Preparation and characterization of SiO2-pillared H2Ti4O9 and its photocatalytic activity for methylene blue degradation

SiO(2) pillared layered titanate (SiO(2)-H(2)Ti(4)O(9)) was prepared via intercalating organosilanes into the interlayers of the layered K(2)Ti(4)O(9) followed by calcination at 500 degrees C. The resulting materials were characterized using XRD, N(2) adsorption-desorption isotherms, UV-vis spectra, IR spectroscopy and Raman spectroscopy. The photocatalytic activity of SiO(2)-H(2)Ti(4)O(9) was evaluated by photocatalytic degradation of aqueous methylene blue dye (MB). XRD and specific surface area results showed that SiO(2)-H(2)Ti(4)O(9) had an interlayer distance of 1.45 nm and a specific surface area of 148 m(2)g(-1). UV-vis absorption spectrum of SiO(2)-H(2)Ti(4)O(9) showed a red shift, indicative of a narrower band gap compared to K(2)Ti(4)O(9). In addition, SiO(2)-H(2)Ti(4)O(9) showed higher MB adsorption capacity compared to H(2)Ti(4)O(9) and K(2)Ti(4)O(9). MB photodegradation over H(2)Ti(4)O(9), K(2)Ti(4)O(9) and SiO(2)-K(2)Ti(4)O(9) followed zero-order kinetics under our experimental conditions, and the photocatalytic activity of SiO(2)-H(2)Ti(4)O(9) was found to be three times higher than that of K(2)Ti(4)O(9), which could be attributed to the increase of interlayer space and specific surface area of SiO(2)-pillared layered titanate.     

Chromium and zinc uptake by algae Gelidium and agar extraction algal waste: kinetics and equilibrium

Biosorption of chromium and zinc ions by an industrial algal waste, from agar extraction industry has been studied in a batch system. This biosorbent was compared with the algae Gelidium itself, which is the raw material for agar extraction, and the industrial waste immobilized with polyacrylonitrile (composite material). Langmuir and Langmuir-Freundlich equilibrium models describe well the equilibrium data. The parameters of Langmuir equilibrium model at pH 5.3 and 20 degrees C were for the algae, q(L)=18 mg Cr(III)g(-1) and 13 mgZn(II)g(-1), K(L) = 0.021l mg(-1)Cr(III) and 0.026l mg(-1) Zn(II); for the algal waste, q(L)=12 mgCr(III)g(-1) and 7mgZn(II)g(-1), K(L)=0.033lmg(-1) Cr(III) and 0.042l mg(-1) Zn(II); for the composite material, q(L) = 9 mgCr(III)g(-1) and 6 mgZn(II)g(-1), K(L)=0.032l mg(-1)Cr(III) and 0.034l mg(-1)Zn(II). The biosorbents exhibited a higher preference for Cr(III) ions and algae Gelidium is the best one. The pseudo-first-order Lagergren and pseudo-second-order models fitted well the kinetic data for the two metal ions. Kinetic constants and equilibrium uptake concentrations given by the pseudo-second-order model for an initial Cr(III) and Zn(II) concentration of approximately 100 mgl(-1), at pH 5.3 and 20 degrees C were k(2,ads)=0.04 g mg(-1)Cr(III)min(-1) and 0.07 g mg(-1)Zn(II)min(-1), q(eq)=11.9 mgCr(III)g(-1) and 9.5 mgZn(II)g(-1) for algae; k(2,ads)=0.17 g mg(-1)Cr(III)min(-1) and 0.19 g mg(-1)Zn(II)min(-1), q(eq)=8.3 mgCr(III)g(-1) and 5.6 mgZn(II)g(-1) for algal waste; k(2,ads)=0.01 g mg(-1)Cr(III)min(-1) and 0.18 g mg(-1)Zn(II)min(-1), q(eq)=8.0 mgCr(III)g(-1) and 4.4 mgZn(II)g(-1) for composite material. Biosorption was modelled using a batch adsorber mass transfer kinetic model, which successfully predicts Cr(III) and Zn(II) concentration profiles. The calculated average homogeneous diffusivities, D(h), were 4.2 x 10(-8), 8.3 x 10(-8) and 1.4 x 10(-8)cm(2)s(-1) for Cr(III) and 4.8 x 10(-8), 9.7 x 10(-8) and 6.2 x 10(-8)cm(2)s(-1) for Zn(II), respectively, for Gelidium, algal waste and composite material. The algal waste has the lower intraparticle resistance.     

