Facile and practical enantioselective synthesis of propargylic alcohols by direct addition of alkynes to aldehydes catalyzed by chiral disulfide–oxazolidine ligands

The enantioselective alkynylation reaction of aldehydes with alkynes and diethylzinc, catalyzed by chiral disulfide–oxazolidine ligands, provides a simple, practical and inexpensive method to access chiral propargylic alcohols in good yields and satisfactory ee's.     

On-line preconcentration of mercury by sorption on an anion-exchange resin loaded with 1,5-bis[(2-pyridyl)-3-sulphophenyl methylene] thiocarbonohydrazide and determination by cold-vapour inductively coupled plasma atomic emission

1,5-Bis[(2-pyridyl)-3-sulphophenyl methylene] thiocarbonohydrazide (PSTH) immobilized on an anion-exchange resin (Dowex) has been used for the on-line preconcentration of mercury from biological samples and waters prior to its determination by inductively coupled plasma atomic emission spectroscopy. The metal was eluted from the column using a solution of 2 M HNO(3) and mixed on-line with SnCl(2). The optimum experimental conditions were evaluated for the continuous preconcentration of Hg, the direct generation of mercury vapour and the final determination of this element by ICP-AES. The enrichment, together with low blank levels of the optimized procedure, allow the simple determination of this toxic element at concentrations down to a few nanograms per milliliter. The proposed method has a linear calibration range 5-1000 ng ml(-1) of mercury, with a detection limit of 4 ng ml(-1) (S/N=3) and a sampling rate of 40 h(-1), investigated with a 9 ml sample volume. The precision of the method (evaluated as the relative standard deviation obtained after analyzing ten series of ten replicates) was +/-3.6% at the 10 ng ml(-1) level of Hg(II) and +/-1.3% at the 100 ng ml(-1) level. The accuracy of the method was examined by the analysis of certified reference materials.     

Characterisation of botulinum toxins type C, D, E, and F by matrix-assisted laser desorption ionisation and electrospray mass spectrometry

In a follow-up of the earlier characterisation of botulinum toxins type A and B (BTxA and BTxB) by mass spectrometry (MS), types C, D, E, and F (BTxC, BTxD, BTxE, BTxF) were now investigated. Botulinum toxins are extremely neurotoxic bacterial toxins, likely to be used as biological warfare agent. Biologically active BTxC, BTxD, BTxE, and BTxF are comprised of a protein complex of the respective neurotoxins with non-toxic non-haemagglutinin (NTNH) and, sometimes, specific haemagglutinins (HA). These protein complexes were observed in mass spectrometric identification. The BTxC complex, from Clostridium botulinum strain 003-9, consisted of a 'type C1 and D mosaic' toxin similar to that of type C strain 6813, a non-toxic non-hemagglutinating and a 33 kDa hemagglutinating (HA-33) component similar to those of strain C-Stockholm, and an exoenzyme C3 of which the sequence was in full agreement with the known genetic sequence of strain 003-9. The BTxD complex, from C. botulinum strain CB-16, consisted of a neurotoxin with the observed sequence identical with that of type D strain BVD/-3 and of an NTNH with the observed sequence identical with that of type C strain C-Yoichi. Remarkably, the observed protein sequence of CB-16 NTNH differed by one amino acid from the known gene sequence: L859 instead of F859. The BTxE complex, from a C. botulinum isolated from herring sprats, consisted of the neurotoxin with an observed sequence identical with that from strain NCTC 11219 and an NTNH similar to that from type E strain Mashike (1 amino acid difference with observed sequence). BTxF, from C. botulinum strain Langeland (NCTC 10281), consisted of the neurotoxin and an NTNH; observed sequences from both proteins were in agreement with the gene sequence known from strain Langeland. As with BTxA and BTxB, matrix-assisted laser desorption/ionisation (MALDI) MS provided provisional identification from trypsin digest peptide maps and liquid chromatography-electrospray (tandem) mass spectrometry (LC-ES MS) afforded unequivocal identification from amino acid sequence information of digest peptides obtained in trypsin digestion.     

Crystalline calcium phenylphosphonate—thermodynamic data on n-alkylmonoamine intercalations

Lamellar crystalline calcium phenylphosphonate, as anhydrous Ca(HO₃PC₆H₅)₂ and hydrated Ca(HO₃PC₆H₅)₂·2H₂O compounds, were used as hosts for intercalation of polar n-alkylmonoamine molecules of the general formula CH₃(CH₂)_nNH₂ (n=0–4, 7) in water or 1,2-dichloroethane. An increase in the interlayer distance was observed. The exothermic enthalpic values for intercalation increased with the number of carbon atoms and with increasing concentration of the amines. The intercalation followed by a titration procedure in the solid/liquid interface with Ca(HO₃PC₆H₅)₂·2H₂O and Ca(HO₃PC₆H₅)₂ gave the enthalpy/number of carbons correlations: Δ_intH=−(1.74±0.43)–(1.30±0.13)n_c and Δ_intH=−(4.15±0.15)–(1.07±0.03)n_c, for water and 1,2-dichloroethane, respectively. A similar correlation Δ_intH=−(4.27±0.80)–(1.85±0.21)n_c was obtained in water by using the ampoule breaking procedure for Ca(HO₃PC₆H₅)₂·2H₂O. The increase in exothermic enthalpic values with the increase in n-aliphatic carbon atoms is more pronounced for the anhydrous compound and also when using the ampoule breaking procedure. The Gibbs free energies are negative. Positive entropic values favor intercalation in these systems.     

