Roseophilin的合成研究进展

Roseophilin是一种从灰绿链霉菌中分离出来的、由一个十三元大环并一个杂环组成的具有抗肿瘤活性的新型抗生素的活性物质。Roseophilin独特的结构及活性引起了很多学者对其合成的兴趣。通过十三元大环和杂环合成Roseophilin,其中十三元大环的主要合成方法有末端双键的RCM关环、扩环、烷基化关环三种反应类型。     

Effect of the sequence of the introduction of foreign substances on the action of papain

Summary In general, aniline, aniline hydrochloride, aniline sulfate, and triethylamine act as inhibitors in the hydrolysis of casein or of a suspension of flour from grain of Cicer arietinum by means of papain. The order in which the enzyme and the substrate is added to the inhibitor often has a significant effect. As a rule, there is a greater retardation when the enzyme is added last to a complex of the substrate and the inhibitor.     

Influence of the stereochemistry of sugars on the selectivity of formation of carbohydrate-derived cyclopentadienyl and indenyl ligands

Interaction of lithium cyclopentadienide with a suitable partially protected alpha-D-allofuranose triflate, 4, epimer at C3 of glucose, gives as a major product, besides the expected glucose-cyclopentadiene, 5, a glucose-disubstituted cyclopentadiene, 6. This unprecedented behaviour, which does not occur with alpha-D-glucofuranose and other sugars, is tentatively explained by a complexation of LiCp and the oxygen atoms of the isopropylidene function of one molecule of 4 and one of 5, giving a termolecular structure as the result of a template effect. The results of other experiments, such as the use of MgCp2 in place of LiCp or the complexation of oxygen atoms by lithium triflate, which changed the selectivity of the reaction largely in favour of the monosubstitution product 5, support this hypothesis. When lithium indenide is reacted with 4, glucose-monosubstituted and glucose-disubstituted indenes, 8 and 9, respectively, are formed, and 9 is obtained with almost total diastereoselectivity. This result can also be rationalised by a stereoselective complexation of lithium, as shown by separate experiments and by molecular mechanics calculations. Methyltricarbonyl molybdenum(II) complexes have been synthesised and characterised from glucose-monosubstituted 5 and glucose-disubstituted 6 cyclopentadienes.     

Modification of the pitch of chiral nematic liquid crystals by means of photoisomerization of chiral dopants

New photoisomerizable chiral dopants have been studied. The dopants used were menthone derivatives, a chiral stilbene derivative and a nematic copolymer of a menthone derivative and a benzoyloxybenzonitrile derivative. NMR, HPLC and UV results showed that the E-Z-isomerization of all the compounds indicated proceeded rapidly upon UV exposure, without the formation of undesired by-products. Isomerization of the menthone derivatives, including the copolymer, induced a substantial decrease in the helical twisting power. The changes in helical twisting power induced by the isomerization of the chiral stilbene derivative were limited to a factor of 2. In mixtures of the photoisomerizable dopants with commercial dopants of opposite twisting senses and a nematic host mixture, the sign of the twisting sense could be reversed by illuminating the mixture with UV light. The viewing angle dependence of irradiated regions of a 90 -twisted nematic cell was rotated 90 with respect to the viewing angle dependence of the non-irradiated regions. It is expected that this approach may be useful in the preparation of dual domain TN cells with a reduced viewing angle dependence.     

Prediction of the effects of imperfect construction of a QMS filter

Modelling techniques have previously predicted the observed behaviour of perfectly manufactured QMS mass filters. These methods are extended to examination of the behaviour of imperfect QMS filters; this examination considers the behaviour of QMS filters with one rod displaced radially inward as this is a simple manufacturing defect that arises when a rod does not fit correctly into the mounting.The results demonstrate the well known, but poorly documented property, that exchanging the connections of a poorly performing QMS device sometimes improves performance. This is shown to arise because only a displacement of a y-rod produces a large effect. The results also show that displacement of a y-rod may produce a spurious additional peak known as a precursor. More detailed investigation suggests that precursors are not separate peaks but are formed because a section of the main peak is removed causing an apparent double peak.Finally results confirm that adjustment of the voltage applied to a displaced rod can be used to significantly improve the QMS behaviour. A small change by a fraction alpha in the position of a single rod may be compensated by a change of 2 x alpha in the voltage applied to that rod.     

