The maximum surface area polyhedron with five vertices inscribed in the sphere {\bb S}^{2}

This article focuses on the problem of analytically determining the optimal placement of five points on the unit sphere {\bb S}^{2} so that the surface area of the convex hull of the points is maximized. It is shown that the optimal polyhedron has a trigonal bipyramidal structure with two vertices placed at the north and south poles and the other three vertices forming an equilateral triangle inscribed in the equator. This result confirms a conjecture of Akkiraju, who conducted a numerical search for the maximizer. As an application to crystallography, the surface area discrepancy is considered as a measure of distortion between an observed coordination polyhedron and an ideal one. The main result yields a formula for the surface area discrepancy of any coordination polyhedron with five vertices.

SYNTHESIS AND CHARACTERIZATION OF NOVEL ORGANOBISMUTH FOR ANTIMICROBIAL AND ANTITUMOR STUDIES

Objectives: The major objective of this manuscript is to present synthesis and biomedical screening of some organic derivatives of bismuth having general formula (R3BiL2) by the method reported and characterized with the help of M.P., elemental, I.R., and NMR spectral analysis along with their antimicrobial and in vitro antitumor activity against human breast (MCF-7) and mammary cancer (EVSA-7) cell line. Methods: All the newly organobismuth having general formula [R3BiL2] were synthesised by the method reported especially using oxidative addition and complexation reactions. Results: It was found that organobismuth compounds have trigonal bipyramidal structure as per their elemental and spectral analysis and show potentiality as antimicrobial and antitumor agents. Conclusion: The newly synthesized organobismuth(V)substituted carboxylates were fully characterized chemically to ascertain their structure by sophisticated instrumental and spectral analysis resulted as trigonal bipyramidal structure. The compounds were also screened 1st time for antitumor and antimicrobial studies. The observations clearly indicated that organobismuth carboxylates show potent antimicrobial and antitumor activity.

Ti3+ Defective SnS2/TiO2 Heterojunction Photocatalyst for Visible-Light Driven Reduction of CO2 to CO with High Selectivity

In recent years, defective TiO2-based composite nanomaterials have received much attention in the field of photocatalysis. In this work, TiB2 was used as a precursor to successfully prepare Ti3+ defective TiO2 (TiO2-B) with a truncated bipyramidal structure by a one-step method. Then, the SnS2 nanosheets were assembled onto the as-prepared TiO2-B through simple hydrothermal reaction. TiO2-B exhibits strong visible light absorption properties, but the recombination rate of the photo-generated electron-hole pair was high and does not exhibit ideal photocatalytic performance. Upon introducing SnS2, the heterojunction catalyst SnS2-Ti3+ defective TiO2 (SnS2/TiO2-B) not only possesses the strong light absorption from UV to visible light region, the lowest photo-generated charge recombination rate but also achieves a more negative conduction band potential than the reduction potential of CO2 to CO, and thereby, exhibits the significantly enhanced selectivity and yield of CO in photocatalytic CO2 reduction. Notably, SnS2/TiO2-B produces CO at a rate of 58 µmol·h−1·g−1 with CO selectivity of 96.3% under visible light irradiation, which is 2 and 19 times greater than those of alone TiO2-B and SnS2, respectively. Finally, a plausible photocatalytic mechanism on SnS2/TiO2-B was proposed that the electron transfer between TiO2 and SnS2 follows the Z-scheme mode. Our results present an effective way to gain highly efficient TiO2 based photocatalysts for CO2 reduction by combining different modification methods of TiO2 and make full use of the synergistic effects.

Photocrystallography and IR spectroscopy of light-induced linkage NO isomers in [RuBr(NO)2(PCyp3)2]BF4

One single photo-induced linkage NO isomer (PLI) is detected and characterized in the dinitrosyl pentacoordinated compound [RuBr(NO)2(PCyp3)2]BF4 by a combination of photocrystallographic and IR analysis. In the ground state, the molecule adopts a trigonal–bipyramidal structure with the two NO ligands almost linear with angles Ru—N1—O1 = 168.92 (16), Ru—N2—O2 = 166.64 (16)°, and exactly equal distances of Ru—N = 1.7838 (17) and O—N = 1.158 (2) Å. After light irradiation of 405 nm at T = 10 K, the angle of Ru—N2—O2 changes to 114.2 (6)° by rotation of the O atom towards the Br ligand with increased distances of Ru—N2 = 1.992 (6) and N2—O2 = 1.184 (8) Å, forming a bent κN bonded configuration. Using IR spectroscopy, the optimal wavelength and maximum population of 39 (1)% of the PLI is determined. In the ground state (GS), the two symmetric νs(NO) and asymmetric νas(NO) vibrations are measured at 1820 and 1778 cm−1, respectively. Upon photo-irradiation, the detection of only one new vibrational ν(NO) stretching band at 1655 cm−1, assigned to the antisymmetric coupled vibration mode and shifted to lower wavenumbers by −123 cm−1, supports the photocrystallographic result. These experimental results are supported by additional DFT calculations, which reproduce the structural parameters and vibrational properties of both the ground state and the photo-induced linkage isomer well. Especially the experimentally characterized molecular structure of the PLI state corresponds to an energy minimum in the calculations; the stabilization of the bent κN bonded configuration of the PLI state originates from specific intramolecular orbital overlap.

