hem Hold them to account By timesofindia.indiatimes.com Published On :: Mon, 25 Jan 2010 00:00:00 IST The legal brains hired by Rathore to defend him in the courts are as responsible as Rathore himself for implicating Ruchika's brother in false cases. Full Article
hem As first batch of onions goes to Bangladesh by train, Maharashtra seeks reintroduction of MEIS scheme By indianexpress.com Published On :: Sat, 09 May 2020 14:14:16 +0000 Full Article Cities Pune
hem 49ers' Trent Williams, Laken Tomlinson building chemistry from afar By sports.yahoo.com Published On :: Sat, 09 May 2020 21:43:31 GMT Laken Tomlinson and Trent Williams can't spend time together at the 49ers facility, but they are still finding a way to bond. Full Article article News
hem Mother’s Day 2020: ‘One Day isn’t enough to thank our mothers’, says Divya Khosla Kumar who feels we should express our gratitude towards them whenever we feel it By Published On :: Mother’s Day 2020: ‘One Day isn’t enough to thank our mothers’, says Divya Khosla Kumar who feels we should express our gratitude towards them whenever we feel it Full Article
hem Government disburses Rs 18,253 crore to 9.13 crore farmers under PM-Kisan scheme By Published On :: Government disburses Rs 18,253 crore to 9.13 crore farmers under PM-Kisan scheme Full Article
hem Govt extends early bird scheme to commercial establishments | Hyderabad News - Times of India By Published On :: Govt extends early bird scheme to commercial establishments | Hyderabad News - Times of India Full Article
hem Punjab to honour cops under 'Appreciate and Commend' scheme By www.newkerala.com Published On :: Mon, 17 Feb 2020 17:06:02 +0530 Full Article
hem Even I don't have birth certificate, half of Punjab can't produce them: Amarinder opposes CAA, NRC, NPR By www.newkerala.com Published On :: Fri, 20 Mar 2020 11:48:01 +0530 Full Article
hem Vigilance arrests chemist selling sanitizers, masks at exorbitant rates in Punjab By www.newkerala.com Published On :: Sat, 28 Mar 2020 14:58:01 +0530 Full Article
hem Rashtriya Chemicals & Fertilisers records 35 per cent hike in sale of ‘Suphala’ fertilisers By www.thehindubusinessline.com Published On :: Sun, 10 May 2020 10:24:24 +0530 A PIB press statement said that Rashtriya Chemicals & Fertilisers Ltd (RCF) has registered a hike of 35.47 per cent in the sale of fertilisers und Full Article Companies
hem DNA Exclusive: Arti Singh remembers how her first letter to mother brought them closer By www.dnaindia.com Published On :: Sun, 10 May 2020 05:23:00 GMT Arti Singh remembered her first letter to mother on the occasion of Mothers' Day Full Article Entertainment Television
hem 'Allow private vehicles to ferry them': Sanjay Raut's advice to Maharashtra govt on migrant situation By www.dnaindia.com Published On :: Sun, 10 May 2020 05:34:00 GMT Sanjay Raut took to his official Twitter handle on Sunday to let know his suggestion via a post regarding the situation. Full Article India
hem Shraddha Kapoor’s airport looks mirror the ‘girl next door’ theme By indianexpress.com Published On :: Sat, 09 May 2020 14:19:19 +0000 Full Article
hem Microfluidic electrochemical cell for in situ structural characterization of amorphous thin-film catalysts using high-energy X-ray scattering By scripts.iucr.org Published On :: 2019-08-09 Porous, high-surface-area electrode architectures are described that allow structural characterization of interfacial amorphous thin films with high spatial resolution under device-relevant functional electrochemical conditions using high-energy X-ray (>50 keV) scattering and pair distribution function (PDF) analysis. Porous electrodes were fabricated from glass-capillary array membranes coated with conformal transparent conductive oxide layers, consisting of either a 40 nm–50 nm crystalline indium tin oxide or a 100 nm–150 nm-thick amorphous indium zinc oxide deposited by atomic layer deposition. These porous electrodes solve the problem of insufficient interaction volumes for catalyst thin films in two-dimensional working electrode designs and provide sufficiently low scattering backgrounds to enable high-resolution signal collection from interfacial thin-film catalysts. For example, PDF measurements were readily obtained with 0.2 Å spatial resolution for amorphous cobalt oxide films with thicknesses down to 60 nm when deposited on a porous electrode with 40 µm-diameter pores. This level of resolution resolves the cobaltate domain size and structure, the presence of defect sites assigned to the domain edges, and the changes in fine structure upon redox state change that are relevant to quantitative structure–function modeling. The results suggest the opportunity to leverage the porous, electrode architectures for PDF analysis of nanometre-scale surface-supported molecular catalysts. In addition, a compact 3D-printed electrochemical cell in a three-electrode configuration is described which is designed to allow for simultaneous X-ray transmission and electrolyte flow through the porous working electrode. Full Article text
