Preparation and Characterization of Three-dimensionally Ordered Crystalline Macroporous CeO2

Three-dimensional ordered macroporous (3DOM) materials are of great potential importance in catalysis, selective separation, sensor arrays and communications with optical band gaps1. Many results in the synthesis of 3DOM materials have been reported, such as closed-packed silica spheres or polystyrenes (PS) templating routes for silica2, metal oxides1-6 and metals7. Recently, poly(methyl methacrylate) (PMMA) colloidal crystal templates have been used to prepare 3DOM materials of metals8,…     

ESR Studies on a Friedel‐Crafts Alkylation Reaction in [bmim]Cl‐AlCl3 Ionic Liquid

The paramagnetic complexes formed in Friedel‐Crafts alkylation reaction systems are invistigated by electron spin resonance (ESR) spectroscopy, in room temperature ionic liquids system 1‐butyl‐3‐methyl‐limidazolium chloride‐aluminium chloride ([bmim]Cl‐AlCl₃). The results indicate that ESR spectra observed are due to polycyclic aromatic radical cations formed from their parent hydrocarbons. ESR spectrum of spin adduct is obtained in an ionic liquid system composed of [bmim]Cl‐AlCl₃. In acidic solution the ¹⁴N hyperfine coupling constant of 4‐oxo‐TEMPO, 2.15 mT, is appreciably larger due to an adduct formed with AlCl₃.     

Syntheses and structures of mono-, di- and tetranuclear rhodium or iridium complexes of thiacalix[4]arene derivatives

The reactions of [Cp*MCl2]2(Cp*=eta5-C5Me5, M = Rh, Ir) with thiacalix[4]arene (TC4A(OH)4) and tetramercaptothiacalix[4]arene (TC4A(SH)4) gave the mononuclear complexes [(Cp*M){eta3-TC4A(OH)2(O)2}] and the dinuclear complexes [(Cp*M)2{eta3eta3-TC4A(S)4}] respectively, while the analogous reactions with dimercaptothiacalix[4]arene (TC4A(OH)2(SH)2) produced the tetranuclear complexes [(Cp*M)2(Cp*MCl2)2-{eta3eta3eta1eta1-TC4A(O)2(S)2}].     

A new-type photoreaction of a carbonyl compound: Part 2. Photoinduced ω-bond dissociation in p-halomethylbenzophenone studied by time-resolved EPR technique and laser flash photolysis

Photodissociation of the carbon-X (X = Br and Cl) bonds in p-bromo- and p-chloromethylbenzophenone (BMBP and CMBP) in solution were investigated by time-resolved EPR and laser flash photolysis techniques. BMBP and CMBP were found to undergo ω-bond cleavage to yield the p-benzoylbenzyl radical (BBR) at 295 K, and the quantum yields (Φ_BBR) were determined. The CIDEP signal originated from BBR formed upon decomposition of CMBP was obtained while that for BMBP was absent. By using triplet sensitization of acetone, the efficiencies (_BBR) of the CX bond fission in the triplet states of BMBP and CMBP were determined. The agreement between the Φ_BBR and _BBR values for CMBP indicates that the CCl bond dissociation occurs only in the triplet state. In contrast to CMBP, the cleavage of the CBr bond in BMBP upon direct excitation was concluded to be the event only in the excited singlet state without triplet formation, whereas the triplet state was also reactive for ω-bond dissociation. The rate of CBr bond dissociation seemed to be greater than that of intersystem crossing from the S₁ to the T₁ state. Schematic energy diagrams of the excited states of BMBP and CMBP were shown, and the reaction profiles were discussed from the viewpoint of the CX bond enthalpies.     

Boride-based nano-laminates with MAX-phase-like behaviour

MAX-phases being usually composed of transition metals, group A elements and carbon/nitrogen are considered interesting materials for many applications because of their tremendous bulk modulus, “reversible” plasticity, and machinability. This is mainly due to their unique kind of bonding comprising covalent, ionic as well as metallic bonds providing “easy” planes of rupture and deformability due to the layered crystal structures.In transition metal boride systems, similar types of bonding are available. In particular the W₂B₅-structure type and its stacking variations allow the synthesis of strongly layered crystal structures exhibiting unique delamination phenomena.The paper presents ab initio calculations showing the similarities of bonding between the ternary carbides and the corresponding ternary or quaternary borides. Formation of boride-based nano-laminates from auxiliary liquid phases, from the melt as well as during sintering and precipitation from supersaturated solid solutions will be discussed by means of SEM and TEM studies. The role of impurities weakening the interlayer bonding will be addressed in particular. The pronounced cleavage parallel to the basal plane gives rise for crack deflection and pull-out mechanisms if the laminates are dispersed in brittle matrices such as boron carbide, silicon carbide or other transition metal borides.     

