancer activity and the selective imaging of cytoplasm in vitro. These xanthone inhibitors presented high fluorescent brightness, working over a wide pH range enabled by a "switchable reaction" of the heterocyclic backbone. The strength and nature of fluorescence were probed via spectroscopic methods and density functional theory calculations on the molecular level, respectively. Along with the potent anticancer activity, which was demonstrated using MTT and clonogenic assays with high fluorescent brightness in the cytoplasm, SLI 3fd could be established as a modeled self-monitoring drug in cancer therapy.

Design, Synthesis, and Biological Evaluation of Novel Benzofuran Derivatives Bearing N-Aryl Piperazine Moiety.

A series of novel hybrid compounds between benzofuran and N-aryl piperazine have been synthesized and screened in vitro for anti-inflammatory activity in lipopolysaccharide (LPS)-stimulated RAW-264.7 macrophages and for anticancer activity against three human tumor cell lines. The results demonstrated that derivative 16 not only had inhibitory effect on the generation of NO (IC50 = 5.28 µM), but also showed satisfactory and selective cytotoxic activity against human lung cancer line (A549) and gastric cancer cell (SGC7901) (IC50 = 0.12 µM and 2.75 µM, respectively), which was identified as the most potent anti-inflammatory and anti-tumor agent in this study.

Enantiopure anion templated synthesis of a zeolitic metal-organic framework.

Utilizing (R)-H3CIA as a chiral template, an unprecedented homochiral metal-organic framework (MOF) with zeotype GIS topology is obtained from achiral 1.4-DIB ligands and Zn(II) ions, which opens up a feasible approach to create zeolitic MOFs with homochirality.

Phenotypic responses of differentiated asthmatic human airway epithelial cultures to rhinovirus.

OBJECTIVES: Human airway epithelial cells are the principal target of human rhinovirus (HRV), a common cold pathogen that triggers the majority of asthma exacerbations. The objectives of this study were 1) to evaluate an in vitro air liquid interface cultured human airway epithelial cell model for HRV infection, and 2) to identify gene expression patterns associated with asthma intrinsically and/or after HRV infection using this model. METHODS: Air-liquid interface (ALI) human airway epithelial cell cultures were prepared from 6 asthmatic and 6 non-asthmatic donors. The effects of rhinovirus RV-A16 on ALI cultures were compared. Genome-wide gene expression changes in ALI cultures following HRV infection at 24 hours post exposure were further analyzed using RNA-seq technology. Cellular gene expression and cytokine/chemokine secretion were further evaluated by qPCR and a Luminex-based protein assay, respectively. MAIN RESULTS: ALI cultures were readily infected by HRV. RNA-seq analysis of HRV infected ALI cultures identified sets of genes associated with asthma specific viral responses. These genes are related to inflammatory pathways, epithelial structure and remodeling and cilium assembly and function, including those described previously (e.g. CCL5, CXCL10 and CX3CL1, MUC5AC, CDHR3), and novel ones that were identified for the first time in this study (e.g. CCRL1). CONCLUSIONS: ALI-cultured human airway epithelial cells challenged with HRV are a useful translational model for the study of HRV-induced responses in airway epithelial cells, given that gene expression profile using this model largely recapitulates some important patterns of gene responses in patients during clinical HRV infection. Furthermore, our data emphasize that both abnormal airway epithelial structure and inflammatory signaling are two important asthma signatures, which can be further exacerbated by HRV infection.

Mineralocorticoid receptor antagonists attenuate pulmonary inflammation and bleomycin-evoked fibrosis in rodent models.

Accumulating evidence indicates protective actions of mineralocorticoid antagonists (MR antagonists) on cardiovascular pathology, which includes blunting vascular inflammation and myocardial fibrosis. We examined the anti-inflammatory and anti-fibrotic potential of MR antagonists in rodent respiratory models. In an ovalbumin allergic and challenged Brown Norway rat model, the total cell count in nasal lavage was 29,348 ± 5451, which was blocked by spironolactone (0.3-60 mg/kg, p.o.) and eplerenone (0.3-30 mg/kg, p.o.). We also found that MR antagonists attenuated pulmonary inflammation in the Brown Norway rat. A series of experiments were conducted to determine the actions of MR blockade in acute/chronic lung injury models. (1) Ex vivo lung slice rat experiments found that eplerenone (0.01 and 10 µM) and spironolactone (10 µM) diminished lung hydroxyproline concentrations by 55 ± 5, 122 ± 9, and 83 ± 8%. (2) In in vivo studies, MR antagonists attenuated the increases in bronchioalveolar lavage (BAL) neutrophils and macrophages caused by lung bleomycin exposure. In separate studies, bleomycin (4.0 U/kg, i.t.) increased lung levels of hydroxyproline by approximately 155%, which was blocked by spironolactone (10-60 mg/kg, p.o.). In a rat Lipopolysaccharide (LPS) model, spironolactone inhibited acute increases in BAL cytokines with moderate effects on neutrophils. Finally, we found that chronic LPS exposure significantly increased end expiratory lung and decreased lung elastance in the mouse. These functional effects of chronic LPS were improved by MR antagonists. Our results demonstrate that MR antagonists have significant pharmacological actions in the respiratory system.