Isomeric characterization via ion neutralization and dissociation. Experimental variables

Major deficiencies of mass spectrometry for characterizing isomeric molecules, and of collisionally activated dissociation for characterizing isomeric ions, can be alleviated by complementary information from new techniques of neutraiization-reionization (NR) mass spectrometry. Mass data can be obtained from most fragments of the original species, irrespective of their ability to retain the charge; dissociation of fast neutrals prepared from isomeric ions can involve novel reaction pathways and can minimize competing isomerization reactions; isomeric neutrals undergoing similar dissociations can be differentiated by forming them with different internal energies; reionization of the neutral products to negative as well as positive ions can provide increased selectivity; and structural information on the resulting ions can be derived using MS/MS/MS, Dissociation by novel non-isomerization pathways can also be effected by a second addition (or subtraction) of an electron to produce an unstable ion of opposite charge. Special techniques can yield neutralized products in favorable dissociative states by collisional activation, by using neutralization targets of selected ionization energy, or through Franck-Condon factors. Optimum excitation of the neutral is important, as this should be high enough to minimize rearrangement, to maximize the differences in the dissociation pathways of isomers, and to minimize the further dissociation of the characteristic primary products of the neutral. NR experiments can, thus, also provide information on the energy surfaces for unimolecular dissociations of neutrals that are difficult to study by conventional techniques. Dissociations of the neutrals can be differentiated from those occurring after reionization by separate collisional activation of the neutrals, by changing the ionization energy of the neutralization agent, or by reionization to ions of opposite charge.     

Structure of Porous Adsorbents

Porous solids are gaining in importance as adsorbents and catalysts both for scientific investigations and for industrial applications. Adsorbents having predetermined pore structure can be prepared by specific synthesis. This pore structure can be described in detail and comprehensively by specific parameters, which can be determined by gas adsorption measurements and by other means. Information concerning the bonding state and the concentration of the functional groups on the surface is obtainable by the use of chemical and physical methods of investigation. Other functional groups can be attached to the surface by chemical reactions. It is possible in this way to prepare selective adsorbents.     

Derivation from coupled channel equations of the resonance raman scattering amplitude for a diatomic molecule

The coupled equations of molecular collision theory can be formulated in such a way as to yield the amplitude for resonance Raman scattering of light by a diatomic molecule. Two variants of the method can be adopted, characterized by different choices for the potential matrices. All molecular potentials, either analytical or numerical, are treated on the same footing. Tests of accuracy are presented for the case of harmonic potentials intersected by linear potentials, for which an exact analytical solution can be given.     

Light activated patterning of dye-labeled molecules on surfaces

This Communication describes a novel method for patterning proteins, ligands, or other organic/inorganic species onto solid substrates. The process works by linking the moiety of interest to a fluorophore that can be subsequently photobleached and bound to the interface. The technique can be performed in aqueous solution and allows several species to be addressed onto the surface simultaneously by using different frequencies of light. Because the method can be used with fluorophores excited by visible light, shorter and more damaging wavelengths can be avoided.     

Separation of different forms of transferrin by isoelectric focusing to detect effects on the liver caused by xenobiotics

Several genetic variants and also isoforms of transferrin differing in carbohydrate structure can be separated by polyacrylamide or agarose gel isoelectric focusing. Numerous blood plasma or serum samples can be analyzed in parallel in each gel. Studies of the heterogeneity of transferrin have already revealed many results of importance to different fields of human medicine. Gene typing can give important and useful information for paternity determination and in forensic medicine. The gene type C 2 seems to have increased frequency in certain malfunctions. Futhermore, functional abnormalities of liver cells can be revealed by determination of the concentrations of transferrin isoforms differing mainly in their carbohydrate parts. The isoforms can be quantified with zone immunoelectrophoresis assay. Thus valuable information can be obtained about important modulated regulations of cell and membrane functions, even when these are disturbed by disease and xenobiotics. The information may be useful e.g. in the detection of individuals suffering from toxic effects, to identify toxic agents and exposure conditions. Studies of house painters revealed that exposure to different types of paints had an effect on transferrin. Determination of the concentration of the isotransferrin with pI 5.7 in blood samples from alcoholics can be used as a marker for the detection of liver dysfunction and for the monitoring of therapy treatments. In addition, by analyzing the isotransferrins a rare genetic abnormality can be detected.     

Thermometric and conductometric observation of copper(ii)-catalyzed reactions in the catalytic-kinetic difference method : Determination of microgram amounts of copper(ii)

The course of reactions in the catalytic-kinetic difference method, previously described, can also be followed by conductometry and thermometry. The copper-catalyzed decomposition of hydrogen peroxide can be followed by thermometry, and the copper-catalyzed oxidation of thiosulfate with hydrogen peroxide by conductometry. Both reactions can be used for the determination of microgram amounts of copper(II).     

