Direct conversion of fructose-based carbohydrates to 5-ethoxymethylfurfural catalyzed by AlCl3·6H2O/BF3·(Et)2O in ethanol

Direct conversion of fructose-based carbohydrates to 5-ethoxymethylfurfural (EMF) catalyzed by Lewis acid in ethanol was investigated. It was found that BF₃·(Et)₂O was favorable for 5-hydroxymethylfurfural (HMF) etherification to EMF. BF₃·(Et)₂O combination with AlCl₃·6H₂O with the molar ratio of 1 was an effective catalyst system for synthesis of EMF from fructose-based carbohydrates. 55.0%, 45.4% and 23.9% of EMF yields were obtained from fructose, inulin and sucrose under optimized conditions, respectively.     

Development of a Sensitive Method for the Determination of 4‐(Methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol in Human Urine Using Solid‐phase Extraction Combined with Ultrasound‐assisted Dispersive Liquid–liquid Microextraction and LC‐MS/MS Detection

An efficient and sensitive analytical method based on molecularly imprinted solid‐phase extraction (MISPE) and reverse‐phase ultrasound‐assisted dispersive liquid–liquid microextraction (USA‐DLLME) coupled with LC–MS/MS detection was developed and validated for the analysis of urinary 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol (NNAL), a tobacco‐specific nitrosamine metabolite. The extraction performances of NNAL on three different solid‐phase extraction (SPE) sorbents including the hydrophilic‐lipophilic balanced sorbent HLB, the mixed mode cationic MCX sorbent and the molecularly imprinted polymers (MIP) sorbent were evaluated. Experimental results showed that the analyte was well retained with the highest extraction recovery and the optimum purification effect on MIP. Under the optimized conditions of MIP and USA‐DLLME, an enrichment factor of 23 was obtained. Good linearity relationship was obtained in the range of 5‐1200 pg/mL with a correlation coefficient of 0.9953. The limit of detection (LOD) was 0.35 pg/mL. The recoveries at three spiked levels ranged between 88.5% and 93.7%. Intra‐ and inter‐day relative standard deviations varied from 3.6% to 7.4% and from 5.4% to 9.7%, respectively. The developed method combing the advantages of MISPE and DLLME significantly improves the purification and enrichment of the analyte and can be used as an effective approach for the determination of ultra‐trace NNAL in complex biological matrices.     

FIPSDock: A new molecular docking technique driven by fully informed swarm optimization algorithm

The accurate prediction of protein–ligand binding is of great importance for rational drug design. We present herein a novel docking algorithm called as FIPSDock, which implements a variant of the Fully Informed Particle Swarm (FIPS) optimization method and adopts the newly developed energy function of AutoDock 4.20 suite for solving flexible protein–ligand docking problems. The search ability and docking accuracy of FIPSDock were first evaluated by multiple cognate docking experiments. In a benchmarking test for 77 protein/ligand complex structures derived from GOLD benchmark set, FIPSDock has obtained a successful predicting rate of 93.5% and outperformed a few docking programs including particle swarm optimization (PSO)@AutoDock, SODOCK, AutoDock, DOCK, Glide, GOLD, FlexX, Surflex, and MolDock. More importantly, FIPSDock was evaluated against PSO@AutoDock, SODOCK, and AutoDock 4.20 suite by cross‐docking experiments of 74 protein–ligand complexes among eight protein targets (CDK2, ESR1, F2, MAPK14, MMP8, MMP13, PDE4B, and PDE5A) derived from Sutherland‐crossdock‐set. Remarkably, FIPSDock is superior to PSO@AutoDock, SODOCK, and AutoDock in seven out of eight cross‐docking experiments. The results reveal that FIPS algorithm might be more suitable than the conventional genetic algorithm‐based algorithms in dealing with highly flexible docking problems. © 2012 Wiley Periodicals, Inc.     

Adsorption Mechanism of Comb Polymer Dispersants at the Cement/Water Interface

Comb polymers are commonly used as dispersants to stabilize highly concentrated cement suspensions. The effectiveness of such polymeric additives to stabilize these suspensions is determined to a large extent by the amount adsorbed. In this study we investigated the adsorption characteristics of various comb dispersant containing different graft densities on surfaces of cement particle. The effect of inorganic salts on their adsorption was also examined in order to elucidate their adsorption mechanism. The results show that the adsorption of comb polymer dispersants on cement surface conforms approximately to Langmuir's adsorption isotherm and the characteristic plateau A _s and adsorption free energy ΔG_ads are largely dependent on the anionic group content of the comb polymers. The A _s and ΔG_ads increase with increasing anionic group content. This information suggests that the adsorption of comb polymers on cement surfaces is dominated by electrostatic interaction between COO-groups on the comb polymers and the positive surface of the cement. This conclusion is supported by effects of inorganics such as calcium and sulfate ions, and diffuse reflectance FTIR spectroscopy. The implication of results for tuning polymers for the required performance in cement manufacture should be noted.     

Novel high birefringence bistolane liquid crystals with lateral fluorosubstituent

Twelve compounds based on lateral fluorinated bistolane moieties with cyano or trifluoromethyl terminal groups were synthesised with Hagihara–Sonogashira cross-coupling reaction. The molecular structures of the compounds were confirmed by Fourier transform infrared, ¹H-nuclear magnetic resonance and mass spectrometry. The transition temperatures, optical textures and optical anisotropies were determined by differential scanning calorimetry, polarizing optical microscopy and ultraviolet microscopy. The effects of the terminal substituents and lateral fluorosubstituent group on their physical properties were investigated and discussed. The compounds with lateral double fluorosubstituent and cyano terminal group exhibited nematogenic texture, while other compounds showed smectic phase. All the compounds exhibited wide liquid crystal temperature ranges and high clearing points. Interestingly, the compounds have the high birefringence in the range of between 0.480 and 0.633.     

