Cooperation between the Cu+ and Cu2+ species in CuCoAl layered double hydroxide and the substrate promoting effect afford a really simple protocol for the efficient synthesis of quinazolines.

In this study, a really simple and efficient catalytic protocol for the construction of quinazolines from alcohol and diamine has been developed based on CuCoAl layered double hydroxide (CuCoAl-LDH). The developed CuCoAl-LDH catalyst could accelerate the cascade reactions without any additives and tolerate various alcohols with satisfactory yields. Cooperation between the Cu+ and Cu2+ species in CuCoAl-LDH was observed in the cascade reaction, and they are believed to be responsible for the oxidation of alcohol and dehydrogenation of the intermediate, respectively. The promoting effect of the substrate diamine was observed in the oxidation of alcohol, which simplifies the reaction system by eliminating the requirement for a base additive. The catalytic system exhibited highly practical potential for the synthesis of quinazolines, as demonstrated through recyclability investigations and scale-up experiments. A possible catalytic mechanism has been proposed based on a series of control experiments and EPR analysis.

Constructing Lanthanide-Organic Complexes for X-ray Scintillation and Imaging.

The photoluminescent properties of lanthanide complexes have been thoroughly investigated; however, there have been much fewer studies showcasing their potential use in ionizing radiation detection. In this work, we delve into the photo- and radio-induced luminescence of a series of lanthanide-bearing organic-inorganic hybrids and their potential as a platform for X-ray scintillation and imaging. The judicious synergy between lanthanide cations and 2,6-di(1H-pyrazol-1-yl)isonicotinate (bppCOO-) ligands affords six new materials with three distinct structures. Notably, Eu-bppCOO-1 and Tb-bppCOO-2 display sharp fingerprint X-ray-excited luminescence (XEL), the intensities of which can be linearly correlated with the X-ray dose rates over a broad dynamic range (0.007-4.55 mGy s-1). Moreover, the X-ray sensing efficacies of Eu-bppCOO-1 and Tb-bppCOO-2 were evaluated, showing that Tb-bppCOO-2 features a lower detection limit of 4.06 µGy s-1 compared to 14.55 µGy s-1 of Eu-bppCOO-1. Given the higher X-ray sensitivity and excellent radiation stability of Tb-bppCOO-2, we fabricated a flexible scintillator film for X-ray imaging by embedding finely ground Tb-bppCOO-2 in the polydimethylsiloxane (PDMS) polymer. The resulting scintillator film can be utilized for high-resolution X-ray imaging with a spatial resolution of approximately 7 lp mm-1.

Microenvironment Modulation of Single-Atom Ru in ZrSBA-15 for CO2 Hydrogenation to Formic Acid.

The chemical microenvironment modulation of active sites holds promise for facilitating their catalytic performance. Herein, single-atom Ru anchored by ZrSBA-15 modified with diverse organic amine groups has been fabricated and enabled CO2 hydrogenation to produce formic acid (FA) under mild conditions. However, the reaction cannot be achieved without the modification of organic amines. The functional groups as the microenvironment around Ru active sites effectively regulated the activity, in which Ru encapsulated in ZrSBA-15 bearing -NH2 groups exhibited the highest activity, with turnover number (TON) and turnover frequency (TOF) values of 505 and 64 h-1, respectively. Both characterization and experimental results validated that the functional group manipulated the adsorption capacity of the reactant, the electronic state of Ru and hydrophilicity/hydrophobicity of the materials, and thus the catalytic performance.

Synergistic Enhancement of Photocatalytic H2 Evolution over NH2-MIL-125 Modified with Dual Cocatalyst.

