聚乙烯醇载体的研究 Ⅲ.由聚乙烯醇衍生的活性酰胺和活性酯及其作为亲合色谱载体的应用

<正> 亲合色谱法在现代生物学和医学上作为新的得力分离分析手段而方兴未艾。合色谱法是将相互在生物学上具有特异亲合力的某一化合物作为固定相接在水不溶性载体上,利用对此固定相的亲合力的差异以分离提纯另一化合物为目的的方法。常用的水不溶性载体如天然纤维素,葡聚糖凝胶,琼脂糖凝胶等或因成型不易,或因对酸,霉菌等的不     

Experiments with active and driven synthetic colloids in complex fluids

In this review, we focus on recent experimental research involving active colloidal particles of non-biological origin evolving in non-Newtonian fluids. This includes self-propelling active particles and particles driven by external fields. We present different propulsion strategies that are either enabled, or strongly modified, by the presence of a complex medium. This paves the way for novel mechanisms of active transport in biofluids or in other non-Newnotian fluids. When considering the medium, we differentiate between disordered complex fluids, such as diluted polymer solutions, and liquid crystals. While the latter are also viscoelastic fluids, the ability to control their molecular orientation results in distinct colloidal driving and steering mechanisms, and enables new types of active soft matter in the form of active quasi-particles.     

Oxygen species on NiO/Al2O3 and their reactivities

Oxygen species on fresh and treated NiO/Al₂O₃ and their activities for oxidation of ethane and ethylene were investigated using catalytic property measurements, ethane and ethylene pulse experiments and O₂–TPD–MS experiments. The results revealed that there are two kinds of active oxygen species (the more active one and the less active one) on fresh NiO/Al₂O₃ catalyst, but there is only one active oxygen species, the less active one, on treated NiO/Al₂O₃ catalyst. The more active oxygen species can convert ethane or ethylene to carbon dioxide by one step while the less active one can only convert ethane to ethylene, but cannot convert ethane and/or ethylene to carbon dioxide. The more active oxygen species can be removed from the catalyst by heating from 350 to 850 °C. The amounts of desorption oxygen on the catalysts are proportional to their selectivity to carbon dioxide.     

Smart nanocontainers as depot media for feedback active coatings

Among the grand challenges at present are ways to develop systems with low consumption of raw materials and with little load on the environment. In view of this it is of utmost importance to avoid or to delay processes causing material destruction. This is especially urgent, since many protective substances have associated health hazards, and new routes to improve the situation are a main concern of this contribution. Nanocapsules (nanocontainers) with controlled release properties of the shell can be used to fabricate a new family of active coatings, with quick response to changes of the coating environment or coating integrity. The release of active materials encapsulated into nanocapsules is triggered by various external and internal factors, thus preventing spontaneous leakage of the active component. The coating can have several active functionalities when several types of nanocapsules loaded with corresponding active agent are incorporated simultaneously into a coating matrix. We highlight recent achievements in development and application of filled responsive containers in biomedical and self-healing protective coatings.     

光学活性氰醇的合成研究进展

光学活性氰醇是合成大量医药、农药产品的重要中间体。本文介绍了通过生物或化学催化剂进行外消旋底物的拆分或前手性底物的不对称化来制备光学活性氰醇的方法,重点讨论了有较大发展前景的有机溶剂中脂肪酶催化氰醇酯的动力学拆分的方法。     

Palladium-promoted asymetric oxyamination of alkenes application to the synthesis of optically active aryloxypropanolamines

Palladium-promoted oxyamination of some alkene using optically active N-methyl-α?enylethylamine as amine nucleophile, or using optically active N,N-dimethyl-α-phenylethylamine as ligand, produces optically active aminoalcohol derivatives in an optically yield of 3–60%. Oxyamination of aryl ethers gives optically active 1-amino-3-aryloxy-propan-2-ol derivatives, which are important β-blockers.     

