Analytical approach to V-shaped characteristics in antiferroelectric liquid crystal displays

Not only in ferroelectric liquid crystal displays (LCDs), but also in antiferroelectric LCDs, grey levels are possible by actively addressing the ‘continuous director rotation mode’. For ferroelectric LCDs this was shown qualitatively and quantitatively in previous articles. In this article it is shown that an exact analytical approach is also possible for antiferroelectric LCDs. In two consecutive layers the director orientations are symmetric, and at zero voltage they are in a splayed state. The conditions on alignment layer thickness and interaction coefficients are related to those of ferroelectric liquid crystal but are easier to fulfill.     

Analytical approach to V-shaped characteristics in antiferroelectric liquid crystal displays

Not only in ferroelectric liquid crystal displays (LCDs), but also in antiferroelectric LCDs, grey levels are possible by actively addressing the 'continuous director rotation mode'. For ferroelectric LCDs this was shown qualitatively and quantitatively in previous articles. In this article it is shown that an exact analytical approach is also possible for antiferroelectric LCDs. In two consecutive layers the director orientations are symmetric, and at zero voltage they are in a splayed state. The conditions on alignment layer thickness and interaction coefficients are related to those of ferroelectric liquid crystal but are easier to fulfill.     

"Flexiball" toolkit: a modular approach to self-assembling capsules.

We report the synthesis and characterization of new, self-assembling molecular capsules. The modular strategy makes use of glycoluril building blocks available in multigram amounts combined with aromatic spacer elements. The lengthy syntheses encountered with earlier generations of capsules are avoided, and several capsules of nanometer dimensions are now accessible. Single bond attachments between spacers and glycoluril modules result in monomers as dimeric capsules that are less rigid than their earlier counterparts. The host-guest properties of the homo- and heterodimeric capsules were studied using a combination of NMR and ESI-mass spectrometry. They show a less pronounced selectivity for guests of different sizes, and their increased flexibility prevents self-assembly when no rigidifying elements are present on the central spacer unit. Some of the new capsules bear inwardly directed, secondary amide N-H protons. These can be further functionalized, as shown by their methylation to give tertiary analogues. The structures hold broader implications for the placement of functional groups on concave molecular surfaces.     

Stille couplings catalytic in tin: the "Sn-O" approach.

A one-pot tandem Pd-catalyzed hydrostannylation/Stille coupling protocol for the stereoselective generation of vinyltins and their subsequent union, employing only catalytic amounts of tin, is described. By recycling the organotin halide Stille byproduct back to organotin hydride, a hydrostannylation/cross-coupling sequence can be carried out with catalytic amounts of tin. Such a process is most effective with Me(3)SnCl serving as the tin source. This protocol allows a 94% reduction of the tin requirement, while maintaining good yields (up to 90%) for a variety of Stille products. Furthermore, since one cycle requires the tin to undergo at least four transformations, each moiety of trialkyltin is experiencing a minimum of 60 reactions over the course of the hydrostannylation/Stille sequence.     

Analytical service: systematic approach to the activity optimization according to accuracy criterion of analysis results

Summary It is taken as an initial conception that the general aim of quantitative analysis is measurement by specific, mainly analytical, methods and instruments. Another important initial position is the necessity to specify the required accuracy of analytical data, taking into account the contribution of analytical error within the error of the whole test result which includes contributions from other sources (sampling, sample storage, transporting, etc.).The approaches to validation of accuracy of field analysis are considered. Taking into account all factors mentioned above, the principles and methods of demonstration of accuracy are stated.The main sources of uncertainty of the really insured accuracy are pointed out. The typical scheme of activity optimization of analytical subdivisions and those systems which use the results on the chemical composition of substances is described. The peculiarities of obtaining basic data and their usage for quality control of field analytical results are discussed.

---

Systemoptimierung durch Genauigkeitskriterien analytischer Ergebnisse

     

Structural features of humic acid of the coastal sediment in Ariake Sea tidelands: use of humic acid as an environmental indicator for river basins and coastal regions.

The structural features of humic acid (HA) at the sediment surface of the tideland at the Hayatsuegawa-river mouth at the Ariake Sea were investigated for the utilization of HA toward an environmental indicator of the features of the river basin and coastal region. 1H NMR analysis revealed a high-content hydrocarbon residue with a similar type of terrigenous HA. Direct and methylation-pyrolysis-GC analysis suggested the incorporation of long-chain carboxylate in HA in the tidelands. The incorporation of branched-chain carboxylate residues in HA is the result of the microbial decomposition of detritus; these residues could be one of the characteristic structural features of HA in this area, which is rich in biodiversity and microbial activity. Because the structural features of coastal zone HA appear to reveal the characteristics and activities of the biological environment, these findings suggest the possibility of becoming an indicator of the detailed analysis of the structural features of coastal zone HA.     

