Exploring the optimal site for modifications of pyranmycins with the extended arm approach

[reaction: see text] Continuing from the syntheses and the antibacterial studies of a library of pyranmycins, we further probed the proximity around ring III of pyranmycin by introducing an "extended arm" that has hydroxyethyl or aminoethyl groups at the O-2' ', O-3' ', or O-4' ' positions. The results from the antibacterial studies reveal the optimal structural motif is the attachment of an extended arm with a terminal hydroxyl group at the O-3' ' position.     

Structural Consequences of S → Se Substitution in some Symmetrical [M(S2CNR2)3] Complexes

The consequences of replacement of the symmetrically chelate ligands in [M(E₂CNR₂)₃] (E = S, Se) complexes of potential 32 symmetry by analogous mixed S,Se unsymmetrical chelates are explored for both small (M = Co) and large (M = In) metal atoms, and R = primary (Et) and secondary (ⁱPr) alkyl substituents by way of low‐temperature single crystal X‐ray studies of [(Co(SSeCNEt₂)₃] ([Co(Se₂CNEt₂)₃] also determined as datum), and [In(SSeCNR₂)₃], R = Et, ⁱPr. The structure of [(ⁱPr₂N·CS·Se)₂] is also recorded.     

Ca(2.5)Sr(0.5)GaMn2O8: diamagnetic Ga in control of the structural and electronic properties of a bilayered manganate

The temperature dependence of the crystal structure and electronic properties of brownmillerite-like Ca(2.5)Sr(0.5)GaMn(2)O(8) has been studied by neutron powder diffraction and muSR spectroscopy. The results show that short-range 2D magnetic order begins to develop within the perovskite-like bilayers of MnO(6) octahedra approximately 50 K above the 3D Néel temperature of approximately 150 K. The bilayers show a structural response to the onset of magnetism throughout this temperature range whereas the GaO(4) layers that separate the bilayers only respond below the 3D ordering temperature. XANES spectroscopy shows that the sample contains Mn(3+) and Mn(4+) cations in a 1:1 ratio, and the behavior in the region of the Néel transition is interpreted as a local charge ordering. Electron diffraction and high-resolution electron microscopy have been used to show that the local microstructure is more complex than the average structure revealed by neutron diffraction, and that microdomains exist in which the GaO(4) tetrahedra show different orientations. It is argued that the bonding requirements of diamagnetic gallium control the electronic behavior within the perovskite-like bilayers.     

Super/subcritical fluid chromatography chiral separations with macrocyclic glycopeptide stationary phases

The chiral recognition capabilities of three macrocyclic glycopeptide chiral selectors, namely teicoplanin (Chirobiotic T), its aglycone (Chirobiotic TAG) and ristocetin (Chirobiotic R), were evaluated with supercritical and subcritical fluid mobile phases. A set of 111 chiral compounds including heterocycles, analgesics (nonsteroidal antiinflamatory compounds), beta-blockers, sulfoxides, N-protected amino acids and native amino acids was separated on the three chiral stationary phases (CSPs). All separations were done with an outlet pressure regulated at 100 bar, 31 degrees C and at 4 ml/min. Various amounts of methanol ranging from 7 to 67% (v/v) were added to the carbon dioxide along with small amounts (0.1 to 0.5%, v/v) of triethylamine and/or trifluoroacetic acid. The Chirobiotic TAG CSP was the most effective closely followed by the Chirobiotic T column. Both columns were able to separate, partially or fully, 92% of the enantiomers of the compound set. The ristocetin chiral selector could partially or baseline resolve only 60% of the enantiomers tested. All separations were done in less than 15 min and 70% were done in less than 4 min. The speed of the separations is the main advantage of the use of SFC compared to normal-phase HPLC. In addition, SFC is advantageous for preparative separations with easy solute recovery and solvent disposal.     

Comments on “Cofino statistics”

Cofino et al. have put forward a method for the analysis of data from interlaboratory studies. The method uses ideas and notation from quantum chemistry, and is quite sophisticated. A critical examination shows that it has some relationship with both kernel density estimation and robust estimation methods. The quantitative results it provides are not founded on any statistical probability model, and it is not at all clear how the variance in particular is to be interpreted. There is no clear argument for adopting Cofino statistics in preference to simple problem-free methods that are at least as effective in estimating a concensus value.This report was prepared for the Statistical Subcommittee by Professor T. Fearn, with the assistance of Mr T. Robinson, and approved by the AMC on 25/11/03. The Statistical Subcommittee comprised: Dr. S.L.R. Ellison, Professor T. Fearn, Mr M. Gardner, Dr. F. Hollywood, Professor R.J. Howarth, Dr. P. Lowthian, Professor J.N. Miller, Dr. E.J. Newman, Professor B.D. Ripley, Professor M. Thompson (Chair), Dr. R. Wood, Dr. A. Williams and Mr J.J. Wilson (Secretary).     

