Search

In this study, the effect of channel baffles and louver baffles on the flow pattern in the large-scale industrial fluidized beds was studied by computational fluid dynamics (CFD) methods. Then, the effect of flow pattern on the chemical reaction performance was studied for the first time. Simulation results showed that the gas velocity distributed more uniformly, solid particles dispersed more homogeneously and aggregation scarcely occurred in the fluidized bed with louver baffles than that with channel baffles. The residence time distribution indicated that louver baffles remarkably suppressed gas back-mixing in comparison with channel baffles. The reasonable agreements of pressure distribution and reaction results between the simulation in the bed with channel baffles and the data on a large-scale industrial apparatus demonstrated the accuracy of the CFD model. The predicted conversion of SiCl4 in the bed with louver baffles (27.44%) was higher than that with channel baffles (22.69%), indicating that louver baffles markedly improved the performance of the fluidized bed. This study could provide useful information for future structural improvements of baffles in large-scale fluidized beds.

Summary Axially chiral compounds are a result of the nonplanar arrangement of four groups in pairs about a chirality axis. Axially chiral molecules not only exist in a range of bioactive compounds, but also are widely applied in chiral ligands and catalysts. With these wide-ranging utilities, the construction of axially chiral compounds is attracting more and more interest from chemists. Recent advances in this rapidly expanding field involving the synthesis of axially chiral compounds via catalytic asymmetric reaction of readily available alkynes are introduced in this review, including transition-metal-catalyzed and organocatalytic reactions. A discussion of the reaction scope, mechanistic insights, and synthetic applications of these catalytic asymmetric reactions of alkynes is presented. We hope that this review will provide timely illumination and beneficial guidance for organic chemists who are interested in this area, and we strongly anticipate continued development of the field in the future.

An efficient copper-catalyzed cyclization of N-propargyl ynamides with borane adducts through B-H bond insertion has been developed. A series of valuable organoboron compounds are constructed in generally good yields with a wide substrate scope and good functional group tolerance under mild reaction conditions. Importantly, this protocol via vinyl cation intermediates constitutes a novel way of B-H bond insertion.

How to directionally design the hollow zeolite via a green route is of great significance. Here, we successfully synthesized the hollow Fe-silicate-1 encapsulated ultra-small Fe2O3 nanoparticles (2.5 nm) with higher yield (85.2%) by mother liquid than traditional dissolution-recrystallization for the first time, which was achieved by precisely regulating the number and distribution of defects in zeolite and cleverly utilizing the TPAOH and nuclei in mother liquor. The effects of synthetic temperature, synthetic period and addition amount of parent zeolite on the formation of hollow zeolite have been investigated and the effect of synthetic conditions on the defects in parent zeolite has been also firstly quantified. The corresponding formation mechanism has been proposed. The abundant inner defects provided by the zeolite synthesized at 130 °C for 1 day and large amount of TPAOH remaining in mother liquid are conducive to the formation of hollow zeolite. Meanwhile, both parent zeolite and nuclei (4-, 5-member rings and structure units) in mother liquid obtained at 130 °C play the crucial roles in enhancing the zeolite yield. Notably, Fe2O3 nanoparticles could decompose into small fragments by the interaction with nuclei in mother liquid. Partial ultra-small Fe2O3 nanoparticles would be encapsulated in cavity and the rest could be inserted in the zeolite framework, which is significantly different from the conventional dissolution-recrystallization mechanism. The obtained encapsulated catalyst shows the superior catalytic performance and stability in phenol and tetracycline degradation reactions.

Vascular hypo-reactivity plays a critical role inducing organ injury during hemorrhagic shock. 17β-estradiol (E2) can induce vasodilation to increase blood flow in various vascular beds. This study observed whether E2 can restore vascular hypo-reactivity induced by hemorrhagic shock, and whether E2 effects are associated with RhoA-Rho kinase (ROCK)-myosin light chain kinase phosphatase (MLCP) pathway. The hemorrhagic shock model (40 ± 2 mm Hg for 1 h, resuscitation for 4 h) was established in ovary intact sham operation (OVI), ovariectomized (OVX), and OVX plus E2 supplement female mice. Intestinal microvascular loop was used to assess blood flow in vivo, mRNA expression and vascular reactivity in vitro. Hemorrhagic shock significantly reduced norepinephrine microvascular reactivity. Decreased microvascular reactivity was exacerbated by OVX and reversed by E2 supplement. U-46619 (RhoA agonist) increased microvascular reactivity, and C3 transferase (an ADP ribosyl transferase that selectively induces RhoA ribosylation) or Y-27632 (ROCK inhibitor) inhibited sham mice microvascular reactivity. Similarly, U-46619 increased microvascular reactivity in OVI and OVX mice following hemorrhagic shock, which was abolished by Y-27632 or concomitant incubation of okadaic acid (OA) (MLCP inhibitor) and Y-27632. In OVX plus E2 supplement mice with hemorrhagic shock, Y-27632 inhibited microvascular reactivity, which was abolished by concomitant U-46619 application. Lastly, hemorrhagic shock remarkably decreased intestinal loop blood flow, RhoA and ROCK mRNA expressions in vascular tissues in OVX females, but not in OVI females, which were reversed by E2 supplement. These results indicate that estrogen improves microvascular reactivity during hemorrhagic shock, and RhoA-ROCK signaling pathway may mediate E2 effects.

Obstructive sleep apnea-hypopnea syndrome (OSAHS) is a widely prevalent problem with many complications, such as hypertension and cerebral vascular diseases. Atherosclerosis, whose most severe outcome is ischemic stroke, is reported being affected by OSAHS. The objective of this article is to investigate the differences of carotid atherosclerosis patients with or without OSAHS by a cross-sectional research. Patients diagnosed with carotid atherosclerosis by ultrasonography were recruited. They were requested to fill the primary screening OSAHS questionnaire. Patients with high tendency of OSAHS underwent polysomnography (PSG) tests into OSAHS group, and patients without OSAHS were into non-OSAHS group. Blood tests and medical history were collected. Carotid atherosclerosis severity was analyzed by carotid artery intima-media thickness (IMT), carotid plaque, blood flow velocity, etc. Differences between the two groups and subgroups were analyzed. A total of 242 carotid atherosclerosis patients were enrolled including 118 non-OSAHS patients (38 males and 80 females) and 124 OSAHS patients (40 mild, 32 moderate, and 52 severe). Significant differences were found in PSV-ICA and EDV-ICA on both sides (p

Hierarchical iron-containing TS-1 zeolites (FTS) were successfully synthesized via post-treatment desilication over microporous Fe-TS-1, which were prepared through a one-step hydrothermal synthesi...