Concise approach to the "higher sugar" core of the nucleoside antibiotic hikizimycin

A highly productive synthesis of phenylthio glycoside 33 is described which constitutes a fully functional surrogate for the hikosamine core of hikizimycin 1, a complex nucleoside antibiotic endowed with promising anthelmintic properties. The chosen approach to this undecose derivative starts from mannofuranose 7 which was one-carbon homologated to alkyne 8 in one step on treatment with lithio (trimethylsilyl)diazomethane. Alkynyl iodide 12 derived from 8 was combined with the tartrate-derived aldehyde 17 by a Nozaki-Hiyama-Kishi reaction that can either be performed using overstoichiometric amounts of CrCl2 or by means of a catalytic manifold based on the turnover of a cat. CrCl2/chlorosilane/manganese redox couple. Semi-hydrogenation of the resulting alkyne 18 to (Z)-olefin 19 required the use of Pd/C as the catalyst, whereas conventional Lindlar reduction was unsatisfactory. Attempted cis-dihydroxylation of alkene 22 (formed from 19 by a Mitsunobu reaction with phthalimide) by using catalytic amounts of OsO4 and NMO as the stoichiometric oxidant essentially failed, whereas a stoichiometric osmylation afforded the stable osmate ester 26 a as a single diastereomer. Since the use of OsO4 in stoichiometric amounts deemed inappropriate for a total synthesis project, recourse was taken to catalytic "Blitz dihydroxylation" with RuO4 in the presence of FeCl2.4H2O as co-catalyst. Application of these conditions to alkene 30 bearing a free aldehyde function at the terminus of the "higher sugar" chain furnished pyranose 32 in good yield and excellent diastereoselectivity, which was converted into the targeted thioglycoside 33 on treatment with PhSSPh/Et3P. It is particularly noteworthy that the conformational constraints of the acyclic substrate 30 enforce the dihydroxylation to violate Kishi's empirical rule for transformations of this type.     

"All possible steps" approach to the accelerated use of Gillespie's algorithm

Many physical and biological processes are stochastic in nature. Computational models and simulations of such processes are a mathematical and computational challenge. The basic stochastic simulation algorithm was published by Gillespie about three decades ago [J. Phys. Chem. 81, 2340 (1977)]. Since then, intensive work has been done to make the algorithm more efficient in terms of running time. All accelerated versions of the algorithm are aimed at minimizing the running time required to produce a stochastic trajectory in state space. In these simulations, a necessary condition for reliable statistics is averaging over a large number of simulations. In this study the author presents a new accelerating approach which does not alter the stochastic algorithm, but reduces the number of required runs. By analysis of collected data the author demonstrates high precision levels with fewer simulations. Moreover, the suggested approach provides a good estimation of statistical error, which may serve as a tool for determining the number of required runs.     

A programmable "build-couple" approach to the synthesis of heterofunctionalized polyvalent molecules

A maximally divergent "build-couple" synthesis of heterofunctionalized polyvalent molecules is described. This strategic approach enables the synthesis of highly diverse polyvalent structures from a pre-programmed combinatorial set of modules.     

Analytical approach on surface active agents in the environment and challenges

Surface active agents (SAAs) are a class of compounds, which is used in variety of products such as detergents, fabric softeners, soaps, paints, adhesives, inks and anti-fogs. After the use of these products containing surfactants are disposed in water reservoirs. The separation and determination of surfactants from complex matrices become challenging for analytical chemists. The fundamentals on separation, preconcentration and analysis of surfactants employing different analytical instrumental techniques for qualitative and quantitative determination of surfactants in environmental samples are discussed. In addition, this compiled work enhanced our knowledge in learning about pathway mechanisms and the degree of their environmental loads. We also discussed the different aspects of method validation in the framework of quality control (QC) and quality assurance (QA). This review provides information on levels of SAAs in various environmental samples including soil, sediments, sewage wastewater, river wastewater and aerosols worldwide.     

Tight-binding "dihedral orbitals" approach to the degree of folding of macromolecular chains

We develop a tight-binding molecular approach to quantify the degree of folding of a macromolecular chain. This approach is based on the linear combination of "dihedral" orbitals to give molecular orbitals (LCDO-MO). The dihedral orbitals are a set of orbitals situated in each dihedral angle of the chain. The LCDO-MO approach remains basically topological, and we display its direct relation to known graph theoretical concepts. Using this approach, we define the dihedral electronic energy and the dihedral electronic partition function of a linear macromolecular chain. We show that the partition function per dihedral angle quantifies the degree of folding of the dihedral graph. We analyze the empirical relationship between these two functions by using a series of 100 proteins. We also study the relation between these two functions and the percentages of secondary structure for these proteins. Finally, we illustrate the use of the dihedral energy and the partition function in structure-property studies of proteins by analyzing the binding of steroids to DB3 antibody.     