The Crystal Structure of Ba3Cu2Al2F16: a Relative of Ba4Cu2Al3F21

Ba₃Cu₂Al₂F₁₆ is monoclinic: a = 7.334(1)Å, b = 5.320(2)Å, c = 16.022(1)Å, β = 96.34(1)°, Z = 2. Its crystal structure was solved in the space group P2₁ (No. 4) from synchrotron X‐ray single crystal data using 2685 unique reflections (2639 with F_o/σ(F_o) > 4). The final R factor is 0.044. The structure consists of a succession along the c‐axis of the cell of three layers of two different kinds of sheets developing in the (a, b) plane. The first one, formulated [(AlF₅)₂]_∞^4— and hereafter named A, is built up from infinite cis‐chains of aluminium‐fluorine octahedra [AlF₆], linked by two vertices and distanced by a. The second one, formulated [Cu₂AlF₁₁]_∞^4— and named B, is bidimensional. It is constituted of distorted copper‐fluorine octahedra [CuF₆], linked by edges, which form infinite chains interconnected by three vertices of isolated [AlF₆] octahedra. The stacking sequence of the sheets is (A, B, B)_∞. The barium ions, 12‐coordinated, are inserted between the sheets. The crystal structure of Ba₃Cu₂Al₂F₁₆ is closely related to that of Ba₄Cu₂Al₃F₂₁. Only the proportion and the stacking sequence of the two kinds of sheets in the c‐direction differ, according to two different compositions and two different symmetries.     

Comparison of dynamic mechanical and dielectric thermal analysis on cure studies for composites

Dielectric measurements covering a wide frequency range provide one of the few practical methods for monitoring the cure of thermosets (epoxy, etc.) using relatively non-intrusive sensors. The measurements form the basis of a manufacturing control cycle, in the autoclave, provided the rheological state of the thermoset can be related to the dielectric constant (¹) and loss factor (tan). The present paper concerns further investigations in our laboratory of the correlation between mechanical and dielectric behaviour during cure (1).

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Zusammenfassung Dielektrische Messungen über einem weiten Frequenzbereich stellen die eine Methode dar, um unter Anwendung verhältnismässig nicht-intrusiver Fühler die Aushärtung von Duroplasten /Epoxid usw./ verfolgen zu können. Die Messungen bilden die Grundlage für einen Pertigungsüberwachungskreis des Autoklaven, da der rheologische Zustand des Duroplast mit der Dielektrizitätskonstanten // und dem dielektrischen Verlustfaktor /tan/ in Verbindung gebracht werden kann. Vorliegende Arbeit berichtet über weitere Untersuchungen unseres Laboratoriums über den Zusammenhang zwischen mechanischem und dielektrischen Verhaltens während der Aushärtung.

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120–230°. 2 3590 . . . 150°, . .

     

Separation of the enantiomers of phenprocoumon and warfarin by high-performance liquid chromatography using a chiral stationary phase. Determination of the enantiomeric ratio of phenprocoumon in human plasma and urine

The enantiomers of the chiral coumarin-type anticoagulants phenprocoumon, warfarin and p-chlorophenprocoumon were separated by high-performance liquid chromatography on a chiral stationary phase (Nucleosil-Chiral 2) and normal-phase conditions. Chromatographic peak identification was performed with authentic reference compounds of the enantiomers and on-line UV spectra comparison. This method was applied to the determination of the enantiomeric ratio of phenprocoumon in plasma and urine extracts from patients under racemic drug therapy. The limit of detection (50 and 80 ng/ml) and precision (less than 5%) of the method are adequate for pharmacokinetic and enantioselective disposition studies, respectively, of phenprocoumon. No racemization was detected during the extraction procedures.     

Determination of rate constants and reaction orders with an open-closed flow-injection configuration

A new, very useful application of open-closed configurations to kinetic studies is reported. The multipeak recordings provided by the manifold used, which features a single conventional photometric detector, were used to calculate the rate constants and reaction orders of a chemical system, namely the ligand displacement reaction between the cobalt(II)-EGTA complex and PAR.     

Silicoaluminophosphate molecular sieves: Characterization of textural and acidic properties

The silicoaluminophosphate SAPO-37 as well as ZSM-20 zeolite have a faujaside-like structure and are potentially useful as catalysts. We report in this work different procedures to decompose the organic template occluded in SAPO-37. The texture of the final products was analyzed by means of nitrogen adsorption. The acid properties of SAPO-37 and ZSM-20 were also compared by IR measurements of adsorbed pyridine and related to the acidic properties of the presently commonly used cracking catalyst zeolite Y.

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-37, ZSM-20 . , -37. . -37 ZSM-20 - . , .

     

Partially and totally asynchronous algorithms for linear complementarity problems

A unified treatment is given for partially and totally asynchronous parallel successive overrelaxation (SOR) algorithms for the linear complementarity problem. Convergence conditions are established and compared to previous results. Convergence of the partially asynchronous method for the symmetric linear complementarity problem can be guaranteed if the relaxation factor is sufficiently small. Unlike previous results, this relaxation factor interval does not depend explicitly on problem size.This material is based on research supported by the Air Force Office of Scientific Research Grant No. AFOSR-89-0410.The author wishes to thank the referee for pointing out how to improve the bound (12). The same technique can be used to reduce the factorn in Ref. 5, p. 553, to .