Global variations in peak bone mass as studied by dual-energy X-ray absorptiometry

In 1994, the International Atomic Energy Agency (IAEA) initiated a 5-year Co-ordinated Research Project (CRP) to determine geographical and racial differences in peak bone mineral density (BMD) in men and women aged 15-49 years. The study demonstrates that there are distinct global differences in BMD at the hip and spine in both men and women approximating to one population standard deviation between populations with the highest and lowest BMD. These differences persist following adjustments for age, sex and body size. Such information is valuable in understanding the reasons for global differences in fracture rate and predicting future trends in fracture incidence. This revised version was published online in August 2006 with corrections to the Cover Date.     

Homo and block copolymers of tert-butyl methacrylate by atom transfer radical polymerization

Atom transfer radical polymerization (ATRP) of tert-butyl methacrylate (tBMA) was investigated using cuprous bromide with different ligands, solvents, deactivators, etc. The polymerization in bulk and diphenyl ether solvent system performed using Cu(I)Br complexed with N, N, N′, N″, N″-pentamethyldiethylenetriamine (PMDETA) catalyst in conjunction with 2-bromopropionitrile as an initiator at room temperature showed a curvature in the first-order kinetic plot. The controlled polymerization in methanol solution resulted in slower rate of polymerization and lower molecular weights. Well-defined diblock copolymers of PSt-b-PtBMA synthesized by polystyrene bromo macroinitiator (PSt-Br) with Cu(I)Cl/PMDETA catalyst system yielded predetermined molecular weights and lower polydispersities. Otherwise, the Cu(I)Br/PMDETA catalytic system showed an inefficient polymerization of tert-butyl methacrylate with lower molecular weights and higher polydispersities. Subsequent hydrolysis of the homopolymer refluxed in dioxane with addition of HCl afforded well-defined poly(methacrylic acid).     

Strong CH⋅⋅⋅Halide Hydrogen Bonds from 1,2,3‐Triazoles Quantified Using Pre‐Organized and Shape‐Persistent Triazolophanes

The structures associated with halide (F^?, Cl^?, Br^?) complexation inside CH hydrogen‐bonding macrocyclic receptors, called triazolophanes, are characterized using density functional theory (DFT). The associated binding energies in the gas and solution phases are evaluated. The ruffles in the empty triazolophane become smoothed‐out upon Cl^?‐ and Br^?‐ion binding directly into the middle of the cavity. The largely pre‐organized cavity morphs into an elliptical shape to facilitate shorter hydrogen bonds in the north and south regions and longer ones west and east. The smaller F^? ion sits in, and flattens‐out, only the north (or south) region. The 1,2,3‐triazoles show shorter CH???Cl^? contacts than for the phenylenes. Both Cl^? and Br^? show the same binding geometries but Cl^? has a larger binding energy consistent with its stronger Lewis basicity. Model triads were used to decompose the overall binding energy into those of its components. In the course of this triad analysis, anion polarization was identified and its contribution to the triad???Cl^? binding energy estimated. Consequently, the binding energies for the individual aryl units within the comparatively non‐polarized triazolophanes were estimated. The 1,2,3‐triazoles are twice as strong as the phenylenes thus contributing most of the interaction energy to Cl^?‐ion binding. Therefore, the 1,2,3‐triazoles appear to approach the hydrogen bond strengths of the NH donors of pyrrole units.     

A DSC Study on Cure Kinetics of HTPB-IPDI Urethane Reaction

The kinetics of theurethane-forming cure reaction of hydroxyl terminated polybutadiene (HTPB) with isophorone diisocyanate (IPDI) in presence of ferric tris (acetyl acetonate) (FeAA) catalyst was investigated using differential scanning calorimetry (DSC). The Arrhenius activation parameters, viz., activation energy E and pre-exponential factor A were evaluated using the non-isothermal integral Coats-Redfern equation. The cure reaction was catalysed by ferric acetyl acetonate (FeAA), as revealed from the decrease in reaction temperatures and the increase in rate constants; however, the computed activation energy did not show any correlation to the catalyst concentration. The values of E and A for the uncatalysed reaction at different heating rates showed interdependence through kinetic compensation (KC) effect. Using KC correction, E values were normalised for the value of A for the uncatalysed reaction under identical conditions. The normalised E values decreased exponentially with increase in concentration of FeAA, showing high propensity of the HTPB-IPDI system for catalysis.This revised version was published online in November 2005 with corrections to the Cover Date.     

Synthesis of on resin poly(propylene imine) dendrimer and its use as organocatalyst

Solid phase synthesis of poly(propylene imine) dendrimer is described. An iterative synthesis including double Michael addition of acrylonitrile to the primary amino groups on crosslinked polystyrene support followed by reduction of nitrile groups to amino groups give poly(propylene imine) dendrimers up to third generation attached to the polystyrene support. The supported dendrimer is used as an organocatalyst to Knoevenagel condensations. The supported catalyst showed good selectivity and the product was obtained in excellent yield under green reaction conditions. Densely packed amino groups enhance catalysis by a co-operative effect. The catalyst is recoverable and reusable.     