Natural gas hydrate, oil and gas were all found together in the Qilian Mountain permafrost area, northeast of Qinghai-Tibet Plateau, China. They are closely associated with each other in space, but whether they are in any genetic relations are unknown yet. In this paper, a hydrocarbon gas-generation series, gas-fluid migration series and hydrocarbon gas-accumulation series are analyzed to probe the spatial, temporal and genetic relationships among natural natural gas hydrate, oil and gas. The subsequent results show that natural gas hydrate, oil and gas actually form a natural gas hydrate-oil-gas system. Based on the Middle Jurassic and the Upper Triassic hydrocarbon gas-generation series, it is divided into four major sub-systems in the study area: (1) A conventional Upper Triassic gas-bearing sub-system with peak hydrocarbon gas-generation in the late Middle Jurassic; (2) a conventional Middle Jurassic oil-bearing sub-system with low to mature hydrocarbon gas-generation in the late Middle Jurassic; (3) a natural gas hydrate sub-system with main gas source from the Upper Triassic gas-bearing sub-system and minor gas source from the Middle Jurassic oil-bearing sub-system as well as little gas source from the Middle Jurassic coal-bed gas and the microbial gas; (4) a shallower gas sub-system with microbial alteration of the main gas source from the Upper Triassic gas-bearing sub-system. This natural gas hydrate-oil-gas system and its sub-systems are not only theoretical but also practical, and thus they will play an important role in the further exploration of natural gas hydrate, oil and gas, even other energy resources in the study area.

A metal-free intramolecular alkoxylation-initiated cascade cyclization of allyl ether-tethered ynamides has been developed. Various highly functionalized 3-isochromanones can be obtained in generally good to excellent yields under mild reaction conditions. Moreover, this asymmetric cyclization has also been realized via a stereocontrolled [3,3] rearrangement by employing a traceless chiral directing group. In addition, an unexpected [1,3] O-to-C rearrangement is observed in the case of the ynamide substrate bearing a phenyl-substituted alkene, which is distinctively different from the related gold catalysis.

Congenital cataract is one of the leading causes of childhood blindness worldwide. About half of heredity cataracts are caused by mutations in various crystallins. However, the underlying mechanisms have not been elucidated for most of crystallin mutations. In this research, we studied the effect of a cataract-causing mutation G75V on γS-crystallin structure, stability and aggregatory propensity. Spectroscopic experiments indicated that the mutation had little impact on γS-crystallin oligomeric status and secondary structure components, but led to large perturbations in tertiary structure. Compared with the WT protein, the G75V mutant had more solvent-accessible Trp fluorophores and hydrophobic exposure. The modified native state of mutant γS-crystallin was more susceptible to environmental stresses such as heat treatment, guanidine hydrochloride and acid conditions. The destabilized mutated protein was more prone to form large aggregates when denatured by high temperature or UV-irradiation. The thermal aggregation of the G75V mutant could be successfully inhibited by excess amount of αA-crystallin with a higher efficiency than the WT protein. Our results suggested that the aberrant modifications in γS-crystallin structure might contribute to the lower stability and higher aggregatory potency of the mutated protein, which subsequently resulted in cataracts in the patients.

Hierarchical TS-1 stacked nanoplates with constrained mesopores were hydrothermally synthesized via a self-assembly process with the aid of P123 lamellar micelles. P123 lamellar micelles serve concomitantly as mesotemplate for hierarchical TS-1 zeolite and nanostructure regulator for TS-1 nanoplates. The successful preparation of TS-1 stacked nanoplates were verified by Scanning and Transmission electron microscope, X-ray diffraction patterns, FTIR spectra and UV–vis spectra. Moreover, their formation processes with crystallization time were investigated, and accordingly the possible mechanism was proposed. Hierarchical TS-1 stacked nanoplates displayed a chemical composition similar to that of hierarchical TS-1 zeolite with P123 spherical micelles as mesotemplate and showed remarkably enhanced catalytic activity in oxidative desulfurization of dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT) and benzothiophene (BT) with tert-butyl hydroperoxide (TBHP) or hydrogen peroxide (H2O2) as oxidant.

Hierarchical Fe-doped MFI/MCM-41 composites (Fe-HMZs) were one-pot hydrothermal synthesized by partial transformation strategy using conventional CTAB as a dual-functional template. The hierarchical Fe-doped MFI/MCM-41 composites possess ordered mesopores and crystallized MFI structure. The effect of addition amount of NaOH and CTAB as well as the type of the alkali source on the formation of hierarchical Fe-MFI/MCM-41 composites have been investigated in detail. In addition, the temperature-gradient treatment plays the vital roles in the formation of MFI and the possible formation mechanism has been proposed. The obtained hierarchical Fe-HMZ-40 sample exhibits outstanding catalytic performance for phenol hydroxylation and 48% of phenol conversion as well as 89% of dihydroxybenzene selectivity could be achieved, which are ascribed to the more accessible active sites endowed by the significant diffusion ability of ordered mesopores. Compared with Fe-MCM-41 sample, the hydrothermal stability is improved because of the presence of MFI structure.