Rapid and sensitive determination of protein by light-scattering technique with Eriochrome Blue Black R

Based on the interaction between Eriochrome Blue Black R (EBBR) and proteins, which causes a strong light-scattering signal with the maximum scattering peak located at 398 nm, a simple, rapid, sensitive and selective method is developed for the determination of proteins by the light-scattering technique using a common spectrofluoremeter. Under proper experimental conditions, the protein determination can be performed in the range of 0.1-25, 0.1-20 and 0.25-25 μg ml⁻¹ for bovine serum albumin (BSA), human serum albumin (HSA) and human immunoglobulin G (IgG), respectively. The detection limit, calculated as 3 times the S.D. of nine blank measurements, are 33 μg l⁻¹ for BSA, 25 μg l⁻¹ for HSA and 38 μg l⁻¹ for IgG. Moreover, there is no significant difference among the scattering signals yielded by HSA, IgG and BSA, and almost no interference of many amino acids and metal ions. The method has been satisfactorily applied to the direct determination of the total protein in human serum, saliva and urine samples. The results obtained from the studies on the binding characteristics of EBBR to BSA indicated that an electrostatic force existed in the binding system, and the binding constant (K) and the number of the binding sites (n) at 25 °C are 1.69×10⁵ l mol⁻¹ and 0.946, respectively.     

Preparation,structures, and redox and emission characteristics of the isothiocyanate complexes of hexarhenium(III) clusters [Re6(mu3-E)8(NCS)6]4- (E = S,Se)

Hexarhenium(III) complexes with terminal isothiocyanate ligands, [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)(NCS)(6)] (1) and (L)(4)[Re(6)(mu(3)-Se)(8)(NCS)(6)] (L(+) = PPN(+) (2a), (n-C(4)H(9))(4)N(+) (2b)), have been prepared by three different methods. Complex 1 was prepared by the reaction of [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)Cl(6)] with molten KSCN at 200 degrees C, while 2b was obtained by refluxing the chlorobenzene-DMF (2:1 v/v) solution of [Re(6)(mu(3)-Se)(8)(CH(3)CN)(6)](SbF(6))(2) and [(n-C(4)H(9))(4)N]SCN. The [Re(6)(mu(3)-Se)(8)(NCS)(6)](4)(-) anion was also obtained from a mixture of Cs(2)[Re(6)(mu(3)-Se)(8)Br(4)] and KSCN in C(2)H(5)OH by a mechanochemical activation at room temperature for 20 h and isolated as 2a. The X-ray structures of 1 and 2a.4DMF have been determined (1, C(70)H(144)N(10)S(14)Re(6), monoclinic, space group P2(1)/n (No. 14), a = 14.464(7) A, b = 22.059(6) A, c = 16.642(8) A, beta = 113.62(3) degrees, V = 4864(3) A(3), Z = 2; 2a.4DMF, C(162)H(144)N(14)O(4)P(8)S(6)Se(8)Re(6), triclinic, space group P1 (No. 2), a = 15.263(2) A, b = 16.429(2) A, c = 17.111(3) A, alpha = 84.07(1) degrees, beta = 84.95(1) degrees, gamma = 74.21(1) degrees, V = 4098.3(8) A(3), Z = 1). All the NCS(-) ligands in both complexes are coordinated to the metal center via nitrogen site with the Re-N distances in the range of 2.07-2.13 A. The redox potentials of the reversible Re(III)(6)/Re(III)(5)Re(IV) process in acetonitrile are +0.84 and +0.70 V vs. Ag/AgCl for [Re(6)(mu(3)-S)(8)(NCS)(6)](4)(-) and [Re(6)(mu(3)-Se)(8)(NCS)(6)](4)(-), respectively, which are the most positive among the known hexarhenium complexes with six terminal anionic ligands. The complexes show strong red luminescence with the emission maxima (lambda(max)/nm), lifetimes (tau(em)/micros), and quantum yields (phi(em)) being 745 and 715, 10.4 and 11.8, and 0.091 and 0.15 for 1 and 2b, respectively, in acetonitrile. The data reasonably well fit in the energy-gap plots of other hexarhenium(III) complexes. The temperature dependence of the emission spectra and tau(em) of 1 and [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)Cl(6)] are also reported.     

Metal-ion-assisted hydrolysis of dipeptides involving a serine residue in a neutral aqueous solution

Dipeptides having a serine residue at the C-terminus, X-Ser, where X is an appropriate amino acid residue, were efficiently hydrolyzed in the presence of ZnCl2 at pH 7.0. The rapid hydrolysis of X-Ser is due to an autocatalysis of the hydroxy group in the serine residue, and is found to be accelerated by a metal ion, in particular by ZnCl2. Roles of the metal ion in the hydrolysis of peptides involving a serine residue, in relation to the recently reported protein cleavages, are discussed.     

Low frequency limits of third-order harmonic coefficients for atomic hydrogen in any level of discrete energy spectrum

In this paper the analytical expression is derived for the third-order optical harmonic coefficients x _abcd ^v (,,) of the atomic hydrogen at very low frequencies 0 in many level of the discrete energy spectrum.The author expresses his thank to Prof. Nguyen Van Hieu for suggesting the problem and fruitful discussions.     

Asymmetric synthesis of β-fluoroaryl-β-amino acids

The conjugate addition of lithium (R)-N-benzyl-N-(α-methylbenzyl)amide to a range of β-fluoroaryl-α,β-unsaturated esters gave the corresponding β-amino esters with high diastereoselectivity and in good isolated yields. Sequential treatment of the resultant β-fluoroaryl-β-amino esters under optimised hydrogenolysis conditions, followed by ester hydrolysis with 2.0 M aq HCl, provided access to a range of β-fluoroaryl-β-amino acids in good yield.