Fast and accurate quantification using Genetic Algorithm optimized H-1-C-13 refocused constant-time INEPT

Using Genetic Algorithm, a global optimization method inspired by nature's evolutionary process, we have improved the quantitative refocused constant-time INEPT experiment (Q-INEPT-CT) of Makela et al. (JMR 204 (2010) 124-130) with various optimization constraints. The improved `average polarization transfer' and `min-max difference' of new delay sets effectively reduces the experimental time by a factor of two (compared with Q-INEPT-CT, Makela et al.) without compromising on accuracy. We also discuss a quantitative spectral editing technique based on average polarization transfer. (C) 2013 Elsevier Inc. All rights reserved.

X-ray Structure of Gelonin at 1.8 Å Resolution

Gelonin is a single chain ribosome inactivating protein (RIP) with potential application in the treatment of cancer and AIDS. Diffraction quality crystals grown using PEG3350, belong to the space group P2(1), with it a = 49.4 Angstrom b = 44.9 Angstrom, c = 137.4 Angstrom and beta = 98.4 degrees, and contain two molecules in the asymmetric unit. Diffraction data collected to 1.8 Angstrom resolution has a R(m) value of 7.3%. Structure of gelonin has been solved by the molecular replacement method, using ricin A chain as the search model. Crystallographic refinement using X-PLOR resulted in a model for which the r.m.s deviations from ideal bond lengths and bond angles are 0.012 Angstrom and 2.7 degrees, respectively The final R-factor is 18.4% for 39,806 reflections for which I > 1.0 sigma(I).The C-alpha atoms of the two molecules in the asymmetric unit superpose to within 0.38 Angstrom for 247 atom pairs. The overall fold of gelonin is similar to that of other RIPs such as ricin A chain and alpha-momorcharin, the r.m.s.d. for C-alpha superpositions being 1.3 and 1.4 Angstrom, respectively The-catalytic residues (Glu166, Arg169 and Tyr113) in the active site form a hydrogen bond scheme similar to that observed in other RIPs. The conformation of Tyr74 in the active site, however, is significantly different from that in alpha-momorcharin. Three well defined water molecules are located in the active site cavity and one of them, X319, superposes to within 0.2 Angstrom of a corresponding water molecule in the structure of alpha-momorcharin. Any of the three could be the substrate water molecule in the hydrolysis reaction catalysed by gelonin.Difference electron density for a N-linked sugar moiety has been observed near only one of the two potential glycosylation sites in the sequence. The amino acid at position 239 has been established as Lys by calculation of omit electron density maps.The two cysteine residues in the sequence, Cys44 and Cys50, form a disulphide bond, and are therefore not available for disulphide conjugation with antibodies. Based on the structure, the region of the molecule that is involved in intradimer interactions is suggested to be suitable for introducing a Cys residue for purposes of conjugation with an antibody to produce useful immunotoxins.

Electron spin resonance absorption in organic metal polyaniline and its blend with PMMA

The electron spin resonance absorption in the synthetic metal polyaniline (PANI) doped with PTSA and its blend with poly(methylmethacrylate) (PMMA) is investigated in the temperature range between 4.2 and 300 K. The observed line shape follows Dyson's theory for a thick metallic plate with slowly diffusing magnetic dipoles. At low temperatures the line shape become symmetric and Lorentzian when the sample dimensions are small in comparison with the skin depth. The temperature dependence of electron spin relaxation time is discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.

Ethyl 1-(2-cyanoethyl)-3,5-dimethyl-1H-indole-2-carboxylate

The title compound, C16H18N2O2, is an important precursor in the synthesis of 1,2,3,4-tetrahydropyrazinoindoles, which show excellent antihistamine, antihypertensive and central nervous system depressant properties. The carbethoxy group attached to C2 and the planar cyanoethyl group attached to N1 make dihedral angles of 11.0(4) and 75.0(3)degrees, respectively, with the mean plane of the indole ring, The C-C=N chain is linear with a bond angle of 179.3 (4)degrees.

3-Phenylisoquinolin-1(2H)-one

The title compound, C15H11NO, consists of a planar isoquinolinone group to which a phenyl ring is attached in a twisted fashion [dihedral angle = 39.44 (4)degrees]. The crystal packing is dominated by intermolecular N-H center dot center dot center dot O and C-H center dot center dot center dot O hydrogen bonds which define centrosymmetric dimeric entitities.

Methyl 1H-1,2,3-triazole-4-carboxylate

The title compound, C4H5N3O2, features an essentially planar molecule (r.m.s. deviation for all non-H atoms = 0.013 angstrom). The crystal structure is stabilized by intermolecular N-H center dot center dot center dot O hydrogen bonds and pi-pi stacking interactions (centroid centroid distance 3.882 angstrom).

1-(4-Chloro-3-fluorophenyl)-2-[(3-phenylisoquinolin-1-yl)sulfanyl]ethanone

In the title compound, C23H15ClFNOS, the isoquinoline system and the 4-chloro-3-fluorophenyl ring are aligned at 80.4 (1)degrees. The dihedral angle between the isoquinoline system and the pendant (unsubstituted) phenyl ring is 19.91 (1)degrees.