hem Coherent Bragg imaging of 60 nm Au nanoparticles under electrochemical control at the NanoMAX beamline By scripts.iucr.org Published On :: 2019-08-27 Nanoparticles are essential electrocatalysts in chemical production, water treatment and energy conversion, but engineering efficient and specific catalysts requires understanding complex structure–reactivity relations. Recent experiments have shown that Bragg coherent diffraction imaging might be a powerful tool in this regard. The technique provides three-dimensional lattice strain fields from which surface reactivity maps can be inferred. However, all experiments published so far have investigated particles an order of magnitude larger than those used in practical applications. Studying smaller particles quickly becomes demanding as the diffracted intensity falls. Here, in situ nanodiffraction data from 60 nm Au nanoparticles under electrochemical control collected at the hard X-ray nanoprobe beamline of MAX IV, NanoMAX, are presented. Two-dimensional image reconstructions of these particles are produced, and it is estimated that NanoMAX, which is now open for general users, has the requisites for three-dimensional imaging of particles of a size relevant for catalytic applications. This represents the first demonstration of coherent X-ray diffraction experiments performed at a diffraction-limited storage ring, and illustrates the importance of these new sources for experiments where coherence properties become crucial. Full Article text
hem Contributions of charge-density research to medicinal chemistry By journals.iucr.org Published On :: Contributions of experimental and selected theoretical charge-density research to medicinal chemistry are reviewed; combining experimental methods from high-resolution small-molecule and macromolecular crystallography with theory proves to be fruitful. Full Article text
hem Chemical crystallography and crystal engineering By journals.iucr.org Published On :: Today, there is very little doubt that chemistry owes as much to crystallography as crystallography does to chemistry. This mutual synergy defines modern chemical crystallography. Full Article text
hem London soil pollution worst on former Blitz bomb sites - Chemistry World By www.chemistryworld.com Published On :: Mon, 15 Jan 2018 08:00:00 GMT London soil pollution worst on former Blitz bomb sites Chemistry World Full Article
hem The crystal structure of the heme d1 biosynthesis-associated small c-type cytochrome NirC reveals mixed oligomeric states in crystallo By journals.iucr.org Published On :: The crystal structure of the c-type cytochrome NirC from Pseudomonas aeruginosa has been determined and reveals the simultaneous presence of monomers and 3D domain-swapped dimers in the same asymmetric unit. Full Article text
hem 5,13-Bis(4-methoxyphenyl)dinaphtho[2,3-b:2',3'-d]thiophene S,S-dioxide dichloromethane hemisolvate By scripts.iucr.org Published On :: 2019-11-19 The title compound, C34H24O4S·0.5CH2Cl2, crystallizes with two independent molecules and one dichloromethane solvent molecule in the asymmetric unit. The crystal packing is consolidated by C—H⋯O hydrogen bonds. Full Article text
hem 5-(3-Hydroxyphenyl)-1,3,4-oxadiazole-2(3H)-thione hemihydrate By scripts.iucr.org Published On :: 2019-11-15 The title 1,3,4-oxadiazole derivative crystallizes as a hemihydrate, C8H6N2O2S·0.5H2O, with the water molecule located on a twofold rotation axis. The 1,3,4-oxadiazole molecule is essentially planar, the r.m.s. deviation of the non-H atoms being 0.0443 Å. The dihedral angle between the mean planes of the phenyl and oxadiazole rings is 6.101 (17)°. In the crystal, molecules are linked via O—H⋯S and N—H⋯O hydrogen bonds involving the water molecule, the N—H group and the thione S atom into undulating ribbons. Additional π–π interactions generate a two-dimensional supramolecular framework extending parallel to (001). Full Article text
hem N-[(E)-Quinolin-2-ylmethylidene]-1,2,4-triazol-4-amine hemihydrate By scripts.iucr.org Published On :: 2020-02-03 The title hemihydrate, C12H9N5·0.5H2O, was isolated from the condensation reaction of quinoline-2-carbaldehyde with 4-amino-4H-1,2,4-triazole. The Schiff base molecule adopts an E configuration about the C=N bond and is approximately planar, with a dihedral angle between the quinoline ring system and the 1,2,4-triazole ring of 12.2 (1)°. In the crystal, one water molecule bridges two Schiff base molecules via O—H⋯N hydrogen bonds. The Schiff base molecules are interconnected by π–π stacking interactions [centroid-centroid distances of 3.7486 (7) and 3.9003 (7) Å] into columns along [1overline{1}0]. Full Article text