Mechanism of Ziegler-Natta polymerization of propylene and α-d-propylene

Rates of propylene homopolymerization and α-d-propylene-propylene copolymerization were determined by using constant-pressure polymerization conditions. It could be demonstrated that the rate of propylene homopolymerization was constant under the conditions used. However, the initial rate of copolymerization was faster and decreased with time to the rate obtained for propylene homopolymerizations. The higher initial copolymerization rate was attributed to the stabilization of potentially active centers in solution when the deuterated monomer was present. These active centers are assumed to be formed by reactions of tetravalent titanium with monomer. These active centers, which are formed in solution, are said to be destroyed by isotopically controlled reactions, i. e., abstraction of the hydrogen or the α-deuterium atom from these monomer-alkylated species in solution or at the interface. These active centers are believed to be adsorbed and/or chemisorbed onto the precipitated catalyst surface and to be responsible for a polymer of considerably lower steric order. This scheme predicts a stereoregular polymer of high molecular weight produced by polymerization on a Ti(III) surface and a largely amorphous polymer of lower molecular weight produced by adsorbed and/or chemisorbed species. This prediction was verified by fractionation of the deuterated polymers into crystalline and amorphous portions.     

The restricted active space followed by second-order perturbation theory method: theory and application to the study of CuO2 and Cu2O2 systems

A multireference second-order perturbation theory using a restricted active space self-consistent field wave function as reference (RASPT2/RASSCF) is described. This model is particularly effective for cases where a chemical system requires a balanced orbital active space that is too large to be addressed by the complete active space self-consistent field model with or without second-order perturbation theory (CASPT2 or CASSCF, respectively). Rather than permitting all possible electronic configurations of the electrons in the active space to appear in the reference wave function, certain orbitals are sequestered into two subspaces that permit a maximum number of occupations or holes, respectively, in any given configuration, thereby reducing the total number of possible configurations. Subsequent second-order perturbation theory captures additional dynamical correlation effects. Applications of the theory to the electronic structure of complexes involved in the activation of molecular oxygen by mono- and binuclear copper complexes are presented. In the mononuclear case, RASPT2 and CASPT2 provide very similar results. In the binuclear cases, however, only RASPT2 proves quantitatively useful, owing to the very large size of the necessary active space.     

2-取代芳基苯并呋喃类化合物生物活性及合成研究进展

综述了近十几年来报道的具有良好生物活性的2-芳基苯并呋喃类化合物, 以及这一类化合物结构骨架的构建与合成方法.     

Binary Mixtures in Linear Convection Arrays

We numerically investigated the dynamics of a mixture of finite-size active and passive disks in a linear array of two-dimensional convection rolls. The interplay of advection and steric interactions produces a number of interesting effects, like the stirring of a passive colloidal fluid by a small fraction of slow active particles, or the separation of the mixture active and passive colloidal fractions by increasing the motility of the active one, which eventually clusters in stagnation areas along the array walls. These mechanisms are quantitatively characterized by studying the dependence of the diffusion constants of the active and passive particles on the parameters of the active mixture fraction.     

STUDY ON THE MECHANISM OF 1-OCTENE ZIEGLER-NATTA POLYMERIZATION BASED ON THE NUMBER OF ACTIVE CENTERS

The number of active centers (C_p)-t and k_p-t profiles of Solvay type TiCl_3 - AlR_3 (R=C_2H_5, i-C_4H_9) or Stauffer AA TiCl_3-Al (C_2H_5)_3 catalyzed 1-octene polymerization were determined by using an acetyl chloride quenching method as well as kinetic data. The results show that in the studied systems k_p decreases when C_p increases, indicating the presence of two or more types of different active centers. The C_(p~(-t)) plots of the Solvay TiCl_3-AlR_3 systems show the presence of both stable active centers and unstable centers which decay in the polymerization process. The phenomena are explained based on a model of active center plurality. The increases of C_p in the induction periods are also discussed.     

Main-Chain Chirality and Optical Activity in Polymers Consisting of C?C Chains

Main-chain chirality is the optical activity resulting from the configurational or conformational arrangement in the main chain of a polymer. The chirality of the most important types of structures has been investigated on the basis of systematic considerations of symmetry. This has led to the surprising result that even in polymers derived from 1-substituted or nonsymmetric 1,1-disubstituted olefins (the technologically most important polymers) several types of chiral structures exist, which are expected to result in optical activity if a particular enantiomer is favorably formed. By carrying out an asymmetric cyclopolymerization, it has been possible to obtain certain structural types in the form of optically active copolymers or homopolymers (e.g., copolymers of styrene with methyl methacrylate, or even the homopolymer of styrene). Another new group of optically active polymers consists of the atropisomeric helical polyisocyanides, poly(trityl methacrylates), and polychlorals. Optically active polymers are already used as adsorbents for the chromatographic separation of racemic mixtures. Further applications are likely to emerge.     

