Synthesis of spherical and hemispherical sugar‐containing poly(ornithine) dendrimers

A novel sugar‐containing poly(ornithine) dendrimer is synthesized for possible antigen delivery and related applications. The dendrimer contains an ornithine dendron as interior scaffolding and oligosaccharides on the periphery, which provide an attachment site for a peptide antigen. Maltose or lactose is bound to both hemispherical and spherical poly(ornithine) dendrimer generation 3 (G3) by reductive amination between its reducing end and the peripheral amino group of the dendrimer using a borane‐pyridine complex in a buffer solution at 50 °C. The degree of substitution of sugar is changed by varying the molar ratio of sugar to dendrimer. When the surface of spherical poly(ornithine) dendrimer G3 is modified by binding β‐alanine to the 16 amino groups, highly substituted maltose‐ or lactose‐β‐alanine‐poly(ornithine) dendrimer G3 is obtained in high yield after 7 days of reaction. The structures of these sugar‐containing dendrimers are characterized by NMR and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analyses. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1400–1414, 2004     

Spectral distributions in nuclei: General principles and applications

The subject of spectral distribution methods where one derives and applies the locally smoothed forms of observables in nuclei is briefly reviewed. It is well understood that the local forms (with respect to energy) of the level density function, expectation values and strength densities are Gaussian, linear (or ratio of Gaussians) and a bivariate Gaussian respectively. To accomodate symmetries in the above forms, one has to deal with multivariate distributions in general; for example the angular-momentum (J) decomposition leads to a bivariate Gaussian form for the level density. These results extend to indefinitely large spaces by method of partitioning and they generate convolution forms. The origin of these remarkable spectral properties is discussed and shell model examples are given to substantiate their applicability to nuclear systems. Spectral distribution theory is a practical, usable theory because the smoothed forms are defined in terms of traces of low particle-rank operators, and the trace information propagates. Finally we discuss the application of the spectral methods for a wide range of nuclear problems; these include binding energies, orbit occupancies, electromagnetic andβ-decay sum rule quantities, analysis of operators, symmetry breaking, numerical level densities, and determination of bounds on time-reversal non-invariant part of nucleon-nucleon interaction.     

The chemical synthesis of a cyclic oligosaccharide derivative with branching

A cyclic oligosaccharide derivative was synthesized by cationic ring-opening polymerization of an anhydrodisaccharide derivative under high vacuum in dichloromethane with 20 mol% of PF₅ as initiator. Analysis of the spectral results showed that the oligomer chain is composed of only 3 glucose units connected by -1,6 linkages with a glucopyranosyl branching unit at C-4 of each sugar residue in the main chain.     

Novel simulated moving-bed adsorber for the fractionation of gas mixtures

The separation of propylene-propane mixture is an energy intensive operation commercially practiced using cryogenic distillation. The separation by pressure swing adsorption has been studied as an alternative. A fixed-bed pressure swing adsorption yields the heavy component as a pure product. The product recovery and the productivity are not high. In a moving-bed process, because of the counter-current solid-gas contact, the separation achieved is similar to that of the fractionation by distillation. Although the moving-bed operation offers the upper limit for the performance of a cyclic adsorptive process, due to mechanical complexities in the handling of solids the 'simulated' moving-bed is preferred. By moving the inlet and outlet ports of streams located along the length of the bed, a moving-bed process can be realized in a fixed bed. We describe here a 'moving-port' system which permits injection or withdrawal of the fluid along the axial direction in a fixed bed. A fixed bed embedded with the moving-port systems emulates a simulated moving-bed adsorber. The proposed adsorber can fractionate a binary gas mixture into two product streams with high purities. It is similar to the Sorbex process of UOP but does not have the eluent as an additional separating agent. A parametric study indicates that high purity products and a higher productivity by an order of magnitude can be achieved with simulated moving-beds compared to the fixed beds.     

Post-biotinylation of photocrosslinking by Staudinger-Bertozzi ligation of preinstalled alkylazide tag

Post-biotinylation of the alkyl azide derivative of trifluoromethyl phenyldiazirine (TPD) was elucidated to apply a photoaffinity biotinylation technique. A photo-modified polyvinilidene difluoride (PVDF) membrane was used as a photolabeled component and we introduced biotin by Staudinger-Bertozzi ligation. The 15 pmol amount of biotinylated reagent was still effective for the visualization of cross-linked product on the matrix. The results show the potential utility of alkyl azide carrying TPD derivatives in the application of photoaffinity biotinylation, which could be useful for the ligands with tight structural requirements.     

Cross-linking chemistry and biology: development of multifunctional photoaffinity probes

An efficient method of photoaffinity labeling has been developed based on rationally designed multifunctional photoprobes. Photoaffinity techniques have been used to elucidate the protein structure at the interface of biomolecules by the photochemical labeling of interacting sites. However, the identification of labeled sites within target proteins is often difficult. Novel biotinyl bioprobes bearing a diazirine photophore have contributed significantly to the rapid elucidation of ligand binding sites within proteins, thereby extending conventional photoaffinity methods. This article discusses the synthesis and applications of various photoprobes bearing a biotin, including strategies using cleavable linkages between photophores. The combination of photoaffinity methods with chip technology is also described as a novel entry to rapid affinity-based screening of inhibitors. This review focuses on a rapid and reliable photoaffinity method utilizing diazirine-based multifunctional photoprobes with numerous potential applications in functional proteomics of biomolecular interactions.