The construction of efficient photocatalysts for water splitting to enable H2 evolution is pivotal to alleviate energy issues and environmental concerns. In this work, carbon dots (CDs) were prepared by employing "green solvent" ionic liquids as carbon sources and then combined with Pt/NH2-MIL-125, resulting in the emergence of a high-efficiency photocatalyst termed CDs-Pt/NH2-MIL-125 for the first time. This composite photocatalyst exhibited outstanding photocatalytic activity in H2 production under visible light irradiation. Notably, the H2 production rate of CDs100-Pt/NH2-MIL-125 reaches up to 951.4 µmol/g/h, which was 3.1 times that of Pt/NH2-MIL-125. The characterization results indicate that CDs and Pt uniformly dispersed on the surface of NH2-MIL-125 and fabricated a synergistic compact structure, providing a high BET surface area (985 m2 g-1) and a suitable band gap. Furthermore, the distinctive embeddable-dispersed CDs and Pt, as dual cocatalyst, can harvest light and facilitate the transfer of photogenerated electrons, thereby significantly augmenting the exploitation of visible light. The plausible mechanism of photocatalytic H2 evolution over the CDs-Pt/NH2-MIL-125 catalyst was also discussed. This work introduces a promising strategy for designing high-performance CDs-MOFs-based photocatalysts, an innovative step toward achieving efficient photocatalytic water splitting for H2 production.

Ligand-Mediated Regulation of the Chemical/Thermal Stability and Catalytic Performance of Isostructural Cobalt(II) Coordination Polymers.

Regulating the chemical/thermal stability and catalytic activity of coordination polymers (CPs) to achieve high catalytic performance is topical and challenging. The CPs are competent in promoting oxidative cross-coupling, yet they have not received substantial attention. Here, the ligand effect of the secondary ligand of CPs for oxidative cross-coupling reactions was investigated. Specifically, four new isostructural CPs [Co(Fbtx)1.5(4-R-1,2-BDC)]n (denoted as Co-CP-R, Fbtx = 1,4-bis(1,2,4-triazole-1-ylmethyl)-2,3,5,6-tetrafluorobenzene, 4-R-1,2-BDC = 4-R-1,2-benzenedicarboxylate, R = F, Cl, Br, CF3) were prepared. It was found that in the reactions of oxidative amination of benzoxazoles with secondary amines and the oxidative coupling of styrenes with benzaldehydes, both the chemical and thermal stabilities of the four Co-CPs with the R group followed the trend of -CF3 > -Br > -Cl > -F. Density functional theory (DFT) calculations suggested that the difference in reactivity may be ascribed to the effect of substituent groups on the electron transition energy of the cobalt(II) center of these Co-CPs. These findings highlight the secondary ligand effect in regulating the stability and catalytic performance of coordination networks.

Catalytic behavior of a ZnO/TiO2 composite in the synthesis of polycarbonate diol.

ZnO/TiO2 catalysts with different ZnO contents have been prepared through equal volume impregnation method, characterized by XRD, SEM, Py-IR, ICP, XPS, NH3-TPD and N2 adsorption/desorption, and evaluated in the synthesis of polycarbonate diol (PCDL) through transesterification. The results showed that titanium zinc oxide formed in these catalysts, and the content of acidic sites varied with the ZnO content, and ZnO/TiO2 (10%) has the highest acid amount. The ZnO/TiO2 (20%) with medium acidic sites showed the highest catalytic activity. The synthesis process of polycarbonate glycol was also optimized. Under the optimal reaction conditions, the yield of PCDL was 72.5%, and the M n reached 4829 g mol-1 with a PDI of 1.6.

A MOF-based luminometric sensor for ultra-sensitive and highly selective detection of chromium oxyanions.

Sensitization of Cr(VI) oxyanions in environmentally or industrially relevant aquatic media is highly desired owning to their biological toxicity and essential role in nuclear fuel cycle. However, many chemosensors of CrO42- and Cr2O72- suffer from critical drawbacks, including insufficient sensitivity, selectivity, and/or hydrolytic stability. In this work, we prepared a hydrolytically stable metal-organic framework, namely Hf-BITD, which can retain its crystallinity and structural integrity in solutions over a wide pH range (0-12) and in 3 M HCl. The strong emission via rigidifying fluorescent linkers allows for sensing of CrO42- and Cr2O72- in a luminescence quenching manner, with excellent linear correlations (I0/I = 1+ Ksv [Q]) in the ranges of 0-80 µM and 0-50 µM for CrO42- and Cr2O72-, respectively. The adsorption of Cr(VI) oxyanions and the concomitant resonance energy transfer between framework and analysts efficiently turn the emission of Hf-BITD off, which allows for selective recognition of CrO42- and Cr2O72- with detection limits of 0.38 nM and 0.33 nM, respectively. Furthermore, fabrication of Hf-BITD incorporating PVDF membrane makes Hf-BITD@PVDF a promising candidate for facile and effective sensitization of Cr(VI) oxyanions.