Design of catalyst particles bearing excellent diffusion performance and suitable surface wettability is of great importance to the successful application of Pickering interfacial catalysis. In this study, selective oxidation reactions over hydrophobized hollow TS-1 zeolite were applied as probe reactions to investigate the influence of catalyst diffusion performance closely related to mesopore size on its catalytic activity. Hydrophobized hollow TS-1 zeolite particles were prepared via a post desilication treatment accompanied with precrystallization treatment. The synthesized hydrophobized hollow TS-1 zeolite was characterized by Scanning electron microscopy, Transmission electron microscopy, X-ray diffraction, UV–vis absorption spectrometry, Fourier-transform infrared spectroscopy and Nitrogen adsorption-desorption. Stable Pickering emulsions including 1-hexene-hydrogen peroxide, cyclohexene-hydrogen peroxide and cyclohexanone-water were prepared with hydrophobized hollow TS-1 zeolite particles as emulsifier. HTS-1–393(2)-S zeolite synthesized with precrystallization at 393 K for 2 h presented the maximum values of 43.9 mol/(Ti-mol·h) for 1-hexene epoxidation, 15.7 mol/(Ti-mol·h) for cyclohexene epoxidation and 247.3 mol/(Ti-mol·h) for cyclohexanone ammoximation. In addition, HTS-1–393(2)-S zeolite particles displayed good reusability for more than five cycles.

Background Alisma orientalis beverage (AOB) is a Chinese traditional medicine formulated with a diversity of medicinal plants and used for treating metabolic syndrome and atherosclerosis (AS) since time ago. Given the current limited biological research on AOB, the mechanism by which AOB treats AS is unknown. This study investigats the role of AOB-induced gut microbiota regulation in the expansion of AS. Methods We established an AS model in male apolipoprotein E-deficient (ApoE-/-) mice that are fed with a high-fat diet (HFD), treated with numerous interventions, and evaluated the inflammatory cytokines and serum biochemical indices. The root of the aorta was stained with oil red O, and the proportion of the lesion area was quantified. Trimethylamine N-oxide (TMAO) and trimethylamine (TMA) levels in serum were evaluated through liquid chromatography with mass spectrometry. Flavin-containing monooxygenase 3 (FMO3) liver protein expression was assessed by Western blotting. 16S rDNA sequencing technique was adopted to establish the changes in the microbiota structure. Results After 8 weeks of HFD feeding, an inflammatory cytokine, and AS development expression were significantly decreased in mice treated with AOB; the same parameters in the mice treated with the antibiotics cocktail did not change. In the gut microbiota study, mice treated with AOB had a markedly different gut microbiota than the HFD-fed mice. Additionally, AOB also decreased serum TMAO and hepatic FMO3 expression. Conclusion The antiatherosclerotic effects of AOB were found associated with changes in the content of gut microbiota and a reduction in TMAO, a gut microbiota metabolite, suggesting that AOB has potential therapeutic value in the treatment of AS.

Here an efficient copper-catalyzed cascade cyclization of azide-ynamides via α-imino copper carbene intermediates is reported, representing the first generation of α-imino copper carbenes from alkynes. This protocol enables the practical and divergent synthesis of an array of polycyclic N-heterocycles in generally good to excellent yields with broad substrate scope and excellent diastereoselectivities. Moreover, an asymmetric azide-ynamide cyclization has been achieved with high enantioselectivities (up to 98:2 e.r.) by employing BOX-Cu complexes as chiral catalysts. Thus, this protocol constitutes the first example of an asymmetric azide-alkyne cyclization. The proposed mechanistic rationale for this cascade cyclization is further supported by theoretical calculations.

Objective: Interleukin (IL)-33 has been attracting more and more attention as a new member of theIL-1 cytokine family in recent years. However, the underlying mechanisms referred to the regulation of endogenous IL-33 production are not fully illustrated. Paeoniflorin (PF) has been reported to possess multiple pharmacological activities, including anti-inflammation and anti-allergy. In this study, we aimed to investigate the effect of PF on IL-33 production by macrophages and explore the underlying mechanisms.Methods:In vivo, IL-33 production in mice after lipopolysaccharide (LPS) injection together with PF application was detected by enzyme-linked immunosorbent assay (ELISA). In vitro, MTT, Real-time PCR, ELISA, Calcium (Ca2+) imaging and Western blot were used to assess the cytotoxicity of PF, IL-33 expression at mRNA and protein levels, Ca2+ influx, protein kinase C (PKC) activity, nuclear factor-kappa B (NF-κB), and mitogen-activated protein kinase (MAPK) activation in LPS-stimulated RAW264.7 macrophages with PF administration.Results: Our results indicated that PF (5 and 25 mg/kg) significantly reduced the production of TNF-a, IL-1β, and IL-33 in the peritoneal exudate of LPS-treated mice. In vitro assay, upregulation of PF concentration (≥ 20 μM) showed an increased cytotoxicity in RAW264.7 cells during the 24-h cell culture. PF (10 μM) inhibited IL-33 production, Ca2+ influx, PKC activity, NF-κB (p65) activation, and P38MAPK phosphorylation in LPS-treated macrophages. Notably, NF-κB inhibitor (BAY 11-7085), P38MAPK inhibitor (SB203580), and Ca2+ blocker (NiCl2) also curbed LPS-induced IL-33 production, respectively.Conclusions: PF suppresses IL-33 production by macrophages via inhibiting NF-κB and P38MAPK activation associated with the regulation of Ca2+ mobilization.

Background Intracellular bacteria, especially Mycobacterium tuberculosis, are important pathogenic microorganisms that endanger human health. Purified and synthesized cecropin A-magainin 2 (CAMA-syn) can exhibit a higher antibacterial activity and lower cytotoxicity. To enhance such antimicrobial potential, it would be desirable to deliver CAMA-syn expressed in lung epithelial cells by an adenovirus vector using gene therapy. Methods A549 cells in vitro and lung epithelial cells in vivo were used to express CAMA-syn by transducing recombinant adenovirus Ad-SPC-CAMA/GFP, and the expression of CAMA-syn was determined by a reverse transcriptase-polymerase reaction (RT-PCR) and immunofluorescence. The antimicrobial activity in cells was investigated by colony-forming rate and growth curve. Forty Kunming mice of a Bacillus Calmette-Guerin (BCG) infection animal model were randomly divided into three groups: adenoviruses delivery of Ad-SPC-CAMA/GFP, Ad-CMV-CAMA/GFP and empty-virus Ad-CMV-GFP. The expression of CAMA-syn in mice was confirmed by RT-PCR and immunofluorescence. After tracheal injection of adenoviral vector for 3 days, lungs from the mouse model were extracted and homogenized for detection of colony-forming efficiency. Results CAMA-syn expressed in lung epithelial cells A549 conferred antimicrobial activity against a series of bacteria, including Salmonella abortusovis and BCG. The results obtained in vivo showed that the colony-forming rate of Ad-SPC-CAMA/GFP (74.54%) and Ad-CMV-CAMA/GFP (62.31%) transduced into mice was significantly lower than that of the control group. Conclusions Lung epithelial-specific expression of antimicrobial peptide CAMA-syn mediated by adenovirus suppressed the growth of intracellular bacteria, providing a promising approach for the control of refractory intracellular infection.

