Kinetics and mechanisms of gas‐phase decarbonylation of α‐methyl‐trans‐cinamaldehyde and E‐2‐methyl‐2‐pentenal under homogeneous catalysis of hydrogen chloride

The kinetics of the gas‐phase elimination of α‐methyl‐trans‐cinamaldehyde catalyzed by HCl in the temperature range of 399.0–438.7 °C, and the pressure range of 38–165 Torr is a homogeneous, molecular, pseudo first‐order process and undergoing a parallel reaction to produce via (A) α‐methylstyrene and CO gas and via (B) β‐methylstyrene and CO gas. The decomposition of substrate E‐2‐methyl‐2‐pentenal was performed in the temperature range of 370.0–410.0 °C and the pressure range of 44–150 Torr also undergoing a molecular, pseudo first‐order reaction gives E‐2‐pentene and CO gas. These reactions were carried out in a static system seasoned reactions vessels and in the presence of toluene free radical inhibitor. The rate coefficients are given by the following Arrhenius expressions:

• Products formation from α‐methyl‐trans‐cinamaldehyde
• α‐methylstyrene :
• β‐methylstyrene :
• Products formation from E‐2‐methyl‐2‐pentenal
• E‐2‐pentene :

The kinetic and thermodynamic parameters for the thermal decomposition of α‐methyl‐trans‐cinamaldehyde suggest that via (A) proceeds through a bicyclic transition state type of mechanism to yield α‐methylstyrene and carbon monoxide, whereas via (B) through a five‐membered cyclic transition state to give β‐methylstyrene and carbon monoxide. However, the elimination of E‐2‐methyl‐2‐pentenal occurs by way of a concerted cyclic five‐membered transition state mechanism producing E‐2‐pentene and carbon monoxide. The present results support that uncatalyzed α‐β‐unsaturated aldehydes decarbonylate through a three‐membered cyclic transition state type of mechanism. Copyright © 2014 John Wiley & Sons, Ltd.     

液相色谱电化学安培检测乳粉中的脂溶性维生素A, E和D3

利用维生素A、D3、E均有电化学活性的特点,采用电化学安培检测,建立了HPLC检测奶粉中的脂溶性维生素A、D3、E的新方法.流动相为甲醇∶水=95∶5(V/V),含0.05 mol/L高氯酸钠.检测器采用玻碳电极,直流安培模式(DC),氧化电位 1.3 V.方法检测限为:VA、VD3、-αVE、-γVE、-δVE分别为0.08、2.3、0.16、0.19、0.28ng.回收率分别为:90.2%~98.2%、91.2%~103%、92.7%~99.5%、92.6%~97.4%、90.7%~98.0%.同紫外检测比较,方法具有灵敏度高、抗干扰强的特点.     

防治心脑血管疾病药物——灯盏细辛酚的研究与开发

灯盏细辛是著名的传统中药,全草用于治疗脑血管病中风及其后遗症偏瘫有良好疗效的中药材。自20世纪80年代,已开发了两种制剂（片剂和注射剂）在临床上用于治疗脑栓塞、脑血栓形成、脑血栓引起的瘫痪、冠心病、心绞痛、急性肾功能衰退以及肾变病综合症等。在临床上有很好疗效。为此,灯盏细辛已收载于2005年版《中华人民共和国药典》一部。自1992年始,我们再次对灯盏细辛的化学和活性成分进行了深入研究,发现了一系列二咖啡酰基奎宁酸酯类化合物同样为其主要活性成分,这些酚性成分为：1,5-,3,5-和4,5-二咖啡酰基奎宁酸和飞蓬酯乙等。为此,我们研发了包括灯盏乙素和上述系列酚类化合物为有效部位的、名灯盏细辛酚的注射液。已于2007年7月完成III期临床研究,正在申请新药证书。经临床研究表明,与同类药物相比是起效快、对重症病人疗效尤为显著、总有效率达98%以上的,有效成分清楚,质量可控,疗效确切的新一代制剂。     

NMR investigation of chlorophosphorylation products of N‐vinylazoles

The structure of novel phosphorus‐containing N‐vinylazoles prepared by action of phosphorus pentachloride has been studied by multinuclear ¹H, ¹³C, ¹⁵N, ³¹P and two‐dimensional (2D) NMR spectroscopy. N‐vinyl‐substituted 1,2‐diazoles and 1,2,3‐triazoles have undergone phosphorylation, exclusively, on double bond. N‐vinylazoles‐based hexa‐coordinated phosphorus compounds have been synthesized for the first time. ³¹P NMR spectroscopy provides the most convenient and unambiguous method for the investigation of E—Z‐isomeric structures of phosphorylated enamines. Copyright © 2008 John Wiley & Sons, Ltd.     

Graft copolymerization onto cellulose-based filter paper and its further development as silver nanoparticles loaded antibacterial food-packaging material

The present work describes ceric ammonium nitrate (CAN) initiated graft copolymerization of acrylamide onto cellulose-based filter paper followed by entrapment of silver nanoparticles. The copolymerization was carried out in aqueous solution, containing 2 M acrylamide monomer and 16 mM N,N’-methylene bisacrylamide (MB) crosslinker. The optimum initiation time and grafting reaction temperature were found to be 15 min and 30 °C, respectively. The silver nanoparticles were loaded into grafted filter paper by equilibration in silver nitrate solution followed by citrate reduction. The formation of silver nanoparticles has been confirmed by TEM and SAED analysis. The novel nano silver loaded filter paper has been investigated for its antimicrobial properties against E.coli. This newly developed material shows strong antibacterial property and thus offers its candidature for possible use as antibacterial food-packaging material.     

Size of random Galois lattices and number of closed frequent itemsets

Given a sample of binary random vectors with i.i.d. Bernoulli(p) components, that is equal to 1 (resp. 0) with probability p (resp. 1−p), we first establish a formula for the mean of the size of the random Galois lattice built from this sample, and a more complex one for its variance. Then, noticing that closed α-frequent itemsets are in bijection with closed α-winning coalitions, we establish similar formulas for the mean and the variance of the number of closed α-frequent itemsets. This can be interesting for the study of the complexity of some data mining problems such as association rule mining, sequential pattern mining and classification.     

Homotopic properties of confluent maps in the proper category

We establish some properties of homotopical nature for confluent maps in the proper category. We analyze in this setting the characterization of tree-like continua by J.H. Case and R.E. Chamberlin as well as the theorem by T.B. McLean on the preservation of tree-likeness under confluent maps. We give counterexamples for the corresponding proper analogues and we extend results of several authors in classical continuum theory to non-compact spaces. Finally, we describe the behavior of these maps with respect to the fundamental pro-group, generalizing results of J. Grispolakis and other authors. Two questions of interest are still open (Open Question 15 and Conjecture 24).     

One-dimensional locally connected S-spaces

We construct, assuming Jensen's principle ?, a one-dimensional locally connected hereditarily separable continuum without convergent sequences.     

Analysis of diffusive two-competing-prey and one-predator systems with Beddington-Deangelis functional response

In this paper, a diffusive two-competing-prey and one-predator system with Beddington-DeAngelis functional response is considered. The sufficient and necessary conditions for the existence of coexistence states are provided using the fixed point index theory developed. In addition, the stability and uniqueness of coexistence states are investigated. Finally, this paper discusses the sufficient conditions for extinction and permanence of the time-dependent system.