hem Crystal structure and DFT study of (E)-2-chloro-4-{[2-(2,4-dinitrophenyl)hydrazin-1-ylidene]methyl}phenol acetonitrile hemisolvate By scripts.iucr.org Published On :: 2019-05-10 The title Schiff base compound, C13H9ClN4O5·0.5CH3CN, crystallizes as an acetonitrile hemisolvate; the solvent molecule being located on a twofold rotation axis. The molecule is nearly planar, with a dihedral angle between the two benzene rings of 3.7 (2)°. The configuration about the C=N bond is E, and there is an intramolecular N—H⋯Onitro hydrogen bond present forming an S(6) ring motif. In the crystal, molecules are linked by O—H⋯O and N—H⋯O hydrogen bonds, forming layers lying parallel to (10overline{1}). The layers are linked by C—H⋯Cl hydrogen bonds, forming a supramolecular framework. Within the framework there are offset π–π stacking interactions [intercentroid distance = 3.833 (2) Å] present involving inversion-related molecules. The DFT study shows that the HOMO and LUMO are localized in the plane extending from the phenol ring to the 2,4-dinitrobenzene ring, and the HOMO–LUMO gap is found to be 0.13061 a.u. Full Article text
hem 2-[(4-Bromophenyl)sulfanyl]-2-methoxy-1-phenylethan-1-one: crystal structure, Hirshfeld surface analysis and computational chemistry By scripts.iucr.org Published On :: 2019-05-17 The title compound, C15H13BrO2S, comprises three different substituents bound to a central (and chiral) methine-C atom, i.e. (4-bromophenyl)sulfanyl, benzaldehyde and methoxy residues: crystal symmetry generates a racemic mixture. A twist in the molecule is evident about the methine-C—C(carbonyl) bond as evidenced by the O—C—C—O torsion angle of −20.8 (7)°. The dihedral angle between the bromobenzene and phenyl rings is 43.2 (2)°, with the former disposed to lie over the oxygen atoms. The most prominent feature of the packing is the formation of helical supramolecular chains as a result of methyl- and methine-C—H⋯O(carbonyl) interactions. The chains assemble into a three-dimensional architecture without directional interactions between them. The nature of the weak points of contacts has been probed by a combination of Hirshfeld surface analysis, non-covalent interaction plots and interaction energy calculations. These point to the importance of weaker H⋯H and C—H⋯C interactions in the consolidation of the structure. Full Article text
hem 2-Methyl-4-(4-nitrophenyl)but-3-yn-2-ol: crystal structure, Hirshfeld surface analysis and computational chemistry study By scripts.iucr.org Published On :: 2019-07-23 The di-substituted acetylene residue in the title compound, C11H11NO3, is capped at either end by di-methylhydroxy and 4-nitrobenzene groups; the nitro substituent is close to co-planar with the ring to which it is attached [dihedral angle = 9.4 (3)°]. The most prominent feature of the molecular packing is the formation, via hydroxy-O—H⋯O(hydroxy) hydrogen bonds, of hexameric clusters about a site of symmetry overline{3}. The aggregates are sustained by 12-membered {⋯OH}6 synthons and have the shape of a flattened chair. The clusters are connected into a three-dimensional architecture by benzene-C—H⋯O(nitro) interactions, involving both nitro-O atoms. The aforementioned interactions are readily identified in the calculated Hirshfeld surface. Computational chemistry indicates there is a significant energy, primarily electrostatic in nature, associated with the hydroxy-O—H⋯O(hydroxy) hydrogen bonds. Dispersion forces are more important in the other identified but, weaker intermolecular contacts. Full Article text
hem Crystal structure and chemistry of tricadmium digermanium tetraarsenide, Cd3Ge2As4 By scripts.iucr.org Published On :: 2019-08-02 A cadmium germanium arsenide compound, Cd3Ge2As4, was synthesized using a double-containment fused quartz ampoule method within a rocking furnace and a melt-quench technique. The crystal structure was determined from single-crystal X-ray diffraction (SC-XRD), scanning and transmission electron microscopies (i.e. SEM, STEM, and TEM), and selected area diffraction (SAD) and confirmed with electron backscatter diffraction (EBSD). The chemistry was verified with electron energy loss spectroscopy (EELS). Full Article text