Kinetics of Fe(3)O(4)-CoO/Al(2)O(3) catalytic ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid

The presence of Fe(3)O(4)-CoO/Al(2)O(3) can improve degradation efficiency significantly during the ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid (2,4-DP). The main factors affecting degradation efficiency, such as pH, the catalyst concentration and addition of the scavenger, were investigated. The kinetics of the catalytic ozonation are also discussed. The results indicate that two factors, the oxidation after adsorption of 2,4-DP and the oxidation of hydroxyl radicals (OH), lead to a great enhancement in ozonation efficiency during the catalytic ozonation of 2,4-DP in the presence of Fe(3)O(4)-CoO/Al(2)O(3), in which the oxidation of the OH plays an important role. Under controlled conditions, the apparent reaction rate constants for the degradation of 2,4-DP were determined to be 2.567 × 10(-4)s(-1) for O(3) and 1.840 × 10(-3)s(-1) for O(3)/Fe(3)O(4)-CoO/Al(2)O(3). The results from the analysis of the reaction kinetics using the relative method showed that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) possessed a larger R(ct) (R(ct) is defined as the ratio of the ·OH exposure to the O(3) exposure, R(ct) = ∫C(t)(OH) dt/C(t)O(3)dt) than O(3), indicating that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) produced more hydroxyl radicals.     

Role of late transition metals on pitting resistance of Zr-Ti-(Cu,Ni,Co)-Al bulk metallic glasses in 0.6 M NaCl aqueous solution

Four quanternary Zr-based bulk metallic glasses(BMGs)were selected,including the Zr_(46)Ti_2Cu_(45)Al_7,Zr_(61)Ti_2Cu_(25)Al_(12),Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15),due to their robust glass-forming ability and containing a single species of late transition metal(LTM)in compositions.Their pitting resistances in 0.6 M Na Cl aqueous solution were investigated to examine the role of LTM elements in the alloys,with electrochemical measurements,surface morphology observation and x-ray photoelectron spectrometry analysis.It is shown that in comparision with two Cu-bearing BMGs,Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15)BMGs exhibited significantly superior resistance to pitting.Zr_(61)Ti_2Cu_(25)Al_(12),Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15)BMGs manifested distinct passivation behaviour,because of the formation of surface passive film mainly comprising of Zr O_2,Ti O_2and Al_2O_3.However,no significant differences in the electrochemical resistive properties and thicknesses of passive films were found between Zr_(61)Ti_2Cu_(25)Al_(12)and Zr_(55)Ti_4Ni_(22)Al_(19)BMGs.Nevertheless,at the passive film/metal interface,copper enrichment took place in Zr_(61)Ti_2Cu_(25)Al_(12),whereas the nickel was slightly deficient at the interface in Zr_(55)Ti_4Ni_(22)Al_(19).During pitting propagation,selective dissolution of the zirconium,titanium and aluminum over the copper took place in Zr_(61)Ti_2Cu_(25)Al_(12),but it was not the case in Zr_(55)Ti_4Ni_(22)Al_(19).For the two Cu-bearing BMGs,reduction of passive base metal elements in composition resulted in local selective dissolution,even absence of the passivation.     

Cobalt 1,3-Diisopropyl-1H-imidazol-2-ylidene Complexes: Synthesis, Solid-State Structures, and Quantum Chemistry Calculations

The reaction of (η(5)-C(5)H(5))Co(PPh(3))(2) with 1,3-bis(isopropyl)imidazol-2-ylidene (Im(i)Pr(2)) leads to the formation of (η(5)-C(5)H(5))Co(PPh(3))(Im(i)Pr(2)). In a similar fashion (η(5)-C(5)H(5))Co(Im(i)Pr(2))(CO) is formed from (η(5)-C(5)H(5))Co(CO)(2). The barrier to rotation about the Co-C(carbene) bond in the latter complex has been determined by variable-temperature (1)H NMR spectroscopy (13.6 kcal/mol) and by computation (13.3 kcal/mol). The structural and dynamic properties of (η(5)-C(5)H(5))Co(ImMe(2))(CO) (ImMe(2) = 1,3-dimethylimidazol-2-ylidene) and (η(5)-C(5)H(5))Co(ImAr(2))(CO) (ImAr(2) = 1,3-dimesityl-2-ylidene) were examined by quantum chemistry calculations.     