Two new inorganic–organic hybrid complexes, namely, {[Co4(L)2(HCOO)2(OH)2][SiO4(W3O9)4]}·6DMF·5H2O (1) and {[Zn4(L)2(HCOO)2(OH)2][SiO4(W3O9)4]}·6DMF·5H2O (2), have been solvothermally prepared by using a new methyl imidazole functionalized resorcin[4]arene (L), polyoxometalate (POM), and metal cation. Isostructural 1 and 2 feature porous supramolecular architectures and represent an unusual example of a successful combination of resorcin[4]arenes with polyoxometalates. Remarkably, selective adsorptions for organic dyes were studied by using 1 and 2 as adsorbents. Moreover, their electrocatalytic activities for the oxidation of ascorbic acid and reduction of NaBrO3 were also studied.

The deficient active sites and poor conductivity of transition metal sulfides result in low energy density of supercapacitors that limits their extensive application. In this work, hollow manganese-cobalt-nickel sulfide nanotube arrays with the pore diameter about 40 nm are synthesized by three steps, and then chemical reduction strategy is used to build hollow trimetallic electrode materials with internal and external defects. During the whole process, due to the strong reducibility and small radius of H−, metal ions, which locate inside and outside the tube, are partially reduced from high oxidation states to low oxidation states, then the corresponding metal-sulfur bonds are broken and sulfide ions escape from active materials to form sulfur vacancies. Enhanced electrochemical performance of the electrode with vacancy (from 2944F g−1 to 3794F g−1 at 1 A g−1) demonstrates that the introduce of vacancy can facilitate electrochemical reaction kinetics due to the increased electron density of metal ions and active sites. In addition, the assembled asymmetric supercapacitor has a maximum voltage window of 1.8 V and displays a high energy density of 85.2 Wh kg−1 under a power density of 1030 W kg−1, showing the promising application in electrochemical energy storage fields.

Summary In recent years, significant advances have been made on photoredox-catalyzed N-radical addition to C-C unsaturated bond via N-H bond cleavage. However, these N-centered radical additions have so far been mostly limited to the alkenes, and to our knowledge, N-radical 5-endo-dig cyclizations of alkynes have been less exploited. Herein, we disclose an 5-endo-dig N-radical cascade cyclization of o-ethynylacetamides by photoredox catalysis involving rare radical cleavage of C-C triple bond, allowing the practical and controllable synthesis of a diverse array of valuable benzoxazinones and 2-hydroxy-3-indolinones in moderate to good yields under mild conditions. Furthermore, a mechanistic rationale for this radical cyclization cascade is supported by various control experiments and theoretical calculations.

Herein, experiments and DFT calculations were co-researched on high-performance catalysts for acetylene hydrochlorination. Firstly, the mesoporous carbon materials with adjustable N-doping content (MC-xN, x = 0, 0.5, 1, 2) were successfully synthesized. And the oxidized Ru species were further loaded (Ru-MC-xN) through simple hydrothermal method. Under the experimental condition of T = 170 °C, GHSV(C2H2) = 360 h−1, V(HCl)/V(C2H2) = 1.15, Ru-MC-2N shows excellent catalytic activity, with the acetylene conversion of 98.0 %. Characterized by various techniques, N-doping is confirmed to relatively inhibit the coke deposition and increase the percentage of oxidized Ru species which is attributed to regulation of the adsorption energy. Catalytic pathways of Ru in different valences are also revealed by DFT method. Results show that oxidized Ru species own higher catalytic activities than Ru0 species and manifest the molecular mechanism for HCl activation of RuO2. These findings provide theoretical basis for designs and applications of Ru-based catalysts in acetylene hydrochlorination.

Constructing porous three dimensional (3D) structure is an effective strategy for electrode materials to solve the urgent problem of low utilization of active sites in pseudocapacitors. Herein, the in situ scaffolding formation of well-distribute 3D NiFe Prussian blue analogue (NiFe PBAs) nanocubes penetrated 2D NiFe-layered double hydroxides (NiFe LDHs) on stainless steel mesh (SS) are synthesized, and then the precursors are transferred into 3D oxide arrays (SS@NiFe NSs@NiFe NCs) via thermal annealing in air. The 3D arrays show high specific surface area as well as excellent electrochemical performance including a high specific capacity and an outstanding cycling performance. Density functional theory (DFT) is also used to investigate reasons for the enhanced electrochemical performance of SS@NiFe NSs@NiFe NCs, and results show that the self-built heterointerfacial can form a long-range continuous interfaces, thereby increasing the conductivity and facilitate the charge transfer. In addition, a hybrid supercapacitor (HSC) SS@NiFe NSs@NiFe NCs//SS@Fe2O3 device is assembled and show an impressive electrochemical performance. This work gives a new insight for rational design of 3D PBA-based functional nanomaterials and can be used to explore the mass transfer mechanism of supercapacitor based on the special open structure of PBAs.

Sustainable biomass-derived carbon used as electrode features the concept of green chemistry. Herein, Typha orientalis leaves, which show tunable porous structure with high phosphorus content, were used as precursor to prepare P-doped hierarchical porous carbon material and then acted as negative electrode for supercapacitor. Different with the traditional activation methods, the biomass was pretreated by ZnCl2 then activated with KOH (Zn-K-ATC). Owing to the hierarchical porous structure, large specific surface area (1975 m2 g−1) and pseudocapacitance provided by P self-doping, Zn-K-ATC had a high specific capacitance of 324 F g−1 at 1 A g−1 in 1 M KOH. Zn-K-ATC was further used as support to grow MnO2 (Zn-K-ATC/MnO2) as the positive electrode material with a specific capacitance of 384 F g−1 at 1 A g−1 in 1 M Na2SO4. The assembled Zn-K-ATC/MnO2//Zn-K-ATC asymmetric supercapacitor device had a voltage window of 2 V with a high energy density of 46 Wh kg−1 at 1000 W kg−1. This work gives a systematic research and complete inspection on the preparation of supercapacitor from biomass-derived materials, which expects to provide a valuable method for the preparation of green, low-cost, high-performance supercapacitor materials.

