Nuclear magnetic relaxation induced by exchange-mediated orientational randomization: Longitudinal relaxation dispersion for spin I = 1

The frequency dependence of the longitudinal relaxation rate, known as the magnetic relaxation dispersion (MRD), can provide a frequency-resolved characterization of molecular motions in complex biological and colloidal systems on time scales ranging from 1 ns to 100 μs. The conformational dynamics of immobilized proteins and other biopolymers can thus be probed in vitro or in vivo by exploiting internal water molecules or labile hydrogens that exchange with a dominant bulk water pool. Numerous water (1)H and (2)H MRD studies of such systems have been reported, but the widely different theoretical models currently used to analyze the MRD data have resulted in divergent views of the underlying molecular motions. We have argued that the essential mechanism responsible for the main dispersion is the exchange-mediated orientational randomization (EMOR) of anisotropic nuclear (electric quadrupole or magnetic dipole) couplings when internal water molecules or labile hydrogens escape from orientationally confining macromolecular sites. In the EMOR model, the exchange process is thus not just a means of mixing spin populations but it is also the direct cause of spin relaxation. Although the EMOR theory has been used in several studies to analyze water (2)H MRD data from immobilized biopolymers, the fully developed theory has not been described. Here, we present a comprehensive account of a generalized version of the EMOR theory for spin I = 1 nuclides like (2)H. As compared to a previously described version of the EMOR theory, the present version incorporates three generalizations that are all essential in applications to experimental data: (i) a biaxial (residual) electric field gradient tensor, (ii) direct and indirect effects of internal motions, and (iii) multiple sites with different exchange rates. In addition, we describe and assess different approximations to the exact EMOR theory that are useful in various regimes. In particular, we consider the experimentally important dilute regime, for which approximate analytical results are derived. As shown by the analytical expressions, and confirmed by exact numerical calculations, the dispersion is governed by the pure nuclear quadrupole resonance frequencies in the ultraslow-motion regime, where the relaxation rate also exhibits a much stronger dependence on the electric field gradient asymmetry than in the motional-narrowing regime.     

Heats of formation of C(6)H(5)(•), C(6)H(5)(+), and C(6)H(5)NO by threshold photoelectron photoion coincidence and active thermochemical tables analysis

Threshold photoelectron photoion coincidence has been used to prepare selected internal energy distributions of nitrosobenzene ions [C(6)H(5)NO(+)]. Dissociation to C(6)H(5)(+) + NO products was measured over a range of internal energies and rate constants from 10(3) to 10(7) s(-1) and fitted with the statistical theory of unimolecular decay. A 0 K dissociative photoionization onset energy of 10.607 ± 0.020 eV was derived by using the simplified statistical adiabatic channel model. The thermochemical network of Active Thermochemical Tables (ATcT) was expanded to include phenyl and phenylium, as well as nitrosobenzene. The current ATcT heats of formation of these three species at 0 K (298.15 K) are 350.6 (337.3) ± 0.6, 1148.7 (1136.8) ± 1.0, and 215.6 (198.6) ± 1.5 kJ mol(-1), respectively. The resulting adiabatic ionization energy of phenyl is 8.272 ± 0.010 eV. The new ATcT thermochemistry for phenyl entails a 0 K (298.15 K) C-H bond dissociation enthalpy of benzene of 465.9 (472.1) ± 0.6 kJ mol(-1). Several related thermochemical quantities from ATcT, including the current enthalpies of formation of benzene, monohalobenzenes, and their ions, as well as interim ATcT values for the constituent atoms, are also given.     

The chemical reactivity of a known anti-psoriasis drug. Part 1: Further insights into the products resulting from oxidative cleavage

The oxidative cleavage of the known anti-psoriasis drug 1 to give 2 has been reported previously. Due to the importance of accessing medium-sized ring containing systems via oxidative cleavage, this reaction has been revisited revealing additional information about the structure of 2. Alternative reaction products were identified when the reaction was carried out in the presence of water. The conversion of 1 to 2 has also been carried out using ruthenium tetroxide. A detailed variable temperature NMR and computational study of the restricted rotation of the N-aryl ring in 2 is presented.     

A Unique Tryptophan C‐Prenyltransferase from the Kawaguchipeptin Biosynthetic Pathway

Cyanobactins are a rapidly growing family of linear and cyclic peptides produced by cyanobacteria. Kawaguchipeptins A and B, two macrocyclic undecapeptides reported earlier from Microcystis aeruginosa NIES‐88, are shown to be products of the cyanobactin biosynthetic pathway. The 9 kb kawaguchipeptin (kgp) gene cluster was identified in a 5.26 Mb draft genome of Microcystis aeruginosa NIES‐88. We verified that this gene cluster is responsible for the production of the kawaguchipeptins through heterologous expression of the kgp gene cluster in Escherichia coli. The KgpF prenyltransferase was overexpressed and was shown to prenylate C‐3 of Trp residues in both linear and cyclic peptides in vitro. Our findings serve to further enhance the structural diversity of cyanobactins to include tryptophan‐prenylated cyclic peptides.     