Transmitted-light microscopy - a new method for surface structure analysis of cleanable non-woven dust filter media

A series of CeO(2)-ZrO(2) mixed oxides were prepared using coprecipitation method and characterized by BET, oxygen storage capacity (OSC), X-ray diffraction (XRD) and H(2)-temperature-programmed reduction (H(2)-TPR). The catalytic activities toward toluene combustion were investigated in a micro-reactor. The results demonstrate that the catalytic activity of Pt/gamma-Al(2)O(3)/Ce(0.50)Zr(0.50)O(2) monolithic catalyst can be greatly improved by doping metal into Ce(0.50)Zr(0.50)O(2). When doping Y and Mn into Ce(0.50)Zr(0.50)O(2) simultaneously, the catalyst Pt/gamma-Al(2)O(3)/Ce(0.40)Zr(0.40)Y(0.10)Mn(0.10)O(X) shows the highest activity. The T(10) (the temperature of 10% toluene conversion) and the complete conversion temperature (the temperature of 90% toluene conversion) of toluene are 443 and 489K, respectively. Gas hourly space velocity (GHSV) results show that the prepared catalyst can be applied in a wide range of GHSV (from 12,000 to 20,000h(-1)). The catalyst prepared shows great potential for practical application.     

Physical and chemical modification of distillery sludge for Pb(II) biosorption

The waste distillery sludge from sugar-cane industry was pretreated physically (boiled, heated and autoclaved) as well as chemically (HCl, H(2)SO(4), H(3)PO(4), NaOH, Ca(OH)(2), Al(OH)(3), C(6)H(6), HCHO, CH(3)OH and C1(2)H(25)OSO(3)Na (sodium dodecyl sulphate (SDS)) for assessing the comparative sorption capacity of untreated and modified distillery sludge for Pb(II) biosorption from aqueous solutions. Experiments were conducted in shake flasks on a batch basis to access the effect of different experimental parameters such as pH, biosorbent dosage, biosorbent size, initial Pb(II) concentration and contact time. The uptake capacity 'q' (mg/g) of untreated and pretreated distillery sludge was in following order: NaOH (51.29+/-1.21)>HCl (49.82+/-1.22)>HCHO (49.56+/-1.14)>H(2)SO(4) (47.71+/-1.20)>HgCl(2) (45.32+/-1.06)>Ca(OH)(2) (44.01+/-1.18)>MeOH (43.73+/-1.23)>C(6)H(6) (42.72+/-1.19)>H(3)PO(4) (42.01+/-1.17)>SDS (40.87+/-1.27)>autoclaved (40.23+/-1.24)>Boiled (39.95+/-1.19)>heated (38.87+/-1.32)>Al (OH)(3) (38.30+/-1.14)>untreated (37.76+/-1.21). In further parameter studies, the optimized biosorbent size was 0.250 mm at pH 5 and best dose was 0.05 g of biosorbent. The applicability of the Langmuir and Freundlich models for sorption process was tested and best fitted model was Langmuir with the coefficient of determination (R(2)) value, 0.97, the process followed second order kinetic mechanism.     

Vanadium pentoxide nanobelts and nanorolls: from controllable synthesis to investigation of their electrochemical properties and photocatalytic activities

Uniform V(2)O(5)· xH(2)O nanobelts with high aspect ratios and ultra-long V(2)O(5)· xH(2)O nanorolls with novel scroll-like structures were synthesized on a large scale by a simple hydrothermal growth route using NH(4)VO(3) as the raw material in the presence of different acids at 180?°C for 24?h. Their morphologies were observed by scanning electron microscopy (SEM). X-ray powder diffraction measurement and thermal gravimetric analysis revealed the composition of nanobelts and nanorolls to be V(2)O(5)·0.9H(2)O and V(2)O(5)·0.6H(2)O, respectively. The possible mechanisms of formation of the nanobelts and nanorolls were schematically elucidated based on the layered structure of vanadium pentoxide. In addition, corresponding anhydrous V(2)O(5) nanostructures with better crystallinity were obtained by calcining the precursors of V(2)O(5)·0.9H(2)O nanobelts or V(2)O(5)·0.6H(2)O nanorolls. Furthermore, we have investigated the electrochemical intercalation properties with Li(+) and the photocatalytic activities of the synthesized V(2)O(5)·0.9H(2)O nanobelts, V(2)O(5)·0.6H(2)O nanorolls and their corresponding post-annealing products. It was observed that the morphologies and compositions of the synthesized products had an evident influence on the electrochemical intercalation properties with Li(+) and photocatalytic activities.     

