Energy controlled insertion of polar molecules in dense fluids

We present a method to search low energy configurations of polar molecules in the complex potential energy surfaces associated with dense fluids. The search is done in the configurational space of the translational and rotational degrees of freedom of the molecule, combining steepest-descent and Newton-Raphson steps which embed information on the average sizes of the potential energy wells obtained from prior inspection of the liquid structure. We perform a molecular dynamics simulation of a liquid water shell which demonstrates that the method enables fast and energy-controlled water molecule insertion in aqueous environments. The algorithm finds low energy configurations of incoming water molecules around three orders of magnitude faster than direct random insertion. This method represents an important step towards dynamic simulations of open systems and it may also prove useful for energy-biased ensemble average calculations of the chemical potential.     

A novel synthesis of enantiopure octahydropyrrolo[3,4-b]pyrroles by intramolecular [3 + 2] dipolar cycloaddition on chiral perhydro-1,3-benzoxazines

[reaction: see text] Condensation of N-substituted glycines with chiral 3-allyl-2-formyl perhydro-1,3-benzoxazines forms an azomethine ylide that cyclizes to give octahydropyrrolo[3,4-b]pyrrole derivatives. The [3 + 2] dipolar cycloadditions are stereoespecific leading to a single diastereoisomer. The chemical yields are dependent on the reaction temperature and the presence or absence of a base.     

Phospholipid mesophases at solid interfaces: in-situ X-ray diffraction and spin-label studies

In this work, we report on recent investigations, both on the global and on the local molecular architecture of supported phospholipid model membranes. A brief theoretical introduction explains how global structural information on supramolecular lipid ensembles can be retrieved from surface X-ray diffraction measurements as well as how spin-label electron paramagnetic resonance spectroscopy (EPR) provides complementary information on the local environment of probe molecules. The combination of especially designed X-ray cells with the technique of small- and wide-angle X-ray surface scattering makes it possible to explore various fields of lipid research and its applications. Examples for different physico-chemical conditions are presented: (i) in situ chemistry under excess of water conditions demonstrating how solid-supported lipid films sense salinity, (ii) the 3D electron density reconstruction of a vesicle-fusion intermediate under controlled humidity, and (iii) complementary temperature and pressure effects on oriented phospholipid samples. Further, special attention has been given to the influence of different film preparation techniques with respect to quality and the defect structure manifestation. To resolve the proportions and local properties of defects in a hydrated lipid-deposited surface, spin-label EPR was applied. The results from 9.6 GHz EPR as well as from 1.2 GHz EPR suggest the alignment to be in the range between 30% and 80%. In addition, slow time-dependent EPR measurements point to nano-structural rearrangements due to water flow and reduction of alignment quality.     

One-step axial acetoxylation at C-23. A new method for the functionalization of the side chain of steroid sapogenins

Treatment of steroid sapogenins with diacetoxyiodobenzene (DIB) and boron trifluoride ethyl etherate in acetic acid led to the introduction of an axial acetoxyl group at position C-23 of the side chain.     

The reaction of β-aminoenones with substituted acetonitriles. Regiospecific synthesis of 2(1H)-pyridones

Unsymmetrically substituted β-aminoenones react with malononitrile, cyanomethylphenylsulfone, benzoyl-acetonitrile and ethyl cyanoacetate, in very mild conditions, to yield regiospecifically 3-functionalized 2(1H)-pyridones in high yields.     

Potentiometric, luminescence and NMR study of the interaction of Eu with glyceryl phosphates

Complexation of europium(III) with glyceryl-1- and -2-phosphates has been studied by metal ion luminescence, ¹H and ¹³C NMR spectroscopy and potentiometry. From the luminescence and NMR studies, the formation of a 1:1 inner-sphere complex, in which the glyceryl phosphate is directly bound to the metal, is confirmed. Similar apparent binding constants at pH 2 were obtained by the three methods. Values obtained by NMR at pH 2 are 53 M⁻¹ and 12 M⁻¹ for glyceryl-1- and -2-phosphate, respectively. By comparison with literature data on related systems it is suggested that the ligands bind through the phosphate group. To obtain structural information from the NMR data, complexation has also been studied with the lanthanide ions Dy(III), Er(III) and Gd(III) using both chemical shift and relaxation data. From this, metal-proton distance ratios have been calculated. Comparison of ¹H and ¹³C NMR spectral data in the presence of paramagnetic lanthanides suggests conformational equilibria in the solutions. From the potentiometric studies, global formation constants have been determined, and speciation diagrams obtained over the pH range 1.5pH7.0 for ligand/metal ratios of 1 and 30. Implications of these results on lanthanide induced fusion of phospholipid membranes are discussed.     