Enhancing photosensitivity via the assembly of a uranyl coordination polymer.

Synergistic assembly of uranyl centres and luminescent 2,6-bis(pyrazol-1-yl)pyridine-4-carboxylates (bppCOOH) gives rise to a uranyl coordination polymer, namely U-bppCOO, which exhibits a luminescence quenching response toward UV or X-ray irradiation doses. Notably, the photosensitivity of U-bppCOO has been significantly enhanced via metal-ligand assembly compared with that of the naked bppCOOH ligand.

IL-10/IL-10 receptor 1 pathway promotes the viability and collagen synthesis of pulmonary fibroblasts originated from interstitial pneumonia tissues.

Interstitial pneumonia is a pulmonary interstitial inflammatory and fibrosis disease with a variety of causes that causes respiratory disorders and threatens the lives of patients. The present study aimed to investigate the expression of interleukin (IL)-10 in peripheral blood of patients with interstitial pneumonia and its biological functions in pulmonary fibroblasts. A total of 42 patients with idiopathic pulmonary fibrosis (IPF) and 20 healthy subjects were included. ELISA was used to determine IL-10 concentration in serum from the patients and healthy subjects. Primary fibroblasts were isolated from lung tissue successfully and determined by morphology. The CCK-8 assay was performed to determine the effect of IL-10 expression on cell viability. Western blotting was used to determine COL1a1, COL1a2 and IL-10R1 protein expression. Flow cytometry was used for cell cycle analysis and to determine the number of IL-10+ cells. Expression of IL-10 in serum from IPF patients was higher compared to that from healthy subjects. IL-10 promoted the viability and collagen synthesis and secretion of MRC-5 cells and primary pulmonary fibroblasts. IL-10 and IL-10 receptor (R) 1 served regulatory roles in the viability and collagen synthesis of MRC-5 cells. The ratio of peripheral mononuclear lymphocytes with positive expression of IL-10 was elevated in peripheral blood from patients with IPF. The present study demonstrated that IL-10 expression in peripheral blood of patients with IPF is increased significantly compared with healthy subjects. Activation of the IL-10/IL-10R1 signaling pathway promoted the viability and collagen synthesis and secretion of pulmonary fibroblasts, leading to pulmonary fibrosis. The present study provided experimental basis for further understanding the development mechanism of pulmonary fibrosis.

Emergence of Thorium-Based Polyoxo Clusters as a Platform for Selective X-ray Dosimetry.

A brand-new application of thorium-bearing clusters in the field of ionizing radiation detection is exemplified by two novel hexanuclear thorium clusters, Th-bppCOO-1 and Th-bppCOO-2, which incorporate carboxylate-functionalized 2,6-di(pyrazol-1-yl)pyridine ligands. Notably, Th-bppCOO-1 is composed of an unprecedented [Th6(OH)4O4(H2O)5]12+ secondary building unit, the Th6 core of which is decorated by five H2O molecules. Furthermore, selective photoluminescence quenching responses of Th-bppCOO-1 and Th-bppCOO-2 toward X-ray over UV radiation have been demonstrated for the first time.

Achieving colour tuneable and white-light luminescence in a large family of dual-emission lanthanide coordination polymers.

Expanding the family of lanthanide terpyridine coordination polymers has yielded eighteen new complexes with two different phases, Ln(TPC)2(HCOO)(H2O) (Ln-1) and Ln(TPC)(HCOO)2 (Ln-2) (Ln = Sm-Lu, except Tm). Both structures are composed of lanthanide cations interconnected by 2,2':6',2''-terpyridine-4'-carboxylate ligands to yield one-dimensional chain topologies. However, the incorporation of an additional crystallographically unique decorative TPC ligand into Ln-1 gives rises to a distinct phase. The encapsulation of both metal- and ligand-based phosphors within single coordination polymers leads to dual-emission of the afforded materials. Furthermore, judicious lanthanide doping in heterometallic Ln-1 and Ln-2 allows for fine-tuning the photoluminescent colours over a wide range of gamut. Such a combination showcases the capability to fine-tune the emission colours from deep green, to red, and to blue. In addition, direct white-light emission upon UV excitation can be achieved in the SmxGd1-x-1 system.