Self‐Assembly of DNA–Oligo(p‐phenylene‐ethynylene) Hybrid Amphiphiles into Surface‐Engineered Vesicles with Enhanced Emission

Surface‐addressable nanostructures of linearly π‐conjugated molecules play a crucial role in the emerging field of nanoelectronics. Herein, by using DNA as the hydrophilic segment, we demonstrate a solid‐phase “click” chemistry approach for the synthesis of a series of DNA–chromophore hybrid amphiphiles and report their reversible self‐assembly into surface‐engineered vesicles with enhanced emission. DNA‐directed surface addressability of the vesicles was demonstrated through the integration of gold nanoparticles onto the surface of the vesicles by sequence‐specific DNA hybridization. This system could be converted to a supramolecular light‐harvesting antenna by integrating suitable FRET acceptors onto the surface of the nanostructures. The general nature of the synthesis, surface addressability, and biocompatibility of the resulting nanostructures offer great promises for nanoelectronics, energy, and biomedical applications.     

Polymer blend nanocomposites: effect of mercapto silane modified kaolin clay on the thermal properties of Polypropylene/Polystyrene blend

Nanocomposites based on polypropylene/polystyrene blends were prepared by melt mixing in a Thermo Haake Rheochord mixer. The effect of mercapto silane modified kaolin clay on the properties of nanocomposites has been studied. The characterization of polypropylene/polystyrene/clay nanocomposites was made by dynamic mechanical analysis, scanning electron microscope, and transmission electron microscopic, and the thermal stability was determined by using Thermogravimetric analysis. The activation energy of degradation was determined using three mathematical models, namely Horowitz–Metzger, Coats–Redfern and Broido's methods, and the results were compared. TGA results show an improved thermal stability for nanocomposite than the pure blend. The improvement in thermal stability of nanocomposites was confirmed by increasing the activation energy. Transmission electron microscopic observations showed that nanoclay layers were intercalated on the polymer matrix and were located at the interface between the two polymers Copyright © 2014 John Wiley & Sons, Ltd.     

The first polymorph in the family of nucleobases: a second form of cytosine

A new polymorph of cytosine, C₄H₅N₃O, is reported half a century after the report of its first known crystal structure [Barker & Marsh (1964). Acta Cryst. 17 , 1581–1587]. Cytosine thus provides the first polymorphic example in the category of parent nucleobases. The new form, denoted (Ib), was observed unexpectedly during an attempt to cocrystallize cytosine with catechol. Form (Ib) crystallizes in the orthorhombic centrosymmetric space group Pccn with two molecules in the asymmetric unit. The previously known form, denoted (Ia), crystallizes in the orthorhombic noncentrosymmetric space group P2₁2₁2₁. The cytosine molecule is planar in both forms. Hydrogen‐bonding interactions are also similar for both forms. Infinite one‐dimensional ribbons composed of cytosine base‐pair dimers in R₂²(8) arrangements are observed in both (Ia) and (Ib). However, the way that the ribbons are packed differs in (Ia) and (Ib). This appears to guide the centrosymmetric versus noncentrosymmetric space‐group selection through the formation of an inversion‐related motif in polymorph (Ib) and a helical propagation in polymorph (Ia). A few selected polymorphic systems have been gathered from the Cambridge Structural Database to understand possible structural features responsible for achiral molecules adopting centro‐ and noncentrosymmetric space groups.     

Four oxoindole‐linked α‐alkoxy‐β‐amino acid derivatives

Four structures of oxoindolyl α‐hydroxy‐β‐amino acid derivatives, namely, methyl 2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐methoxy‐2‐phenylacetate, C₂₄H₂₈N₂O₆, (I), methyl 2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐ethoxy‐2‐phenylacetate, C₂₅H₃₀N₂O₆, (II), methyl 2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐[(4‐methoxybenzyl)oxy]‐2‐phenylacetate, C₃₁H₃₄N₂O₇, (III), and methyl 2‐[(anthracen‐9‐yl)methoxy]‐2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐phenylacetate, C₃₈H₃₆N₂O₆, (IV), have been determined. The diastereoselectivity of the chemical reaction involving α‐diazoesters and isatin imines in the presence of benzyl alcohol is confirmed through the relative configuration of the two stereogenic centres. In esters (I) and (III), the amide group adopts an anti conformation, whereas the conformation is syn in esters (II) and (IV). Nevertheless, the amide group forms intramolecular N—H...O hydrogen bonds with the ester and ether O atoms in all four structures. The ether‐linked substituents are in the extended conformation in all four structures. Ester (II) is dominated by intermolecular N—H...O hydrogen‐bond interactions. In contrast, the remaining three structures are sustained by C—H...O hydrogen‐bond interactions.