hem Crystal structures and Hirshfeld surface analyses of (E)-N'-benzylidene-2-oxo-2H-chromene-3-carbohydrazide and the disordered hemi-DMSO solvate of (E)-2-oxo-N'-(3,4,5-trimethoxybenzylidene)-2H-chromene-3-carbohydrazide: lattice ene By scripts.iucr.org Published On :: 2019-09-03 The crystal structures of the disordered hemi-DMSO solvate of (E)-2-oxo-N'-(3,4,5-trimethoxybenzylidene)-2H-chromene-3-carbohydrazide, C20H18N2O6·0.5C2H6OS, and (E)-N'-benzylidene-2-oxo-2H-chromene-3-carbohydrazide, C17H12N2O3 (4: R = C6H5), are discussed. The non-hydrogen atoms in compound [4: R = (3,4,5-MeO)3C6H2)] exhibit a distinct curvature, while those in compound, (4: R = C6H5), are essential coplanar. In (4: R = C6H5), C—H⋯O and π–π intramolecular interactions combine to form a three-dimensional array. A three-dimensional array is also found for the hemi-DMSO solvate of [4: R = (3,4,5-MeO)3C6H2], in which the molecules of coumarin are linked by C—H⋯O and C—H⋯π interactions, and form tubes into which the DMSO molecules are cocooned. Hirshfeld surface analyses of both compounds are reported, as are the lattice energy and intermolecular interaction energy calculations of compound (4: R = C6H5). Full Article text
hem Crystal structure, Hirshfeld surface analysis and physicochemical characterization of bis[4-(dimethylamino)pyridinium] di-μ-chlorido-bis[dichloridomercurate(II)] By scripts.iucr.org Published On :: 2019-10-03 The title molecular salt, (C7H11N2)2[Hg2Cl6], crystallizes with two 4-(dimethylamino)pyridinium cations (A and B) and two half hexachloridodimercurate(II) anions in the asymmetric unit. The organic cations exhibit essentially the same features with an almost planar pyridyl ring (r.m.s. deviations of 0.0028 and 0.0109 Å), which forms an inclined dihedral angle with the dimethyamino group [3.06 (1) and 1.61 (1)°, respectively]. The dimethylamino groups in the two cations are planar, and the C—N bond lengths are shorter than that in 4-(dimethylamino)pyridine. In the crystal, mixed cation–anion layers lying parallel to the (010) plane are formed through N—H⋯Cl hydrogen bonds and adjacent layers are linked by C—H⋯Cl hydrogen bonds, forming a three-dimensional network. The analyses of the calculated Hirshfeld surfaces confirm the relevance of the above intermolecular interactions, but also serve to further differentiate the weaker intermolecular interactions formed by the organic cations and inorganic anions, such as π–π and Cl⋯Cl interactions. The powder XRD data confirms the phase purity of the crystalline sample. Furthermore, the vibrational absorption bands were identified by IR spectroscopy and the optical properties were studied by using optical UV–visible absorption spectroscopy. Full Article text
hem Crystal structures, syntheses, and spectroscopic and electrochemical measurements of two push–pull chromophores: 2-[4-(dimethylamino)benzylidene]-1H-indene-1,3(2H)-dione and (E)-2-{3-[4-(dimethylamino)phenyl By scripts.iucr.org Published On :: 2019-10-03 The title pull–push chromophores, 2-[4-(dimethylamino)benzylidene]-1H-indene-1,3(2H)-dione, C18H15NO2 (ID[1]) and (E)-2-{3-[4-(dimethylamino)phenyl]allylidene}-1H-indene-1,3(2H)-dione, C20H17NO2 (ID[2]), have donor–π-bridge–acceptor structures. The molecule with the short π-bridge, ID[1], is almost planar while for the molecule with a longer bridge, ID[2], is less planar. The benzene ring is inclined to the mean plane of the 2,3-dihydro-1H-indene unit by 3.19 (4)° in ID[1] and 13.06 (8)° in ID[2]. The structures of three polymorphs of compound ID[1] have been reported: the α-polymorph [space group P21/c; Magomedova & Zvonkova (1978). Kristallografiya, 23, 281–288], the β-polymorph [space group P21/c; Magomedova & Zvonkova (1980). Kristallografiya, 25 1183–1187] and the γ-polymorph [space group Pna21; Magomedova, Neigauz, Zvonkova & Novakovskaya (1980). Kristallografiya, 25, 400–402]. The molecular packing in ID[1] studied here is centrosymmetric (space group P21/c) and corresponds to the β-polymorph structure. The molecular packing in ID[2] is non-centrosymmetric (space group P21), which suggests potential NLO properties for this crystalline material. In both compounds, there is short intramolecular C—H⋯O contact present, enclosing an S(7) ring motif. In the crystal of ID[1], molecules are linked by C—H⋯O hydrogen bonds and C—H⋯π interactions, forming layers parallel to the bc plane. In the crystal of ID[2], molecules are liked by C—H⋯O hydrogen bonds to form 21 helices propagating along the b-axis direction. The molecules in the helix are linked by offset π–π interactions with, for example, a centroid–centroid distance of 3.9664 (13) Å (= b axis) separating the indene rings, and an offset of 1.869 Å. Spectroscopic and electrochemical measurements show the ability of these compounds to easily transfer electrons through the π-conjugated chain. Full Article text
