Kinetics and equilibrium of multicomponent adsorption on chiraly templated surfaces

In this contribution we propose a simple model of adsorption of a binary (racemic) mixture on a chiraly templated surface. As an example, the adsorption of a liquid mixture of enantiomers on a chiral stationary phase (CSP) is considered. In particular, we study the effect of the lateral interactions in the adsorbed phase on the kinetic and equilibrium isotherms of the enantiomers. Additionally, we investigate the influence of the composition of the surface on the performance of the CSP in the presence of the lateral interactions. To that end, the adsorption of the mixture is modeled by using Monte Carlo simulations as well as by applying an analytical approach involving rate equations coupled with the Mean Field Approximation (MFA). The predictions of the theory are found to be in good agreement with the results of the simulations.     

Racemic ofloxacin separation by supported-liquid membrane extraction with two organic phases

As the relation of chirality and activities of drugs is researched deeply, people become to re-alize the clinic importance of chirality. The different enantiomers of a drug can have vastly differ-ent pharmacological activities, pharmacokinetic processes and toxicity[1,2]. The most well-docu- mented example is that of the drug substance thalidomide. Bitter lessons and scientific research promote the interest in single-enantiomer drugs, so the potential of the chiral drug market is enormous[3]. …     

用胆甾型苯并—15—冠—5气相色谱固定相分离乳酸和乳酸乙酯光学异构体

胆甾型苯并－１５－冠－５（简称ＣＨ－Ｂ－１５－Ｃ－５）在不同温度范围内的相态不同，在同一温 度范围内因处理方式不同而物性亦相去甚远，用其作成的ＧＣ固定相兼具气固色谱（ＧＳＣ）、 普通气液色谱（ＧＬＣ）和冠醚液晶气液色谱（ＣＬ－ＧＬＣ）多种功能。用该固定相在不同条件下对 乳酸和乳酸乙酯光学异构体混合物的分高效果进行了比较研究，并探讨了手性拆分机理。     

四-α-(2，2，4-三甲基-3-戊氧基)酞菁金属配合物(M=Co，Ni，Cu，Zn)的合成与光谱性质(英)

A series of [tetra-α-(2,2,4-tirmethyl-3-pentoxy) phthalocyaninato] metal complexes(M=Co, Ni, Cu, Zn)were prepared by cyclotetramerization of 3-(2,2,4-tirmethyl-3-pentoxy)phthalonitrile with corresponding anhydrous metal salts， using 1.8-diazabicyclo[5.4.0] undec-7-ene (DBU) as the catalyst. HPLC analysis shows that one isomer predominates in the product of nickel complex, while at least two main constitutional isomers exist in the product of other metal complexes. The complexes (in the form of mixture of constitutional isomers) were characterized by elemental analyses, MS, IR and UV-Vis spectroscopy.     

Photooptical Properties of Polymethacrylates Having Cyanoazobenzene‐Containing Side Groups with Lateral Methyl Substituents and Different Spacer Length

New photochromic polymethacrylates with different spacer length having azobenzene side groups and lateral methyl substituents were synthesized. The phase behavior of polymethacrylates and their photooptical properties were studied and compared with unsubstituted analogues. It is shown that an introduction of lateral methyl substituents results in almost complete suppression of liquid crystalline (LC) phase formation and strong decrease of photoinduced dichroism values. It is found that rates of the photoinduced E‐Z isomerization and back thermal Z‐E isomerization are almost independent on spacer lengths. Due to the presence of lateral substituents, the photoinduced azobenzene Z‐form shows remarkable long lifetime, and back thermal conversion at room temperature takes more than 10 days. Specific peculiarities of the photoorientation process in polymer films under the polarized UV and visible light action were studied and their mechanism is suggested. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1337–1342     

Fused-Pentagon Isomers of C60 Fullerene Isolated as Chloro and Trifluoromethyl Derivatives

