Convenient Synthesis of 3,5‐Biscarbamoyl‐pyridine Derivatives

An efficient and convenient method for synthesis of 3,5‐bis‐carbamoyl‐2,6‐dimethylpyridine derivatives was achieved in good to excellent yields by reaction of anilines with 3,5‐bis(3′,5′‐dimethyl‐1′‐pyrazolyl‐carbonyl)‐2,6‐dimethylpyridine, in which pyrazoles served as leaving groups. The structures of products were confirmed by spectra data and microanalysis.     

Phase transformation and negative thermal expansion in TaVO5

Two phase transformations of TaVO(5) were observed by DSC and/or dilatometry measurements in the studied temperature range. X-ray diffraction and neutron powder diffraction structure refinements indicated a phase transformation at -14 °C from a monoclinic symmetry with space group P2(1)/c to an orthorhombic symmetry with space group Pnma above this temperature. The rigid TaO(6) octahedron in orthorhombic phase becomes nonregular at -14 °C, which results in the transition from Pnma to P2(1)/c. TaVO(5) was found to be a negative thermal expansion material above room temperature. The calculated volumetric thermal expansion coefficients (TECs) are -8.92 × 10(-6) °C(-1) in the range of 20-600 °C, and -2.19 × 10(-5) °C(-1) above 600 °C, respectively. The negative thermal expansion behavior is accounted for by the tilt of the TaO(6) and VO(4) polyhedra, where the shrinkage of the VO(4) tetrahedra result in the increase of Ta-O-V angles on heating, while the angle of Ta-O1-Ta maintains at 180° in the framework.     

An efficiently halogen-free flame-retardant long-glass-fiber-reinforced polypropylene system

In order to solve the “candlewick effect” caused by glass fibers, which results in the decrease of flame retardancy of flame-retardant long-glass-fiber-reinforced polypropylene (LGFPP) systems, and the deterioration of mechanical properties caused by adding an additional amount of flame retardants compared with flame-retardant non-glass-fiber-reinforced polypropylene systems so as to keep a same flame retardancy, a novel intumescent flame retardant (IFR) system, which is composed of a charring agent (CA), ammonium polyphosphate (APP) and organically-modified montmorillonite (OMMT), was used to flame retard LGFPP. The thermal stability, combustion behavior, char formation, flame retardant mechanism and mechanical properties of the IFR-LGFPP samples were investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), UL-94 test, cone calorimeter test, scanning electronic microscopy, and mechanical property tests. When the content of IFR is 20 wt%, the LOI value of IFR-LGFPP reaches 31.3, and the vertical burning test reaches UL-94 V-0 rating, solving the “candlewick effect” caused by long glass fiber without additional amount of the IFR. All the relevant cone calorimeter parameters also show that IFR-LGFPP has much better flame-retardant behaviors than LGFPP. Furthermore, the mechanical properties of IFR-LGFPP almost remain unchanged in comparison with those of LGFPP containing no IFR. The flame retardant mechanism was also discussed.     

High throughput identification of components from traditional Chinese medicine herbs by utilizing graphene or graphene oxide as MALDI-TOF-MS matrix

In this work, graphene or graphene oxide was utilized, for the first time, to identify small molecular components from traditional Chinese medicine (TCM) herbs, by acting as matrix of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Due to the large surface area of graphene or graphene oxide, the analytes were trapped tightly to the matrix, which avoids the contamination of the ion source and vacuum system. Besides, their excellent electronic, thermal and mechanical properties make them desired matrices for MALDI-TOF-MS. Stable analysis was achieved with no background inference even at the concentration of 100 nM. Moreover, the limit of detection (LOD) could be greatly lowered by utilizing graphene or graphene oxide as a pre-enrichment adsorbent. In summary, the promoted MALDI-TOF-MS methodology was demonstrated to be simple, sensitive, fast, cost effective and, most importantly, high throughput.     