hem Crystal structure and Hirshfeld surface analysis of 2,2'-{(1E,1'E)-[ethane-1,2-diylbis(azanylylidene)]bis(methanylylidene)}bis[4-(trifluoromethoxy)phenol]copper(II) hydroquinone hemisolvate By scripts.iucr.org Published On :: 2019-10-29 In the title complex, [Cu(C18H12F6N2O4)]·0.5C6H6O2, the CuII ion has a square-planar coordination geometry, being ligated by two N and two O atoms of the tetradentate open-chain Schiff base ligand 6,6'-{(1E,1'E)-[ethane-1,2-diylbis(azanylylidene)]bis(methanylylidene)}bis[2-(trifluoromethoxy)phenol]. The crystal packing is stabilized by intramolecular O—H⋯O and intermolecular C—H⋯F, C—H⋯O and C—H⋯π hydrogen bonds. In addition, weak π–π interactions form a three-dimensional structure. Hirshfeld surface analysis and two-dimensional fingerprint plots were performed and created to analyze the intermolecular interactions present in the crystal, indicating that the most important contributions for the crystal packing are from F⋯H/H⋯F (25.7%), H⋯H (23.5%) and C⋯H/H⋯C (12.6%) interactions. Full Article text
hem An iridium complex with an unsupported Ir—Zn bond: diiodido(η5-pentamethylcyclopentadienyl)bis(trimethylphosphane)iridiumzinc(Ir—Zn) benzene hemisolvate By scripts.iucr.org Published On :: 2019-11-05 The title compound, [IrZnI2(C10H15)(C3H9P)2]·0.5C6H6 or [Cp*(PMe3)2Ir]-[ZnI2] (Cp* = cyclo-C5Me5) was obtained and characterized as its benzene solvate [Cp*(PMe3)2Ir]-[ZnI2]·0.5C6H6. The bimetallic complex in this structure contains the Lewis-acidic fragment ZnI2 bonded to the Lewis-basic fragment Cp*(PMe3)2Ir, with an Ir—Zn bond distance of 2.452 (1) Å. The compound was obtained by reacting [Cp*(PMe3)IrI2] with 2-Ad2Zn (2-Ad = 2-adamantyl), resulting in the reduction of the IrIII complex and formation of the IrI–ZnII adduct. The crystal studied was a twin by non-merohedry with a refined BASF parameter of 0.223 (1). Full Article text
hem Crystal structures and Hirshfeld surface analyses of (E)-N'-benzylidene-2-oxo-2H-chromene-3-carbohydrazide and the disordered hemi-DMSO solvate of (E)-2-oxo-N'-(3,4,5-trimethoxybenzylidene)-2H-chromene-3-carbohydrazide: lattice ene By scripts.iucr.org Published On :: 2019-11-29 In the paper by Gomes et al. [Acta Cryst. (2019), E75, 1403–1410], there was an error and omission in the author and affiliation list. Full Article text
hem An unusually short intermolecular N—H⋯N hydrogen bond in crystals of the hemi-hydrochloride salt of 1-exo-acetamidopyrrolizidine By scripts.iucr.org Published On :: 2020-01-01 The title compound [systematic name: (1R*, 8S)-2-acetamidooctahydropyrrolizin-4-ium chloride–N-[(1R, 8S)-hexahydro-1H-pyrrolizin-2-yl)acetamide (1/1)], 2(C9H16N2O)·HCl or C9H17N2O+·Cl−·C9H16N2O, arose as an unexpected product when 1-exo-acetamidopyrrolizidine (AcAP; C9H16N2O) was dissolved in CHCl3. Within the AcAP pyrrolizidine group, the unsubstituted five-membered ring is disordered over two orientations in a 0.897 (5):0.103 (5) ratio. Two AcAP molecules related by a crystallographic twofold axis link to H+ and Cl− ions lying on the rotation axis, thereby forming N—H⋯N and N—H⋯Cl⋯H—N hydrogen bonds. The first of these has an unusually short N⋯N separation of 2.616 (2) Å: refinement of different models against the present data set could not distinguish between a symmetrical hydrogen bond (H atom lying on the twofold axis and equidistant from the N atoms) or static or dynamic disorder models (i.e. N—H⋯N + N⋯H—N). Computational studies suggest that the disorder model is slightly more stable, but the energy difference is very small. Full Article text
hem A redetermination of the crystal structure of the mannitol complex NH4[Mo2O5(C6H11O6)]·H2O: hydrogen-bonding scheme and Hirshfeld surface analysis By scripts.iucr.org Published On :: 2020-03-10 The redetermined structure [for the previous study, see: Godfrey & Waters (1975). Cryst. Struct. Commun. 4, 5–8] of ammonium μ-oxido-μ-[1,5,6-trihydroxyhexane-2,3,4-tris(olato)]bis[dioxidomolybdenum(V)] monohydrate, NH4[Mo2(C6H11O6)O5]·H2O, was obtained from an attempt to prepare a glutamic acid complex from the [Co2Mo10H4O38]6− anion. Subsequent study indicated the complex arose from a substantial impurity of mannitol in the glutamic acid sample used. All hydrogen atoms have been located in the present study and the packing displays N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds. A Hirshfeld surface analysis was also performed. Full Article text
