Synthesis of alkylated sugar amino acids: conformationally restricted L-Xaa-L-Ser/Thr mimics

Two synthetic strategies for the generation of delta-substituted pyranoid sugar amino acids (SAAs) are evaluated. The first employs chiral nonracemic tert-butane sulfinamides as key reagents. Regardless of the stereochemistry of the applied sulfinamide, the product formed has a stereochemistry resembling that of a d amino acid at C7. Direct Grignard reaction on formyl-tetra-O-benzyl-beta-D-C-glucopyranoside in the second strategy and subsequent Mitsunobu inversion, yields the l,l-dipeptide isosters.     

A new homobimetallic arenediyl diplatinum(II) unit as building block for macromolecular synthesis. X-ray crystal structure of [C6H2{CH2NMe2}2-1,5-{PtCl(PPh3)}2-2,4]

Treatment of the diaminobenzene [C₆H₄{CH₂NMe₂}₂-1,3] (NCN-H, 1) with one or two equivalents of cis-PtCl₂(DMSO)₂ leads to exclusive formation of the doubly cycloplatinated species [C₆H₄{CH₂NMe₂}₂-1,5-{PtCl(DMSO)}₂-2,4] (3), which upon addition of triphenylphosphine yields the bisphosphine adduct [C₆H₄{CH₂NMe₂}₂-1,5-{PtCl(PPh₃)}₂-2,4] (4). The X-ray molecular structure of 4 revealed the presence of highly distorted square planar Pt(II) centers which is caused by close proximity of the two phosphine donor ligands. Complexes of type 3 can be regarded as suitable starting materials for the directional build-up of larger macromolecular structures.     

Controlled,micro‐scale film formation of waterborne dispersions

The film formation on a micro‐scale of latex material is described. Waterborne polymer dispersions dried below their Tg are treated by laser or direct heat treatment by means of a tip (diameter 5 µ m) of a micro thermal analysis apparatus (µ ‐TA). Both methods give a linewidth, line thickness and dot‐sizes in the micron range. The layer thickness decreases during fusion of the particles because of the loss of voids during film formation. Non treated areas can be washed away selectively. Laser treatment gives a more smooth surface than direct thermal treatment with a µ‐TA tip. Copyright © 2001 John Wiley & Sons, Ltd.     

Use of a Drying Cartridge in On-Line Solid-Phase Extraction–Gas Chromatography–Mass Spectrometry

A drying cartridge was used and optimized for the in-line elimination of water from the desorption eluent in on-line solid phase extraction–gas chromatography (SPE–GC). The cartridge is essentially a small stainless-steel precolumn packed with a drying agent which can be regenerated by simultaneous heating and purging with a moisture-free gas. The drying cartridge was mounted on an additional valve instead of between the SPE–GC transfer valve and the on-column injector to enable regeneration of the cartridge during the GC run and, thus, to increase sample throughput. Three drying agents were tested, viz. sodium sulfate, silica, and molecular sieves. Although molecular sieves have the highest capacity, silica was preferred because of practical considerations. Large-volume injections were performed through the in-line drying cartridge using a mixture of 23 microcontaminants ranging widely in polarity and volatility. Four solvents were tested. With pentane and hexane, the more polar analytes were retained by the drying cartridge. Ethyl acetate and methyl acetate gave much better (and closely similar) recoveries for all analytes. Because water elimination on the silica cartridge proved to be less critical than with ethyl acetate, this solvent was finally selected. The entire SPE–drying cartridge–GC set-up was combined with mass spectrometric (MS) detection for the determination of a mixture of micropollutants in real-life water samples. With 10-ml tap water samples spiked at the 0.5 μg/l level, for the majority of the test compounds the analyte recoveries generally were 60–106%, and (full-scan) detection limits typically were 0.01–0.03 μg/l. Some very polar analytes such as, e.g. dimethoate, were (partially) sorbed onto the silica packing of the drying cartridge.     