Determination of Cd, Cr, Hg and Pb in plastics from waste electrical and electronic equipment by inductively coupled plasma mass spectrometry with collision-reaction interface technology

A procedure based on the use of a quadrupole inductively coupled plasma-mass spectrometer equipped with a collision-reaction interface (CRI) for control of spectral overlap interferences was developed for simultaneous determination of Cd, Cr, Hg, and Pb in plastics from waste electrical and electronic equipment (WEEE). The injection of H(2) and He (80 and 60 mL min(-1), respectively) into the sampled plasma, colliding and reacting with potentially interfering polyatomic ions, allows interference-free determination of chromium via its isotopes (52)Cr and (53)Cr that are freed from overlap due to the occurrence of (40)Ar(12)C(+), (40)Ar(12)C(1)H(+), (36)S(16)O(+) or (1)H(36)S(16)O(+). Cadmium, Hg and Pb were directly determined via their isotopes (110)Cd, (111)Cd, (112)Cd, (199)Hg, (200)Hg, (201)Hg, (202)Hg, (206)Pb, (207)Pb, and (208)Pb, without using CRI. The CRI can be quickly activated or deactivated before each analyte measurement. Limits of detection for (52)Cr were 0.04 or 0.14 μg L(-1) with He or H(2) injected in CRI. Cadmium and Pb have LODs between 0.02 and 0.08 μg L(-1) and Hg had 0.93-0.98 μg L(-1), without using CRI. Analyte concentrations for samples varied from 16 to 43, 1 to 11, 4 to 12, and 5 to 13 mg kg(-1) for Cr, Cd, Hg and Pb, respectively.     

Highly sensitive and selective trimethylamine sensor using one-dimensional ZnO-Cr2O3 hetero-nanostructures

Highly selective and sensitive detection of trimethylamine (TMA) was achieved by the decoration of discrete p-type Cr(2)O(3) nanoparticles on n-type ZnO nanowire (NW) networks. Semielliptical Cr(2)O(3) nanoparticles with lateral widths of 3-8 nm were deposited on ZnO NWs by the thermal evaporation of CrCl(2) at 630 °C, while a continuous Cr(2)O(3) shell layer with a thickness of 30-40 nm was uniformly coated on ZnO NWs at 670 °C. The response (R(a)/R(g): R(a), resistance in air; R(g), resistance in gas) to 5 ppm TMA of Cr(2)O(3)-decorated ZnO NWs was 17.8 at 400 °C, which was 2.4 times higher than that to 5 ppm C(2)H(5)OH and 4.3-8.4 times higher than those to 5 ppm p-xylene, NH(3), benzene, C(3)H(8), toluene, CO, and H(2). In contrast, both pristine ZnO and ZnO (core)-Cr(2)O(3) (shell) nanocables (NCs) showed comparable responses to the different gases. The highly selective and sensitive detection of TMA that was achieved by the deposition of semielliptical Cr(2)O(3) nanoparticles on ZnO NW networks was explained by the catalytic effect of Cr(2)O(3) and the extension of the electron depletion layer via the formation of p-n junctions.     

Non-Redox Assisted Oxygen-Oxygen Bond Homolysis in Titanocene Alkylperoxide Complexes: [Cp(2)Ti(eta-OOBu)L], L = Cl, OTf, Br, OEt(2), Et(3)P

The titanium(IV) alkylperoxide complex Cp(2)Ti(OO(t)Bu)Cl (1) is formed on treatment of Cp(2)TiCl(2) with NaOO(t)Bu in THF at -20 degrees C. Treatment of 1 with AgOTf at -20 degrees C gives the triflate complex Cp(2)Ti(OO(t)Bu)OTf (2), which is rapidly converted to the bromide Cp(2)Ti(OO(t)Bu)Br (3) on addition of (n)Bu(4)NBr. The X-ray crystal structures of 1 and 3 both show eta(1)-OO(t)Bu ligands. Complex 2 is stable only below -20 degrees C; (1)H, (13)C, and (19)F NMR spectra suggest that it also contains an eta(1)-OO(t)Bu ligand. Removal of the chloride from 1 with [Ag(Et(2)O)(2)]BAr'(4) (Ar' = 3,5-(CF(3))(2)C(6)H(3))) yields the etherate complex [Cp(2)Ti(OO(t)Bu)(OEt(2))]BAr'(4) (4). Again, coordination of a fourth ligand to the Ti center indicates an eta(1)-OO(t)Bu ligand in 4. These peroxide complexes do not directly oxidize olefins or phosphines. For instance, the cationic etherate complex 4 reacts with excess Et(3)P simply by displacement of the ether to form [Cp(2)Ti(eta(1)-OO(t)Bu)(Et(3)P)]BAr'(4) (5). Compounds 1-5 all decompose by O-O bond homolysis, based on trapping and computational studies. The lack of direct oxygen atom transfer reactivity is likely due to the eta(1) coordination of the peroxide and the inability to adopt more reactive eta(2) geometry. DFT calculations indicate that the steric bulk of the (t)Bu group inhibits formation of the hypothetical [Cp(2)Ti(eta(2)-OO(t)Bu)](+) species.     