2-[2-(Hydroxymethyl)phenyl]-1-phenylethanol

The title compound, C15H16O2, has a dihedral angle of 19.10 (5)degrees between the mean planes of the two benzene rings. There is an intramolecular O-H center dot center dot center dot O hydrogen bond and the C-C-C-C torsion angle across the bridge between the two rings is 173.13 (14)degrees. The molecules form intermolecular O-H center dot center dot center dot O hydrogen-bonded chains extending along the a axis. C-H center dot center dot center dot pi contacts are also observed between molecules within the chains.

3-(1,3-Dioxolan-2-yl)-2-hydrazino-7-methylquinoline

In the title molecule, C13H15N3O2, the dihedral angle between the mean plane of the 1,3-dioxolane group and the 2-hydrazino-7-methylisoquinoline unit is 85.21 (5)degrees. The conformation of the molecule is influenced by bifurcated N-H center dot center dot center dot(O, O) and N-H center dot center dot center dot N intramolecular hydrogen bonds. In the crystal structure, molecules are linked via intermolecular N-H center dot center dot center dot O hydrogen bonds, forming extended chains along [001].

1,3-Dimethyl-2,6-diphenylpiperidin-4-one

In the title moleclue, C19H21NO, the 4-piperidone ring adopts a chair conformation in which the two benzene rings and the methyl group attached to C atoms all have equatorial orientations. In the crystal structure, centrosymmetric dimers are formed through weak intermolecular C-H center dot center dot center dot O hydrogen bonds [the dihedral angle between the aromatic rings is 58.51 (5)degrees].

Time-Resolved Resonance Raman Spectroscopic Studies on the Radical Anions of Menaquinone and Naphthoquinone

Quinones and their radical ion intermediates have been much studied by vibrational spectroscopy to understand their structure-function relationships in various biological processes. In this paper, we present a comprehensive analysis of vibrational spectra in the structure-sensitive region of both the naphthoquinone (NQ) and 2-methyl-1,4-naphthoquinone (MQ, menaquinone) radical anions using time-resolved resonance Raman and ab initio studies. Specific vibrational mode assignments have been made to all the vibrational frequencies recorded in the experiment. It is observed that the carbonyl and C-C stretching frequencies show considerable coupling in NQ and MQ radical anions. Further, the asymmetric substitution present in MQ with respect to NQ shows important signatures in the radical anion spectrum. It is concluded that assignments of vibrational frequencies of asymmetrically substituted quinones must take into consideration the influence of asymmetry on structure and reactivity.

Helium Gas Purity Monitor based on Low Frequency Acoustic Resonance

Monitoring gas purity is an important aspect of gas recovery stations where air is usually one of the major impurities. Purity monitors of Katherometric type ate commercially available for this purpose. Alternatively, we discuss here a helium gas purity monitor based on acoustic resonance of a cavity at audio frequencies. It measures the purity by monitoring the resonant frequency of a cylindrical cavity filled with the gas under test and excited by conventional telephone transducers fixed at the ends. The use of the latter simplifies the design considerably. The paper discusses the details of the resonant cavity and the electronic circuit along with temperature compensation. The unit has been calibrated with helium gas of known purities. The unit has a response time of the order of 10 minutes and measures the gas purity to an accuracy of 0.02%. The unit has been installed in our helium recovery system and is found to perform satisfactorily.

Thermodynamics of ligand (substrate end product) binding to endoxylanase from Chainia sp. (NCL-82-5-1): isothermal calorimetry and fluorescence titration studies

The binding of xylo-oligosaccharides to Chainia endoxylanase resulted in a decrease in fluorescence intensity of the enzyme with the formation of 1:1 complex. Equilibrium and thermodynamic parameters of ligand binding were determined by fluorescence titrations and titration calorimetry. The affinity of xylanase for the oligosaccharides increases in the order X-2 < X-3 < X-4 less than or equal to X-5. Contributions from the enthalpy towards the free energy change decreased with increasing chain length from X-2 to X-4, whereas an increase in entropy was observed, the change in enthalpy and entropy of binding being compensatory. The entropically driven binding process suggested that hydrophobic interactions as well as hydrogen bonds play a predominant role in ligand binding.

Role of TATATAA element in the regulation of tRNA(1)(Gly) gene expression in Bombyx mori is position dependent

Transcription of tRNA genes by RNA polymerase III is controlled by the internal conserved sequences within the coding region and the immediate upstream flanking sequences. A highly transcribed copy of glycyl tRNA gene tRNA1(Gly)-1 from Bombyx mori is down regulated by sequences located much farther upstream in the region -150 to -300 nucleotides (nt), with respect to the +1 nt of tRNA. The negative regulatory effect has been narrowed down to a sequence motif 'TATATAA', a perfect consensus recognised by the TATA binding protein, TBP. This sequence element, when brought closer to the transcription start point, on the other hand, exerts a positive effect by promoting transcription of the gene devoid of other cis regulatory elements. The identity of the nuclear protein interacting with this 'TATATAA' element to TBP has been established by antibody and mutagenesis studies. The 'TATATAA' element thus influences the transcription of tRNA genes positively or negatively in a position-dependent manner either by recruitment or sequestration of TBP from the transcription machinery.