Structural Diversity in Multinuclear PdII Assemblies that Show Low- Humidity Proton Conduction

Systematic investigation on synergetic effects of geometry, length, denticity, and asymmetry of donors was performed through the formation of a series of uncommon Pd-II aggregates by employing the donor in a multicomponent self-assembly of a cis-blocked 90 degrees Pd-II acceptor and a tetratopic donor. Some of these assemblies represent the first examples of these types of structures, and their formation is not anticipated by only taking the geometry of the donor and the acceptor building units into account. Analysis of the crystal packing of the X-ray structure revealed several H bonds between the counteranions (NO3-) and water molecules (OHON). Moreover, H-bonded 3D-networks of water are present in the molecular pockets, which show water-adsorption properties with some variation in water affinity. Interestingly, these complexes exhibit proton conductivity (1.87x10(-5)-6.52x10(-4)Scm(-1)) at 296K and low relative humidity (ca. 46%) with activation energies of 0.29-0.46eV. Moreover, the conductivities further increase with the enhancement of humidity. The ability of these assemblies to exhibit proton-conducting properties under low-humidity conditions makes these materials highly appealing as electrolytes in batteries and in fuel-cell applications.

Effect of methylene group insertions on the structural rigidity of Aib containing helices

Nonprotein amino acids are being extensively used in the design of synthetic peptides to create new structure mimics. In this study we report the effect of methylene group insertions in a heptapeptide Boc-Ala(1)-Leu(2)-Aib(3)-Xxx(4)-Ala(5)-Leu(6)-Aib(7)-OMe which nicely folds into a mixed 3(10)-/-helical structure when Xxx= Ala. Analogs of this peptide have been made and studied by replacing central Xxx(4) residue with Glycine (-residue), -Alanine (-la), -aminobutyric acid (Gaba), and epsilon-aminocaproic acid (epsilon-Aca). NMR and circular dichroism were used to study the solution structure of these peptides. Crystals of the peptides containing alanine, -la, and Gaba reveal that increasing the number of central methylene (-CH2-) groups introduces local perturbations even as the helical structure is retained. (c) 2015 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 104: 720-732, 2015.

Beta-Turn Conformations In Crystal-Structures Of Model Peptides Containing Alpha,Alpha-Di-N-Propylglycine And Alpha,Alpha-Di-N-Butylglycine

The crystal state conformations of three peptides containing the alpha, alpha-dialkylated residues, alpha,alpha-di-n-propylglycine (Dpg) and alpha,alpha-di-n-butylglycine (Dbg), have been established by x-ray diffraction. Boc-Ala-Dpg-Ala-OMe (I) and Boc-Ala-Dbg-Ala-OMe (III) adopt distorted type II beta-turn conformations with Ala (1) and Dpg/Dbg (2) as the corner residues. In both peptides the conformational angles at the Dxg residue (I: phi = 66.2 degrees, psi = 19.3 degrees; III: phi = 66.5 degrees, psi = 21.1 degrees) deviate appreciably from ideal values for the i + 2 residue in a type II beta-turn. In both peptides the observed (N...O) distances between the Boc CO and Ala(3) NH groups are far too long (I: 3.44 Angstrom; III: 3.63 Angstrom) for an intramolecular 4 --> 1 hydrogen bond. Boc-Ala-Dpg-Ala-NHMe (II) crystallizes with two independent molecules in the asymmetric unit. Both molecules IIA and IIB adopt consecutive beta-turn (type III-III in IIA and type III-I in IIB) or incipient 3(10)-helical structures, stabilized by two intramolecular 4 --> 1 hydrogen bonds. In all four molecules the bond angle N-C-alpha-C' (tau) at the Dxg residues are greater than or equal to 110 degrees. The observation of conformational angles in the helical region of phi,psi space at these residues is consistent with theoretical predictions.

Synthesis, reactivity and structural characterisation of bicyclic tetraphosphapentazanes

The diphenoxy bicyclic tetraphosphapentazane derivatives (EtN)(5)P-4(OPh)(2) 2 and its monoxide (EtN)(5)P-4(O)(OPh)(2) 3 have been prepared. Both 2 and 3 exist as a mixture of two isomers. One isomer of (EtN)(5)P-4(O)(OPh)(2) 3a has been isolated and its reaction with tetrachloro-1,2-benzoquinone yielded (EtN)(5)P-4(O)(OPh)(2)(O2C6Cl4) 5 in which the junction phosphorus atom becomes five-co-ordinated. Treatment of 2 or 3a with [Mo(CO)(4)(nbd)] (nbd = norbornadiene, bicyclo[2.2.1]hepta-2,5-diene), on the other hand, yielded the chelate complex [Mo(CO)(4){(EtN)(5)P-4(O)(n)(OPh)(2)}] (n = 0 or 1; 6 or 7) in which the peripheral phosphorus atoms are bonded to the metal. The structures of 3a and 5-7 have been confirmed by single-crystal X-ray diffraction studies. The two P3N3 rings in 3a and 5 adopt twist/twist and irregular/twist conformations respectively; the phenoxy substituents occupy the 'pseudo axial' positions. However, an ideal chair conformation is observed for the P3N3 rings in 6 and 7 with the phenoxy substituents taking up the 'pseudo equatorial' positions. The NMR spectroscopic data for the compounds are discussed.