Synthesis, characterization, and functional evaluation of branched dodecyl phenol polyoxyethylene ethers: a novel class of surfactants with excellent wetting properties.

A series of branched dodecyl phenol polyoxyethylene ethers (b-DPEO n ) were successfully synthesized via alkylation and ethylene oxide addition reactions. The alkylation reaction was conducted by using a branched internal olefin as the raw material. Furthermore, the conversion rate of the branched dodecene was measured to be 98.1% and the selectivity towards branched dodecyl phenol (b-DP) was 95.9%. Moreover, b-DPEO n (b-DPEO7, b-DPEO10, b-DPEO12) were obtained via the reaction of ethylene oxide with b-DP. Notably, b-DPEO10 can efficiently reduce the surface tension of water below 31.55 mN m-1 at the critical micelle concentration (cmc) and the cmc value in water was approximately 1.3 × 10-2 g L-1 at 25 °C. The preferable wetting ability of b-DPEO10 was superior to that of commercialized dodecyl phenol polyoxyethylene ether (c-DPEO n ), so it will be promoted and used in the textile and pesticide industries.

Auxiliary Ligand-Dependent Adaptive Regulation of Uranyl Coordination in Mixed-Ligand Uranyl Compounds of Flexible Biphenyltetracarboxylic Acid.

The mixed-ligand strategy is one of the important methods for preparing new materials and regulating the properties of materials. In this work, by introducing different auxiliary ligands (ALs), we have obtained a series of mixed-ligand uranyl complexes (1-6) from a flexible biphenyltetracarboxylic acid (H4bptc) with an adjustable orthogonal conformation and studied the influence of different organic base molecules on the coordination and assembly of H4bptc with a uranyl cation. It is found that the coordinated ALs, including 4,4'-bipyridine-1,1'-dioxide and 1,10-phenanthroline, partially occupy the coordination sites of the uranyl center and directly affect the molecular conformations and uranyl coordination of flexible bptc linkers. On the other hand, noncoordinated ALs such as protonated 4,4'-bipyridine ([H2(4,4'-bpy)]2+) or dimethylammonium, which work as counterions in the form of encapsulated guests or hydrogen-bonded templates, also have a nonnegligible impact on the conformation and coordination of bptc linkers. Most interestingly, the AL-mediated evolution of uranyl coordination by the bptc linker and coordination geometry of the uranyl center is clearly observed, which suggests the adaptability of flexible bptc linkers to take suitable molecular configurations and uranyl coordination modes so as to adapt to the external regulator agents and varying environment. The physicochemical characterization of these uranyl compounds, especially photoluminescence, is addressed and discussed, and the results reveal that compound 5 has the potential to serve as a multifunctional radiation detection material for UV light and X-ray radiation.

Resilient Properties of Soil-Rock Mixture Materials: Preliminary Investigation of the Effect of Composition and Structure.

The physical composition and stress state of soil-rock mixture (SRM) materials have a crucial influence on their mechanical properties, and play a vital role in improving the performance of subgrade. To reveal the resilient behavior and mesostructure evolution of SRM materials, triaxial tests and discrete element method (DEM) numerical analysis have been carried out. In the triaxial test section, the mechanical response of SRM materials was investigated by preparing samples under different stress states and physical states and conducting triaxial tests on samples. Simultaneously, a new irregular particle modeling method was developed and applied to the discrete element modeling process to analyze the mesostructure evolution of SRM materials under cycling loading. First, a cyclic triaxial test of SRM material is performed on the SRM material, and the effects of bulk stress, octahedral shear stress and rock content on the resilient modulus of the SRM material are analyzed. It is revealed that the resilient modulus increases with increasing bulk stress and rock content, and decreases with increasing octahedral shear stress. Based on a new resilient modulus prediction model, the relationships among the rock content, stress state and resilient modulus are established. Then, based on an improved DEM modeling method, a discrete element model of the SRM is established, and the influence of rock content on coordination number and mesostructure evolution of the SRM is analyzed. The results show that in SRM materials, the increase of crushed rock changes the mesostructure of the SRM material. With the increase of rock content, the internal contact force changes from "between soil and rock" to "between rocks", and the skeleton formed in the rocks gradually develops overall stiffness. Under the condition of low stress, the anisotropy of the SRM material is mainly caused by the shape and grade distribution of crushed rock. The induced anisotropy caused by the change of stress state has little effect on its mechanical behavior, which may lead to the greater dispersion of multiple SRM test results.

