Azinoiminophosphorane mediated synthesis of 5H, 7H‐1,2,4‐triazolo[1,5‐c][1,3]benzoxazepin‐7‐ones and 6H,8H‐1,2,4‐triazolo‐[1,5‐c][1,3]oxazepin‐6‐ones

The aza‐Wittig reactions of benzophenone‐, acetophenone‐ and benzaldehyde l‐[(triphenylphosphoranyl‐idene)amino]ethylidenehydrazones (4) with phthalic anhydride, 2,3‐dimethylmaleic anhydride and 7‐oxabi‐cyclo[2,2,l]hept‐5‐ene‐2,3‐dicarboxylic anhydride ( 5a ) provide a new route to 5H,7H‐1,2,4‐triazolo[1,5‐c]‐[1,3]benzoxazepin‐7‐ones 8a‐c or 6H,8H‐1,2,4‐triazolo[1,5‐c][1,3]oxazepin‐6‐ones 8d‐h via the thermal reaction of the expected azinoimine lactones 6 .     

In situ Fe K-edge X-ray absorption fine structure of a nitrosyl adduct of iron phthalocyanine irreversibly adsorbed on a high area carbon electrode in an acidic electrolyte

Key aspects of the microenvironment surrounding the Fe center in the nitrosyl adduct of iron phthalocyanine, [Fe(Pc)(NO)], have been elucidated from the analysis of the Fe K-edge extended X-ray absorption fine structure (EXAFS) of the material adsorbed on the surface of a high area carbon electrode recorded in situ, in 0.5 M H(2)SO(4). Statistical best fits to the EXAFS data place the Fe center in a five-coordinated square pyramidal configuration shifted away from the Pc plane toward the axially bound NO bent at an angle of ca. 40 degrees with respect to the normal to the Pc plane. This environment is analogous to that of Fe in the nitrosyl adduct of crystalline [Fe(TPP)], where TPP = meso-tetraphenylporphyrinato(2-), determined from X-ray diffraction.     

Synthesis and magnetic properties of poly(p‐phthaloyl‐disacetylaceton‐ethylenediimine) metal complexes

Macrocyclic Schiff‐base ligand, bisacetylaceton‐ethylenediimine (BAE) and its transition metal complexes M(BAE) (M = Cu²⁺, Ni²⁺) were synthesized. The complexes having characteristics of aromatic systems and well‐defined one‐dimensional structures, reacted with p‐phthaloyl chloride, to obtain polymer complexes. The complexes were characterized by elemental analysis, inductively coupled plasma (ICP), FT‐IR, and thermal analysis and show good thermal stability. ESR spectra analysis discovered that there are free radicals in the chain of polymers, indicating that a weak magnetic spin‐exchange interaction operates between the metal ions and free radicals. It is found that, as the bridging p‐phthaloyl group is able to propagate the magnetic exchange interaction, the polymer complexes show paramagnetic properties by measurement of temperature dependence of the magnetic property, and obey Curie–Weiss law. Copyright © 2001 John Wiley & Sons, Ltd.     

Preparation and crystal structure ofexo-2,exo-6-dihydroxy-2,6-dimethyl-9-oxabicyclo[3.3.1]nonane

In a further exploration of the structural factors causing alicyclic diols such asexo-2,exo-6-dihydroxy-2,6-dimethylbicyclo[3.3.1]nonane (1) to adopt the helical tubuland inclusion host structure, the title compound (8) has been synthesized and its crystal structure determined. This 9-oxa analogue of (1) has a totally different structure [C₁₀H₁₈O₃; orthorhombic;P2₁2₁2;a 18.989(4),b 19.064(3),c 14.256(3) Å;Z 20; with finalR 0.065] due to involvement of the ether oxygen atom in the hydrogen bonding network. The structure of the diol (8) approximatesP¯42₁ c symmetry, and 16 of the 20 molecules per cell create a hostlike structure of this symmetry, which consists of tightly bound hydrogen bonded pillars parallel toc. The remaining guestlike molecules occupy inequivalent pseudo ¯4 sites separated byc/2 to form weakly bound columns parallel toc. Hydrogen bonds also occur between the pillars and columns. An ordered structure with sensible intermolecular contacts can be formed inP2₁2₁2₁ with thec axis doubled. A difference betweena andb axial lengths correlates with a difference in occupancies of pseudo-¯4-related sites for the guest-like component of the structure.     

Short and stereoselective synthesis of C-glycosylated glycine derivatives from glycals by radical addition and reduction

Only three steps are required for the convenient synthesis of 2-C-branched glyco-amino acids from glycals with good yields and stereoselectivities.     

Single‐Crystalline and Near‐Monodispersed NaMF3 (M=Mn,Co, Ni,Mg) and LiMAlF6 (M=Ca,Sr) Nanocrystals from Cothermolysis of Multiple Trifluoroacetates in Solution

We report the synthesis of single‐crystalline and near‐monodispersed NaMF₃ (M=Mn, Co, Ni, Mg), LiMAlF₆ (M=Ca, Sr), and NaMgF₃:Yb,Er nanocrystals (quasisquare nanoplates, nanorods, and nanopolygons) by the cothermolysis of multiple trifluoroacetates in hot combined organic solvents (oleic acid, oleylamine, and 1‐octadecene). The nanocrystals were characterized by XRD, TEM, superconductive quantum interference device (SQUID), and upconversion luminescence spectroscopy. By regulating the polarity of the dispersant, the NaMF₃ (M=Mn, Co, Ni) nanoplates were partially aligned to form nanoarrays on copper TEM grids. The sizes of the NaMF₃ nanocrystals were easily tuned by the use of proper synthetic conditions such as reaction temperature and time and solvent composition. On the basis of a series of experiments in which the reaction conditions were varied, together with GC–MS and FTIR analysis, the reaction pathways for the formation of these nanocrystals from trifluoroacetate precursors were proposed. The magnetic measurements showed that the differently sized NaMnF₃ square plates displayed interesting weak ferromagnetic behavior on the nanometer scale. The strong red upconversion luminescence emitted from the NaMgF₃:Yb,Er nanorods under 980‐nm near‐IR laser excitation suggests that NaMgF₃ may be a good candidate host material for red upconversion luminescence.     