Structural characteristics of a giant tropical liana and its mode of canopy spread in an alien environment

To circumvent the practical difficulties in research on tropical rainforest lianas in their natural habitat due to prevailing weather conditions, dense camouflaging vegetation and problems in transporting equipment for experimental investigations, Entada pursaetha DC (syn. Entada scandens Benth., Leguminosae) was grown inside a research campus in a dry subtropical environment. A solitary genet has attained a gigantic size in 17 years, infesting crowns of semi-evergreen trees growing in an area roughly equivalent to 1.6 ha. It has used aerially formed, cable-like stolons for navigating and spreading its canopy across tree gaps. Some of its parts which had remained unseen in its natural habitat due to dense vegetation are described. The attained size of this liana in a climatically different environment raises the question as to why it is restricted to evergreen rainforests. Some research problems for which this liana will be useful are pointed out.

Structural studies of analgesics and their interactions .10. A hydrated 1-1 complex between niflumic acid and ethanolamine, c13h8f3n2o-2.c2h8no+.h2o.

Mr= 361.3, triclinic, P1, a = 6-239 (2), b=11.280(2), c=12-451(2)A, a=101.2 (1), B= 92.3 (1), 7=99.9(1)°, V=844.123 A3, Z=2, Dx= 1.42, D m = 1.42 (1) Mg m -3, n(Cu Ka) = 1.5418 ,A., g = 1-102 mm -1, F(000) = 376, T= 293 K. Final R = 0.064 for 2150 observed reflections. The niflumic acid anions consist essentially of three planar groupings, namely, two six-membered rings and a carboxylate group attached to one of them. The invariant common structural features observed in the crystal structures of fenamates, namely, the coplanarity of the carboxyl group and the six-membered ring bearing it, and the internal hydrogen bond between the carboxyl group and the imino N atom that bridges the two sixmembered rings, are retained in the complex. The amino N atom is gauche with respect to the terminal hydroxyl group in the ethanolamine cation. The complexation between the two molecules is achieved through ionic and hydrogen-bonded interactions involving the carboxylate group in niflumic acid.

Structural Response of Partially Fibrous Concrete Beams

The inclusion of fibers into a matrix over only a partial thickness of the beam is regarded as partially fiber reinforcing a beam. This concept is fully invoked in the present investigation. A tensile strain enhancement factor, t, as determined by a direct tension test, forms a convenient engineering parameter that takes care of the influence of the aspect ratio and volume fraction of the given type of fiber. The appropriate thickness of the beam section to be reinforced with fibers is computed using the above parameter. Necessary analytical expressions were developed to compute the moment enhancement factor associated with different values of the parameter, t. The validity of the approach was experimentally demonstrated. Practically similar deflection patterns for fully and partially fibrous sections were observed. The applicability of the method developed in practical situations, such as the design of airfield and highway pavements with fiber conretes, is cited.

The Broad-Line Type Ic Supernoava SN 2007ru: Adding To The Diversity Of Type Ic Supernovae

Photometric and spectral evolution of the Type Ic supernova SN 2007ru until around 210 days after maximum are presented. The spectra show broad spectral features due to very high expansion velocity, normally seen in hypernovae. The photospheric velocity is higher than other normal Type Ic supernovae (SNe Ic). It is lower than SN 1998bw at similar to 8 days after the explosion, but is comparable at later epochs. The light curve (LC) evolution of SN 2007ru indicates a fast rise time of 8 +/- 3 days to B-band maximum and postmaximum decline more rapid than other broad-line SNe Ic. With an absolute V magnitude of -19.06, SN 2007ru is comparable in brightness with SN 1998bw and lies at the brighter end of the observed SNe Ic. The ejected mass of Ni-56 is estimated to be similar to 0.4 M-circle dot. The fast rise and decline of the LC and the high expansion velocity suggest that SN 2007ru is an explosion with a high kinetic energy/ejecta mass ratio (E-K/M-ej). This adds to the diversity of SNe Ic. Although the early phase spectra are most similar to those of broad-line SN 2003jd, the [O I] line profile in the nebular spectrum of SN 2007ru shows the singly peaked profile, in contrast to the doubly peaked profile in SN 2003jd. The singly peaked profile, together with the high luminosity and the high expansion velocity, may suggest that SN 2007ru could be an aspherical explosion viewed from the polar direction. Estimated oxygen abundance 12 + log(O/H) of similar to 8.8 indicates that SN 2007ru occurred in a region with nearly solar metallicity.