In Situ Generation of Nitrilimines from Aryldiazonium Salts and Diazo Esters: Synthesis of Fully Substituted Pyrazoles under Room Temperature.

A novel one-pot synthesis for fully substituted pyrazoles has been well developed via the in situ generation of nitrilimines from aryldiazonium salts and diazo esters and a subsequent cycloaddition with 1,3-dicarbonyl compounds. High yields, mild conditions, wide substrate scope, and operational simplicity are the significant advantages of this methodology.

Highly Doped Carbon Nanobelts with Ultrahigh Nitrogen Content as High-Performance Supercapacitor Materials.

Nitrogen-doped and nitrogen and oxygen codoped carbon nanobelts (CNBs) (denoted as N-CNBs and N-O-CNBs, respectively) are respectively obtained by pyrolyzing the self-aligned polypyrrole (PPy) NBs and Se@poly(2-methoxy-5-nitroaniline) core@shell nanowires. Particularly, the uniform size, unique nanostructure, and well-defined edges of the PPy NBs result in the uniform size of the doped CNBs with an extraordinarily high N doping level (≈16 at%), especially the very large concentrations of the redox active pyridinic (9 at%) and pyrrolic N (3.5 at%) species. Furthermore, the precursors in highly self-aligned, dense arrays give rise to a very high packing density for the N-CNBs and N-O-CNBs. These incomparable features provide not only appropriate pathways for the introduction of pseudocapacitance via rapid Faradaic reactions and enhancement of volumetric capacitance but also structural design and synthesis approach to new types of nanostructured carbon. Notably, the N-CNBs obtained at the pyrolysis temperature of 800 °C (N-CNB8) in symmetric electrochemical cells deliver a specific capacitance of 458 F g-1 and ultrahigh volumetric capacitance of 645 F cm-3 in aqueous solution, which are among the best performance ever reported for carbon-based supercapacitive materials.

The combination of plasma glutamate and physical impairment after acute stroke as a potential indicator for the early-onset post-stroke depression.

OBJECTS: The present study aimed to investigate the relationship of plasma glutamate levels with the early-onset of post-stroke depression (PSD) and to further explore the prognostic value of plasma glutamate combined with clinical characteristics for the early-onset PSD in the acute ischemic stroke patients. METHODS: Seventy-four patients who admitted to the hospital within 24h of acute ischemic stroke were consecutively recruited and followed up for 2weeks. The Beck Depression Inventory (BDI) and 17-item Hamilton Depression Rating Scale (HAMD-17) were used to screen for depressive symptoms 14days after stroke. Diagnoses of depression were made in accordance with DSM-IV. Plasma glutamate levels were determined by High Performance Liquid Chromatography (HPLC) on days 1 and 14 after stroke for all patients. RESULTS: Plasma glutamate levels were significantly lower in PSD patients than those of non-PSD patients on day 1 after stroke. ROC curve analyses revealed an AUC (area under the ROC curve) of 0.724 (95% CI: 0.584-0.863, p=0.004) and of 0.669 (95% CI: 0.523-0.814, p=0.030) for National Institute of Health Stroke Scale (NIHSS) scores and plasma glutamate levels on day 1 respectively. Combined ROC analyses using the two factors revealed the highest AUC of 0.804 (95% CI: 0.685-0.922, P<0.0001). CONCLUSIONS: These results indicated an association between the early-onset PSD and a low plasma glutamate level following acute ischemic stroke. The combination of reduced plasma glutamate levels and physical impairment (determined by NIHSS) 1day after acute ischemic stroke was a potential diagnostic indicator for early-onset PSD.

Serum pro-gastrin-releasing peptide in diagnosis of small cell lung cancer: A meta-analysis.

