Raman spectral probe on increased local vibrational modes and phonon lifetimes in Ho3+‐doped Bi2O3 micro‐rods

We report the appearance and enhancement in intensity of impurity related local vibrational modes in Bi₂O₃ : Ho micro‐rods along with normal modes. Pure and Ho‐doped Bi₂O₃ micro‐rods were synthesized by conventional co‐precipitation method at 60 °C. The structural and morphological studies were carried out using powder X‐ray diffraction technique and scanning electron microscopy, respectively. Raman spectroscopic studies reveal the existence of local phonon vibrational modes (LVM) due to the incorporation of Ho³⁺. Harmonic approximation method was employed to find the dopant‐related peak in the Raman spectra. Variation in full width at half maximum for LVM with increase in Ho³⁺ was also investigated. This increase in FWHM indicates the decrease in crystallinity of the doped samples. The phonon lifetime calculation carried out for each samples and the decrease in phonon lifetime with doping concentration make this material a potential candidate for optical and electronic applications. Copyright © 2016 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.     

Ultrasonic sizing of embedded vertical cracks in ferritic steel welds

Embedded vertical cracks are very often encountered in structural components necessitating reliable procedure for determining their size. Specialized ultrasonic techniques are required for estimation of through thickness height of these cracks [Mater. Eval. (1970) 28; J. NDI 26 (1977) 320; NND (1975) 146]. The conventional pulse-echo technique has serious limitations for quantitative estimation of vertical cracks because it is subject to variations due to reflectivity, coupling factors etc. The present study aims to improve the accuracy of embedded crack height measurement based on transit time rather than the reflected amplitude [NDT Int. (1982) 315; J. JSNDT 27 (1978) 118]. A unique method has been developed for generating known sizes of fatigue cracks ranging from 2.5 to 18 mm in height and 15 mm in length. These cracks were generated in rectangular steel specimens and subsequently embedded at predetermined locations using welding. These welded specimens containing the embedded vertical cracks were examined using ultrasonic techniques based on transit time like (a) flaw tip echo method and (b) mode conversion method. Using both the techniques excellent agreement was obtained between the estimated crack height and actual crack height with an accuracy of ±1 mm.     

Diastereoselective Mukaiyama aldol reaction of (N-alkyl) isatins with 2-(trimethylsilyloxy)furan by using lanthanum triflate

An efficient vinylogous Mukaiyama aldol reaction (VMAR) of 2-(trimethylsilyloxy)furan with various (N-alkyl)isatins is described in the presence of lanthanum(III) triflates (5 mol %). The reaction proceeds rapidly and affords the corresponding 3-hydroxy-(5-oxo-2,5-dihydrofuran-2-yl)indolin-2-one in high yields with good diastereoselectivities (threo:erythro ratio up to ≤95:5).     

Biocompatible functionalization of polymersome surfaces: a new approach to surface immobilization and cell targeting using polymersomes

Vesicles assembled from amphiphilic block copolymers represent promising nanomaterials for applications that include drug delivery and surface functionalization. One essential requirement to guide such polymersomes to a desired site in vivo is conjugation of active, targeting ligands to the surface of preformed self-assemblies. Such conjugation chemistry must fulfill criteria of efficiency and selectivity, stability of the resulting bond, and biocompatibility. We have here developed a new system that achieves these criteria by simple conjugation of 4-formylbenzoate (4FB) functionalized polymersomes with 6-hydrazinonicotinate acetone hydrazone (HyNic) functionalized antibodies in aqueous buffer. The number of available amino groups on the surface of polymersomes composed of poly(dimethylsiloxane)-block-poly(2-methyloxazoline) diblock copolymers was investigated by reacting hydrophilic succinimidyl-activated fluorescent dye with polymersomes and evaluating the resulting emission intensity. To prove attachment of biomolecules to polymersomes, HyNic functionalized enhanced yellow fluorescent protein (eYFP) was attached to 4FB functionalized polymersomes, resulting in an average number of 5 eYFP molecules per polymersome. Two different polymersome-antibody conjugates were produced using either antibiotin IgG or trastuzumab. They showed specific targeting toward biotin-patterned surfaces and breast cancer cells. Overall, the polymersome-ligand platform appears promising for therapeutic and diagnostic use.     