Stereoselective Synthesis of Enantiomerically Pure Natural Products—Estrone as Example

Natural products have been synthesized for billions of years in animals, plants, and microorganisms. As a rule they occur enantiomerically pure. Their chiral character corroborates their use in metabolism or as biologically active agents. Natural products may be insufficient in quality or quantity. They have recently begun to become accessible, either unchanged or modified, by biological synthesis; here, too, they are obtained enantiomerically pure. In the last twenty years chemical synthesis has become a major concern of organic chemists. Their target compounds are primarily enantiomerically pure natural products or biologically active variants thereof.     

Reaction of 2, 6-dimethylthiapyrone with compounds containing active methyl or methylene groups

The reaction of 2, 6-dimethylthiapyrone with compounds containing active methyl or methylene groups is investigated. Position 4 in the thiapyrone ring is found to react. If the components with active methylene groups are malonodinitrile or cyclic diketomethylene compounds, the methylene groups in the resultant 2, 6-dimethylthiapyrane compounds are still reactive towards electrophilic reagents, a property which is utilized for synthesis of nonionic polymethylene dyes containing thiapyrane rings.     

L-selectride-mediated highly diastereoselective asymmetric reductive aldol reaction: access to an important subunit for bioactive molecules

L-selectride reduction of a chiral or achiral enone followed by reaction of the resulting enolate with optically active alpha-alkoxy aldehydes proceeded with excellent diastereoselectivity. The resulting alpha,alpha-dimethyl-beta-hydroxy ketones are inherent to a variety of biologically active natural products.     

Biologically active molecules with a "light switch"

Biologically active compounds which are light-responsive offer experimental possibilities which are otherwise very difficult to achieve. Since light can be manipulated very precisely, for example, with lasers and microscopes rapid jumps in concentration of the active form of molecules are possible with exact control of the area, time, and dosage. The development of such strategies started in the 1970s. This review summarizes new developments of the last five years and deals with "small molecules", proteins, and nucleic acids which can either be irreversibly activated with light (these compounds are referred to as "caged compounds") or reversibly switched between an active and an inactive state.     

Bioactive Applications for Electrospun Fibers

Electrospinning is a versatile technique providing highly tunable nanofibrous nonwovens. Many biomedical applications have been developed for nanofibers, among which the production of antimicrobial mats stands out. The production of scaffolds for tissue engineering, fibers for controlled drug release, or active wound dressings are active fields of research exploiting the possibilities offered by electrospun materials. The fabrication of materials for active food packaging or membranes for environmental applications is also reviewed. We attempted to give an overview of the most recent literature related with applications in which nanofibers get in contact with living cells and develop a nano-bio interface.     

Palladium-catalyzed Suzuki cross-coupling of aryl halides with aryl boronic acids in the presence of glucosamine-based phosphines

Carbohydrate-substituted phosphines are easily obtained in quite good yields by coupling of protected or non-protected d-glucosamine with the corresponding diphenylphosphino acid. These neutral ligands, in association with palladium acetate, are very active catalysts in the Suzuki cross-coupling reaction. The polyhydroxy phosphines are more active than the peracetylated phosphines. The process tolerates electron-rich as well as electron-poor substituents. Excellent turnovers, up to 97?000 are observed.     

Thermogravimetric study of alcohol adsorption on active charcoal

Interest of using the Mac Bain thermogravimetric balance in order to characterize alcohol adsorption or desorption on various active charcoal is developed. Precautions and peculiarities of proposed method are indicated. They result from very good precision and reproducibility in the thermal range of 273.15 to 313.5 K, and in the pressure range of 666.6 Nm⁻² to 26664 Nm⁻².Some results are given to illustrate the statics, and kinetics of adsorption desorption process of alcohol on various active charcoals.These results are important to develop and optimize refrigerating machines, or heat pumps, or physico-chemical storage using these systems.     

New aromatic azo compounds: syntheses and liquid-crystalline properties

The chemical syntheses of 12 new azo dyes are reported. The optically active compounds were prepared by the Mitsunobu reaction, amide formation, and esterification with optically active alcohols or acids. Several new compounds showed liquid-crystalline properties, and their phase transition behavior was investigated.