Novel open-chain and cyclic conformationally constrained (R)- and (S)-α,α-disubstituted tyrosine analogues

A series of novel open-chain and cyclic conformationally constrained (R)- and (S)-α,α-disubstituted tyrosine analogues 1a–e were synthesized in good yields and high optical purities (Schemes 1 and 2). The absolute configurations of these tyrosine analogues were unambiguously determined based on the X-ray structures of the precursor diastereoisomeric peptides of type 4 and 5 . Four of these structures are described (Figs. 1–4), showing β-turn type-I geometries for dipeptides 4a, 5b , and 4c and an extended conformation for peptide 5c (Table 3). The conversion of the free amino acids 1a–c into suitably protected building blocks 11a–d and 15d,e for peptide synthesis is discussed (Schemes 3 and 4).     

An operando DRIFTS investigation into the resistance against CO2 poisoning of a Rh/alumina catalyst during toluene hydrogenation

CO(2) is a major contaminant of renewable H(2) derived from biomass fermentation. The effect of the presence of CO(2) on the activity of alumina-supported Pt and Rh catalysts used for the hydrogenation of toluene at 348 K was investigated. The use of operando diffuse reflectance spectroscopy (DRIFTS) was crucial in unravelling the changes in the nature and abundance of species adsorbed at the sample surface and relating those to the changes of catalytic activity. Rhodium supported on alumina was only partly deactivated by the introduction of CO(2) during the hydrogenation of toluene, contrary to the case of Pt/alumina. Rh was only partially covered by carbonyl species derived from CO(2) and it was shown that toluene could successfully compete with some of the linearly adsorbed carbonyls for adsorption. The alumina support stored many CO(2)-derived adsorbates (carbonates, hydrogenocarbonates, carboxylates) that could spill over to the metal and form carbonyl species even after the removal of CO(2) from the feed.     

A four coordinate parent imide via a titanium nitridyl

Treatment of d(1) [(nacnac)TiCl(Ntol(2))] with NaN(3) results in NaCl formation and N(2) ejection to yield the first four coordinate, parent imide [(nacnac)Ti=NH(Ntol(2))] (nacnac(-)=[ArNC(CH(3))](2)CH, Ar = 2,6-iPr(2)C(6)H(3), tol = 4-CH(3)C(6)H(4)).     

Probing intramolecular CH-π interactions in o-quinodimethane adducts of [60]fullerene using variable temperature NMR

Several o-quinodimethane adducts of [60]fullerene were synthesized and their intramolecular aryl CH-fullerene π interactions were studied using variable temperature-NMR (VT-NMR). Evaluation of the rate constants associated with the first-order transition states for cyclohexene boat-to-boat inversions enables quantification of ΔG(?) values for each inversion. A comparison between two constitutional isomers, only one of which is capable of intramolecular CH-π interactions, provides a lower limit of 0.95 kcal/mol for each aryl CH-fullerene π interaction.     

Surface area controlled heterogeneous nucleation

Heterogeneous nucleation of liquid from a gas phase on nanoparticles has been studied under various saturation ratios and nuclei size. The probability of liquid droplet nucleation, especially at a low degree of deviation from equilibrium, was measured for both atmospheric aerosol particles and engineered nanoparticles Cr(2)O(3). The concept of a critical saturation ratio and the validity of the one-to-one relationship between the nuclei number and the number of droplets were examined. A transient zone between no nucleation and established nucleation termed the surface area controlled nucleation was observed. In this zone, the probability of stable phase formation is determined by the surface area of nuclei. There are two distinctive features of the surface area controlled nucleation: the nucleation probability is much less than 1 and is proportional to the surface area of nuclei. For condensation particle counters (CPCs) counting nanoparticles, these features mean that counts measured are proportional to the surface area of nanoparticles and, therefore, the CPCs counts can be calibrated to measure the surface area.     

RNA encapsidation by SV40-derived nanoparticles follows a rapid two-state mechanism

Remarkably, uniform virus-like particles self-assemble in a process that appears to follow a rapid kinetic mechanism. The mechanisms by which spherical viruses assemble from hundreds of capsid proteins around nucleic acid, however, are yet unresolved. Using time-resolved small-angle X-ray scattering (TR-SAXS), we have been able to directly visualize SV40 VP1 pentamers encapsidating short RNA molecules (500mers). This assembly process yields T = 1 icosahedral particles comprised of 12 pentamers and one RNA molecule. The reaction is nearly one-third complete within 35 ms, following a two-state kinetic process with no detectable intermediates. Theoretical analysis of kinetics, using a master equation, shows that the assembly process nucleates at the RNA and continues by a cascade of elongation reactions in which one VP1 pentamer is added at a time, with a rate of approximately 10(9) M(-1) s(-1). The reaction is highly robust and faster than the predicted diffusion limit. The emerging molecular mechanism, which appears to be general to viruses that assemble around nucleic acids, implicates long-ranged electrostatic interactions. The model proposes that the growing nucleo-protein complex acts as an electrostatic antenna that attracts other capsid subunits for the encapsidation process.     

Cyclo[m]pyridine[n]pyrroles: hybrid macrocycles that display expanded π-conjugation upon protonation

Novel hybrid cyclo[m]pyridine[n]pyrroles have been synthesized using Suzuki coupling. Their NMR and optical spectroscopic features and solid state structural parameters provide support for the proposal that these species are best described as locally aromatic compounds devoid of long-range intersubunit conjugation. However, an extension of the π-conjugation in the macrocycles can be realized through protonation, as inferred from optical spectroscopic and X-ray diffraction-based structural studies.     

Efficient simultaneous reverse Monte Carlo modeling of pair-distribution functions and extended x-ray-absorption fine structure spectra of crystalline disordered materials

An efficient implementation of simultaneous reverse Monte Carlo (RMC) modeling of pair distribution function (PDF) and EXAFS spectra is reported. This implementation is an extension of the technique established by Krayzman et al. [J. Appl. Cryst. 42, 867 (2009)] in the sense that it enables simultaneous real-space fitting of x-ray PDF with accurate treatment of Q-dependence of the scattering cross-sections and EXAFS with multiple photoelectron scattering included. The extension also allows for atom swaps during EXAFS fits thereby enabling modeling the effects of chemical disorder, such as migrating atoms and vacancies. Significant acceleration of EXAFS computation is achieved via discretization of effective path lengths and subsequent reduction of operation counts. The validity and accuracy of the approach is illustrated on small atomic clusters and on 5500-9000 atom models of bcc-Fe and α-Fe(2)O(3). The accuracy gains of combined simultaneous EXAFS and PDF fits are pointed out against PDF-only and EXAFS-only RMC fits. Our modeling approach may be widely used in PDF and EXAFS based investigations of disordered materials.     

Experimental evidence for excess entropy discontinuities in glass-forming solutions

Glass transition temperatures T(g) are investigated in aqueous binary and multi-component solutions consisting of citric acid, calcium nitrate (Ca(NO(3))(2)), malonic acid, raffinose, and ammonium bisulfate (NH(4)HSO(4)) using a differential scanning calorimeter. Based on measured glass transition temperatures of binary aqueous mixtures and fitted binary coefficients, the T(g) of multi-component systems can be predicted using mixing rules. However, the experimentally observed T(g) in multi-component solutions show considerable deviations from two theoretical approaches considered. The deviations from these predictions are explained in terms of the molar excess mixing entropy difference between the supercooled liquid and glassy state at T(g). The multi-component mixtures involve contributions to these excess mixing entropies that the mixing rules do not take into account.