Direct Synthesis of High-Quality Water-Soluble CdTe:Zn(2+) Quantum Dots

The synthesis of water-soluble and low-cytotoxicity quantum dots (QDs) in aqueous solution has received much attention recently. A one-step and convenient method has been developed for synthesis of water-soluble glutathione (GSH)-capped and Zn(2+)-doped CdTe QDs via a refluxing route. Because of the addition of Zn ions and the epitaxial growth of a CdS layer, the prepared QDs exhibit superior properties, including strong fluorescence, minimal cytotoxicity, and enhanced biocompatibility. The optical properties of QDs are characterized by UV-vis and fluorescence (FL) spectra. The structure of QDs was verified by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectrometry (XPS), energy dispersive spectroscopy (EDS), atomic absorption spectrometry (AAS), and Fourier transform infrared spectroscopy (FTIR). Furthermore, the low cytotoxicity of the prepared QDs was proved by the microcalorimetric technique and inductively coupled plasma-atomic emission spectrometry (ICP-AES).     

Selective conversion of cellobiose and cellulose into gluconic acid in water in the presence of oxygen, catalyzed by polyoxometalate-supported gold nanoparticles

Gold nanoparticles loaded onto Keggin-type insoluble polyoxometalates (Cs(x)H(3-x)PW(12)O(40)) showed superior catalytic performances for the direct conversion of cellobiose into gluconic acid in water in the presence of O(2). The selectivity of Au/Cs(x)H(3-x)PW(12)O(40) for gluconic acid was significantly higher than those of Au catalysts loaded onto typical metal oxides (e.g., SiO(2), Al(2)O(3), and TiO(2)), carbon nanotubes, and zeolites (H-ZSM-5 and HY). The acidity of polyoxometalates and the mean-size of the Au nanoparticles were the key factors in the catalytic conversion of cellobiose into gluconic acid. The stronger acidity of polyoxometalates not only favored the conversion of cellobiose but also resulted in higher selectivity of gluconic acid by facilitating desorption and inhibiting its further degradation. On the other hand, the smaller Au nanoparticles accelerated the oxidation of glucose (an intermediate) into gluconic acid, thereby leading to increases both in the conversion of cellobiose and in the selectivity of gluconic acid. The Au/Cs(x)H(3-x)PW(12)O(40) system also catalyzed the conversion of cellulose into gluconic acid with good efficiency, but it could not be used repeatedly owing to the leaching of a H(+)-rich hydrophilic moiety over long-term hydrothermal reactions. We have demonstrated that the combination of H(3)PW(12)O(40) and Au/Cs(3.0)PW(12)O(40) afforded excellent yields of gluconic acid (about 85%, 418 K, 11 h), and the deactivation of the recovered H(3)PW(12)O(40)-Au/Cs(3.0)PW(12)O(40) catalyst was not serious during repeated use.     

固定床煤贫氧燃烧有机气体排放特性的GC-MS研究

在设计的可移动式固定床上对神木煤在煤颗粒尺寸为3～5mm、烟气在炉膛内的停留时间为1.76s、过量空气系数为0.4和燃烧温度分别为1100、1400和1600 K条件下进行了燃烧实验。采用气相色谱质谱联用仪(GC-MS)测试分析了烟气中有机气体的排放特性。结果显示,随着炉膛温度的升高,烟气中饱和脂肪烃的含量减少了42.98%,芳香烃含量增加了50.84%。这是由于存在的氧或含氧基团与部分饱和脂肪烃反应生成了二氧化碳和水,而芳香烃由于其氧化能力较差,在氧量不足时不容易发生氧化反应所致。     

Effect of Side Chains and Sulfonic Groups on the Performance of Polycarboxylate-Type Superplasticizers in Concentrated Cement Suspensions

Polycarboxylate-type superplasticizers (PCs) containing different side chains and sulfonic groups have been synthesized, and the effect of side chains and sulfonic groups on their performance in cementitious systems has been intensively investigated by measuring zeta potential, thickness of absorption layer, paste fluidity, rheological properties as well as the setting time in this paper. Results show that the PC containing both short poly(ethylene oxide) (PEO) side chains and long PEO side chains with the molar ratio of 1:1 has a better dispersibility than the PC containing only short PEO side chains or only long PEO side chains in cement suspensions. The shorter the side chain of the PC, the longer the setting time of cement paste incorporating it. An appropriate increase of sulfonic group content is beneficial for the improvement of dispersibility for the PC and leads to no obvious change for the setting time. It also suggests that there is a geometrical balance between the PEO side chains and sulfonic groups for the performance of PC. This work is not only helpful for understanding the relationship of molecular structure of PCs and their performance, but also further designing optimum molecular structure of PC to meet the requirement in different concrete system.