Structural requirements in chiral diphosphine-rhodium complexes. VIII. Asymmetric hydrogenation of N-acetyldehydroamino acids with rhodium(I) complexes containing chiral carbocyclic analogues of DIOP.

Z--acetamidocinnamic acid was hydrogenated with neutral diphosphine-rhodium(I) complexes containing trans-1,2-bis(diphenylphosphinomethyl) cycloalkanes to give N-acetylphenylalanine: 86 % e.e.-(R) [(1R,2R)-cyclobutane]; 63 % e.e.-(R) [(1R,2R)-cyclopentane]; 35 % e.e.-(S) [(1S,2S)-cyclohexane]; and 82 % e.e.-(R) [(2R,3R)-DIOP]. Similarly, -acetamidoacrylic acid was hydrogenated to give N-acetylalanine: 72 % e.e.-(R) [(1R,2R)-cyclobutane]; 72 % e.e.-(R) [(1R,2R)-cyclopentane]; 40 % e.e.-(S) [(1S,2S)-cyclohexane]; and 73 % e.e.-(R) [(2R,3R)-DIOP].     

On hydrogen activation in the hydroformylation of olefins with Rh4(CO)12 or Co2(CO)8 as catalyst precursors

In the hydroformylation of ethylene with approximately equimolar H₂/D₂ mixtures and Rh₄(CO)₁₂ or Co₂(CO)₈ as the catalyst precursor about 50% of propionaldehyde-d₁ was formed. The propionaldehyde-d₀/d₂ ratio was ～ 3 for rhodium and ～ 2.6 for the cobalt catalyst. On the basis of the results and assuming that there is no rapid M(H)₂/M(D)₂ scrambling, activation of hydrogen through M(H)₂ or M(H)₂(olefin) complexes can be excluded.     

CHARGE TRANSFER ACROSS PIGMENTED BILAYER LIPID MEMBRANE AND ITS INTERFACES

Abstract— The technique of forming bilayer lipid membranes (BLM) has made it possible to study photoreactions of pigments in an environment that is much closer to those in photosynthetic and visual membranes. A pigmented BLM system with Mg²⁺-porphyrins as membrane-bound pigments and with ferricyanide and ferrocyanide as the aqueous electron acceptor and donor, respectively, was used to illustrate the photoelectric effects due to coupled interfacial charge transfer reactions.
The steady-state continuous photoresponse was studied by means of the voltage clamp method and a null current method. The independence of the pigment conductance channel and the ionic conductance channel was demonstrated. A tunable voltage clamp method was used to study the transient pulsed photoresponses. Such a measurement permits us to characterize the photosystem in terms of an equivalent circuit model which contains a novel chemical capacitance. Molecular interpretation of this equivalent circuit model was given.
A microscopic model based on the Gouy–Chapman theory and chemical kinetics calculation leads to an equivalent circuit which is also equivalent to the previous one. Generalization of this microscopic model further leads to a physical mechanism of the generation of the early receptor potential (ERP) in visual membranes. Relevance of pigmented BLM research to photosynthesis and other disciplines was also discussed.     

Formation of Zn(1-x)MnxS nanowires within mesoporous silica of different pore sizes

Arrays of highly ordered Zn(1-x)MnxS quantum wires with x ranging from 0.01 to 0.3 and with lateral dimensions of 3, 6, and 9 nm were synthesized within mesoporous SiO2 host structures of the MCM-41 and SBA-15 type. The hexagonal symmetry of these arrays (space group p6m) and the high degree of order was confirmed by X-ray diffraction and transmission electron microscopy (TEM) studies. Physisorption measurements show the progressive filling of the pores of the SiO2 host structures, while TEM and Raman studies reveal the wire-like character of the incorporated Zn(1-x)MnxS nanostructures. X-ray absorption near-edge structure, extended X-ray absorption fine structure, photoluminescence excitation (PLE), and electron paramagnetic resonance studies confirm the good crystalline quality of the incorporated Zn(1-x)MnxS guest species and, in particular, that the Mn2+ ions are randomly distributed and are situated on tetrahedrally coordinated cation sites of the Zn(1-x)MnxS wires for all x up to 0.3. The amount of Mn2+ ions loosely bound to the surface of the Zn(1-x)MnxS nanowires is less than 4% of the total Mn content even for the 3 nm nanostructures up to the highest Mn content of x = 0.3. The effects of the reduction of the lateral dimensions on electronic properties of the diluted magnetic semiconductor were studied by PLE spectroscopy. Due to the quantum confinement of the excitons in the wires an increase of the direct band gap with decreasing particle size is observed.     

Kinetic dehydroxylation of nontronite,estimated from isothermal and nonisothermal thermogravimetry

Dehydroxylation of an American nontronite (Manito) was followed via records of isothermal and dynamic thermogravimetry. Analysis of the isothermal weight-change curves (673-753 K). was performed with the procedure suggested by Hancock and Sharp. A fourteen-kinetic equation procedure was employed for analysis of the non-isothermal weight change in the range 623–1023 K. (A second-order decomposition equation seems to fit the dehydroxylation better under these conditions). The activation energies associated with the isothermal and nonisothermal processes are 118.8 and 136.8 kJ/mol^–1, respectively.