Determination of Levofloxacin in Human Urine with Capillary Electrophoresis and Fluorescence Detector

In this study, we developed an analytical method for the enantioseparation of ofloxacin, using capillary electrophoresis with fluorescence detection. The optimum background electrolyte was obtained to be 60 mM hydroxylpropyl‐β‐cyclodextrin (HP‐β‐CD) in 50 mM phosphate buffer at pH 2.30. Under these conditions, the (+) and (‐) ofloxacin were completely separated, with the detection limit of 10 nM when the sample was prepared in deionized water. The linear ranges of levofloxacin in deionized water and untreated urine were 10^?7 to 5 × 10^?3 M with R² = 0.9989 and 5 × 10^?6to 5 × 10^?3 M with R² = 0.9943, respectively. We also applied this method to investigate the purity of a commercial drug. The results revealed that the ratio between (+)‐ofloxacin and (‐)‐ofloxacin (levofloxacin) was 99.9:0.1, and there is about 93 mg levofloxacin per tablet (200 mg). The concentration of levofloxacin in patient's urine was founded to be 7.9 × 10^?4M, and the ratio between the two optical isomers was 99.3:0.7.     

Dispersion of silica nano-particles in sol-gel hybrid resins for fabrication of multi-scale hybrid nanocomposite

Multi-scale hybrid nanocomposites containing both ∼15 nm silica colloids and ∼2 nm oligosiloxanes in a methacryl polymer matrix were newly designed and fabricated. Colloidal silica sols were dispersed in methacryl oligosiloxanes nano-hybrid resins synthesized by sol-gel reaction of methacryloxypropylmethoxysilane and diphenylsilanediol. On the basis of TEM and SANS analyses, it was confirmed that the silica colloids were compatibly dispersed and different sizes of colloidal silica and oligosiloxanes co-exist in the solutions. Multi-scale hybrid nanocomposites fabricated by UV and thermal curing with incorporation of silica colloids in the nano-hybrid materials show enhanced mechanical and thermal characteristics.     

Helicity‐Encoded Molecular Strands: Efficient Access by the Hydrazone Route and Structural Features

Control over the folding of molecular strands may be achieved by appropriate choice of the constituting subunits, in particular for chains of specific heterocycles such as sequences of directly connected pyridine (py) and pyrimidine (pym) rings, which are known to fold into extended helical structures. Since the hydrazone (hyz) group represents an isomorphic analogue of a py site, the condensation of hydrazine and carboxaldehyde derivatives of pym offers a very efficient approach to strands incorporating hyz instead of py units and constituted by sequences of alternating hyz and pym groups. A series of such strands of different lengths, up to ten hyz units, i.e., 1 – 7 , were synthesized. Their spectral properties indicate that they fold indeed into helical shapes. Extensive characterization was performed in solution by ¹HNMR spectroscopy and in the solid state by determination of the crystal structures of eight such strands. They all display the expected helical geometry with up to 3 ¹/₃ turns and direct stacking contacts. The efficiency and flexibility of the synthetic approach as well as its wide potential for generation of diversity through lateral decoration make the (hyz? pym) subunit a particularly attractive helicity codon.     

Preparation ,Structural Characterization and Luminescent Property of Binucleasr Silver（Ⅰ）Complex Formed by Benzotriazole and 1—Hydroxymethyl Benzotriazole

Dinuclear silver (I) six‐membered ring complex [Ag₂ (bta)₂ ‐(hmbta)₂] (ClO₄)₂ (3) has been synthesized by the reaction of benzotriazole (bta) (1) and 1‐hydroxymethyl benzotriazole (hmbta) (2) with Ag (CH₃CN)₄ClO₄. The structures of compound 2 and Complex 3 have been studied by single crystal X‐ray diffraction analysis. The change of luminescent intensity of 1, 2 and 3 was reported. Compound 2 crystallizes in the monoclinic system with space group P2 (1)/c, a = 0.7655 (10) nm, b = 1.0126 (14) nm, c =0.9502 (13) nm, β = 95.07 (2)°, V = 0.7337 (17) nm³ and Z = 4. Complex 3 crystallizes in the triclinic system with space group P1, a = 0.73611 (18) nm, b = 0.9152 (2) nm, c = 1.2277 (3) nm, β = 87.170 (5)°, V = 0.8221 (3) nm³ and Z = 1. The main structural feature of complex 3 is a symmetric dinuclear six‐membered ring formed by two silver (I) atoms and four N‐atoms from two benzotriazoles. The second structural feature of complex 3 is the τ‐τ stacking interaction between two adjacent molecular planes, which forms the two‐dimentional layer structure. Besides, compared with 2, the luminescent intensity of complex 3 shows a remarkable enhancement.