Faced with the problems of poor activity and inferior selectivity, highly dispersed Pd catalysts pre-modified by minimal 3-aminopropyltriethoxysilane (APTES) were prepared via impregnation reduction method. The amount of APTES was adjusted according to molar ratios of the APTES to Pd (APTES/Pd). The catalytic hydrogenation efficiency exhibited a volcano-shape trend with the amount of APTES. Grafting of suitable amount of APTES improved the dispersion of the Pd, increased the weak acid content of the γ-Al2O3 and regulated the reducibility of the catalysts. The catalyst having APTES/Pd = 2 with 0.192 wt% Pd showed the highest catalytic activity and selectivity, with 100 % in the selectivity and the improvement of 27.3 % in the hydrogenation efficiency and 104.8 % in the H2O2 productivity compared with the commercial catalyst (0.298 wt%). Furthermore, the APTES aggregated with the amount of APTES, which provided intense anchoring sites for the Pd and resulted in the increase in larger palladium nanoparticles.

The generation of metal carbenes from readily available alkynes represents a significant advance in metal carbene chemistry. However, most of these transformations are based on the use of noble-metal catalysts and successful examples of such an asymmetric version are still very scarce. Here a copper-catalyzed enantioselective cascade cyclization of N-propargyl ynamides is reported, enabling the practical and atom-economical construction of diverse chiral polycyclic pyrroles in generally good to excellent yields with wide substrate scope and excellent enantioselectivities (up to 97:3 e.r.). Importantly, this protocol represents the first copper-catalyzed asymmetric diyne cyclization. Moreover, mechanistic studies revealed that the generation of donor/donor copper carbenes is presumably involved in this 1,5-diyne cyclization, which is distinctively different from the related gold catalysis, and thus it constitutes a novel way for the generation of donor/donor metal carbenes.

Highly active and stable framework Fe-doped ZSM-5 (f-Fe-ZSM-5) zeolites with different Fe contents, which were synthesized using a facile one-pot hydrothermal method, could effectively resolve the loss of iron element during the catalytic degradation of basic dyes. The successful introduction of Fe species into the framework of ZSM-5 was confirmed by elemental mappings, Fourier transform infrared (FT-IR) spectroscopy and Ultraviolet-visible spectroscopy (UV-vis spectra). The operational parameters, such as Fe content, H2O2 concentration, reaction temperature, types of dyes as well as the stability of the synthesized samples were extensively evaluated. It was demonstrated that the f-Fe(0.10)-ZSM-5 exhibited an efficient catalytic ability and excellent stability even after seven consecutive runs. The degradation efficiency of f-Fe-ZSM-5 for basic dyes was higher than that for acid dye. Therefore, f-Fe-ZSM-5 zeolites may present major potential for the treatment of basic dyes waste water without adjusting the initial pH value.

A better understanding of the role of exercise and nutrition in bone health is significant for preventing osteoporosis. The aim of this review was to assess the combined effects of physical activity and calcium intake on improving bone mineral density in children and adolescents. A search of electronic databases (MedLine, ISI Web of Science, Science Direct) and the literature references were performed. Randomized controlled trials published between 1997 and 2017, evaluating the effect of both physical activity and calcium intake intervention on bone mineral density or bone mineral content among children aged 3–18 years were selected. The Improved Jadad Rating Scale was used to assess the methodological quality of the included studies. Study characteristics were summarized in accordance with the review’s PICO criteria. Changes in bone mineral content were detected at several different bone sites. A total of nine studies involving 908 participants were included in this review. The combined intervention of physical activity and calcium increased bone mineral in children and adolescents, especially when baseline calcium intake level was low and among participants on the stage of early puberty. Regular physical activity combined with high level of calcium intake is beneficial for bone health in young population. Further research is needed to evaluate the dose–response associations and long-term effects of the interaction between physical activity and calcium intake.

Development of economical routes for synthesis of hollow zeolites with high amount of framework iron and high effectiveness factor is of great importance. Here, we provide a one-step and free-mesoporogen strategy to synthesize high-amount Fe-doped hollow silicate-1 with various cheap organic acids or derivative salts of organic acids. The contents of iron in zeolite and zeolite framework are ca. 3.3 wt% and 2.7 wt%, respectively. The hollow structures with the surface rich in iron have also been demonstrated. The presence of organic acid anions and the content of iron salts play the vital roles in the formation of hollow structure. In addition, the evolution process of Fe-doped hollow zeolite has been also investigated. The proposed mechanism based on the Kirkendall effect involves that high-amount iron-containing zeolite nanoparticles migrate outward relative to the nanoparticles interacted with carboxylate anions and carboxylate anions. The strategy can be successfully extended to TS-1 and ZSM-5. The high-amount Fe-doped hollow silicate-1 with high effectiveness factor exhibits an excellent catalytic performance for degradation reaction at mild conditions.

Vanadium-MFI zeolites with enhanced vanadium insertion were synthesized through an ammonium carbonate-assisted hydrothermal synthesis and applied as heterogeneous catalyst for the oxidation of organosulfur compounds DBT and 4,6-DMDBT. The prepared vanadium-MFI zeolites were characterized by Scanning electron microscope, Transmission electron microscope, X-ray diffraction, Fourier-transform infrared spectroscopy, UV–vis diffuse reflectance spectroscopy and Raman spectroscopy. The obtained UV–vis spectra disclosed that addition of ammonium carbonate could effectively strengthen the insertion of vanadium element, and on the same time enhance the tetrahedral framework vanadium percentage in vanadium species. The synthesized N-VS(4) zeolite could realize almost complete oxidation of DBT in 240 min, which is obviously better than N-VS(3) and N-VS(5) zeolite. Moreover, the calcined recycled N-VS(4) zeolite shows good re-usability for more than four cycles, which indicates it is an active and stable heterogeneous catalyst.