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Zusammenfassung Anhand isothermer und herkömmlicher Thermogravimetrie wurde die Dehydroxylierung eines amerikanischen Nontronites (Manito) verfolgt. Die isothermen TG-Kurven (673–753 K) wurden mittels der von Hancock und Sharp (1972). Ein kinetisches Vierzehngleichungsverfahren wurde zur Analyse der nichtisothermen TG-Kurven im Bereich 623–1023 K angestellt. Einer Dehydroxylierung unter diesen Bedingungen scheint eine Zersetzungsgleichung zweiter Ordnung besser zu entsprechen. Die Aktivierungsenefgie für die isothermen bzw. nichtisothermen Prozesse beträgt 118,8 bzw. 136,8 kJ/mol.

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(). (673–753 ) . , 623–1023, . . , , 118,8 136,8 /.

     

Die Millon'sche Reaktion des Harns und ihre Beeinflussung durch Zufuhr von Tyrosin

Zusammenfassung Es werden einige Versuche an Kaninchen und Menschen über die Millon'sche Reaktion des Harns mitgeteilt. Ihre Intensität steigt an, wenn Tyrosin zugeführt wird, und zwar erheblich mehr nach dl-Tyrosin als nach l-Tyrosin. Ein Teil der Millon-Substanzen ist in Äther löslich, der ebenfalls nach der razemisierten stärker zunimmt als der nach der natürlichen Aminosäure.     

Application of a universal force field to mixed Fe/Mo-S/Se cubane and heterocubane clusters. 1. Substitution of sulfur by selenium in the series [Fe4X4(YCH3)4]2-; X = S/Se and Y = S/Se

A series of Fe-S and Fe-Se cubane clusters containing all four combinations of the general formula [Fe(4)X(4)(Y-CH(3))(4)](2)(-) (X = S/Se, Y = S/Se) is investigated with FTIR and Raman spectroscopy. The terminally selenolate coordinated clusters (Y = Se) are prepared by a new synthetic route. All four cluster compounds are structurally characterized by X-ray single-crystal structure determination. Infrared and Raman spectra of all compounds are presented and interpreted with normal coordinate analysis. The corresponding force fields are based on that developed for the Fe(4)S(4)-benzyl cluster (Czernuszewicz, R. S.; Macor, K. A.; Johnson, M. K.; Gewirth, A.; Spiro, T. G. J. Am.Chem. Soc. 1987, 109, 7178-7187). An empirical procedure is presented to convert Fe-S into Fe-Se force constants. Only minor changes in force constants are found upon S --> Se exchange, reflecting the similarity of the Fe-S and Fe-Se bonds. The drastic frequency shifts in the metal-ligand region observed upon substitution of sulfur by selenium are, therefore, primarily due to the corresponding mass changes.     

Mass-spectrometric studies on alkylated 6-thiopurines

6-Thiopurine and its N- or C-alkyl derivatives all form an [M – 1]-ion upon fragmentation. In the 7-alkyl derivatives, this ion represents the major component of the spectrum. This is ascribed to formation of a five-membered thiazoline-like ring. Similar ring formation stabilises the [M – 1]-ion in the 7-methyl derivatives of hypoxanthine, adenine and 6-selenopurine.     

Aqueous solutions—A new perspective. Amorphous carbohydrates: Science and application technology

At a recent meeting of the International Symposium on Solution Chemistry I presented a paper dealing with aqueous solutions in which water was present not in excess but as one component of a supersaturated solution with polyhydroxy compounds. In response to a request from the Editor of this Journal I have submitted this article in which I outline my general interest in the subject and its importance as a new direction for solution chemists.     

Formation and stability of N-heterocyclic carbenes in water: the carbon acid pKa of imidazolium cations in aqueous solution

We report second-order rate constants kDO (M-1 s-1) for exchange for deuterium of the C(2)-proton of a series of simple imidazolium cations to give the corresponding singlet imidazol-2-yl carbenes in D2O at 25 degrees C and I = 1.0 (KCl). Evidence is presented that the reverse protonation of imidazol-2-yl carbenes by solvent water is limited by solvent reorganization and occurs with a rate constant of kHOH = kreorg = 10(11) s-1. The data were used to calculate reliable carbon acid pK(a)s for ionization of imidazolium cations at C(2) to give the corresponding singlet imidazol-2-yl carbenes in water: pKa = 23.8 for the imidazolium cation, pKa = 23.0 for the 1,3-dimethylimidazolium cation, pKa = 21.6 for the 1,3-dimethylbenzimidazolium cation, and pKa = 21.2 for the 1,3-bis-((S)-1-phenylethyl)benzimidazolium cation. The data also provide the thermodynamic driving force for a 1,2-hydrogen shift at a singlet carbene: K12 = 5 x 10(16) for rearrangement of the parent imidazol-2-yl carbene to give neutral imidazole in water at 298 K, which corresponds to a favorable Gibbs free energy change of 23 kcal/mol. We present a simple rationale for the observed substituent effects on the thermodynamic stability of N-heterocyclic carbenes relative to a variety of neutral and cationic derivatives that emphasizes the importance of the choice of reference reaction when assessing the stability of N-heterocyclic carbenes.