Visualization of structural changes in cellulosic substrates during enzymatic hydrolysis using multimodal nonlinear microscopy

Enzymatic hydrolysis of cellulose provides a renewable source of monosaccharides for production of variety of biochemicals and biopolymers. Unfortunately, the enzymatic hydrolysis of cellulose is often incomplete, and the reasons are not fully understood. We have monitored enzymatic hydrolysis in terms of molecular density, ordering and autofluorescence of cellulose structures in real time using simultaneous CARS, SHG and MPEF microscopy with the aim of contributing to the understanding and optimization of the enzymatic hydrolysis of cellulose. Three cellulose-rich substrates with different supramolecular structures, pulp fibre, acid-treated pulp fibre and Avicel, were studied at microscopic level. The microscopy studies revealed that before enzymatic hydrolysis Avicel had the greatest carbon-hydrogen density, while pulp fibre and acid-treated fibre had similar density. Monitoring of the substrates during enzymatic hydrolysis revealed the double exponential SHG decay for pulp fibre and acid-treated fibre indicating two phases of the process. Acid-treated fibre was hydrolysed most rapidly and the hydrolysis of pulp fibre was spatially non-uniform leading to fractioning of the particles, while the hydrolysis of Avicel was more than an order of magnitude slower than that of both fibres.     

Benign‐by‐Design Solventless Mechanochemical Synthesis of Three‐, Two‐, and One‐Dimensional Hybrid Perovskites

Organic–inorganic hybrid perovskites have attracted significant attention owing to their extraordinary optoelectronic properties with applications in the fields of solar energy, lighting, photodetectors, and lasers. The rational design of these hybrid materials is a key factor in the optimization of their performance in perovskite‐based devices. Herein, a mechanochemical approach is proposed as a highly efficient, simple, and reproducible method for the preparation of four types of hybrid perovskites, which were obtained in large amounts as polycrystalline powders with high purity and excellent optoelectronics properties. Two archetypal three‐dimensional (3D) perovskites (MAPbI₃ and FAPbI₃) were synthesized, together with a bidimensional (2D) perovskite (Gua₂PbI₄) and a “double‐chain” one‐dimensional (1D) perovskite (GuaPbI₃), whose structure was elucidated by X‐ray diffraction.     

Regioselective Hydrolysis of Cocaine and A Convenient Acylation Procedure by Benzoylecgonine

Regioselective hydrolysis of cocaine led, according to the reaction conditions, either to benzoylecgonine or to ecgonine methyl ester. Acylation with benzoylecgonine was readily achieved when benzotriazolyloxytrisdimethylamino-phosphonium (BOP) was used as a coupling agent.     

Evolution of femtosecond laser-induced damage in doped GaN thin films

Mg- and Si-doped GaN layers deposited by metalorganic chemical vapor deposition method were irradiated with femtosecond pulse duration laser of three different wavelengths 1,030, 515 and 343 nm. Both single and multiple shot laser induced damage thresholds of doped GaN layers were evaluated and discussed. The scanning electron microscopy employed with electron beam induced current and energy dispersive X-ray techniques were used to study laser damage morphology. It was observed that ablated area and laser-induced damage increased with irradiation fluence. The mechanism of damage generation by Gaussian beam profile laser was considered.     

Synthesis,structural characterization and in vitro cytotoxic activity of novel polymeric triorganotin(IV) complexes of urocanic acid

Two novel triorganotin carboxylate complexes of the biologically active urocanic acid have been synthesized and characterized. Elemental analysis, melting point, spectroscopic techniques – IR, ¹H, ¹³C and ¹¹⁹Sn NMR – mass spectrometry and X‐ray diffraction studies have been used for structural characterization. Crystal structures of the tin(IV) derivatives show that urocanic acid acts as a bridging bidentate ligand through its imidazole nitrogen atom and its carboxylic group, producing a polymeric one‐dimensional chain. The molecular structures of the complexes, catena‐poly‐tri(n‐butyl)tin(IV) 3‐(3H‐imidazol‐4‐yl)prop‐2‐enoate (1) and catena‐poly‐triphenyltin(IV) 3‐(3H‐imidazol‐4‐yl)prop‐2‐enoate (2), present a distorted trigonal–bipyramidal configuration. This is further confirmed by ¹¹⁹Sn NMR in the solid state. The tin(IV) derivatives form double‐stranded ribbons via N―H^…O―H bonds. Nevertheless, the compounds are essentially monomeric in solution, with a tetrahedral configuration as observed by ¹¹⁹Sn NMR in solution. The cytotoxic activity of the titled compounds has been tested against six human cell lines and the corresponding IC₅₀ values are reported. Both tin(IV) compounds have a high to very high in vitro cytotoxic activity against the tumor cell lines K562, HCT‐15 and MCF‐7. Compound 1 is 86 times more active than cisplatin in the HTC‐15 cell line. Copyright © 2012 John Wiley & Sons, Ltd.