Nano-scale Au supported on Fe3O4: characterization and application in the catalytic treatment of 2,4-dichlorophenol

Catalytic hydrodechlorination (HDC) is an effective means of detoxifying chlorinated waste. Gold nanoparticles supported on Fe(3)O(4) have been tested in the gas phase (1 atm, 423 K) HDC of 2,4-dichlorophenol. Two 1% w/w supported gold catalysts have been prepared by: (i) stepwise deposition of Au on α-Fe(2)O(3) with subsequent temperature-programmed reduction at 673 K (Au/Fe(3)O(4)-step); (ii) direct deposition of Au on Fe(3)O(4) (Au/Fe(3)O(4)-dir). TEM analysis has established the presence of Au at the nano-scale with a greater mean diameter (7.6 nm) on Au/Fe(3)O(4)-dir relative to Au/Fe(3)O(4)-step (4.5 nm). We account for this difference in terms of stronger (electrostatic) precursor/support interactions in the latter that can be associated with the lower pH point of zero charge (with respect to the final deposition pH) for Fe(2)O(3). Both catalysts promoted the preferential removal of the ortho-Cl substituent in 2,4-dichlorophenol, generating 4-chlorophenol and phenol as products of partial and total HDC, respectively, where Au/Fe(3)O(4)-step delivered a two-fold higher rate (2 × 10(-4) mol(Cl) h(-1) m(Au)(-2)) when compared with Au/Fe(3)O(4)-dir. This unprecedented selectivity response is attributed to activation of the ortho-C-Cl bond via interaction with electron-deficient Au nanoparticles. The results demonstrate the feasibility of a controlled recovery/recycling of chlorophenol waste using nano-structured Au catalysts.     

Synthesis, Characterization, and Reactions of Isolable (β-Diketiminato)Nb(III) Imido Complexes

We have investigated both the chemical reduction of (BDI)Nb(V) imido complexes (BDI = HC[C(Me)NAr](2); Ar = 2,6-(i)Pr(2)-C(6)H(3)) to the formal Nb(III) oxidation state and the ability of these Nb(III) complexes to behave as two-electron reductants. The reduction of the Nb(V) species was found to depend heavily on the nature of available supporting ligands, but the chemistry of the reduced compounds proceeded cleanly with a number of unsaturated organic reagents. Accordingly, the novel Nb(V) bis(imido) complexes supported by the monoazabutadiene (mad) ligand (mad)Nb(N(t)Bu)(NAr)(L') (L' = py, thf) were formed by either KC(8) reduction of (BDI)Nb(N(t)Bu)Cl(2)(py) in the absence of strong π-acids or by H(2) reduction of the Nb(V) dimethyl complex (BDI)Nb(N(t)Bu)Me(2) in THF. These products are likely formed though an intramolecular, 2 e(-) reductive C-N bond cleavage, as has been observed previously for related Group 4 systems, suggesting that transient Nb(III) intermediates were present in both cases. In the presence of 1,2-bis(dimethylphosphino)ethane (dmpe), KC(8) reduction of (BDI)Nb(N(t)Bu)Cl(2)(py) was arrested at the Nb(IV) oxidation state to give (BDI)Nb(N(t)Bu)Cl(dmpe), which was characterized by solution-state EPR spectroscopy as a Nb-centered paramagnet with strong coupling to the two equivalent phosphorus nuclei (A(iso){(93)Nb} = 120.5×10(-4) cm(-1), A(iso){(31)P} = 31.0×10(-4) cm(-1), g(iso) = 1.9815). When strong π-acids were used to intercept the thermally unstable Nb(III) complex (BDI)Nb(N(t)Bu)(py) prior to reductive cleavage of the ligand C-N bond, the thermally stable Nb(III) species (BDI)Nb(N(t)Bu)(CX)(2)(L″) (X = O, L″ = py; X = NXyl, L″ = CNXyl; Xyl = 2,6-Me(2)-C(6)H(3)) were obtained in good yields. The Nb(III) complexes (BDI)Nb(N(t)Bu)py, (BDI)Nb(N(t)Bu)(CO)(2)(py) and (BDI)Nb(N(t)Bu)(CO)(2) were subsequently investigated for their ability to serve as two-electron reducing reagents for both metal-ligand multiple bond formation and for the reduction of organic π-systems. The reduction of mesityl azide by (BDI)Nb(N(t)Bu)(py) and diphenylsulfoxide by (BDI)Nb(N(t)Bu)(CO)(2) led to the monomeric bis(imido) and dimeric oxo complexes (BDI)Nb(N(t)Bu)(NMes)(py) and [(BDI)Nb(N(t)Bu)](2)(μ2-O)(2), respectively. MeLi addition to (BDI)Nb(N(t)Bu)(CO)(2)(py) resulted in the formation of a Nb-acylate via methide addition to one of the carbonyl carbons. The acylate product was revealed to have a short Nb-C(acylate) bond distance (2.059(4) ?), consistent with multiple Nb-C bond character resulting from Nb(III) back-bonding into the acylate carbon. The interaction of (BDI)Nb(N(t)Bu)(CO)(2) with two equivalents of 4,4'-dichlorobenzophenone resulted in the clean, quantitative formation of the corresponding pinacol coupling product, but introduction of the ketone in 1: 1 molar ratios resulted in mixtures of the pinacol product and the starting material, suggesting that ketone coordination to the Nb(III) complex may be reversible. Relatedly, addition of 1-phenyl-1-propyne to (BDI)Nb(N(t)Bu)(CO)(2) formed a thermally unstable 1: 1 Nb/alkyne complex, as characterized by NMR and IR spectroscopies; reaction of this species with HCl/MeOH yielded a 2: 1 mixture of 1-phenyl-1-propene and the free alkyne, suggesting a high degree of covalency in the Nb-C bonds.     

