Stable bundles and the first eigenvalue of the Laplacian

In this article we study the first eigenvalue of the Laplacian on a compact manifold using stable bundles and balanced bases. Our main result is the following: Let M be a compact Kähler manifold of complex dimension n and E a holomorphic vector bundle of rank r over M. If E is globally generated and its Gieseker point T_e is stable, then for any Kähler metric g on M\(\lambda _1 (M,g) \leqslant \frac{{4\pi h^0 (E)}}{{r(h^0 (E) - r)}} \cdot \frac{{\left\langle {C_1 (E) \cup [\omega ]^{n - 1} ,[M]} \right\rangle }}{{(n - 1)!vol(M,[\omega ])}}\) where ω = ω_g is the Kähler form associated to g.By this method we obtain, for example, a sharp upper bound for λ₁ of Kähler metrics on complex Grassmannians.     

Mesoscopic and microscopic investigation on poly(vinyl alcohol) hydrogels in the presence of sodium decylsulfate

The structure of poly(vinyl alcohol) (PVA) hydrogels formed as a result of freeze/thaw treatments of aqueous solutions of the polymer (11 wt % PVA) in the freshly prepared state is analyzed through the combined use of small (SANS) and ultrasmall (USANS) angle neutron scattering techniques. The structure of these hydrogels may be described in terms of polymer rich regions, with dimensions of the order of 1-2 microm, dispersed in a water rich phase, forming two bicontinuous phases. The PVA chains in the polymer rich phase form a network where the cross-linking points are mainly crystalline aggregates of PVA having average dimensions of approximately 45 A. The structural organization of freeze/thaw PVA hydrogel membranes does not change either after rehydration of dried gels or in the presence of a tensile force. Finally, addition of surfactant micelles inside the gel provides a formulation with both hydrophobic and hydrophilic regions, which demonstrates the potential of the system for drug delivery. Both SANS and EPR measurements show that sodium decylsulfate (C10OS) micelles do not significantly interact with the PVA gel. Variation of the gel structure by the number of freeze/thaw cycles should modulate the rate of release of an active constituent, for example, in a dermal patch.     

Two-dimensional infrared spectral signatures of 3(10)- and alpha-helical peptides

Two-dimensional infrared (2D IR) spectra of Calpha-alkylated model octapeptides Z-(Aib)8-OtBu, Z-(Aib)5-L-Leu-(Aib)2-OMe, and Z-[L-(alphaMeVal)]8-OtBu have been measured in the amide I region to acquire 2D spectral signatures characteristic of 3(10)- and alpha-helical conformations. Phase-adjusted 2D absorptive spectra recorded with parallel polarizations are dominated by intense diagonal peaks, whereas 2D rephasing spectra obtained at the double-crossed polarization configuration reveal cross-peak patterns that are essential for structure determination. In CDCl3, all three peptides are of the 3(10)-helix conformation and exhibit a doublet cross-peak pattern. In 1,1,1,3,3,3-hexafluoroisopropanol, Z-[L-(alphaMeVal)]8-OtBu undergoes slow acidolysis and 3(10)-to-alpha-helix transition. In the course of this conformational change, its 2D rephasing spectrum evolves from an elongated doublet, characteristic of a distorted 3(10)-helix, to a multiple-peak pattern, after becoming an alpha-helix. The linear IR and 2D absorptive spectra are much less informative in discerning the structural changes. The experimental spectra are compared to simulations based on a vibrational exciton Hamiltonian model. The through-bond and through-space vibrational couplings are modeled by ab initio coupling maps and transition dipole interactions. The local amide I frequency is evaluated by a new approach that takes into account the effects of hydrogen-bond geometry and sites. The static diagonal and off-diagonal disorders are introduced into the Hamiltonian through statistical models to account for conformational fluctuations and inhomogeneous broadening. The sensitivity of cross-peak patterns to different helical conformations and the chain length dependence of the spectral features for short 3(10)- and alpha-helices are discussed.     

Diffusion and residence time of hydrogen peroxide and water in crowded protein environments

Reactive oxygen species (ROS) have important functions in cell signaling and, when present at overly high levels, may cause oxidation of important biological molecules. Kinetic models to study diffusion of ROS inside of mitochondria often assume dynamics similar to that in solution. However, it is well-known that separation of proteins in the cytosol or inside of mitochondria, where ROS are most predominant, can be smaller than 1 nm. Diffusion of small molecules can be better regarded as a percolation process. In this article, we report results of diffusivity and residence of water and hydrogen peroxide in the proximity of proteins. In carrying out this study, we found some issues with the conventional way of computing residence times by means of survival time correlation functions. The main problem is that particles remaining on the surface of a protein for long times and for which one has very poor statistics contribute significantly to the short time behavior of the survival time correlation function. We mathematically describe this problem and propose methodology to overcome it.     

Machine‐Assisted Organic Synthesis

In this Review we describe how the advent of machines is impacting on organic synthesis programs, with particular emphasis on the practical issues associated with the design of chemical reactors. In the rapidly changing, multivariant environment of the research laboratory, equipment needs to be modular to accommodate high and low temperatures and pressures, enzymes, multiphase systems, slurries, gases, and organometallic compounds. Additional technologies have been developed to facilitate more specialized reaction techniques such as electrochemical and photochemical methods. All of these areas create both opportunities and challenges during adoption as enabling technologies.     

