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41.
Hioki A  Kubota M  Kawase A 《Talanta》1991,38(4):397-404
A precise and accurate method in which ammonia and ammonium ions are coulometrically titrated with electrogenerated hypobromite was studied. Through the measurement of the current efficiency for generating hypobromite and the dependencies of titration results on electrolysis current and delay time between sampling and starting electrolysis, precision and accuracy of 0.01 and 0.02%, respectively, were obtained. The accuracy of the titration was compared with that of acidimetric coulometric titration of ammonia.  相似文献   
42.
In the Sc2O3---Ga2O3---CuO, Sc2O3---Ga2O3---ZnO, and Sc2O3---Al2O3---CuO systems, ScGaCuO4, ScGaZnO4, and ScAlCuO4 with the YbFe2O4-type structure and Sc2Ga2CuO7 with the Yb2Fe3O7-type structure were obtained. In the In2O3---A2O3---BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, or Zn), InGaFeO4, InGaNiO4, and InFe3+MgO4 with the spinel structure, InGaZnO4, InGaMgO4, and InAlCuO4 with the YbFe2O4-type structure, and In2Ga2MnO7 and In2Ga2ZnO7 with the Yb2Fe3O7-type structure were obtained. InGaMnO4 and InFe2O4 had both the YbFe2O4-type and spinel-type structures. The revised classification for the crystal structures of AB2O4 compounds is presented, based upon the coordination numbers of constituent A and B cations.  相似文献   
43.
A new nano-biomachine has been created from microtubules (MTs) and hetero-bifunctional polymer particles bearing pyruvate kinase, which is propelled on glass surfaces coated with kinesin by use of self-supplying ATP.  相似文献   
44.
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.  相似文献   
45.
Formate was determined as benzimidazole by high-performance liquid chromatography after reaction with o-phenylenediamine at 130 degrees C for 2 h in 1 M perchloric acid. The useful concentration range was 1.6-40 mumol/l and the determination limit was 20 pmol. The recoveries from rat liver homogenate and human urine were 90.3 +/- 2.9 and 89.4 +/- 2.5%, respectively. Using this method, the activity of formaldehyde dehydrogenase in biological samples could be measured, and also the formate concentration in the liver and urine of rats to which methanol had been administered.  相似文献   
46.
Anionic copolymerizations of acrylonitrile (monomer 1) with β-propiolactone (monomer 2) and the structures of the resulting copolymers were studied. The copolymerization with sodium cyanide in N,N-dimethylformamide gave copolymers of the structure I containing acid anhydride linkage in the molecular chains, with the monomer reactivity ratios, r1 = 1.20, r2 = 0.00. The copolymerization with potassium hydroxide gave either copolymers of the structure II (r1 = 0.00, r2 = 3.64 at 30°C; r1 = 0.00, r2 = 5.00 at 40°C) in N,N-dimethylformamide or only β-propiolactone homopolymer in toluene.   相似文献   
47.
Although known since the 1950s, free-radical carbonylation has not received much attention until only recently. In the last few years the application of modern free-radical techniques has revealed the high synthetic potential of this reaction as a tool for introducing CO into organic molecules. Clearly now is the time for a renaissance of this chemistry. Under standard conditions (tributyltin hydride/CO) primary, secondary, as well as tertiary alkyl bromides and iodides can be efficiently converted into the corresponding aldehydes. Aromatic and α,β-unsaturated aldehydes can also be prepared from the parent aromatic and vinylic iodides. If the reaction is carried out in the presence of alkenes containing an electron-withdrawing substituent, the initially formed acyl radical subsequently adds to the alkene, leading to a general method for the synthesis of unsymmetrical ketones. This three-component coupling reaction can be extended successfully to allyltin-mediated reactions. Thus, β,γ-enones can be prepared from organic halides, CO, and allyltributylstannanes. In a remarkable one-pot procedure alkyl halides can be treated with a mixture of alkene, allyltributylstannane, and carbon monoxide in a four-component coupling reaction that provides β-functionalized δ,?-unsaturated ketones by the formation of three new C? C bonds. The reaction of 4-pentenyl radicals with CO leads to acyl radical cyclization, which provides a useful method for the synthesis of cyclopentanones. Certain useful one-electron oxidations can be combined efficiently with free-radical carbonylations. These findings and others discussed in this article clearly demonstrate that free-radical carbonylation can now be considered a practical alternative to transition metal mediated carbonylation.  相似文献   
48.
Based on the element maps of twenty-two gibberellin methyl esters fragmentations are discussed, which are characteristic of the common structural features as well as structural modification in gibberellin homologues.  相似文献   
49.
Summary This study establishes an error estimate for a penalty-finite element approximation of the variational inequality obtained by a class of obstacle problems. By special identification of the penalty term, we first show that the penalty solution converges to the solution of a mixed formulation of the variational inequality. The rate of convergence of the penalization is where is the penalty parameter. To obtain the error of finite element approximation, we apply the results obtained by Brezzi, Hager and Raviart for the mixed finite element method to the variational inequality.  相似文献   
50.
trans-Stilbene, 1, 1-diphenylethylene, and α-methylstyrene were allowed to react with dibenzylmagnesium to form their oligomers in hexamethylphosphortriamide (HMPA). One and two molecules of stilbene and 1, 1-diphenylethylene were incorporated into the magnesium carbon bond, and the carbanions obtained in HMPA were stable in analogy with the anionic living polymer having alkali cation as the gegenion in eithers. Intense coloration was observed during the reaction between α-methylstyrene and dibenzylmagnesium as well as in the case of stilbene and 1, 1-diphenylethylene. The low molecular weight products which were formed after a long time in the reaction between α-methylstyrene and dibenzylmagnesium were found to have no magnesium-carbon bond. It was considered that the cleavage of the propagating chain occurred gradually after the rapid propagation had proceeded to consume the monomer.  相似文献   
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