纳米层状双金属氢氧化物改性PU/PMMA的制备及其弛豫行为

采用原位聚合法,制备了聚氨酯(PU)/聚甲基丙烯酸甲酯(PMMA)/层状双金属氢氧化物(LDH)纳米复合体系(PU/PMMA/LDH).通过广角X射线衍射(WXRD)、透射电子显微镜(TEM)对其结构和形貌进行了表征,并通过热失重(TGA)、动态力学分析(DMA)和宽频介电谱(BDRS)研究了LDH含量(φ)对PU/PMMA体系热稳定性和弛豫行为的影响.结果表明,当φ<1 wt%时,LDH在聚合物基体中以剥离结构为主,PU/PMMA/LDH体系的玻璃化温度(Tg)降低,最大损耗因子(tanδmax)增大;而当φ>1 wt%时,LDH在聚合物基体中以插层结构为主,插层结构对聚合物分子链的限制使复合体系的Tg升高、tanδmax降低.LDH表面与PU硬段间的氢键作用,使复合体系的α介电弛豫转变随φ增加而向高温方向移动,弛豫过程激活参数增大.     

Practical and Highly Selective C?H Functionalization of Structurally Diverse Ethers

A trityl ion mediated C H functionalization of ethers with a wide range of nucleophiles at ambient temperature has been developed. The reaction displays high chemoselectivity and good functional group tolerance. The protocol also exhibits excellent regio‐ and diastereoselectivities for the unsymmetric ethers, thus stereoselectively generating highly functionalized disubstituted 2,5‐trans tetrahydrofurans (THF), 2,6‐trans tetrahydropyrans (THP), 2,6‐trans dihydropyrans (DHP), and 1,3‐trans isochromans, and highlighting the capacity of the protocol in complex molecule synthesis.     

Glucose detection at attomole levels using dynamic light scattering and gold nanoparticles

Glucose is directly related to brain activity and to diabetes.Therefore,developing a rapid and sensitive method for glucose detection is essential.Here,label-free glucose detection at attomole levels was realized by detecting the average diameter change of gold nanoparticles(AuNPs)utilizing dynamic light scattering(DLS).Single-strand DNA(ssDNA)adsorbed into the AuNPs’surfaces and prevented them from aggregating in solution that contained NaCl.However,ssDNA cleaved onto ssDNA fragments upon addition of glucose,and these fragments could not adsorb onto the AuNPs’surfaces.Therefore,in high-salt solution,AuNPs would aggregate and their average diameter would increase.Based on monitoring the average diameter of AuNPs with DLS,glucose could be detected in the range from 15 pmol/L to 2.0 nmol/L,with a detection limit of 8.3 pmol/L.Satisfactory results were also obtained when the proposed method was applied in human serum glucose detection.     

Pure Ion Chromatograms Combined with Advanced Machine Learning Methods Improve Accuracy of Discriminant Models in LC–MS-Based Untargeted Metabolomics

Untargeted metabolomics based on liquid chromatography coupled with mass spectrometry (LC–MS) can detect thousands of features in samples and produce highly complex datasets. The accurate extraction of meaningful features and the building of discriminant models are two crucial steps in the data analysis pipeline of untargeted metabolomics. In this study, pure ion chromatograms were extracted from a liquor dataset and left-sided colon cancer (LCC) dataset by K-means-clustering-based Pure Ion Chromatogram extraction method version 2.0 (KPIC2). Then, the nonlinear low-dimensional embedding by uniform manifold approximation and projection (UMAP) showed the separation of samples from different groups in reduced dimensions. The discriminant models were established by extreme gradient boosting (XGBoost) based on the features extracted by KPIC2. Results showed that features extracted by KPIC2 achieved 100% classification accuracy on the test sets of the liquor dataset and the LCC dataset, which demonstrated the rationality of the XGBoost model based on KPIC2 compared with the results of XCMS (92% and 96% for liquor and LCC datasets respectively). Finally, XGBoost can achieve better performance than the linear method and traditional nonlinear modeling methods on these datasets. UMAP and XGBoost are integrated into KPIC2 package to extend its performance in complex situations, which are not only able to effectively process nonlinear dataset but also can greatly improve the accuracy of data analysis in non-target metabolomics.     

Experimental Investigation on the Mass Diffusion Behaviors of Calcium Oxide and Carbon in the Solid-State Synthesis of Calcium Carbide by Microwave Heating

Microwave (MW) heating was proven to efficiently solid-synthesize calcium carbide at 1750 °C, which was about 400 °C lower than electric heating. This study focused on the investigation of the diffusion behaviors of graphite and calcium oxide during the solid-state synthesis of calcium carbide by microwave heating and compared them with these heated by the conventional method. The phase compositions and morphologies of CaO and C pellets before and after heating were carefully characterized by inductively coupled plasma spectrograph (ICP), thermo gravimetric (TG) analyses, X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The experimental results showed that in both thermal fields, Ca and C inter-diffused at a lower temperature, but at a higher temperature, the formed calcium carbide crystals would have a negative effect on Ca diffusion to carbon. The significant enhancement of MW heating on carbon diffusion, thus on the more efficient synthesis of calcium carbide, manifested that MW heating would be a promising way for calcium carbide production, and that a sufficient enough carbon material, instead of CaO, was beneficial for calcium carbide formation in MW reactors.