Study of the photocatalytic transformation of synephrine: a biogenic amine relevant in anti-doping analysis

The occurrence of some cases of positive results in anti-doping analysis of octopamine requires clarification as to whether its methylated derivative synephrine could be a metabolic precursor of octopamine itself. Synephrine is a natural phenylethylamine derivative present in some food supplements containing Citrus aurantium, permitted in sport regulations. A simulative laboratory study had been done using a photocatalytic process, to identify all possible main and secondary transformation products, in a clean matrix; these were then sought in biological samples obtained from three human volunteers and four rats treated with synephrine; the parent compound and its new potential metabolic products were investigated in human urine and rat plasma samples. The transformation of synephrine and octopamine and the formation of intermediate products were evaluated, adopting titanium dioxide as photocatalyst. Several products were formed and characterized using the HPLC-HRMSⁿ technique. The main intermediates identified in these experimental conditions were compared with the major synephrine metabolites found in in vivo studies on rats and humans. Some more oxidized species, already formed in the photocatalytic process, were also found in urine and plasma samples of treated animals. These new findings could be of interest in further metabolism studies. The main photocatalytic pathway involving synephrine appears to be N-demethylation to give octopamine. On the contrary, we demonstrate the inconsistency of this reaction in both rat and human in vivo determinations, resulting in forensic importance.     

Selective Formation of Methyl α-Methylsulfanyl Dimethylphosphonothioacetate and Thiopropanoate by Phase Transfer Catalysis

The sulfanylation of methyl dimethylphosphonothioacetate was investigated by a phase transfer catalysis procedure which was shown to be superior to the noncatalytic method. The possibility of electrophilic substitution of the α-sulfanylated phosphonothioacetate to give a quaternary α-carbon atom is shown by the reaction with methyl iodide.

     

New generation of sterically protected C18 stationary phases containing embedded urea groups for use in high-performance liquid chromatography

New monofunctional C18 urea stationary phases with sterically protecting dimethyl and diisopropyl groups were prepared by a single step modification process. ProntoSil spherical silica (3 microm) was chemically modified with the monofunctional ethoxysilanes, [(3-octadecylurea)propyl]dimethyl and [(3-octadecylurea)propyl]diisopropyl ethoxysilanes. The phases were characterized by elemental analysis, infrared and solid-state 29Si and 13C NMR spectroscopies. Chromatographic characterizations of the new phases in 50x3.9 mm HPLC columns were performed by the separation of two different test mixtures, containing nonpolar, polar and highly basic compounds.     

Reactions of GeCl2 with the Thiolate LiSC(SiMe3)3: From thf Activation to Insertion of GeCl2 Molecules into C−S Bonds

The reaction system GeCl₂ ⋅ dioxane/LiSTsi (Tsi=C(SiMe₃)₃) opens a fruitful area in germanium chemistry, depending on the stoichiometry and solvent used during the reaction. For example, the reaction of GeCl₂ ⋅ dioxane in toluene with two equivalents of the thiolate gives the expected germylene Ge(STsi)₂ in excellent yield. This germylene readily reacts with hydrogen and acetylene, however, in a non-selective way. By using an excess amount of the thiolate and toluene as the solvent, the germanide [Ge(STsi)₃][Li(thf)] is obtained. Performing the same reaction in thf leads to a C−H activation of thf to give (H₇C₄O)Ge[STsi](μ²-S)₂Ge[STsi]₂, in which the thf molecule is still intact. Using a sub-stoichiometric amount of the thiolate leads to the heteroleptic compound [ClGe(STsi)]₂ and to the insertion product (thf)Ge[S-GeCl₂-Tsi]₂, in which additional GeCl₂ molecules insert into the C−S bonds of Ge(STsi)₂. The synthesis and the experimentally determined structures of all compounds are presented together with first reactivity studies of Ge(STsi)₂.     

Inhibition of mild steel corrosion in HCl solution using chitosan

The efficiency of chitosan (a naturally occurring polymer) as a corrosion inhibitor for mild steel in 0.1 M HCl was investigated by gravimetric, potentiodynamic polarization, electrochemical impedance spectroscopy measurements, scanning electron microscopy, and UV–visible analysis. The polymer was found to inhibit corrosion even at a very low concentration. Inhibition efficiency increases with a rise in temperature up to 96 % at 60 °C and then drops to 93 % at 70 °C, while it slightly increases with an increase in chitosan concentration. Polarization curves indicate that chitosan functions as a mixed inhibitor, affecting both cathodic and anodic partial reactions. Impedance results indicate that chitosan was adsorbed on the metal/solution interface. Adsorption of chitosan at the mild steel surface is found to be in agreement with Langmuir adsorption isotherm model. Chemical adsorption is the proposed mechanism for corrosion inhibition considering the trend of protection efficiency with temperature. Calculated kinetic and thermodynamic parameters corroborate the proposed mechanism.