Mechanistic Investigation of Cycloreversion/Cycloaddition Reactions between Zirconocene Metallacycle Complexes and Unsaturated Organic Substrates

Treatment of the diazametallacycle Cp(2)Zr(N(t-Bu)C=N(SiMe(3))N(SiMe(3))) (4a) with diphenylacetylene resulted in the formation of the azametallacyclobutene Cp(2)Zr(N(t-Bu)C(Ph)=C(Ph)) (6a) and Me(3)SiN=C=NSiMe(3) in high yield. A kinetic study using UV-vis spectroscopy was carried out on the transformation. Saturation kinetic behavior was observed for the system, which is supportive of a mechanism that involves a reversible formal [2 + 2] retrocycloaddition of 4a to generate the transient imido species Cp(2)Zr=N-t-Bu (7a) and Me(3)-SiN=C=NSiMe(3). Trapping 7a with diphenylacetylene in an overall [2 + 2] cycloaddition reaction affords zirconacycle 6a. The study of cycloreversion/cycloaddition reactions between diazametallacycle complexes and diphenylacetylene was extended to other zirconocene systems. Detailed kinetic studies were performed for the exchange reactions between the diazametallacycle complexes Cp(2)Zr(N(2,6-Me(2)Ph)C=N(SiMe(3))N(SiMe(3))) (8a) and Cp(2)Zr-(N(2,6-Me(2)Ph)C=N(t-Bu)N(t-Bu)) (8b) with diphenylacetylene (5a) to give the corresponding azametallacyclobutene complex Cp(2)Zr(N(2,6-Me(2)Ph)C(Ph)=C(Ph)) (6c) and extruded carbodiimides (Me(3)SiN=C=NSiMe(3) for 8a and (t-Bu)N=C=N(t-Bu) for 8b). For both systems, the reactions were found to be first order in metallacycle and zero order in alkyne. Treatment of the diazametallacycle complexes Cp(2)Zr(N(2,6-i-Pr(2)Ph)C=N(Cyc)N(Cyc)) (9a) and Cp(2)Zr-(N(2,6-i-Pr(2)Ph)C=N(i-Pr(2))N(i-Pr(2))) (9b) with alkyne 5a resulted in the formation of the six-membered zirconacycles 10a,b, respectively, upon heating at 75 degrees C. The products 10a,b are generated from the overall insertion of alkyne 5a into the nitrogen-carbon bond of the zirconium-containing diazacyclobutane. Complex 10a has been characterized by an X-ray crystallographic study. When the azacyclobutene Cp(2)Zr(N(2,6-i-Pr(2)Ph)C(Ph)=C(Ph)) (6e) was treated with CycN=C=NCyc or (i-Pr)N=C=N(i-Pr), the same six-membered zirconacycle complexes 10a,b were obtained. Kinetic analysis of the reaction of 6e and (i-Pr)N=C=N(i-Pr) to yield 10b supports an associative process wherein alkyne 5a directly inserts into the zirconium-carbon bond of 6e. The diazametallacycle complex 4a underwent a stoichiometric metathetical exchange with symmetrical carbodiimides RN=C=NR (R = p-Tol, m-Tol, i-Pr, Cyc) to generate new cyclic zirconocene complexes and Me(3)SiN=C=NSiMe(3). Kinetic studies were carried out on the exchange reaction between 4a and (m-Tol)N=C=N(m-Tol) to form 4e and Me(3)SiN=C=NSiMe(3). The experimental rate data obtained are consistent with a dissociative mechanism. Additionally, the saturation rate constant derived for this system from the data is the same (within experimental error) as the saturation rate constant obtained from the kinetic study of 4a and diphenylacetylene to form 6a and Me(3)SiN=C=NSiMe(3). These findings provide additional support for a dissociative mechanistic pathway in the exchange reactions, since the rate constant in the formal [2 + 2] retrocycloaddition reaction to generate imidozirconocene species Cp(2)Zr=N-t-Bu (7a) and Me(3)SiN=C=NSiMe(3) should be the same for both reactions.     

