Effect of pressure on the low-temperature reaction of ethylene with N2O4

Calorimetric monitoring of the autoclave reaction N₂O₄ + C₂H₄ at –85 to +10 °C under argon pressure 10–30 bar revealed that the exothermic chemical reaction started at temperatures above –52 °C at 10 bar, whereas an intensive exothermic reaction started at –85 °C and pressure of 30 bar. IR study showed that oligo/polynitroethylene was formed at 30 bar, while carbonyl and hydroxy compound as well as nitrate R–ONO₂ formation occurred upon processing at 10 bar.     

新型功能碳材料的高压截获

高性能功能材料在诸多领域具有广泛的应用前景,是人们一直关注的研究热点。高压可以有效地改变物质的原子间距和成键方式,是获得新型功能材料的重要途径。在碳材料的高压研究中,许多有趣的功能碳材料,如光学透明碳、高强度弹性碳和超硬非晶碳等,已经通过不同的碳前驱体合成。本文简要介绍了作者近年来在低维碳基纳米复合材料高压研究中取得的进展,基于设计的不同低维碳前驱体,高压下截获了具有超硬特性、新型压致共价聚合及发光增强的碳材料。     

坚硬顶板爆破切顶在沿空留巷中的应用研究

当煤层上方为坚硬顶板时,在工作面回采期间容易出现大面积悬顶,导致巷旁充填体出现大变形破坏,极大威胁采煤安全.为解决这一问题,以某矿1205工作面沿空留巷为工程背景,分析了爆炸围岩裂隙范围和坚硬顶板破断特征,建立了切顶卸压围岩结构力学模型,研究表明,相邻炮孔爆炸后,炮孔间裂隙互相贯穿,降低了顶板强度,同时当切顶角为15°时,巷道稳定性较好.工程实践结果表明:采用爆破切顶技术后,顶板下沉量减小了62.3%,较好地保证了围岩稳定性.     

Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.     

Changes of microflora in high pressure treated Indian white prawn (Fenneropenaeus indicus)

ABSTRACT

This study was to investigate the piezotolerance and diversity indices of microflora of Indian white prawn (Fenneropenaeus indicus) after high pressure (HP)-treatment. Indian white prawns subjected to HP-treatments and its effect was studied up to species level and compared with unpressurized samples. The bacterium was identified by using bacterial identification schemes, biochemical tests and API kits (bioMérieux, Marcyl’Etoile, France). Diversity analysis was performed using PRIMER (Plymouth Routines in Multivariate Research) software v 5.2.2. The significant elimination of microflora was found to be proportional with the pressure level. In the case of spore formers, mere destruction was noticed after HP-treatment. Arthrobacter spp., Listeria grayi and Corynebacterium spp. were the most piezotolerant bacteria in HP-treated samples. Diversity indices revealed a significant reduction of microflora of Indian white prawn. The apparent reduction of microflora with pressure level was clearly evident from the diversity indices; moreover a diminished piezotolerance of Gram negative spoilage bacteria was also observed.     

介绍一个与材料相关的研究型综合化学实验——壳聚糖的制备与表征

在中国科学技术大学夏季学期的研究型实验课程"化学科研基础训练"中开设"壳聚糖的制备与表征"综合实验,以龙虾壳为原料,通过除蛋白、脱盐、脱色、脱乙酰等一系列反应,制备得到目标产物壳聚糖。运用红外光谱、核磁共振仪、黏度法、滴定等对产品的结构及性能进行表征。     

Synthesis of nano-polycrystalline diamond from glassy carbon at pressures up to 25 GPa

ABSTRACT

Nano-polycrystalline diamond (NPD) with various grain sizes has been synthesized from glassy carbon at pressures 15–25?GPa and temperatures 1700–2300°C using multianvil apparatus. The minimum temperature for the synthesis of pure NPD, below which a small amount of compressed graphite was formed, significantly increased with pressure from ～1700°C at 15?GPa to ～1900°C at 25?GPa. The NPD having grain sizes less than ～50?nm was synthesized at temperatures below ～2000°C at 15?GPa and ～2300°C at 25?GPa, above which significant grain growth was observed. The grain size of NPD decreases with increasing pressure and decreasing temperature, and the pure NPD with grain sizes less than 10?nm is obtained in a limited temperature range around 1800–2000°C, depending on pressure. The pure NPD from glassy carbon is highly transparent and exhibits a granular nano-texture, whose grain size is tunable by selecting adequate pressure and temperature conditions.     

煤直接液化油中混合酚的分离研究

利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。     

Can a Procedure for the Growth of Single-layer Graphene on Copper be used in Different Chemical Vapor Deposition Reactors?

In the last decade, catalytic chemical vapor deposition (CVD) has been intensively explored for the growth of single-layer graphene (SLG). Despite the scattering of guidelines and procedures, variables such as the surface texture/chemistry of catalyst metal foils, carbon feedstock, and growth process parameters have been well-scrutinized. Still, questions remain on how best to standardize the growth procedure. The possible correlation of procedures between different CVD setups is an example. Here, two thermal CVD reactors were explored to grow graphene on Cu foil. The design of these setups was entirely distinct, one being a “showerhead” cold-wall type, whereas the other represented the popular “tubular” hot-wall type. Upon standardizing the Cu foil surface, it was possible to develop a procedure for cm²-scale SLG growth that differed only by the carrier gas flow rate used in the two reactors.     

Metabolomics techniques applied in the investigation of phenolic acids from the agro-industrial by-product of Carapa guianensis Aubl

Processing of Carapa guianensis seeds to obtain oil on an industrial scale generates a significant amount of by-product, approximately 66% w/w, which is called cake and is a potential source of biomolecules, including simple phenolic structures. For this reason, studies were carried out on the chemical profiles of hydrolyzed extract from this agro-industrial by-product through High Performance Thin-Layer Chromatography (HPTLC) and Gas Chromatography coupled to Mass Spectrometry (GC–MS). These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product. The sample antioxidant capacity was determined by methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH)and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS⁺) radicals direct sequestration. The hydrolyzed fraction showed a total of 63.47% in the relative abundance of the total of compounds, standing out: p-hydroxybenzoic acid (39.19%) and protocatechuic acid (3,4-dihydroxybenzoic acid) (5.62%), both from hydroxybenzoic acids and 3-(3,4-dihydroxyphenyl)lactic acid, (7.76%) hydroxycinnamic acids derivatives. In these results, the fraction rich in simple phenolic acids was obtained, attributing the prominent behavior of this matrix antioxidant activity, expressed by (IC₅₀: of 16.42 µg/mL and 6.52 µg/mL for DPPH and ABTS⁺ radicals, respectively). The research demonstrated an alternative to applicability that involves sustainability from agro-industrial. These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product, generating a process capable of converting biomass into a bioproduct, consisting of bioactive compounds, in addition to adding value to the industrial chain.