hem Why is interoperability between the two fields of chemical crystallography and protein crystallography so difficult? By scripts.iucr.org Published On :: 2019-08-13 The interoperability of chemical and biological crystallographic data is a key challenge to research and its application to pharmaceutical design. Research attempting to combine data from the two disciplines, small-molecule or chemical crystallography (CX) and macromolecular crystallography (MX), will face unique challenges including variations in terminology, software development, file format and databases which differ significantly from CX to MX. This perspective overview spans the two disciplines and originated from the investigation of protein binding to model radiopharmaceuticals. The opportunities of interlinked research while utilizing the two databases of the CSD (Cambridge Structural Database) and the PDB (Protein Data Bank) will be highlighted. The advantages of software that can handle multiple file formats and the circuitous route to convert organometallic small-molecule structural data for use in protein refinement software will be discussed. In addition some pointers to avoid being shipwrecked will be shared, such as the care which must be taken when interpreting data precision involving small molecules versus proteins. Full Article text
hem Expression and interactions of stereochemically active lone pairs and their relation to structural distortions and thermal conductivity By scripts.iucr.org Published On :: 2020-03-31 In chemistry, stereochemically active lone pairs are typically described as an important non-bonding effect, and recent interest has centred on understanding the derived effect of lone pair expression on physical properties such as thermal conductivity. To manipulate such properties, it is essential to understand the conditions that lead to lone pair expression and provide a quantitative chemical description of their identity to allow comparison between systems. Here, density functional theory calculations are used first to establish the presence of stereochemically active lone pairs on antimony in the archetypical chalcogenide MnSb2O4. The lone pairs are formed through a similar mechanism to those in binary post-transition metal compounds in an oxidation state of two less than their main group number [e.g. Pb(II) and Sb(III)], where the degree of orbital interaction (covalency) determines the expression of the lone pair. In MnSb2O4 the Sb lone pairs interact through a void space in the crystal structure, and their their mutual repulsion is minimized by introducing a deflection angle. This angle increases significantly with decreasing Sb—Sb distance introduced by simulating high pressure, thus showing the highly destabilizing nature of the lone pair interactions. Analysis of the chemical bonding in MnSb2O4 shows that it is dominated by polar covalent interactions with significant contributions both from charge accumulation in the bonding regions and from charge transfer. A database search of related ternary chalcogenide structures shows that, for structures with a lone pair (SbX3 units), the degree of lone pair expression is largely determined by whether the antimony–chalcogen units are connected or not, suggesting a cooperative effect. Isolated SbX3 units have larger X—Sb—X bond angles and therefore weaker lone pair expression than connected units. Since increased lone pair expression is equivalent to an increased orbital interaction (covalent bonding), which typically leads to increased heat conduction, this can explain the previously established correlation between larger bond angles and lower thermal conductivity. Thus, it appears that for these chalcogenides, lone pair expression and thermal conductivity may be related through the degree of covalency of the system. Full Article text
hem Biochemical and structural explorations of α-hydroxyacid oxidases reveal a four-electron oxidative decarboxylation reaction By scripts.iucr.org Published On :: 2019-07-30 p-Hydroxymandelate oxidase (Hmo) is a flavin mononucleotide (FMN)-dependent enzyme that oxidizes mandelate to benzoylformate. How the FMN-dependent oxidation is executed by Hmo remains unclear at the molecular level. A continuum of snapshots from crystal structures of Hmo and its mutants in complex with physiological/nonphysiological substrates, products and inhibitors provides a rationale for its substrate enantioselectivity/promiscuity, its active-site geometry/reactivity and its direct hydride-transfer mechanism. A single mutant, Y128F, that extends the two-electron oxidation reaction to a four-electron oxidative decarboxylation reaction was unexpectedly observed. Biochemical and structural approaches, including biochemistry, kinetics, stable isotope labeling and X-ray crystallography, were exploited to reach these conclusions and provide additional insights. Full Article text