Removal of copper by oxygenated pyrolytic tire char: kinetics and mechanistic insights

The kinetics of copper ion (Cu(II)) removal from aqueous solution by pyrolytic tire char was modeled using five different conventional models. A modification to these models was also developed through a modified equation that accounts for precipitation. Conventional first- and second-order reaction models did not fit the copper sorption kinetics well, indicating a lack of simple rate-order dependency on solute concentration. Instead, a reversible first-order rate reaction showed the best fit to the data, indicating a dependence on surface functional groups. Due to the varying solution pH during the sorption process, modified external and internal mass transfer models were employed. Results showed that the sorption of copper onto oxygenated chars was limited by external mass transfer and internal resistance with and without the modification. However, the modification of the sorption process produced very different results for unoxygenated chars, which showed neither internal nor external limitation to sorption. Instead, its slow sorption rate indicates a lack of surface functional groups. The sorption of Cu(II) by oxygenated and unoxygenated chars was also found to occur via three and two distinct stages, respectively.     

Coordination polymers of zinc with (η6-benzenecarboxylate) chromium tricarbonyl

Different coordination polymers were obtained by the reaction of (benzoic acid) chromium tricarbonyl with zinc acetate in the presence of various organic dipyridyl linkers. Depending on the nature of the linker either monomeric or polymeric compounds were obtained. Reactions of (benzoic acid) chromium tricarbonyl with zinc acetate and bidentate pyridine based ligands 4,4'-bipyridine (4,4'-bipy), 1,2-bis(4-pyridyl)ethane (bpe), 1,3-bis(4-pyridyl)propane (tmdp), and 2,2'dipyridylamine (DPA) afforded the novel coordination polymers [Zn[{η(6)-C(6)H(5)COO}Cr(CO)(3)](2)(4,4'-bipy)](n), [Zn[{η(6)-C(6)H(5)COO}Cr(CO)(3)](2)(bpe)](n), [Zn[{η(6)-C(6)H(5)COO}Cr(CO)(3)](2)(tmdp)}](n), and the monomeric complex [Zn[{η(6)-C(6)H(5)COO}Cr(CO)(3)](2)(DPA)]. The solid state structures of all compounds were determined by single crystal X-ray diffraction. By using 1,3-bis(4-pyridyl)propane as a linker a chiral infinite helical structure was formed in the solid state. Thermogravimetric analysis (TGA) studies showed that upon heating the carbonyl groups of the {η(6)-C(6)H(5)COO}Cr(CO)(3) anion were lost before the organic ligand sphere was thermally decomposed.     

Li2MnO3-based composite cathodes for lithium batteries: A novel synthesis approach and new structures

A new, simple technique has been demonstrated for fabricating high-capacity composite electrode structures. In this technique, Li₂MnO₃ is leached in acid in the presence of soluble transition metal ions and subsequently annealed between 450 and 850 °C. The technique can be used to prepare a wide variety of composite compounds, in particular, a new family of ‘layered–rocksalt’ xLi₂MnO₃·(1−x)MO (e.g., M = Ni and Co) structures and modifications thereof, as well as ‘layered–layered’ xLi₂MnO₃·(1−x)LiMO₂ (e.g., M = Mn, Ni, and Co) and ‘layered–spinel’ xLi₂MnO₃·(1−x)LiM₂O₄ (e.g., M = Mn and Ni). This novel approach also holds promise for 1) synthesizing materials that reduce the extent of internal phase transitions of composite cathode structures with a high manganese content, and 2) minimizing the extent to which cells need to be electrochemically activated to remove Li₂O, thereby reducing the extent of the irreversible capacity loss on the first charge/discharge cycle.