Study of the mechanism of formation of transparent polyacrylonitrile

The kinetics of bulk polymerization of acrylonitrile, leading to a transparent polymer, was studied. The reaction was followed by a dilatometer specially designed for high degrees of conversion and for continuous supply of monomer during the reaction. The last stages of polymerization were followed by density determinations. It was found that the kinetic scheme did not show any irregularities, and that the major condition for obtaining a transparent polymer is a continuous supply of monomer to fill up the gaps formed by the contraction during the polymerization process.     

Effect of stress-jump condition on electrophoretic behavior of a spherical dispersion of soft particles

The electrophoresis of a concentrated dispersion of soft particles, where a particle comprises a rigid core and an ion-penetrable membrane layer, is modeled theoretically, taking the effect of double-layer polarization into account. In particular, the influence of a stress-jump condition of the flow field at the membrane layer-liquid interface on the electrophoretic mobility of a particle is investigated. The type of particles considered mimic biocolloids, such as cells and microorganisms, and inorganic colloids covered by an artificial polymer layer such as surfactant molecules. A unit cell model is adopted to simulate the present spherical dispersion, and the governing equations and the associated boundary conditions are solved by a pseudo-spectral method based on Chebyshev polynomials. We show that while the stress-jump condition, characterized by a stress-jump coefficient, can have a significant influence on the mobility of a particle, the associated flow field is not influenced appreciably. Also, the influence of the stress-jump condition on the mobility of a particle depends largely on the nature of the membrane layer, characterized by its friction coefficient.     

Regularities of binary condensation of vapors when one of them is undersaturated

Simple analytical expressions are derived for the stationary concentration of a binary solution in a markedly supercritical droplet growing exothermically in diffusion or free-molecular regimes in mixed vapors when one of condensing vapors is supersaturated and present in a small amount and another vapor is slightly undersaturated and present in a large amount. The condensation of sulfuric acid and water vapors on a droplet under the conditions of Earth atmosphere is considered as an example of practical importance. Under isothermic conditions, analytical expressions are obtained for the time of establishing a power law for variations in a droplet radius with time under the diffusion and free-molecular regimes of the droplet growth. The power laws are derived in an explicit form under these regimes, which describe the rapid establishment of a stationary concentration of a solution in a growing droplet.     

Total synthesis of pinnatoxins A and G and revision of the mode of action of pinnatoxin A

Pinnatoxins belong to an emerging class of potent marine toxins of the cyclic imine group. Detailed studies of their biological effects have been impeded by unavailability of the complex natural product from natural sources. This work describes the development of a robust, scalable synthetic sequence relying on a convergent strategy that delivered a sufficient amount of the toxin for detailed biological studies and its commercialization for use by other research groups and regulatory agencies. A central transformation in the synthesis is the highly diastereoselective Ireland-Claisen rearrangement of a complex α,α-disubstituted allylic ester based on a unique mode for stereoselective enolization through a chirality match between the substrate and the lithium amide base. With synthetic pinnatoxin A, a detailed study has been performed that provides conclusive evidence for its mode of action as a potent inhibitor of nicotinic acetylcholine receptors selective for the human neuronal α7 subtype. The comprehensive electrophysiological, biochemical, and computational studies support the view that the spiroimine subunit of pinnatoxins is critical for blocking nicotinic acetylcholine receptor subtypes, as evidenced by analyzing the effect of a synthetic analogue of pinnatoxin A containing an open form of the imine ring. Our studies have paved the way for the production of certified standards to be used for mass-spectrometric determination of these toxins in marine matrices and for the development of tests to detect these toxins in contaminated shellfish.     

Method of computer-aided determination of the type of normal vibrations of polyatomic molecules

Correct assignment of calculated and experimental frequencies, as well as corservation of the initial assignment in case of a random coincidence of two frequencies during the solution of an inverse spectral problem, are important problems in spectroscopy of polyatomic molecules. Vibrations are classified according to their form, which is thought to be a more reliable basis for assignment than frequency. We offer a PC program to determine the type of vibrations according to their form (obtained by solving a direct vibrational problem) in a given system of vibrational basis set functions. Optimization of systems of basis set functions for molecules with six-membered rings is discussed. L. Ya. Karpov Physicochemical Scientific Research Institute. Translated fromZhurnal Strukturnoi Khimii, Vol. 36, No. 2, pp. 298–303, March–April, 1995. Translated by L. Smolina     