浅谈理论与实际相结合的原则在分析化学教学中的运用

理论与实际相结合是教学工作中必须坚持的一项基本原则,在分析化学教学中,结合学生的专业特点对教学内容进行合理的规划,将教学内容与日常生活、生产实践、新闻事件及学科发展相结合,努力激发学生的学习兴趣,增强教学内容的实用性、时代感和历史感,让学生在掌握分析化学基础知识、基本理论的同时,提高分析、解决问题的能力,也为提高科学素养和创新能力打下良好的基础。     

Oriented attachment mechanism in anisotropic nanocrystals: a "polymerization" approach.

The kinetic model of stepwise polymerization is revisited, with some adaptations for its application to the kinetics of oriented attachment of nanoparticles in colloidal suspensions, which results in the formation of anisotropic particles. A comparison with experimental data reported in the literature shows good agreement with the model and supports comparisons with other systems.     

“互联网+教育”助力分析化学课程群建设

在"互联网+教育"和传统课堂教育交融时期,将微课融入传统课堂,逐步向慕课、翻转课程过渡,将专业基础课程和方向课程组建成分析化学课程群新体系,优化教学内容,传授学科思想,提升学生的专业学习兴趣和教学质量。     

An alternative to the use of delta-lactam urethanes in the "ring switch" approach to higher homologues of AMPA-type glutamate antagonists

In an alternative strategy to the use of delta-lactam urethanes for the preparation of homologues of AMPA-type glutamate antagonists, we have used 5-exomethylene derivatives of pyroglutamate esters. The homochiral pyrazole amino acid derivatives 18 and 19 have been prepared in this way. Although this synthesis yields products with a glycine residue separated from a heterocyclic ring by two carbon atoms, the substitution of the heterocyclic ring is different from that in compounds prepared from delta-lactam urethanes. The branched chain compounds 32 and 33 have also been prepared in this way but the second chiral centre is epimerised during the synthesis. An interesting reaction, giving the pyridone 27 from the imino ether 24 and tert-butyl acetoacetate, is also reported.     

Reduction of a "cation pool": a new approach to radical mediated C--C bond formation.

Carbocations, carbon radicals, and carbanions are important reactive carbon intermediates in organic chemistry, and their interconversions can be carried out by redox processes. Although, such relationships have been well recognized, experimental work has been limited to analytical studies on highly stabilized intermediates. In this study such interconversions were examined using electrochemical reduction of "cation pools". Acyliminium cations, which were generated by low-temperature electrolysis of carbamates, were reduced electrochemically in the absence of radical acceptors. The homo coupling products formed effectively, suggesting that the one-electron reduction of the acyliminium cation produced the corresponding carbon-centered radical. Next, the electrochemical reduction of the acyliminium cations in the presence of electron-deficient olefins was examined. The cross coupling products were obtained in good-to-moderate yields. A mechanism involving radical addition to the double bond followed by the reduction of the resulting radical to the carbanion was suggested. The overall transformation serves as redox-mediated formal addition of C-H to C=C. The present strategy opens new opportunities to manipulate reactive carbon species using redox processes in organic synthesis.     

分析化学中“检出限”的物理意义及测定方法探究

阐述了分析化学中各类分析方法的检出限的物理意义、测定方法及可能存在的问题,并论述了经典的检出限定义的局限性。在利用凝血酶适配体与凝血酶的特异性结合抑制Pt纳米颗粒对量子点荧光猝灭检测凝血酶和基于CuGeO_3纳米线和葡萄糖氧化酶(GOx)修饰的玻碳电极(GCE)生物传感器测定葡萄糖的分析方法中,由于测定信号与被检测物质浓度或浓度的对数成负相关关系,导致分析方法的检出限与经典的检出限测定产生一定的冲突,出现了测定精密度越高,检出限越差的异常情况。     

Analytical approach for description of ion motion in quadrupole mass spectrometer

Implementation of the analytical method of the solution of the Mathieu equation in conjunction with the algebraic presentation of Mathieu functions is discussed in this work. This approach is used for the analytical expression of fundamental properties of the quadrupole field such as ion trajectory stability and transmission. Extensive comparison with the matrix method is presented with demonstration of the fundamental advantages of the analytical method. However, contrary to the matrix method, the analytical method is limited to the cos trapping waveforms.