hem Improved chemistry restraints for crystallographic refinement by integrating the Amber force field into Phenix By scripts.iucr.org Published On :: 2020-01-01 The refinement of biomolecular crystallographic models relies on geometric restraints to help to address the paucity of experimental data typical in these experiments. Limitations in these restraints can degrade the quality of the resulting atomic models. Here, an integration of the full all-atom Amber molecular-dynamics force field into Phenix crystallographic refinement is presented, which enables more complete modeling of biomolecular chemistry. The advantages of the force field include a carefully derived set of torsion-angle potentials, an extensive and flexible set of atom types, Lennard–Jones treatment of nonbonded interactions and a full treatment of crystalline electrostatics. The new combined method was tested against conventional geometry restraints for over 22 000 protein structures. Structures refined with the new method show substantially improved model quality. On average, Ramachandran and rotamer scores are somewhat better, clashscores and MolProbity scores are significantly improved, and the modeling of electrostatics leads to structures that exhibit more, and more correct, hydrogen bonds than those refined using traditional geometry restraints. In general it is found that model improvements are greatest at lower resolutions, prompting plans to add the Amber target function to real-space refinement for use in electron cryo-microscopy. This work opens the door to the future development of more advanced applications such as Amber-based ensemble refinement, quantum-mechanical representation of active sites and improved geometric restraints for simulated annealing. Full Article text
hem What is the structural chemistry of the living organism at its temperature and pressure? By scripts.iucr.org Published On :: 2020-02-06 The three probes of the structure of matter (X-rays, neutrons and electrons) in biology have complementary properties and strengths. The balance between these three probes within their strengths and weaknesses is perceived to change, even dramatically so at times. For the study of combined states of order and disorder, NMR crystallography is also applicable. Of course, to understand biological systems the required perspectives are surely physiologically relevant temperatures and relevant chemical conditions, as well as a minimal perturbation owing to the needs of the probe itself. These remain very tough challenges because, for example, cryoEM by its very nature will never be performed at room temperature, crystallization often requires nonphysiological chemical conditions, and X-rays and electrons cause beam damage. However, integrated structural biology techniques and functional assays provide a package towards physiological relevance of any given study. Reporting of protein crystal structures, and their associated database entries, could usefully indicate how close to the biological situation they are, as discussed in detail in this feature article. Full Article text
hem The crystal structure of the heme d1 biosynthesis-associated small c-type cytochrome NirC reveals mixed oligomeric states in crystallo By scripts.iucr.org Published On :: 2020-03-25 Monoheme c-type cytochromes are important electron transporters in all domains of life. They possess a common fold hallmarked by three α-helices that surround a covalently attached heme. An intriguing feature of many monoheme c-type cytochromes is their capacity to form oligomers by exchanging at least one of their α-helices, which is often referred to as 3D domain swapping. Here, the crystal structure of NirC, a c-type cytochrome co-encoded with other proteins involved in nitrite reduction by the opportunistic pathogen Pseudomonas aeruginosa, has been determined. The crystals diffracted anisotropically to a maximum resolution of 2.12 Å (spherical resolution of 2.83 Å) and initial phases were obtained by Fe-SAD phasing, revealing the presence of 11 NirC chains in the asymmetric unit. Surprisingly, these protomers arrange into one monomer and two different types of 3D domain-swapped dimers, one of which shows pronounced asymmetry. While the simultaneous observation of monomers and dimers probably reflects the interplay between the high protein concentration required for crystallization and the structural plasticity of monoheme c-type cytochromes, the identification of conserved structural motifs in the monomer together with a comparison with similar proteins may offer new leads to unravel the unknown function of NirC. Full Article text
hem Solid/liquid-interface-dependent synthesis and immobilization of copper-based particles nucleated by X-ray-radiolysis-induced photochemical reaction By journals.iucr.org Published On :: Full Article text