Structures of substrate- and nucleotide-bound propionate kinase fromSalmonella typhimurium: substrate specificity and phosphate-transfer mechanism

Kinases are ubiquitous enzymes that are pivotal to many biochemical processes. There are contrasting views on the phosphoryl-transfer mechanism in propionate kinase, an enzyme that reversibly transfers a phosphoryl group from propionyl phosphate to ADP in the final step of non-oxidative catabolism of L-threonine to propionate. Here, X-ray crystal structures of propionate- and nucleotide-boundSalmonella typhimuriumpropionate kinase are reported at 1.8–2.0 Å resolution. Although the mode of nucleotide binding is comparable to those of other members of the ASKHA superfamily, propionate is bound at a distinct site deeper in the hydrophobic pocket defining the active site. The propionate carboxyl is at a distance of ∼5 Å from the γ-phosphate of the nucleotide, supporting a direct in-line transfer mechanism. The phosphoryl-transfer reaction is likely to occurviaan associative SN2-like transition state that involves a pentagonal bipyramidal structure with the axial positions occupied by the nucleophile of the substrate and the O atom between the β- and the γ-phosphates, respectively. The proximity of the strictly conserved His175 and Arg236 to the carboxyl group of the propionate and the γ-phosphate of ATP suggests their involvement in catalysis. Moreover, ligand binding does not induce global domain movement as reported in some other members of the ASKHA superfamily. Instead, residues Arg86, Asp143 and Pro116-Leu117-His118 that define the active-site pocket move towards the substrate and expel water molecules from the active site. The role of Ala88, previously proposed to be the residue determining substrate specificity, was examined by determining the crystal structures of the propionate-bound Ala88 mutants A88V and A88G. Kinetic analysis and structural data are consistent with a significant role of Ala88 in substrate-specificity determination. The active-site pocket-defining residues Arg86, Asp143 and the Pro116-Leu117-His118 segment are also likely to contribute to substrate specificity.

Physicochemical, Spectral, and Biological Studies of Mn(II), Cu(II), Cd(II), Zr(OH)2(IV), and UO2(VI) Compounds with Ligand Containing Thiazolidin-4-one Moiety

The Schiff base (I) upon reacting with mercaptoacetic acid in dry benzene undergoes cyclization and forms N-(2-carbamoylthienyl)-C-(3′-carboxy-2′-hydroxyphenyl)thiazolidin-4-one, LH3(II). A MeOH solution ofIIreacts with Mn(II), Cu(II), Cd(II), Zr(OH)2(IV), and UO2(VI) ions and forms the coordination compounds, [Mn(LH)(MeOH)2], [Cu(LH)]2, [Cd(LH)], [Zr(OH)2(OAc)2(LH3)], and [UO2(NO3)(LH2)(MeOH)]. The compounds have been characterized on the basis of elemental analyses, molar conductance, molecular weight, spectral (IR, reflectance, and EPR) studies and magnetic susceptibility measurements. LH3behaves as a neutral tridentate ONS donor ligand in [Zr(OH)2(OAc)2(LH3)], monobasic tridentate ONS donor ligand in [UO2(NO3)(LH2)(MeOH)], dibasic tridentate OOS donor ligand in [Cu(LH)]2and dibasic tetradentate OONO donor ligand in [Mn(LH)(MeOH)2] and [Cd(LH)]. [Cu(LH)]2is dimer, while all other compounds are monomers in diphenyl. A square-planar structure for [Cu(LH)]2, a tetrahedral structure for [Cd(LH)], an octahedral structure for [Mn(LH)(MeOH)2], a pentagonal-bipyramidal structure for [Zr(OH)2(OAc)2(LH3)], and an eight-coordinate structure for [UO2(NO3)(LH2)(MeOH)] are proposed. The ligand (II) and its compounds show antibacterial activities towardsE. coli. (Gram negative) andS. aureus(Gram positive).