Ten coordination compounds, namely {[Cd(L)(die)]·2/3H 2 O} n ( 1 ), [Cd(L)(dib)] n ( 2 ), [Cd(L)(bmimb)] n ( 3 ), {[Cd(L)(bimb)]·1/2EtOH} n ( 4 ), [Zn(L)(bimb)] n ( 5 ), [Co(L)(bimb)] n ( 6 ), {[Cd(L)(phen)]·EtOH} n ( 7 ), [Cu(L)(phen)] n ( 8 ), [Zn(L)(mtpy)] n ( 9 ) and [Ni(L)(mtpy)]·1/2H 2 O ( 10 ) (H 2 L = 4′-((2-carboxyphenoxy)methyl)biphenyl-2-carboxylic acid, die = 1,2-di(1 H -imidazol-1-yl)ethane, dib = 1,4-di(1 H -imidazol-1-yl)butane, bmimb = 1,4-bis((2-methyl-1 H -imidazol-1-yl)methyl)benzene, bimb = 1,4-bis((1 H -imidazol-1-yl)methyl)benzene, phen = 1,10-phenanthroline and mtpy = 4′-(4-methylphenyl)-2,2′:6′,2″-terpyridine), have been solvothermally synthesized. These compounds were characterized by X-ray crystallography, elemental analysis, infrared spectra (IR) and powder X-ray diffraction (PXRD). In compounds 1 – 3 , similar dimeric [Cd 2 (L) 2 ] units are connected by different N-donor ligands to form diverse architectures. Strikingly, compound 3 displays a 2D → 3D interdigitated framework. Compounds 4 – 6 are essentially isostructural and reveal 2D sheet structures. Compound 7 shows a 2D 4 4 -sql network stabilized by π – π interactions between the pyridine rings of the phen ligands. Compound 8 exhibits a 3D supramolecular architecture constructed from a 1D chain via π – π interactions. Compound 9 possesses a 1D chain structure, which is further extended into a 2D supramolecular layer through hydrogen-bonding interactions. Compound 10 displays a [Cd 2 (L) 2 (mtpy) 2 ] dimeric structure. Adjacent dimers further interact through hydrogen-bonding interactions to afford a 1D supramolecular chain. Moreover, the luminescent properties of 1 – 5 , 7 and 9 have also been investigated in this work.

Allergic contact dermatitis (ACD), characterized predominantly by erythema, vesiculation, and pruritus, is a T cell-mediated skin inflammatory condition. Among immune cells involved in ACD, mast cells (MCs) play an essential role in its pathogenesis. As an inhibitor of proinflammatory IL-1 family members, interleukin 37 (IL-37) has been shown to ameliorate inflammatory responses in various allergic diseases. In this study, we assessed the immunomodulatory effect of IL-37 on allergic inflammation using a 2,4-dinitrofluorobenzene (DNFB)-induced ACD rat model and isolated rat peritoneal mast cells (RPMCs). Systematic application of IL-37 significantly relieved ear swelling, reduced inflammatory cell infiltration, decreased inflammatory cytokine production (TNF-α, IL-1β, IFN-γ, and IL-13), inhibited MC recruitment, lowered IgE levels, and reduced IL-33 production in the local ear tissues with DNFB challenge. Additionally, RPMCs isolated from ACD rats with IL-37 intervention showed downregulation of IL-6, TNF-α, IL-13, and MCP-1 production following IL-33 stimulation, and reduction of β-hexosaminidase and histamine release under DNP-IgE/HSA treatment. Moreover, IL-37 treatment also significantly restrained NF-κB activation and P38 phosphorylation in ACD RPMCs. SIS3, a specific Smad3 inhibitor, abolished the suppressive effects of IL-37 on MC-mediated allergic inflammation, suggesting the participation of Smad3 in the anti-ACD effect of IL-37. These findings indicated that IL-37 protects against IL-33-regulated MC inflammatory responses via inhibition of NF-κB and P38 MAPK activation accompanying the regulation of Smad3 in rats with ACD.

A Gram-staining-positive, rod-shaped, aerobic bacterium, designated strain LAM0410T, was isolated from an oil-contaminated water sample from the Dagang Oilfield, PR China. The temperature and pH ranges for growth were 4 °C to 50 °C and pH 4.4 to pH 12.0, respectively. The strain did not need NaCl for growth, but could tolerate a concentration of up to 12 % (w/v). Cell wall hydrolysates from the isolate showed that the diamino acid was ornithine. The cell wall sugars contained ribose and galactose. The glycan moiety of the cell wall contained N-glycolyl residues. The major respiratory quinones were MK-10, MK-11 and MK-12. The major polar lipids were diphosphatidylglycerol, phosphatidylglycerol and nine unknown glycolipids. The major fatty acids were anteiso-C15 : 0, anteiso-C17 : 0 and iso-C16 : 0. 16S rRNA gene sequence analysis indicated that the isolate belonged to the genus Microbacterium and was closely related to Microbacterium sediminis MCCC 1A06153T and Microbacterium murale DSM 22178T with 97.5 % and 97.4 % sequence similarities, respectively; while the DNA–DNA hybridization values were 33.1±3.4 % and 21.8±1.6 %, respectively. The DNA G+C content was 67.4 mol%, as determined by the T m method. Based on its phenotypic and genotypic properties, strain LAM0410T represents a novel species of the genus Microbacterium , for which the name Microbacterium petrolearium sp. nov. is proposed; the type strain is LAM0410T ( = ACCC 00719T = JCM 19612T).