OBJECTIVE: The purpose of this study was to assess the diagnostic sensitivity and specificity for serum pro-gastrin-releasing peptide (Pro-GRP) in diagnosis of small cell lung cancer (SCLC) through pooling all the open published data. MATERIALS AND METHODS: Databases of PubMed, Cochrane, ISI Web of Knowledge, and CNKI were electronic, searched by two reviewers to find the diagnostic study serum Pro-GRP in diagnosis of SCLC. The diagnostic sensitivity, specificity, positive likelihood ratio (PLR), negative likelihood ratio (NLR), diagnostic odds ratio (DOR), and area under the receiver operating characteristic (ROC) were calculated by Med DiSc1.4 software. RESULTS: Finally, 21 studies were included in this meta-analysis. Because of statistical heterogeneity, the specificity, specificity, positive/negative likelihood ratio, and DOR were pooled by random effect model. The pooled sensitivity, specificity, PLR, NLR, DOR, and area under the ROC were 64% (95% confidence interval [CI]: 62%-66%), 94% (95% CI: 94%-95%), 11.87% (95% CI: 8.62-11.35), 0.32% (95% CI: 0.26%-0.39%), 40.98% (95% CI: 27.77%-60.64%), and 0.94 (95% CI: 0.91%-0.96%). CONCLUSION: Serum Pro-GRP was promising biomarker for SCLC diagnosis.

X-ray cross-complementing groups 1 rs1799782 C>T polymorphisms and colorectal cancer susceptibility: A meta-analysis based on Chinese Han population.

OBJECTIVE: X-ray cross-complementing groups 1 (XRCC1) rs1799782 C>T polymorphisms and colorectal cancer susceptibility were not clear. The purpose of this study was to evaluate the association between XRCC1 rs1799782 C>T polymorphisms and colorectal cancer susceptibility by meta-analysis. MATERIALS AND METHODS: Related databases of Medline, CNKI, and Wanfang were systematic searched for the studies related to XRCC1 rs1799782 C>T polymorphisms and colorectal cancer risk in Chinese Han population. The genotype distribution of CC, CT and TT were extracted from each included studies in the colorectal cancer patients and healthy control subjects. The odds ratio (OR) and its 95% confidence interval (95% CI) was used to assess the correlation between genetype and colorectal cancer risk. The publications for this study was evaluated by Begg's funnel plot and Egger's line regression test. RESULTS: The median frequency of CC, CT, and TT genotype in cancer group were 48%, 41% and 11%; For control group, they were 51%, 40% and 8%; the pooled results showed that OR = 1.32 (95% CI: 1.041-1.67, P < 0.05). The pooled results indicated that XRCC1 rs1799782 C>T polymorphisms was associated with colorectal cancer susceptibility in recessive genetic model OR = 1.32 (95% CI: 1.041-1.67, P < 0.05), dominant genetic model OR = 1.21 (95% CI: 1.00-1.46, P < 0.05) and homozygous genetic model OR = 1.43 (95% CI: 1.07-1.91, P < 0.05). The funnel plot was significant asymmetric at the bottom and the Egger's test also indicated significant publication bias (t = 2.43, P = 0.04) for recessive genetic model. But, no publication bias was found in dominant and homozygous model (P > 0.05). CONCLUSION: Chinese Han people with rs1799782 TT/CT genotype of XRCC1 gene may have increased risk of developing colorectal.

Cogeneration of biodiesel and nontoxic rapeseed meal from rapeseed through in-situ alkaline transesterification.

In-situ alkaline transesterification of rapeseed oil with methanol for the production of biodiesel and nontoxic rapeseed meal was carried out. Water removal from milled rapeseed by methanol washing was more effective than vacuum drying. The conversion rate of rapeseed oil into FAME was 92%, FAME mass was 8.81 g, glucosinolates content in remaining rapeseed meal was 0.12% by methanol washing, while by vacuum drying the values were 46%, 4.44 g, 0.58%, respectively. In the presence of 0.10 mol/L NaOH in methanol, with methanol/oil molar ratio of 180:1 and a 3h reaction at 40 °C, a conversion rate of 98% was achieved, and the glucosinolates content was reduce to 0.07%, a value which below the GB/T 22514-2008 standard in China. Thus the rapeseed meal can be used as a source of protein in animal feed. The FAME prepared through in-situ alkaline transesterification met the ASTM specifications for biodiesel.