Enantioseparation of basic pharmaceutical compounds by capillary electrophoresis using sulfated cyclodextrins. Application to E-6006, a novel antidepressant

In this study, a chiral capillary electrophoresis method was optimized and validated for E-6006, a thienylpyrazolylethanamine derivative (pK_a 8.9). Enantioselectivity of neutral and anionic cyclodextrins (CDs) was evaluated at acid pH (3), obtaining cathodic and anodic migration, respectively. Hydroxypropyl-β-CD, carboxymethyl-β-CD and sulfobutyl ether-β-CD led to similar and partial selectivity, whereas sulfate (S)-β-CD produced baseline separation of the enantiomers. Four types of sulfated CDs were compared considering: cavity size (, β, γ) and random substitution versus unique derivative (S-β-CD, 6-heptakis-S-β-CD). Complete peak separation was obtained in all cases, but with different affinity and binding strength. Some factors that play a role in the complex formation include: position/region/degree of substitution, size of CD cavity and proportion of derivatives in mixtures. Enantioaffinity and enantioselectivity increased with the average of sulfate groups/mol. β Cavity size complexed better, although and γ cavities did not compromise separation. 6-Heptakis-S-β-CD had less affinity and separation efficiency, attributed to its lower degree and unique position of substitution. The method was optimized with S-β-CD (Aldrich, randomly substituted, 7–11 groups/mol). With this selector, the effect of pH value (3–9) was evaluated. Around pH 7 the cross-over point with change in the direction and order of migration was observed, associated with great enantioselectivity and long migration times. Fine tuning was done by adjusting the CD concentration and the buffer counterion. Definitive conditions were: uncoated silica capillary, 10 mM S-β-CD–25 mM sodium phosphate, pH 3. Validation parameters are included.     

Basic alumina supported one-pot synthesis of structurally diverse pyridine/quinolinine-fused novel diazepanium, diazocanium, imidazodilinium and tetrahydro-pyrimidiniums

Basic alumina supported solvent-free one-pot synthesis of pyridine-fused polycyclic diazepaniums was achieved under microwave irradiation. The process was successfully extended to the synthesis of pyridine-fused bicyclic imidazolidiniums and tetrahydro-pyrimidiniums and also of tri- and tetracyclic diaza-heterocycle-fused quinoliniums. The dual characteristic of basic alumina, a solid support as well as a base, was successfully employed in the current investigation. The method emerged to be an effective route in terms of product yield, reaction time, and ease of purification and most importantly for environment friendly protocols.     

Ramanujan-Slater type identities related to the moduli 18 and 24

We present several new families of Rogers-Ramanujan type identities related to the moduli 18 and 24. A few of the identities were found by either Ramanujan, Slater, or Dyson, but most are believed to be new. For one of these families, we discuss possible connections with Lie algebras. We also present two families of related false theta function identities.     

Some identities between basic hypergeometric series deriving from a new Bailey-type transformation

We prove a new Bailey-type transformation relating WP-Bailey pairs. We then use this transformation to derive a number of new 3- and 4-term transformation formulae between basic hypergeometric series.     

A Multidimensional Generalization of Shukla's 8ψ8 Summation

   Abstract. We give an r -dimensional generalization of H. S. Shukla's very-well-poised ₈ ψ ₈ summation formula. We work in the setting of multiple basic hypergeometric series very-well-poised over the root system A _r-1 or, equivalently, the unitary group U(r) . Our proof, which is already new in the one-dimensional case, utilizes an A _r-1 nonterminating very-well-poised ₆ φ ₅ summation by S. C. Milne, a partial fraction decomposition, and analytic continuation.     

On strong and total Lagrange duality for convex optimization problems

We give some necessary and sufficient conditions which completely characterize the strong and total Lagrange duality, respectively, for convex optimization problems in separated locally convex spaces. We also prove similar statements for the problems obtained by perturbing the objective functions of the primal problems by arbitrary linear functionals. In the particular case when we deal with convex optimization problems having infinitely many convex inequalities as constraints the conditions we work with turn into the so-called Farkas-Minkowski and locally Farkas-Minkowski conditions for systems of convex inequalities, recently used in the literature. Moreover, we show that our new results extend some existing ones in the literature.     