Oxidative damage is a major cause of lung diseases, including pulmonary fibrosis. Laminarin is a kind of polysaccharide extracted from brown algae and plays vital roles in various biological processes. However, the functions and mechanisms of laminarin in pulmonary oxidative damage are poorly understood. This study aimed at investigating the protective effect of laminarin against pulmonary oxidative damage and underlying mechanisms. Human lung fibroblasts MRC-5 cells were treated with hydrogen peroxide to induce oxidative damage. Laminarin treatment was performed before or after hydrogen peroxide treatment, and then major indexes of oxidative damage, including superoxide dismutase (SOD), malondialdehyde (MDA), reduced glutathione (GSH) and catalase (CAT), were quantified by biochemical assays. The expression of oxidation-related factor, nuclear factor erythroid 2 like 2 (NRF2) was analyzed by qPCR, Western blot and immunofluorescence assay. NRF2 knockdown and overexpression were performed by cell transfection to reveal possible mechanisms. Results showed that laminarin treatment of 0.020 mg/mL for 24 h, especially the pre-treatment, could significantly relieve changes in SOD, MDA, GSH and CAT that were altered by hydrogen peroxide, and promote NRF2 mRNA (P

Solvothermal reaction of multidentate organic ligand, 5,5′,5″,5‴,5],5]′-[1,2,3,4,5,6-phenylhexamethoxyl]hexaisophthalic acid (H12L), with Cd(NO3)·4H2O produced an anionic 3D metal–organic framework [(CH3)2NH2]4[Cd3(H2L)] (1), which features a novel cage-to-cage connection. Interestingly, the 1D channel, which is stacked by cages, is divided into uniform segments by molecular-scale bricks. The luminescent properties of compound 1 have been explored, which shows that 1 is a potential luminescent sensory material for nitrobenzene.

A series of new chiral side-chain liquid crystalline polysiloxanes(P0-P7) bearing cyano groups were synthesized with a cholesteric LC monomer and a nematic monomer with cyano units(electron withdrawing). The chemical structures and LC properties of the polymers were measured by spectrum and thermal analysis techniques. The obtained polymers were soluble in many solvents and the specific rotations showed negative values and increased with the increasing content of chiral reagent. P1 showed grained texture of smectic A, P2~P7 showed lined texture of chiral smectic C(SC*). XRD curves of P1~P7 samples showed sharp and strong peaks at low angle, but no sharp peak was seen for P0 sample. The temperatures at which 5% weight loss occurred(Td) were greater than 300oC for all the polymers, which reveals all the polymers were stable. And the Tg values of polymers were all low. The Tg and Ti values are all increased with the increasing chiral contents. All the polymers displayed wide range of liquid crystal phase on heating and cooling cycle.

Objective: to explore the relationship between blood lipids/lipoproteins and cognitive function in the Chinese oldest-old. Design: multivariate statistical analysis using cross-sectional data. Setting: community-based setting in longevity areas in China. Subjects: eight hundred and thirty-six subjects aged 80 and older were included in the sample. Methods: plasma total cholesterol, triglycerides, low-density lipoprotein cholesterol, high-density lipoprotein cholesterol, blood pressure and fasting plasma glucose were measured and information about demographics and lifestyle was collected. Cognitive status was assessed using the Mini-Mental State Examination (MMSE). Results: cumulative logit model analysis showed that triglyceride was significantly negatively associated with cognitive impairment. By general linear modelling, there was a significant linear trend of MMSE scores with the level of triglyceride, but not with levels of cholesterol after adjustment. The odds ratio (OR) of cognitive impairment (MMSE score

The (110) crystal plane of SnO2 was found by X-ray diffraction, atomic force microscopy and X-ray photoelectron spectroscopy to grow preferentially in the direction of short-chain sulfonate self-assembled monolayer (SAM) formed from in situ oxidation of 3-mercaptopropyltrimethoxysilane (MPS) treated Si substrates. Molecular simulations were performed to study the optimal packing structure of MPS SAMs on Si (100) surface as well as its induced deposition mechanism to the SnO2 crystal. Molecular mechanics calculations showed that the MPS molecules self-assembled on Si (100) surfaces with a coverage ratio of 50% and a zigzag-like packing pattern. Molecular dynamics calculations reflected that oxidation of the SH of MPS contributed to uniform SO3H-terminated SAMs with narrower distribution of dihedral angles. Density functional theory calculations suggested the existence of strong interactions between the SO3H groups of SAMs and SnO2 (110) plane, which was due to the structural and electrical match between the SO3H group and the unsaturated atoms on SnO2 (110) plane. These results consistently confirmed that the ordered SAMs with SO3H terminal group are beneficial to the epitaxial growth of crystal SnO2. © 2007 American Institute of Chemical Engineers AIChE J, 2007

A Gram-stain-positive, spore-forming, obligately anaerobic bacterium, designated LAM201T, was isolated from sediment samples from an alkaline-saline lake located in Daqing oilfield, Daqing City, PR China. Cells of strain LAM201T were non-motile and straight or spiral rod-shapes. Strain LAM201T was able to utilize glucose, fructose, maltose, trehalose and sorbitol as the sole carbon source. Acetic acid, ethanol, iso-butanoic acid and iso-valeric acid were the main products of glucose fermentation. The major fatty acids of LAM201T were C16 : 0 (26.7 %) and C18 : 0 (11.2 %). The main polar lipids were four unknown glycolipids and five unknown phospholipids. The predominant cell-wall sugars were ribose and galactose. The cell-wall peptidoglycan of strain LAM201T contained alanine, glycine, glutamic acid and aspartic acid. Sodium sulfite was used as the electron acceptor. The G+C content of the genomic DNA was 32±0.8 mol%, as determined by the T m method. Analysis of the 16S rRNA gene sequence indicated that the isolate belonged to the genus Romboutsia and was most closely related to Romboutsia lituseburensis DSM 797T and Romboutsia ilealis CRIBT with 97.3 % and 97.2 % similarities, respectively. The DNA–DNA hybridization values between strain LAM201T and the two reference strains were 37 % and 31 %, respectively. On the basis of its phenotypic, phylogenetic and chemotaxonomic characteristics, strain LAM201T is suggested to represent a novel species within the genus Romboutsia , for which the name Romboutsia sedimentorum sp. nov. is proposed. The type strain is LAM201T ( = ACCC 00717T = JCM 19607T).