hem Detailed surface analysis of V-defects in GaN films on patterned silicon(111) substrates by metal–organic chemical vapour deposition. Corrigendum By scripts.iucr.org Published On :: 2020-02-01 An error in the article by Gao, Zhang, Zhu, Wu, Mo, Pan, Liu & Jiang [J. Appl. Cryst. (2019), 52, 637–642] is corrected. Full Article text
hem Dual-energy crystal-analyzer scheme for spectral tomography By journals.iucr.org Published On :: The principles of using the Laue-analyzer as an X-ray optical element for separating two characteristic lines of an X-ray tube are presented. Full Article text
hem Structure of the archaeal chemotaxis protein CheY in a domain-swapped dimeric conformation By scripts.iucr.org Published On :: 2019-08-30 Archaea are motile by the rotation of the archaellum. The archaellum switches between clockwise and counterclockwise rotation, and movement along a chemical gradient is possible by modulation of the switching frequency. This modulation involves the response regulator CheY and the archaellum adaptor protein CheF. In this study, two new crystal forms and protein structures of CheY are reported. In both crystal forms, CheY is arranged in a domain-swapped conformation. CheF, the protein bridging the chemotaxis signal transduction system and the motility apparatus, was recombinantly expressed, purified and subjected to X-ray data collection. Full Article text
hem Roads kill rainforests. Stop them now, say Smithsonian biologists By insider.si.edu Published On :: Thu, 24 Sep 2009 18:49:29 +0000 Determining the locations of future highways and roads in countries with tropical rainforests will be the greatest single factor in influencing future forest loss, fragmentation and degradation. In broad terms, roads can be thought of as the enemies of rainforests. By spreading people out across the forest, roads inherently promote rapid and widespread deforestation. The post Roads kill rainforests. Stop them now, say Smithsonian biologists appeared first on Smithsonian Insider. Full Article Research News Science & Nature biodiversity conservation conservation biology rain forests Tropical Research Institute
hem Astronomers explore the rich chemistry surrounding an evolved star By insider.si.edu Published On :: Mon, 14 Mar 2011 15:00:23 +0000 Over 170 molecules have been detected in space, from simple diatomic molecules like CO to complex organic molecules with over 70 atoms, such as fullerene. […] The post Astronomers explore the rich chemistry surrounding an evolved star appeared first on Smithsonian Insider. Full Article Research News Science & Nature Space astronomy astrophysics Center for Astrophysics | Harvard & Smithsonian Smithsonian Astrophysical Observatory
hem Male spider’s sexual organs work fastest only when a female breaks them off By insider.si.edu Published On :: Tue, 07 Feb 2012 15:50:44 +0000 In fact, researchers have learned, the detached male pedipalps transfer more sperm faster after copulation is ended by the female rather than the male. The post Male spider’s sexual organs work fastest only when a female breaks them off appeared first on Smithsonian Insider. Full Article Animals Science & Nature insects National Museum of Natural History spiders
hem Yellow pigment in penguin feathers is chemically distinct, spectroscopic studies reveal By insider.si.edu Published On :: Mon, 22 Apr 2013 13:06:25 +0000 Recent spectroscopic analysis of macaroni penguin (Eudyptes chrysolophus) crest feathers and king penguin (Aptenodytes patagonicus) neck feathers have shown they contain a yellow pigment that […] The post Yellow pigment in penguin feathers is chemically distinct, spectroscopic studies reveal appeared first on Smithsonian Insider. Full Article Animals Marine Science Research News Science & Nature birds chromatics materials science
hem Sea hare chemical fights leishmaniasis By insider.si.edu Published On :: Mon, 02 Dec 2013 15:22:37 +0000 Found worldwide in tropical and subtropical seas and oceans, Dolabrifera dolabrifera is a species of sea hare, a marine gastropod mollusk in the family Aplysiidae. […] The post Sea hare chemical fights leishmaniasis appeared first on Smithsonian Insider. Full Article Animals Marine Science Research News Science & Nature biodiversity Tropical Research Institute
hem Feathers yield mysteries of pigment chemistry to spectroscopic analysis By insider.si.edu Published On :: Fri, 30 May 2014 18:37:21 +0000 A research team from the Smithsonian and Arizona State University have developed a new, non-destructive method using spectroscopic analysis to help unravel the complex chemistry […] The post Feathers yield mysteries of pigment chemistry to spectroscopic analysis appeared first on Smithsonian Insider. Full Article Research News Science & Nature birds chromatics endangered species materials science National Museum of Natural History