环境友好型离子液体催化环氧丙烷反应合成丙二醇醚

丙二醇醚类化合物是性能优良的精细化学品,也是环保型高级溶剂.该类化合物具有两个强溶解性功能基团—醚键和羟基,前者具有亲油性,可溶解疏水性物质,后者具有亲水性,可溶解亲水性物质,因而丙二醇醚具有很强的溶解能力,素有"万能溶剂"之称,可广泛应用于涂料、油墨、油漆、印刷、电子化学品、染料、净洗和纺织等行业.丙二醇醚类化合物目前主要由环氧丙烷和低级脂肪醇反应合成,然而,由于环氧丙烷的位阻效应,使其在酸或碱的条件下开环的位置会不同,从而得到不同的醇醚产物.由于碱催化的醇醚产物更加环境友好,因而越来越被人们所关注.工业上丙二醇醚合成多采用传统的强碱性催化剂醇钠以及氢氧化钠,腐蚀性强,产生的废液量大.本文采用环境友好的非卤素离子液体作为催化剂,研究了其催化环氧丙烷醚化合成丙二醇醚的反应特性.本文采用两步法合成了一系列环境友好的醋酸类碱性功能化离子液体,并在温和的条件下将其用于催化环氧丙烷与醇反应合成丙二醇醚.结果表明,该类离子液体可以高效催化该反应的进行.利用紫外-可见光谱测定Hammett指数来表征实验中所用离子液体的碱强度,并构建了离子液体碱性与催化活性之间的关系.结果表明,离子液体的催化性能和其碱性密切相关,随着离子液体碱性的增加,催化活性增强,其中咪唑醋酸类离子液体碱性强于季胺类,表现出优异的催化性能.离子液体的碱性明显弱于NaOH,但却呈现出更优异的催化性能.相同反应条件下,EmimOAc离子液体作为催化剂,PO的转化率分别较NaOH高出20%–30%,选择性略高于NaOH,这可能是由于二者催化机理不同造成的.传统NaOH催化机理的关键步骤是醇在碱性催化剂的作用下去质子化形成电子供体烷氧根离子,促进环氧丙烷的开环加成.而本文提出了离子液体亲电亲核双活化作用机理,即离子液体在阴阳离子之间的氢键和电荷相互作用的共同作用下,促进环氧丙烷开环和醇的去质子化,形成相应的反应中间体.通过电喷雾质谱分析手段检测到了阴阳离子通过协同作用亲电亲核催化过程中的反应中间体,证明了该假设机理的可行性.此外,还考察了催化剂浓度、醇比、反应温度以及醇的空间位阻效应对反应的影响.以EmimOAc催化合成丙二醇丁醚为例,反应的转化率随催化剂浓度的增加而增大,在催化剂添加量1%(催化剂与PO的摩尔比)时,PO转化率达到最大值为98.2%,1-丁氧基-2-丙醇的选择性为86.4%.当正丁醇与环氧丙烷的摩尔比为3时,转化率最高为88.6%,选择性高达94%.该反应为放热反应,最适反应温度约为140 oC,此时转化率高达96.5%.在环氧丙烷和不同的低碳醇合成丙二醇醚的反应中,反应物醇的碳链越短,支链越少,催化反应效率越高.     

单裂隙流-固耦合渗流的试验研究

通过对较大尺寸的单裂隙岩体试块进行不同侧面加载的渗流试验,在实验室里开展了单裂隙流 固耦合渗流研究,模拟核废料贮藏库的围岩自由面的最危险部位的渗流量 应力耦合状态。分析了裂隙岩体渗流与应力的耦合机理,获得了几种典型情况下的试验数据,并拟合出不同应力条件下单裂隙岩体渗流量与应力间数学经验公式。从而说明并非任一方向的应力增加都能使渗流量减小,而是裂隙岩体的渗流量随着双向压应力的增加而减少,随着平行于裂隙面方向的单向压应力的增加而增加。缝隙开度虽然随着法向应力的增加而逐渐减小,但最终不可能完全闭合,所以,此时流量不可能为零。同时,在试验过程中还通过闭环控制来实现被加载面的均匀受力,这为大尺寸岩体试验提供了一种很好的加载方法。     

ANALYSIS OF THE LOCALIZATION OF DAMAGE AND THE COMPLETE STRESS-STRAIN RELATION FOR MESOSCOPIC HETEROGENEOUS ROCK UNDER UNIAXIAL TENSILE LOADING

The mechanical behavior of rock under uniaxial tensile loading is different from that of rock under compressive loads. A micromechanics-based model was proposed for mesoscopic heterogeneous brittle rock undergoing irreversible changes of their microscopic structures due to microcrack growth. The complete stress-strain relation including linear elasticity, nonlinear hardening, rapid stress drop and strain softening was obtained. The influence of all microcracks with different sizes and orientations were introduced into the constitutive relation by using the probability density function describing the distribution of orientations and the probability density function describing the distribution of sizes. The influence of Weibull distribution describing the distribution of orientations and Rayleigh function describing the distribution of sizes on the constitutive relation were researched. Theoretical predictions have shown to be consistent with the experimental results.     

溶蚀岩体三维随机洞体数学模型的设计

溶蚀岩体是地质体中一种特定的岩体 ,它在水流等自然因素作用下 ,生成了许多溶蚀洞体 ,本文首先对作为其载体的三维地质体进行数学描述和显示 ,然后对如何确定椭球洞体形状和大小、复杂洞体的生成、三维随机洞体的数学模型以及确定性洞体的数学描述和计算机显示进行了详尽的阐述。本文提出的溶蚀岩体三维随机洞体的数学模型为溶蚀岩体的溶蚀率和渗透特性的研究提供了可视化手段 ,能够有力地指导溶蚀岩体三维随机洞体的计算机显示的编程实践