Biochemical reaction engineering for redox reactions

Redox reactions are still a challenge for biochemical engineers. A personal view for the development of this field is given. Cofactor regeneration was an obstacle for quite some time. The first technical breakthrough was achieved with the system formate/formate dehydrogenase for the regeneration of NADH2. In cases where the same enzyme could be used for chiral reduction as well as for cofactor regeneration, isopropanol as a hydrogen source proved to be beneficial. The coproduct (acetone) can be removed by pervaporation. Whole-cell reductions (often yeast reductions) can also be used. By proper biochemical reaction engineering, it is possible to apply these systems in a continuous way. By cloning a formate dehydrogenase and an oxidoreductase "designer bug" can be obtained where formate is used instead of glucose as the hydrogen source. Complex sequences of redox reactions can be established by pathway engineering with a focus on gene overexpression or with a focus on establishing non-natural pathways. The success of pathway engineering can be controlled by measuring cytosolic metabolite concentrations. The optimal exploitation of such systems calls for the integrated cooperation of classical and molecular biochemical engineering.     

Polymers Containing Lactone Groups

Polymers containing intact lactone groups are a new class of macromolecules with reactive groups, which are relatively easy to obtain by polymerization, polycondensation and polyaddition, as well as by reactions on existing macromolecules. Polymers with β-lactone Groups in particular can enter into numerous addition reactions, which can be used, for example, to obtain macromolecules containing hydroxy acid or amino acid groupings. The reactions proceed under mild conditions, and can even be carried out in aqueous media, frequently giving water-soluble polymers. The polymers can be cross-linked at low temperatures, even from the aqueous phase, by the addition of bifunctional or oligofunctional reagents. Polymers containing β-lactone groups can also be used as a basis for graft co-polymers; polyester or polyether branches can be grafted on, depending on whether monomeric lactones or monomeric epoxides are used.     

Short-time neutron activation gamma-ray spectroscopy

Short-time instrumental neutron activation analysis, with high throughput, sensitivity and accuracy without matrix interferences, can be achieved in spite of the initial high count rate from both short and long-lived nuclide activation, if the experimental conditions are optimized by the combination of techniques. Thus the initial usually high counting rate can be faced by a loss-free counting system to avoid blocking or distortion of the system. The rapid radioactive decay and the consequent low counting statistics of short lived nuclides can be compensated by source-detector distance variation during the counting period and by cyclic and cumulative activation. Matrix spectral interferences can be reduced by ion exchange before activation for selective element preseparation and by neutron spectrum optimization such as epithermal neutron activation for selective element peak enhancement.     

Short-time neutron activation gamma-ray spectroscopy

Short-time instrumental neutron activation analysis, with high throughput, sensitivity and accuracy without matrix interferences, can be achieved in spite of the initial high count rate from both short and long-lived nuclide activation, if the experimental conditions are optimized by the combination of techniques. Thus the initial usually high counting rate can be faced by a loss-free counting system to avoid blocking or distortion of the system. The rapid radioactive decay and the consequent low counting statistics of short lived nuclides can be compensated by source-detector distance variation during the counting period and by cyclic and cumulative activation. Matrix spectral interferences can be reduced by ion exchange before activation for selective element preseparation and by neutron spectrum optimization such as epithermal neutron activation for selective element peak enhancement.     

Controlling nanoparticle formation via sizable cages of supramolecular soft materials

We present a new generic strategy to fabricate nanoparticles in the "cages" within the fibrous networks of supramolecular soft materials. As the cages can be acquired by a design-and-production manner, the size of nanoparticles synthesized within the cages can be tuned accordingly. To implement this idea, both selenium and silver were chosen for the detailed investigation. It follows that the sizes of selenium and silver nanoparticles can be controlled by tuning the pore size of the fiber networks in the material. When the concentration of the gelator is high enough, monodisperse nanoparticles can be prepared. More interestingly, the morphology of the nanoparticles can be altered: silver disks can be formed when the concentrations of both the gelator and silver nitrate are sufficiently low. As the fiber network serves as a physical barrier and semisolid support for the nanoparticles, the stability in the aqueous media and the ease of application of these nanoparticles can be substantially enhanced. This robust surfactant-free approach will not only allow the controlled fabrication of nanoparticles, but also can be applied to the fabrication of composite materials for robust applications.     