Unusual Structural Isomerization Of Monopropiophenone Thiocarbonohydrazone

Monopropiophenone thiocarbonohydrazone has been isolated in both linear and cyclic isomeric forms. Each form has been shown to isomerize and exist in equilibrium with the other in DMSO-d6 solution by 1H and 13C NMR spectroscopy. The kinetics of this transformation show attainment of equilibrium in approximately 6 h, with a linear to cyclic configuration ratio of 40:60.

Structural Basis of Drug Resistance by Genetic Variants of HIV Type 1 Clade C Protease from India

Using computer modeling of three-dimensional structures and structural information available on the crystal structures of HIV-1 protease, we investigated the structural effects of mutations, in treatment-naive and treatment-exposed individuals from India and postulated mechanisms of resistance in clade C variants. A large number of models (14) have been generated by computational mutation of the available crystal structures of drug bound proteases. Localized energy minimization was carried out in and around the sites of mutation in order to optimize the geometry of interactions present. Most of the mutations result in structural differences at the flap that favors the semiopen state of the enzyme. Some of the mutations were also found to confer resistance by affecting the geometry of the active site. The E35D mutation affects the flap structure in clade B strains and E35N and E35K mutation, seen in our modeled strains, have a more profound effect. Common polymorphisms at positions 36 and 63 in clade C also affected flap structure. Apart from a few other residues Gln-58, Asn-83, Asn-88, and Gln-92 and their interactions are important for the transition from the closed to the open state. Development of protease inhibitors by structure-based design requires investigation of mechanisms operative for clade C to improve the efficacy of therapy.

On the structural features of doped amorphous chalcogenide semiconductors

A study of Bi-doped amorphous (Ge42S58)100−xBix and Ge20S80−xBix has been carried out by differential thermal analysis (DTA) and X-ray diffraction methods so as to elucidate the impurity-induced modifications in the semiconductors. Thermal analysis reveals the presence of complex structural units in the modified material. An interesting feature of this study is the existence of a double glass transition in Ge20S80−xBix, which is reported for the first time in this system.

Structural Polymorphism of the Nucleosomal DNA and Implications for Protein Binding

A nucleosome forms a basic unit of the chromosome structure. A biologically relevant question is how much of the nucleosomal conformational space is accessible to protein-free DNA, and what proportion of the nucleosomal conformations are induced by bound histones. To investigate this, we have analysed high resolution xray crystal structure datasets of DNA in protein-free as well as protein-bound forms, and compared the dinucleotide step parameters for the two datasets with those for high resolution nucleosome structures. Our analysis shows that most of the dinucleotide step parameter values for the nucleosome structures lie within the range accessible to protein-free DNA, indirectly indicating that the histone core plays more of a stabilizing role. The nucleosome structures are observed to assume smooth and nearly planar curvature, implying that ‘normal’ B-DNA like parameters can give rise to a curved geometry at the gross structural level. Different nucleosome

A computerized methodology for structural synthesis of kinematic chains: Part 1- Formulation

In an effort to develop a fully computerized approach for structural synthesis of kinematic chains the steps involved in the method of structural synthesis based on transformation of binary chains [38] have been recast in a format suitable for implementation on a digital computer. The methodology thus evolved has been combined with the algebraic procedures for structural analysis [44] to develop a unified computer program for structural synthesis and analysis of simple jointed kinematic chains with a degree of freedom 0. Applications of this program are presented in the succeeding parts of the paper.

A computerized methodology for structural synthesis of kinematic chains: Part 2 - Application to several fully or partially known cases

The reliability of the computer program for structural synthesis and analysis of simple-jointed kinematic chains developed in Part 1 has been established by applying it to several cases for whuch solutions are either fully or partially available in the literature, such as 7-link, zero-freedom chains; 8- and 10-link, single-freedom chains; 12-link, single-freedom binary chains; and 9-link, two-freedom chains. In the process some discrepancies in the results reported in previous literature have been brought to light.

A computerized methodology for structural synthesis of kinematic chains: Part 3 - application to the new case of 10-link, three- freedom chains

The unified computer program for structural synthesis and analysis developed in Part 1 has been employed to derive the new and complete collection of 97 10-link, three-freedom simple-jointed kinematic chains. The program shows that of these chains, 3 have total freedom, 70 have partial freedom and the remaining 24 have fractionated freedom and that the 97 chains yield a total of 676 distinct mechanisms.