Herein, we report the straightforward synthesis, photoluminescent properties, and cell imaging studies of d-mannose and l-alanine functionalized silicon nanocrystals (SiNCs). Tailoring nanocrystal surface functionalization is essential to interfacing SiNCs with their environment and rendering them stable-surface modification also offers the opportunity to target specific cell types for imaging. A simple and versatile surface modification procedure was developed to tether biomolecules onto the SiNC surfaces and render them water-soluble. The presented approach is precious metal-catalyst free, straightforward, and provides carbohydrate and amino acid functionalized SiNCs. The functionalized SiNCs have been investigated by fluorescence microscopy and our results indicate that they can be internalized by MCF-7 human breast cancer cells as shown in the cell imaging studies. The obtained SiNCs were characterized using FTIR, XPS, PL, and TEM. This journal is

The growth behavior and structure of self-assembled layers of short-chain alkoxysilane of 3-mercaptopropyltrimethoxysilane (MPS) on hydroxyl-terminated substrates were investigated using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. It was indicated that the self-assembled layers of MPS formed island structures and deposited integrally on the substrates. Further, the deposition of SnO2 thin films on the MPS-coated substrates was studied using X-ray diffraction (XRD), AFM, XPS, and the high-resolution stylus profilometers. It was proved that uniform and compact SnO2 thin films indeed formed on the self-assembled layers of short-chain MPS. The as-deposited SnO2 films were cassiterite and showed the property of semiconductors, which would have wide applications in gas sensors, solar cells, catalysts, etc.

A Gram-staining-positive, spore-forming, obligately anaerobic, acetogenic bacterium, designated LAM1030T, was isolated from methanogenic consortia enriched from biogas slurry collected from the large-scale anaerobic digester of Modern Farming Corporation in Hebei Province, China. Cells of strain LAM1030T were motile, straight or spiral-rod-shaped. Strain LAM1030T could utilize glucose, fructose, maltose, galactose, lactose, sucrose, cellobiose, mannitol, pyruvate, succinic acid and tryptophan as the sole carbon source. Acetic acid, isovaleric acid and butanoic acid were the main products of glucose fermentation. Sodium sulfite was used as an electron acceptor. Growth of strain LAM1030T was completely inhibited by the addition of ampicillin, tetracycline, gentamicin or erythromycin at a concentration of 20 µg ml−1. The main polar lipids of strain LAM1030T were diphosphatidylglycerol, phosphatidylglycerol, phosphatidylethanolamine, 11 unknown glycolipids and two unknown phospholipids. No respiratory quinone was detected. The major fatty acids of strain LAM1030T were C16 : 0 (21.1 %), C14 : 0 (10.3 %), summed feature 9 (including C16:0 10-methyl and/or iso-C17:1 ω9c) (11.3% ), summed feature 3 (including C16:1 ω7c and/or C16:1 ω6c) (10.6% ) and iso-C15 : 0 (6.6 %). Analysis of the 16S rRNA gene sequence indicated that strain LAM1030T belonged to the genus Clostridium and was most closely related to Clostridium subterminale DSM 6970T, Clostridium thiosulfatireducens DSM 13105T and Clostridium sulfidigenes DSM 18982T, with 97.0, 96.9 and 96.8 % similarity, respectively. The G+C content of the genomic DNA of strain LAM1030T was 31.2±0.3 mol%. On the basis of its phenotypic, phylogenetic and chemotaxonomic characterization, strain LAM1030T is suggested to represent a novel species of the genus Clostridium , for which the name Clostridium huakuii sp. nov. is proposed. The type strain is LAM1030T ( = ACCC 00698T = JCM 19186T).

A novel aerobic, halotolerant bacterium, designated strain LAM612T, was isolated from saline-alkaline soil samples from Lingxian County, Shandong Province, China. Cells of strain LAM612T were Gram-reaction-positive, endospore-forming, motile and rod-shaped. The optimal temperature and pH for growth were 35 °C and pH 6.0, respectively. Strain LAM612T could grow in the presence of up to 10 % (w/v) NaCl. The genomic DNA G+C conten was 36.4 mol% as detected by the T m method. Comparative analysis of 16S rRNA gene sequences revealed that LAM612T was closely related to Lysinibacillus sinduriensis KACC 16611T (98.0 %), L. chungkukjangi KACC 16626T (97.5 %), L. massiliensis KCTC 13178T (97.4 %), L. xylanilyticus KACC 15113T (97.2 %), L. macroides DSM 54T (97.0 %) and L. manganicus DSM 26584T (96.5 %). The DNA–DNA hybridization values between strain LAM612T and its closest relatives ranged from 20.6 % to 41.9 %. The major fatty acids of strain LAM612T were iso-C15 : 0 (40.8 %), iso-C16 : 0 (15.2 %) and anteiso-C15 : 0 (10.8 %). The cell-wall peptidoglycan content was A4α (l-Lys–d-Asp). The predominant menaquinone was MK-7 and the main polar lipids were diphosphatidylglycerol, phosphatidylglycerol, phosphatidylethanolamine, three unknown phospholipids, five unknown glycolipids and an unknown lipid. Based on the DNA–DNA hybridization results and phenotypic, phylogenetic and chemotaxonomic properties, strain LAM612T could be distinguished from the recognized species of the genus Lysinibacillus , and was suggested to represent a novel species of this genus, for which the name Lysinibacillus halotolerans sp. nov. is proposed. The type strain is LAM612T ( = ACCC 00718T = JCM 19611T).

The fungal strain LZM1 was isolated from activated sludge and found to be capable of utilizing nicosulfuron as the sole nitrogen source for growth. Based on morphological and internal transcribed spacer evaluations, LZM1 was identified as a Talaromyces flavus strain. Under optimum conditions (pH 6.1, 29°C), T. flavus LZM1 degraded 100% of the initially added nicosulfuron (100 mg L(-1)) within 5d. T. flavus LZM1 was also found to be highly efficient in degrading tribenuron methyl, chlorsulfuron, bensulfuron methyl, ethametsulfuron methyl, cinosulfuron, and rimsulfuron. Metabolites from nicosulfuron degradation were identified by liquid chromatography mass spectrometry, and a possible degradation pathway was deduced. These results show that T. flavus LZM1 may possess potential to be used in bioremediation of nicosulfuron-contaminated environments.

Paracoccus sp. strain TRP, isolated from activated sludge, could completely biodegrade chlorpyrifos and 3,5,6-trichloro-2-pyridinol. Here we report the draft genome sequence of Paracoccus sp. strain TRP, which could be used to predict genes for xenobiotic biodegradation and metabolism.