Surface diffusion as a rate-enhancing mechanism in macromolecular association: The effectiveness of one- and two-dimensional surface sliding

The effective rate for a macromolecular association can be increased if the molecules can be held together loosely by nonspecific surface forces while they search for the specific reactive sites. In this way steric constraints can be relieved. In extreme cases, a specific interaction site can be surrounded by extensive surfaces either essentially linear (e.g. a DNA site) or two-dimensional (e.g. a membrane-bound receptor). If ligands can bind nonspecifically and search these surfaces in a lower-dimensional diffusion process, very substantial rate enhancements can be achieved under suitable conditions. The ranges of concentration and affinity of such nonspecific surfaces that can produce rate enhancements are derived and discussed. It is found that under the expected conditions in the living cell, such rate enhancements will be fairly modest. Nonetheless, nonspecific surface diffusion may play an important role.     

Use of astronomy filters in fluorescence microscopy

Monochrome astronomy filters are well suited for use as excitation or suppression filters in fluorescence microscopy. Because of their particular optical design, such filters can be combined with standard halogen light sources for excitation in many fluorescent probes. In this "low energy excitation," photobleaching (fading) or other irritations of native specimens are avoided. Photomicrographs can be taken from living motile fluorescent specimens also with a flash so that fluorescence images can be created free from indistinctness caused by movement. Special filter cubes or dichroic mirrors are not needed for our method. By use of suitable astronomy filters, fluorescence microscopy can be carried out with standard laboratory microscopes equipped with condensers for bright-field (BF) and dark-field (DF) illumination in transmitted light. In BF excitation, the background brightness can be modulated in tiny steps up to dark or black. Moreover, standard industry microscopes fitted with a vertical illuminator for examinations of opaque probes in DF or BF illumination based on incident light (wafer inspections, for instance) can also be used for excitation in epi-illumination when adequate astronomy filters are inserted as excitatory and suppression filters in the illuminating and imaging light path. In all variants, transmission bands can be modulated by transmission shift.     

A simple method for thermoanalysis of evolved gases

Thermoanalytical processes involving the splitting-off of ammonia, water, halogens, inorganic acids or acid anhydrides can be simply observed by using a specimen-holder in which specific reactions with the decomposition products can be induced. A special glass or quartz double crucible can be used for this purpose; the products arising in the lower part of the crucible can be oxidized selectively with reagents placed in the upper part, or can be bound or transformed into other compounds. This double crucible is also suitable for studying reactions taking place between solid and gaseous substances.     

Regio‐ and Stereoselective Modification of Chiral α‐Amino Ketones by Pd‐Catalyzed Allylic Alkylation

Chiral α‐amino ketones are excellent nucleophiles for stereoselective palladium‐catalyzed allylic alkylations. Both chiral as well as achiral allylic substrates can be applied, while the stereochemical outcome of the reaction is controlled by the chiral ketone enolate. The substituted amino ketones formed can be reduced stereoselectively, and up to five consecutive stereogenic centers can be obtained. This approach can be used for the synthesis of highly substituted piperidine derivatives.     

The accurate determination of gold and silver in ores and concentrates by wet-chemical analysis of the lead assay button

Hydroquinone or formic acid can be used as reductant for the quantitative precipitation of gold in the lead perchlorate solution obtained after the lead assay button has been parted with perchloric acid. Silver chloride can be completely precipitated by dilution and overnight standing of the parting solution, thus both gold and silver can be isolated by filtration for the final measurement. The proposed lead-wet chemical method was successfully applied to ores, concentrates, dusts, etc.     

Brillouin scattering from polymer films

Many polymers cannot be prepared as clear amorphous blocks suitable for classical light scattering studies. However, most linear polymers can be prepared as films which are somewhat transparent. With the advent of high contrast multipass interferometers, these films can now be studied by Brillouin scattering. This work demonstrates the wide range of polymeric materials that can now be studied by Brillouin spectroscopy.     

化学信息学网络化教学系统的研制

本文介绍了化学信息学的基本概念与基本内容 ,并重点介绍了我们建立的基于Internet的网络化教学系统。该系统包括课堂教学系统、作业系统以及教学需要的其他内容 ,由HTML文件构成 ,可通过浏览器 (Netscape或InternetExplorer等 )直接调用 ,用于化学信息学课程的教学工作。     

Artificial neural networks for computer-aided modelling and optimisation in micellar electrokinetic chromatography

The separation process in capillary micellar electrochromatography (MEKC) can be modelled using artificial neural networks (ANNs) and optimisation of MEKC methods can be facilitated by combining ANNs with experimental design. ANNs have shown attractive possibilities for non-linear modelling of response surfaces in MEKC and it was demonstrated that by combining ANN modelling with experimental design, the number of experiments necessary to search and find optimal separation conditions can be reduced significantly. A new general approach for computer-aided optimisation in MEKC has been proposed which, because of its general validity, can also be applied in other separation techniques.