Dumbbell-like PtPd-Fe(3)O(4) Nanoparticles for Enhanced Electrochemical Detection of H(2)O(2)

Dumbbell-like Pt(x)Pd(100-x)-Fe(3)O(4) nanoparticles (NPs) were synthesized and studied for electrocatalytic reduction and sensing of H(2)O(2). In 0.1 M phosphate buffered saline (PBS) solution, the 4-10 nm Pt(x)Pd(100-x)-Fe(3)O(4) NPs showed the Pt/Pd composition-dependent catalysis with Pt(48)Pd(52)-Fe(3)O(4) NPs having the best activity. The Pt(48)Pd(52)-Fe(3)O(4) NPs were tested for H(2)O(2) detection, and their H(2)O(2) detection limit reached 5 nM, which was suitable for monitoring H(2)O(2) generated from Raw 264.7 cells. These dumbbell-like PtPd-Fe(3)O(4) NPs are the most sensitive probe ever reported and can be used to achieve real-time quantitative detection of H(2)O(2) in biological environment for biological and biomedical applications.     

Scope and Mechanistic Study of the Coupling Reaction of α, β-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways

The cationic ruthenium-hydride complex [(C(6)H(6))(PCy(3))(CO)RuH](+)BF(4) (-) (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to α,β-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic C-H bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as: rate = k[1](1)[propene](0)[cinnamate](-1). A negligible deuterium kinetic isotope effect (k(H)/k(D) = 1.1±0.1) was measured from both (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) and (E)-C(6)H(5)CD=C(CH(3))CONHCH(3) with styrene. In contrast, a significant normal isotope effect (k(H)/k(D) = 1.7±0.1) was observed from the reaction of (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) with styrene and styrene-d(10). A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C(6)H(5)CH=CHCO(2)Et with propene ((13)C(recovered)/(13)C(virgin) at C(β) = 1.019(6)), while a negligible carbon isotope effect ((13)C(recovered)/(13)C(virgin) at C(β) = 0.999(4)) was obtained from the reaction of (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) with styrene. Hammett plots from the correlation of para-substituted p-X-C(6)H(4)CH=CHCO(2)Et (X = OCH(3), CH(3), H, F, Cl, CO(2)Me, CF(3)) with propene and from the treatment of (E)-C(6)H(5)CH=CHCO(2)Et with a series of para-substituted styrenes p-Y-C(6)H(4)CH=CH(2) (Y = OCH(3), CH(3), H, F, Cl, CF(3)) gave the positive slopes for both cases (ρ = +1.1±0.1 and +1.5±0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, Δ H(?) = 20±2 kcal mol(-1) and S(?) = -42±5 e.u. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies.     

Enrichment of H(2)(17)O from tap water, characterization of the enriched water, and properties of several (17)O-labeled compounds

A low-abundance form of water, H(2)(17)O, was enriched from 0.04% to ～90% by slow evaporation and fractional distillation of tap water. The density and refractive index for H(2)(17)O are reported. Gas chromatography-mass spectrometry (GC-MS) of (16)O- and (17)O-1-hexanols and their trimethyl silyl ethers and of (16)O- and (17)O-hexamethyl disiloxanes was used to determine the percentage of (17)O enrichment in the H(2)(17)O. Furthermore, the chemical shifts of labeled and nonlabeled water dissolved in CDCl(3) differed sufficiently that we could verify the enrichment of H(2)(17)O. (17)O hexanol was synthesized by the reaction of iodohexane with Na(17)OH. (17)O-Labeled trimethylsilanol and (17)O-labeled hexamethyldisiloxane were prepared by the reaction of H(2)(17)O with bis(trimethylsilyl)trifluoroacetamide (BSTFA). To generate standards for (17)O NMR, H(2)(17)O(2), and (17)O camphor were prepared. H(2)(17)O was electrolyzed to form (17)O-labeled hydrogen peroxide which was quantified using two colorimetric assays. (17)O-Labeled camphor was prepared by exchanging the ketone oxygen of camphor using H(2)(17)O. The (17)O-labeled compounds were characterized using (17)O, (1)H, and (13)C NMR and GC-MS. While we were characterizing the labeled camphor, we also detected an unexpected oxygen exchange reaction of primary alcohols, catalyzed by electrophilic ketones such as camphor. The reaction is a displacement of the alcohol OH group by water. This is an example of the usefulness of (17)O NMR in the study of a reaction mechanism that has not been noticed previously.     