One-pot two-step microwave-assisted reaction in constructing 4,5-disubstituted pyrazolopyrimidines

[reaction: see text] A microwave-assisted reaction was developed to facilitate the construction of 4,5-disubstituted pyrazolopyrimidines. This one-pot two-step process involves a sequential S(N)Ar displacement of the C4 chloro substituent with various anilines and amines, followed by a Suzuki coupling reaction with different boronic acids. Using microwave irradiation leads to high product conversion, low side product formation, and shorter reactions.     

Principles of droplet electrohydrodynamics for lab-on-a-chip

Electrically controlled droplet-based labs-on-a-chip operate under the principles of electro-capillarity and dielectrophoresis. The microfluidic mechanics of manipulating electrified droplets are complex and not entirely understood. In this article, we analyse these operating principles, especially electrowetting on dielectric (a form of electro-capillarity) and dielectrophoresis, under a unified framework of droplet electrohydrodynamics. We differentiate them by their electric origins and their energy transduction mechanisms. Our study shows that both electrowetting on dielectric and dielectrophoresis are effective for droplet generation and manipulation. In addition, our study demonstrates: (1) the presence of a wetting contribution to dielectrophoresis; and (2) contact angle reduction is merely an observable consequence of, not a condition for, the occurrence of electrowetting on dielectric. Simulations are used extensively in this article to illustrate device operation, to expose underlying physics, and to validate our conclusions. Simulations of electrically driven droplet generation, droplet translocation, droplet fusion, and droplet fission are presented.     

An experimental study of chromatographic dynamics in open and packed non-cylindrical conduits

A systematic investigation of the influence of the perimeter shape of open and particle packed fused silica capillaries on chromatographic properties such as resistance to flow and dispersion of solutes propelled through these channels has been conducted. Verifications of these uncommon experiments with existing theoretical treatments are presented and the insights transferred to a novel polymer chip design with integrated facilities for complex separations. A comparison of the chromatographic performance of a real life proteomics sample on this chip with a capillary column of "similar" dimensions is presented.     

Determination of Formation Regions of Titanium Phosphates; Determination of the Crystal Structure ofβ-Titanium Phosphate, Ti(PO4)(H2PO4), from Neutron Powder Data

The formation region of the various types of layered titanium hydrogen phosphate hydrates was investigated. The materials were prepared by hydrothermal methods, treating amorphous titanium phosphate with phosphoric acid (8 to 16M) in the temperature range 175 to 250°C. The materials obtained were:α-Ti(HPO₄)₂·H₂O,γ-Ti(PO₄)(H₂PO₄)·2H₂O, and its anhydrous formβ-Ti(PO₄)(H₂PO₄). The structure ofβ-Ti(PO₄)(H₂PO₄) has been determined by Rietveld powder refinement of high resolution neutron diffraction data. The structure is refined in the monoclinic space groupP2₁/n(No. 14). The unit cell parameters are:a=18.9503(4) Å,b=6.3127(1) Å,c=5.1391(1) Å,β=105.366(2)°;Z=4. The final agreement factors were:R_p=2.9% andR_wp=3.8%. The structure ofβ-Ti(PO₄)(H₂PO₄) is built from TiO₆octahedra linked together by tertiary phosphate (PO₄) and dihydrogen phosphate ((OH)₂PO₂) tetrahedra. The layers are held together by hydrogen bonds.     

Zur komplexchemie von 4-zentren-π-systemen : XII. Glyoxaldiiminkomplexe: 1H-nmr-spektren und long range-kopplungen

Glyoxaldiimines (I) RN=CHCH=NR show in the NMR a downfield shift of glyoxalic protons (H_gly) when complexed to

(II: M = Mo, W), but increasing high field shifts when going to

(III) and

complexes (IV). In the tungsten complexes II H_glyW coupling satellites are resolved (J(WH) ≈4–6 Hz); in the phosphine compounds III, IV long range PH_gly coupling is clearly visible. Mechanisms of spinspin interaction are briefly discussed in connection with the EPR results on monoanionic radicals of II–IV.