Enhanced stereoselectivity of a Cu(II) complex chiral auxiliary in the synthesis of Fmoc-L-γ-carboxyglutamic acid

L-γ-Carboxyglutamic acid (Gla) is an uncommon amino acid that binds avidly to mineral surfaces and metal ions. Herein, we report the synthesis of N-α-Fmoc-L-γ-carboxyglutamic acid γ,γ'-tert-butyl ester (Fmoc-Gla(O(t)Bu)(2)-OH), a suitably protected analogue for Fmoc-based solid-phase peptide synthesis. The residue was synthesized using a novel chiral Cu(II) complex, whose structure-based design was inspired by the blue copper protein rusticyanin. The five-coordinate complex is formed by Shiff base formation between glycine and the novel ligand (S)-2-(N-(2-methylthio)benzylprolyl)aminobenzophenone in the presence of copper. Michael addition of di-tert-butyl methylenemalonate to the α-carbon of the glycine portion of the complex occurs in a diastereoselective fashion. The resulting (S,S)-complex diastereomer can be easily purified by chromatography. Metal complex decomposition followed by Fmoc protection affords the enantiomerically pure amino acid. With the use of this novel chiral complex, the asymmetric synthesis of Fmoc-Gla(O(t)Bu)(2)-OH was completed in nine steps from thiosalicylic acid in 14.5% overall yield.     

Routine screening and quantitation of urinary corticosteroids using bench-top gas chromatography-mass-selective detection.

A method was developed for the routine screening, confirmation and quantitation of corticosteroids in human urine using bench top capillary gas chromatography (GC)-mass-selective detection. The free and conjugated corticosteroid fractions were isolated by liquid-liquid partition. After evaporation to dryness under vacuum the corticosteroid residues were derivatized to form the methyloxime trimethylsilyl ether derivatives. Both GC retention data and characteristic spectral data based on authentic reference standards were used for the identification and quantitation of cortisol, cortisone, tetrahydrocortisol and tetrahydrocortisone in the ppb (ng/ml) concentration range. The method is simpler and more efficient than the other GC-mass spectrometric (MS) techniques. It is also more sensitive than the liquid chromatographic-MS method.     

An investigation of pressure transients in pipelines with two-phase bubbly flow

This paper presents a two-dimensional model for the analysis of the pressure transient of a two-phase homogeneous bubbly mixture flowing in a pipeline and the numerical integration using the centre implicit method (CIM). Experiments were conducted to confirm the proposed sonic speed equation of an air–water mixture for an air concentration of less than 1%. The 2D CIM model is compared with the method of characteristics (MoC) for a two-phase bubbly flow in a pipeline. The comparisons show that the proposed 2D CIM model generally gives good agreement with the method of characteristics.     

Some remarks on E-minimal graphs

If G is a planar graph of smallest order such that the stability number of G is less than one quarter of the order of G, then G is said to be E-minimal. In this note, we give some properties of E-minimal graphs.     

A construction of chromatic index critical graphs

We prove that if K is an undirected, simple, connected graph of even order which is of class one, regular of degree p ≥ 2 and such that the subgraph induced by any three vertices is either connected or null, then any graph G obtained from K by splitting any vertex is p-critical. We find that various constructions of critical graphs by S. Fiorini are special cases of a corollary of this result.     

Protein micropatterning using surfaces modified by self-assembled polystyrene microspheres

A technique for micropatterning of proteins on a nonplanar surface to improve the coverage and functionality of biomolecules is demonstrated. A nonplanar microstructure is created by the self-assembly of polystyrene microspheres into an array of microwells on a silicon wafer to allow the integration of a nonplanar spot on a planar chip. After the microspheres were deposited into the microwells, they were conjugated with proteins. The curve surfaces of the microspheres present more surface area for attaching biomolecules which will increase the density of biomolecules and, hence, the sensitivity for detection. Moreover, proteins immobilized on a curved surface can retain their native structures and function better than on a planar surface because of a smaller area of interaction between the protein and the substrate. Patterning of biomolecules was tested with two model fluorescent proteins. The results show that precise patterning of biomolecules on a nonplanar spot can be achieved with this technique.     

Abiotic metallofoldamers as electrochemically responsive molecules

Described are the design, synthesis, and study of nonbiological molecules based on salophen and salen ligands that fold into single-stranded helices in the presence of either Ni(II) or Cu(II). X-ray diffraction studies show that the materials fold into helical structures in the solid state, and a series of NMR studies provide strong evidence that the folded structures are conserved in solution. Metal coordination is required for folding, as NMR and X-ray show that the free ligands do not adopt helical structures. Two of the racemic metallofoldamers spontaneously resolve during crystallization from CHCl3/acetonitrile, and CD spectroscopy and optical rotation show that the resolved, crystalline materials racemize quickly when dissolved at 5 degrees C. This shows that the secondary structures can reorganize easily and can, therefore, provide the basis for responsive materials. By comparison, an analogue from enantiomerically pure (R,R)-(-)-trans-cyclohexanediamine showed a strong CD signal and a large specific rotation. Electrochemical experiments show that a structural reorganization occurs upon metal-centered reduction of a Cu(II)-containing foldamer. When the reduction is carried out in the presence of coordinating ligands, it is proposed that apical binding of those ligands gives square pyramidal complexes. Semiempirical (AM1) calculations support that the helical structure would be disrupted by the reduction to Cu(I) with concomitant reorganization to a square pyramidal complex.     

Effect of oxygen fraction on local entropy generation in a hydrogen–air burner

This study considers numerical simulation of the combustion of hydrogen with air, including oxygen and nitrogen, in a burner and the numerical solution of local entropy generation rate due to the high temperature and velocity gradients in the combustion chamber. The effects of equivalence ratio (ϕ) and oxygen percentage (γ) on the combustion and entropy generation rate are investigated for different ϕs (from 0.5 to 1.0) and γs (from 10 to 30%). The combustion is simulated for the fuel mass flow rate providing the same heat transfer rate to the combustion chamber in the each case. The numerical calculation of combustion is performed individually for all cases with the help of the Fluent CFD code. Furthermore, a computer program has been developed to calculate numerically the volumetric entropy generation rate distributions and the other thermodynamic parameters by using the results of the calculations performed with the FLUENT code. The calculations bring out that the increase of ϕ (or the decrease of λ) reduces significantly the reaction rate levels. The average temperatures in the combustion chamber increase about 70 and 23% with the increases of γ (from 10 to 30%) and ϕ (from 0.5 to 1.0), respectively. With the increase of γ from 10 to 30%, the volumetric local entropy generation rates decrease about 9 and 4% in the cases of ϕ=0.5 and 1.0, respectively, and while the total entropy generation rates decrease exponentially, the merit numbers increase. The useful energy transfer rate to irreversibility rate therefore improves as the oxygen percentage increases.