Double domino Knoevenagel hetero Diels-Alder strategy towards bis-pyrano-1,4-benzoquinones

Several bis-pyrano-l,4-benzoquinones have been synthesized by a double domino Knoevenagel hetero Diels-Alder reaction. The synthetic approach is highly efficient allowing the construction of complex polycyclic scaffolds with six new σ-bonds. These reactions performed more efficiently and more rapidly using microwave irradiation. The resulting bis-pyrano-1,4-benzoquinones are the first examples of a double domino Knoevenagel hetero Diels-Alder reaction. Our approach represents a novel contribution to the chemistry of 2,5-dihydroxy-l,4-benzoquinones and the first general method for the synthesis of bis-pyranobenzoquinones.     

Multipurpose chamber for the implementation of gas diffusion, dialysis, solid-phase extraction and precipitation/dissolution in continuous flow analyzers

A multipurpose chamber capable of implementing a variety of continuous separation techniques is reported. The proposed module can be used in conjunction with flow manifolds coupled on-line to optical detectors in order to develop simple autoanalyzers for full sample pretreatment. The analytical applicability of such a device is discussed with specific regard to gas diffusion, dialysis, solid-phase extraction (SPE), and precipitation/dissolution techniques. Its versatility and simplicity are among the main advantages. Four different automated analyzers based on the use of the multipurpose chamber have been developed for monitoring of different quality control parameters of liquid food samples, namely, carbon dioxide in beer, ascorbic acid in fruit juice, caffeine in soft drinks and lactose, fat and protein in milk. The results obtained were compared with those provided by the existing alternatives for the same applications in terms of sensitivity and precision.     

The triviality of continuous multipliers for the real line

It is proved without resort to calculus methods that every continuous group multiplier for R can be reduced to the identity by a continuous remultiplication. The method introduced may generalize to infinitedimensional Abelian groups such as occur in analyzing the projective representations of the Bondi-Metzner-Sachs (BMS) group.     

Experimental and DFT studies of the conversion of ethanol and acetic acid on PtSn-based catalysts

Reaction kinetics studies were conducted for the conversions of ethanol and acetic acid over silica-supported Pt and Pt/Sn catalysts at temperatures from 500 to 600 K. Addition of Sn to Pt catalysts inhibits the decomposition of ethanol to CO, CH4, and C2H6, such that PtSn-based catalysts are active for dehydrogenation of ethanol to acetaldehyde. Furthermore, PtSn-based catalysts are selective for the conversion of acetic acid to ethanol, acetaldehyde, and ethyl acetate, whereas Pt catalysts lead mainly to decomposition products such as CH4 and CO. These results are interpreted using density functional theory (DFT) calculations for various adsorbed species and transition states on Pt(111) and Pt3Sn(111) surfaces. The Pt3Sn alloy slab was selected for DFT studies because results from in situ (119)Sn M?ssbauer spectroscopy and CO adsorption microcalorimetry of silica-supported Pt/Sn catalysts indicate that Pt-Sn alloy is the major phase present. Accordingly, results from DFT calculations show that transition-state energies for C-O and C-C bond cleavage in ethanol-derived species increase by 25-60 kJ/mol on Pt3Sn(111) compared to Pt(111), whereas energies of transition states for dehydrogenation reactions increase by only 5-10 kJ/mol. Results from DFT calculations show that transition-state energies for CH3CO-OH bond cleavage increase by only 12 kJ/mol on Pt3Sn(111) compared to Pt(111). The suppression of C-C bond cleavage in ethanol and acetic acid upon addition of Sn to Pt is also confirmed by microcalorimetric and infrared spectroscopic measurements at 300 K of the interactions of ethanol and acetic acid with Pt and PtSn on a silica support that had been silylated to remove silanol groups.