Syntheses, Spectral Characterization, and Antimicrobial Studies on the Coordination Compounds of Metal Ions with Schiff Base Containing Both Aliphatic and Aromatic Hydrazide Moieties

An EtOH solution of 3-ketobutanehydrazide and salicylhydrazide on refluxing in equimolar ratio forms the corresponding Schiff base, LH3(1). The latter reacts with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Zr(OH)2(IV), MoO2(VI), and UO2(VI) ions in equimolar ratio and forms the corresponding coordination compounds, [M(LH)(MeOH)3] (2, M = Mn, Co, Ni), [Cu(LH)]2(3), [M′(LH)(MeOH)] (4, M′ = Zn, Cd), [Zr(OH)2(LH)(MeOH)2] (5), [MoO2(LH)(MeOH)] (6), and [UO2(LH)(MeOH)] (7). The coordination compounds have been characterized on the basis of elemental analyses, molar conductance, spectral (IR, reflectance,1H NMR, ESR) studies, and magnetic susceptibility measurements. They are nonelectrolytes in DMSO. The coordination compounds, except3, are monomers in diphenyl. They are active against gram-positive bacteria (S. aureus, B. subtilis), gram-negative bacteria (E. coli, P. aeruginosa), and yeast (S. cerevisiae, C. albicans).1acts as a dibasic tridentate ONO donor ligand in2–7coordinating through its both enolic O and azomethine N atoms. The coordination compounds2and3are paramagnetic, while rest of the compounds are diamagnetic. A square-planar structure to3, a tetrahedral structure to4, an octahedral structure to2,6, and7, and a pentagonal bipyramidal structure to5are proposed.

New Di- and Triorganotin(IV) Tyrosylalaninates as Models for Metal—Protein Interactions: Synthesis, Structural Characterization, and Potentiometric Studies of Tyrosylalanine, Glycyltyrosine, and Glycylisoleucine with Di- and Trimethyltin(IV) Moieties in Aqueous Medium

Di- and triorganotin(IV) derivatives of tyrosylalanine (H2Tyr-Ala) with general formula R2Sn(Tyr-Ala) (where R = Me, n-Bu, n-Oct, and Ph) and R3Sn(HTyr-Ala) (where R = Me and Ph) have been synthesized and structurally characterized in the solid state as well as in solution on the basis of various spectroscopic techniques, namely. FT-IR, multinuclear (1H, 13C and 119Sn) NMR and 119Sn Mössbauer. These investigations suggest that tyrosylalanine in R2Sn(Tyr-Ala) acts as dianionic tridentate ligand coordinating through carboxylate oxygen [–C(O)O−], amino (–NH2), and (CO)Npeptide- nitrogen, while in the case of R3Sn(HTyr-Ala), the ligand acts as monoanionic bidentate coordinating through –C(O)O− and –NH2, and the polyhedron around tin in R2Sn(Tyr-Ala) and R3Sn(HTyr-Ala) is a distorted trigonal-bipyramidal. Equilibrium (pH-metric) studies of the interaction of Me2Sn(IV)2+ and Me3Sn(IV)+ with dipeptides namely, tyrosylalanine (H2Tyr-Ala), glycyltyrosine (H2Gly-Tyr), and glycylisoleucine (H2Gly-Ile), in aqueous solution (I = 0.1 M KNO3, 298 K) have also been carried out. The concentration distribution of the various complex species in solution has been evaluated as a function of pH. It has been found that in these dipeptides, [–C(O)O−, N−, NH2] coordinated complexes are dominant in the neutral pH range with a trigonal-bipyramidal structure. The complex species formed are water soluble in the pH range 2.7–10.5. In all of the studied systems, no polymeric species have been detected in the experimental pH range. Beyond pH 8.0, significant amounts of hydroxo species, namely. Me3Sn(OH) and Me2Sn(OH)2, are formed.

Synthesis and Structure Characterization of some Triorganotin Esters of Heteroaromatic Carboxlic Acid and Crystal Structure of Triphenyltin Esters 5-Chloro-6-Hydroxynicotinic Acid

Reactions of (R3Sn)2O (R=Ph, 2-ClC6H4CH2, 2-FC6H4CH2, 4-CNC6H4CH2) with 5-chloro-6-hydroxynicotinic acid in 1/2 stoichiometry yielded eight triorganotin compounds. These compounds have been characterized by elemental analysis, IR and NMR spectroscopy. The crystal structures of triphenyltin esters of 5-chloro-6-hydroxynicotinic acid were determined by single crystal X-ray diffraction. In the compound, the tin atoms are rendered five-coordinated in a trigonal bipyramidal structure by coordinating though the three phenyl carbon atoms and two oxygen atoms one from carboxylate and other from the phenolic hydroxide. The resulting structure is one-dimensional linear polymers through an interaction between the O atoms of phenolic hydroxide and tin atoms of an adjacent molecule.