29Si and 27Al MAS NMR assessment of the C-(A-) S–H nanomolecular structure of Ultra-High-Performance Concrete (UHPC) modified with pyrogenic oxides

Ultra-High Performance Concrete (UHPC) that contains pyrogenic oxides (Pox) and has been heat-cured with microwave energy reaches as high as 420 MPa after 1 day. The influence of microwave curing on the strength gain is much more pronounced in UHPC than in normal concrete. ²⁹Si and ²⁷Al MAS NMR nanomolecular structure investigation of Ultra-High-Performance Concrete (UHPC) modified with nanoscale pozzolans (pyrogenic oxides) reveals significant differences from other concrete types that may explain such high early strength. There is an increase in polymerization degree of C-(A) S–H (C–S–H containing Al) phase of the UHPC modified with pyrogenic oxides, followed by a trend of substitution of silicon atoms on the Q? sites of C–S–H (calcium-silicate-hydrates) through aluminum atoms. The mean chain length (MCL) and degree of connectivity (Dc) are the highest for pyrogenic oxides containing UHPC that have been cured with microwave energy. The increase of polymerization degree is more pronounced for alumina-based pyrogenic oxide containing UHPC.     

Formal Synthesis of Indolizidine and Quinolizidine Alkaloids from Vinyl Cyclic Carbonates

Cyclic carbonates have long been considered relatively inert molecules acting as protecting groups in complex multistep synthetic routes. This study shows that a concise, yet modular synthesis of indolizidine and quinolizidine alkaloids can be developed from vinyl-substituted cyclic carbonate (VCC) intermediates. Through a highly stereoselective palladium-catalyzed allylic alkylation reaction, these alkaloid motifs can be assembled in four synthetic and only two column purification steps. The combined results help to further advance functionalized cyclic carbonates as useful and reactive intermediates in natural product synthesis.     

Highly Efficient Chirality Transfer from Diamines Encapsulated within a Self‐Assembled Calixarene–Salen Host

A calix[4]arene host equipped with two bis‐[Zn(salphen)] complexes self‐assembles into a capsular complex in the presence of a chiral diamine guest with an unexpected 2:1 ratio between the host and the guest. Effective chirality transfer from the diamine to the calix–salen hybrid host is observed by circular dichroism (CD) spectroscopy, and a high stability constant K_2,1 of 1.59×10¹¹ M ^?2 for the assembled host–guest ensemble has been determined with a substantial cooperativity factor α of 6.4. Density functional calculations are used to investigate the origin of the stability of the host–guest system and the experimental CD spectrum compared with those calculated for both possible diastereoisomers showing that the M,M isomer is the one that is preferentially formed. The current system holds promise for the chirality determination of diamines, as evidenced by the investigated substrate scope and the linear relationship between the ee of the diamine and the amplitude of the observed Cotton effects.     

Organocatalytic Trapping of Elusive Carbon Dioxide Based Heterocycles by a Kinetically Controlled Cascade Process

A conceptually novel approach is described for the synthesis of six-membered cyclic carbonates derived from carbon dioxide. The approach utilizes homoallylic precursors that are converted into five-membered cyclic carbonates having a β-positioned alcohol group in one of the ring substituents. The activation of the pendent alcohol group through an N-heterocyclic base allows equilibration towards a thermodynamically disfavored six-membered carbonate analogue that can be trapped by an acylating agent. Various control experiments and computational analysis of this manifold are in line with a process that is primarily dictated by a kinetically controlled acylation step. This cascade process delivers an ample diversity of six-membered cyclic carbonates in excellent yields and chemoselectivities under mild reaction conditions.     

A Primal-Dual Decomposition Algorithm for Multistage Stochastic Convex Programming

This paper presents a new and high performance solution method for multistage stochastic convex programming. Stochastic programming is a quantitative tool developed in the field of optimization to cope with the problem of decision-making under uncertainty. Among others, stochastic programming has found many applications in finance, such as asset-liability and bond-portfolio management. However, many stochastic programming applications still remain computationally intractable because of their overwhelming dimensionality. In this paper we propose a new decomposition algorithm for multistage stochastic programming with a convex objective and stochastic recourse matrices, based on the path-following interior point method combined with the homogeneous self-dual embedding technique. Our preliminary numerical experiments show that this approach is very promising in many ways for solving generic multistage stochastic programming, including its superiority in terms of numerical efficiency, as well as the flexibility in testing and analyzing the model.Research supported by Hong Kong RGC Earmarked Grant CUHK4233/01E.