Group of symmetry of the periodic system of chemical elements

The concurrence of the group of symmetry of the periodic system of elements with the group of dynamical symmetry of a hydrogenlike atom is employed in the theoretical investigation of atoms. The character of the degeneracy of the eigenvalues of a hydrogenlike atom Hamiltonian, without changing its eigenfunctions, was changed by introducing into this Hamiltonian a term which violates the symmetry in relation to transformations from the subgroup O(4) of the group SO(4, 2). In consequence, it was realized that such “reorganization” of the states of a hydrogenlike atom, which form a representation of the group SO(4, 2), effects the splitting of this representation into finite‐dimensional multiplets, first of which are in full agreement with the experimentally observable composition of electron shells of atoms, and retains the physical meaning of quantum numbers that define electron states. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 499–508, 1999     

Study of the electrochemical reduction of dioxygen in acetonitrile in the presence of weak acids

The electrochemical reduction of dioxygen has been studied in acetonitrile at glassy-carbon electrodes. The initial step is the reversible one-electron reduction to form superoxide. In the presence of hydrogen-bond donors (water, methanol, 2-propanol), the superoxide forms a complex with the donor resulting in a positive shift in the potential that can be analyzed to obtain formation constants for these complexes. Stronger acids result in protonation of the superoxide followed by reduction to produce HO2-. In the absence of hydrogen-bond donors, the reduction of superoxide occurs at very negative potentials, and this second reduction peak is very much drawn-out along the potential axis, indicating a small value of the transfer coefficient, alpha. The addition of hydrogen-bond donors, HA, brings about a positive shift in this peak, without a noticeable change in shape. The reaction occurring at the second peak is a concerted proton and electron transfer (CPET) in which the electron is transferred to superoxide and a proton is transferred from HA to the superoxide, forming HO2- and A- in a concerted process. An estimation of the standard potential for this reaction shows that the second reduction always occurs at a high driving force, which explains the small value of alpha that is observed. Consistent with a CPET, a kinetic isotope effect, HA versus DA, was detected for the three hydrogen-bond donors. The increasing positive shift of the second peak with increasing water concentration has been interpreted as being a consequence of the change in the formal potential, as water is both a reactant in the process and a participant through the hydrogen-bond stabilization of the anions.     

Total synthesis of a stereoisomer of bistramide C and assignment of configuration of the natural product

After the isolation of the bioactive polyether bistramide C from the marine ascidian Lissoclinum bistratum in 1988, NMR spectroscopic investigations over the next 12 years reduced the total number of possible stereoisomers of this compound from 1024 to 32. Based on the preparation of segments of the natural product as well as the total synthesis of a randomly selected stereoisomer of bistramide C, the stereochemical puzzle could be further simplified to eight possible stereoisomers. A convergent three-segment coupling strategy, the use of a common, D-glucose-derived intermediate for the preparation of pyran rings in two segments, a stereoselective photo-spiroketalization, and the use of azides to minimize protective group manipulations before segment couplings are highlights of the synthetic approach. The total synthesis also provided the key segments for a chiroptical analysis according to van't Hoff's principle of optical superposition, which was crucial for the assignment of a sole relative and absolute configuration of the natural product. Bistramide C represents therefore the first member of this class of structurally unusual marine polyethers whose configuration is known as a result of the combined use of synthetic and chiroptical tools.     

Non-Gaussian statistics of electrostatic fluctuations of hydration shells

This paper aims to understand the statistics of the electric field produced by water interfacing a non-polar solute of nanometer dimension. We study, by numerical simulations, the interface between SPC/E water and a Kihara solute, which is a hard-sphere core with a Lennard-Jones layer at its surface. The distribution of the interfacial electric field is monitored as a function of the magnitude of a point dipole placed close to the solute-water interface. The free energy surface as a function of the electric field projected on the dipole direction shows a cross-over with increasing dipole magnitude. While it is a single-well harmonic function at low dipole values, it becomes a double-well surface at intermediate dipole moment magnitudes, transforming into a single-well surface again, with a non-zero minimum position, at still higher dipoles. This transformation, reminiscent of a discontinuous phase transition in bulk materials, has a broad intermediate region where the interfacial waters fluctuate between the two minima. This region is characterized by intense field fluctuations, with non-Gaussian statistics and variance far exceeding expectations from the linear-response approximation. The excited state of the surface water is found to be lifted above the ground state by the energy required to break approximately two hydrogen bonds. This state is pulled down in energy by the external electric field of the solute dipole, making it readily accessible to thermal excitations. The excited state is a surface defect in the hydrogen-bond network, creating a stress in the nearby network, but otherwise relatively localized in the region closest to the solute dipole.     