Emission properties of hydrothermal Yb(3+), Er(3+) and Yb(3+), Tm(3+)-codoped Lu2O3 nanorods: upconversion, cathodoluminescence and assessment of waveguide behavior

Yb(3+) and Ln(3+) (Ln(3+) = Er(3+) or Tm(3+)) codoped Lu(2)O(3) nanorods with cubic Ia3 symmetry have been prepared by low temperature hydrothermal procedures, and their luminescence properties and waveguide behavior analyzed by means of scanning near-field optical microscopy (SNOM). Room temperature upconversion (UC) under excitation at 980 nm and cathodoluminescence (CL) spectra were studied as a function of the Yb(+) concentration in the prepared nanorods. UC spectra revealed the strong development of Er(3+) (4)F(9/2) → (4)I(15/2) (red) and Tm(3+) (1)G(4) → (3)H(6) (blue) bands, which became the pre-eminent and even unique emissions for corresponding nanorods with the higher Yb(3+) concentration. Favored by the presence of large phonons in current nanorods, UC mechanisms that privilege the population of (4)F(9/2) and (1)G(4) emitting levels through phonon-assisted energy transfer and non-radiative relaxations account for these observed UC luminescence features. CL spectra show much more moderate development of the intensity ratio between the Er(3+) (4)F(9/2) → (4)I(15/2) (red) and (2)H(11/2), (4)S(3/2) → (4)I(15/2) (green) emissions with the increase in the Yb(3+) content, while for Yb(3+), Tm(3+)-codoped Lu(2)O(3) nanorods the dominant CL emission is Tm(3+) (1)D(2) → (3)F(4) (deep-blue). Uniform light emission along Yb(3+), Er(3+)-codoped Lu(2)O(3) rods has been observed by using SNOM photoluminescence images; however, the rods seem to be too thin for propagation of light.     

Highly conductive coaxial SnO(2)-In(2)O(3) heterostructured nanowires for Li ion battery electrodes

Novel SnO(2)-In(2)O(3) heterostructured nanowires were produced via a thermal evaporation method, and their possible nucleation/growth mechanism is proposed. We found that the electronic conductivity of the individual SnO(2)-In(2)O(3) nanowires was 2 orders of magnitude better than that of the pure SnO(2) nanowires, due to the formation of Sn-doped In(2)O(3) caused by the incorporation of Sn into the In(2)O(3) lattice during the nucleation and growth of the In(2)O(3) shell nanostructures. This provides the SnO(2)-In(2)O(3) nanowires with an outstanding lithium storage capacity, making them suitable for promising Li ion battery electrodes.     

Interactions of vitamin K3 with herring-sperm DNA using spectroscopy and electrochemistry

By means of ultraviolet-visible (UV-Vis) and fluorescence spectra, the binding ratio between vitamin K(3) and herring-sperm DNA in a physiological pH environment (pH = 7.40) was determined as n(K3):n(DNA) = 2:1, and the binding constants of vitamin K(3) binding to DNA at different temperatures were determined as K(θ)(298K) = 1.28 × 10(5) L·mol(-1) and K(θ)(310K) = 7.19 × 10(4) L·mol(-1), which were confirmed using the double reciprocal method are Δ(r)H(m)(θ) = -3.57 × 10(4) J·mol(-1), Δ(r)G(m)(θ) = -2.92 × 10(4) J·mol(-1), and Δ(r)S(m)(θ) = 217.67 J·mol(-1)K(-1). The driving power of this process was enthalpy. An intercalation binding of the vitamin K(3) with DNA was supported by a competitive experiment using acridine orange (AO) as a spectral probe. By combination analysis of the Scatchard method and cyclic voltammetry, we suggested that the interaction mode between vitamin K(3) and herring-sperm DNA would be a mixed mode. The quinonoid, duality fused-ring of vitamin K(3) can intercalate into the base pairs of DNA, and there is an electrostatic binding along with intercalation binding.