The carbon cage of buckminsterfullerene I_h-C₆₀, which obeys the Isolated-Pentagon Rule (IPR), can be transformed to non-IPR cages in the course of high-temperature chlorination of C₆₀ or C₆₀Cl₃₀ with SbCl₅. The non-IPR chloro derivatives were isolated chromatographically (HPLC) and characterized crystallographically as ¹⁸⁰⁹C₆₀Cl₁₆, ¹⁸¹⁰C₆₀Cl₂₄, and ¹⁸⁰⁵C₆₀Cl₂₄, which contain, respectively two, four, and four pairs of fused pentagons in the carbon cage. High-temperature trifluoromethylation of the chlorination products with CF₃I afforded a non-IPR CF₃ derivative, ¹⁸⁰⁷C₆₀(CF₃)₁₂, which contains four pairs of fused pentagons in the carbon cage. Addition patterns of non-IPR chloro and CF₃ derivatives were compared and discussed in terms of the formation of stabilizing local substructures on fullerene cages. A detailed scheme of the experimentally confirmed non-IPR C₆₀ isomers obtained by Stone–Wales cage transformations is presented.     

Analysis on First-stage Ignition of n-Heptane at Low Temperatures with a Lumped Skeletal Mechanism

Two-stage ignition exists in the low-temperature combustion process of n-heptane and the first-stage ignition also shows a negative temperature coefficient(NTC) phenomenon. To study key reactions and understand chemical principles affecting the first-stage ignition of n-heptane, a lumped skeletal mechanism with 62 species is obtained based on the detailed NUIGMech1.0 mechanism using the directed relation graph method assisted by sensitivity analysis and isomer lumping. The lumped mechanism shows good performance on ignition delay time under wide conditions. The study revealed that the temperature after the first-stage ignition is higher and a larger amount of fuel is consumed at lower initial temperatures. The temperature at the first-stage ignition is relatively insensitive to the initial temperature. Further sensitivity analysis and reaction path analysis carried out based on the lumped mechanism show that the decomposition of RO₂ to produce alkene and HO₂is the most important reaction to inhibit the first-stage ignitions. The chain branching explosion closely related to the first-stage ignition will be terminated when the rate constant for the RO₂ decomposition is larger than that of the isomerization of RO₂ to produce QOOH. The NTC behavior as well as other characteristics of the first-stage ignition can be rationalized from the competition between these two reactions.     

Separation of isomeric disaccharides by traveling wave ion mobility mass spectrometry using CO2 as drift gas

The use of CO₂ as a massive and polarizable drift gas is shown to greatly improve peak‐to‐peak resolution (R_p‐p), as compared with N₂, for the separation of disaccharides in a Synapt G2 traveling wave ion mobility cell. Near or baseline R_p‐p was achieved for three pairs of sodiated molecules of disaccharide isomers, that is, cellobiose and sucrose (R_p‐p = 0.76), maltose and sucrose (R_p‐p = 1.04), and maltose and lactose (R_p‐p = 0.74). Ion mobility mass spectrometry using CO₂ as the drift gas offers therefore an attractive alternative for fast and efficient separation of isomeric disaccharides. Copyright © 2012 John Wiley & Sons, Ltd.     

The First Rotational Isomers of Stable Selenobenzaldehydes and their η1-Tungsten Complexes

The first rotational isomers of stable selenoaldehydes are synthesized by deselenation of cyclic polyselenides having an efficient steric protection group, 2, 4, 6-tris[bis(trimetylsilyl)methyl]phenyl (Tbt). Reactions of these selenoaldehydes with W(CO)₅.THF gives the corresponding η¹-selenoaldehyde tungsten complexes, the structures of which are established by X-ray crystallography.     

Study of “Racemic Compound-Like” Behavior of Diastereomeric Mixture of Pinanyl Sulfoxides by X-Ray Diffraction,IR Spectroscopy,and DFT Calculations

Abstract

The oxidation of a β-hydroxysulfide in the pinane series by use of m-chloroperbenzoic acid resulted in the formation of the corresponding β-hydroxysulfoxide as a mixture of two diastereomers in 4:5 ratio. According to single-crystal X-ray diffraction (XRD) results, it is established that the diastereomeric mixture of sulfoxides crystallizes in the “racemic compound-like” manner under formation of asymmetric dimers through S=O··H–O interactions. This asymmetric dimer formed from diastereomeric molecules is a structural unit in both crystal modifications, the triclinic and the monoclinic one. The behavior of the diastereomeric mixture of pinane derived sulfoxides in crystals, melts and in tetrachloromethane solutions was studied by IR spectroscopy. The density functional theory (DFT) method with 6-31G (d, p) basis set was used to calculate the optimized geometrical parameters and vibrational frequencies of different associates in solutions. The calculated vibrational frequencies are compared with experimental IR spectra.