Fast evaporation of spreading droplets of colloidal suspensions

When a coffee droplet dries on a countertop, a dark ring of coffee solute is left behind, a phenomenon often referred to as the coffee-ring effect. A closely related yet less-well-explored phenomenon is the formation of a layer of particles, or skin, at the surface of the droplet during drying. In this work, we explore the behavior of a mathematical model that can qualitatively describe both phenomena. We consider a thin axisymmetric droplet of a colloidal suspension on a horizontal substrate undergoing spreading and evaporation. In contrast to prior work, precursor films (rather than pinned contact lines) are present at the droplet edge, and evaporation is assumed to be limited by how quickly molecules can transfer out of the liquid phase (rather than by how quickly they can diffuse through the gas phase). The lubrication approximation is applied to simplify the mass and momentum conservation equations, and the colloidal particles are allowed to influence the droplet rheology through their effect on the viscosity. By describing the transport of the colloidal particles with the full convection-diffusion equation, we are able to capture depthwise gradients in particle concentration and thus describe skin formation, a feature neglected in prior models of droplet evaporation. The highly coupled model equations are solved for a range of problem parameters using a finite-difference scheme based on a moving overset grid. The presence of evaporation and a large particle Peclet number leads to the accumulation of particles at the liquid-air interface. Whereas capillarity creates a flow that drives particles to the droplet edge to produce a coffee ring, Marangoni flows can compete with this and promote skin formation. Increases in viscosity due to particle concentration slow down droplet dynamics and can lead to a reduction in the spreading rate.     

Position of coordination of the lithium ion determines the regioselectivity of demethylations of 3,4-dimethoxymorphinans with L-selectride

[reaction: see text] L-Selectride is an efficient agent for the 3-O-demethylation of opioids and is known to cleave the least hindered methoxyl group in a molecule. The treatment of a 3,4-dimethoxymorphinan containing a 6-ketal with L-Selectride gave selective 4-O-demethylation, rather than cleavage of the less hindered 3-methoxyl. In contrast, a 3,4-dimethoxymorphinan lacking a 6-ketal gave selective 3-O-demethylation, suggesting that the regiochemistry of L-Selectride-mediated O-demethylation can be manipulated through altering the position of coordination of the lithium ion.     

Dissipative crystallization of aqueous solutions of hydroxypropyl cellulose

Drying dissipative structures of aqueous solutions of hydroxypropyl cellulose, their viscosities of 2 wt.% solutions ranging from 2 to 2,000 mPa.s were studied on a cover glass, a watch glass, and a Petri glass dish. The thickness profile of the dried film shows the coexistence of a low round hill and a high broad ring on a cover glass. The broad ring size increased as molecular weight and/or concentration of the polymers increased on a cover glass and a watch glass. Microscopic drying crystal patterns of HPC changed as a function of the distance from the film center, which is one of the typical results of the dissipative crystallization. Rod-like microscopic drying patterns originated in the cholesteric liquid crystalline structures were observed. The rods oriented mainly parallel and in some case perpendicularly to the radial direction of the dried film except the central area, where the rods distributed at random. These orientation effects were significant for low molecular weight samples and in a watch glass.     

Synthesis of bifunctional derivatives of nitroxyl radicals of imidazoline

3-Imidazoline derivatives that contain a substituent with a functional group in the 2 position of the heteroring were obtained by the reaction of 1,2-hydroxyamino ketones with functionally substituted ketones and ammonia. The use of the reactivity of the endocyclic imino group makes it possible to accomplish the synthesis of a number of bifunctional derivatives of nitroxyl radicals of imidazoline and imidazolidine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 772–778, June, 1990.     

Electric birefringence of dispersions of platelets

This paper describes the electro-optic response of a suspension of disk-like colloids. We have considered aqueous suspensions of Gibbsite platelets and measured the electrically induced birefringence in the broad frequency range 10(2)-10(8) Hz. When simply dispersed in an electrolyte solution, these particles orient with their major axis parallel to the electric field at all frequencies. The spectral dependence of their Kerr coefficient features three regimes: an electrokinetic α-relaxation within the kHz range, a conductive Maxwell-Wagner-O'Konski (MWO) relaxation having characteristic frequency in the 1-10 MHz range, and a nonzero high frequency asymptote. We quantitatively analyze the MWO spectral component and the high-frequency asymptote on the basis of a model developed for oblate particles. This analysis enables us to obtain the relevant particle properties: surface conductivity, zeta potential, and intrinsic Gibbsite birefringence. When the particles are dispersed in a mixture that also contains smaller spherical particles that have a charge of the same sign, their electric birefringence becomes negative at low frequency. This anomalous orientation of the platelets is analogous to that observed in mixtures of prolate and spherical particles, and demonstrates the anomalous birefringence as a universal property of suspensions of nonspherical particles when surrounded by smaller charged particles.