Dependency of control parameters on a rate coefficient giving the potential curvature in a reaction cascade model

Many chemical reactions in vivo are self-controlled by fluxes of chemical energy and matter through biological systems, so the induction of such reactions can be governed by changes in the control parameters of the rate equation. A potential of a system is assumed to be given by Gibbs' functionG(T, P, x), which is continuously differentiable, and the rate equation can be derived from the differential (–G/x) of Taylor's expansion ofG _(T,P)(x) for the order parameterx, which corresponds to the product number, at around the critical pointC(T _C, P_C). The equation is described bydx/dt=(x)–k₁x–k₂x³, andk ₂>0. In this equation,k ₁ andk ₂ are functions of the control parameters, temperatureT and pressureP, andk ₁ is allowed to have a positive or negative values as (T, P). Thenk ₁ is an important factor that decides the induction conditions of the reactions with a phase transition in the steady statex=0. Because bothk ₁ (the transition parameter) andG are the quantity of state, they are given by the total differential, and functions that decideG andk ₁ are related to a mutual inverse function. From the above relation, the rate of change ink ₁ by G, which corresponds to the reaction energy of the system, is uniquely determined by a function ofk ₁, [f(k ₁ ^± )] andf(k ₁ ^± ) is described approximately by ±₁ k ₁ ^± in the transient process thatk ₁ approaches zero, where ₁ implies 1/RT. These results indicate that internal driving forces caused by a stimulus in a system are proportional tok ₁ ^± and that the system is regulated by competition of the forces. an approximate function fork ₁ in the transient process is described by tanh (G/RT) and Arrhenius' law is elucidated from this theory.Decreased January 19, 1992     

Fluorous reverse-phase silica gel-supported Lewis acids as recyclable catalysts in water

Fluorous reverse-phase silica gel (FRPSG)-supported Lewis acids which have fluorous ligands acted as effective catalysts of Baeyer-Villiger and Diels-Alder reactions in water. Direct esterification of carboxylic acid with alcohol in organic media was also catalyzed. The FRPSG-supported Lewis acids could be recycled by simple filtration after the reaction.     

BIOLUMINESCENCE OF THE BRITTLE STAR OPHIOPSILA CALIFORNICA

The light-emitting principle of the brittle star Ophiopsila californica has been isolated and purified. It was found to be a green-fluorescent photoprotein (molecular weight 45000) which emits green light (λ_max 500 nm) when H₂O₂ is added, independently of the presence or absence of O₂. The green fluorescence (emission maximum 500 nm, excitation maximum 440 nm) spectrally coincided with the H₂O₂-triggered luminescence, indicating that the green fluorescent chromophore is the light-emitter of the photoprotein luminescence.     

Fe(bpb)(CN)2]- as a versatile building block for the design of novel low-dimensional heterobimetallic systems: synthesis, crystal structures, and magnetic properties of cyano-bridged Fe(III)-Ni(II) complexes [(bpb)(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate

A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni(II)-Fe(III) complexes. The presence of steric bpb(2-) ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following J(NiFe) values (based on the spin exchange Hamiltonian H = -2J(NiFe) S(Ni) (S(Fe(1)) + S(Fe(2))): J(NiFe) = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm(-1), respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N[triple bond]C bond angle, the stronger the Ni- - -Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with T(N) = 3.5 K. Below T(N) (1.82 K), a metamagnetic behavior was observed with the critical field of approximately 6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials.     

Polyether-bridged sexithiophene as a complexation-gated molecular wire for intramolecular photoinduced electron transfer

The porphyrin-sexithiophene-fullerene triad 2, where the two central thiophene units of the sexithiophene spacer are bridged with a crown-ether-like polyether chain, undergoes efficient intramolecular electron transfer from the photoexcited porphyrin moiety to the fullerene through the sexithiophene. However, complexation with a sodium cation in the crown ether ring causes complete suppression of electron transfer as a result of a drastic conformational change of the sexithiophene backbone. Furthermore, decomplexation resumes the photoinduced electron transfer. This on/off switching phenomenon indicates that the polyether-bridged sexithiophene can function as a complexation-gated molecular wire.     

Synthesis of (3′R,5′S)-3′-hydroxycotinine using 1,3-dipolar cycloaddition of a nitrone

To synthesize (3′R,5′S)-3′-hydroxycotinine [(+)-1], the main metabolite of nicotine (2), cycloaddition of C-(3-pyridyl)nitrones 3a, 3c, and 15 with (2R)- and (2S)-N-(acryloyl)bornane-10,2-sultam [(2R)- and (2S)-8] was examined. Among them, l-gulose-derived nitrone 15 underwent stereoselective cycloaddition with (2S)-8 to afford cycloadduct 16, which was elaborated to (+)-1.     

Effects of hydrogen bonding on metal ion-promoted intramolecular electron transfer and photoinduced electron transfer in a ferrocene-quinone dyad with a rigid amide spacer

A ferrocene-quinone dyad (Fc-Q) with a rigid amide spacer and Fc-(Me)Q dyad, in which the amide proton acting as a hydrogen-bonding acceptor is replaced by the methyl group, are employed to examine the effects of hydrogen bonding on both the thermal and the photoinduced electron-transfer reactions. The hydrogen bonding of the semiquinone radical anion with the amide proton in Fc-Q(.-) produced by the electron-transfer reduction of Fc-Q is indicated by the significant positive shift of the one-electron reduction potential of Fc-Q. The hyperfine coupling constants of Fc-Q(.-) also indicate the existence of hydrogen bonding, agreeing with those predicted by the density functional calculation. The hydrogen-bonding dynamics in the photoinduced electron transfer from the ferrocene (Fc) to the quinone moiety (Q) in Fc-Q have been successfully detected in the femtosecond laser flash photolysis experiments. Thermal intramolecular electron transfer from Fc to Q in Fc-Q and Fc-(Me)Q also occurs efficiently in the presence of metal ions in acetonitrile at 298 K. The hydrogen bond formed between the semiquinone radical anion and the amide proton in Fc-Q results in remarkable acceleration of the rate of metal ion-promoted electron transfer as compared to the rate of Fc-(Me)Q in which hydrogen bonding is prohibited. The metal ion-promoted electron-transfer rates are well correlated with the binding energies of superoxide ion-metal ion complexes, which are derived from the g(zz) values of the ESR spectra.     

Characterization of amorphous hydrogenated carbon formed by low-pressure inductively coupled plasma enhanced chemical vapor deposition using multiple low-inductance antenna units

Three-dimensional plasma enhanced chemical vapor deposition (CVD) of hydrogenated amorphous carbon (a-C:H) has been demonstrated using a new type high-density volumetric plasma source with multiple low-inductance antenna system. The plasma density in the volume of phi 200 mm x 100 mm is 5.1 x 10(10) cm(-3) within +/-5% in the lateral directions and 5.2 x 10(10)cm(-3) within +/-10% in the axial direction for argon plasma under the pressure of 0.1 Pa and the total power as low as 400 W. The uniformity of the thickness and refractive index is within +/-3.5% and +/-1%, respectively, for the a-C:H films deposited on the substrates placed on the six side walls, the top of the phi 60 mm x 80 mm hexagonal substrate holder in the pure toluene plasma under the pressure is as low as 0.04 Pa, and the total power is as low as 300 W. It is also found that precisely controlled ion bombardment by pulse biasing led to the explicit observation in Raman and IR spectra of the transition from polymer-like structure to diamond-like structure accompanied by dehydrogenation due to ion bombardment. Moreover, it is also concluded that the pulse biasing technique is effective for stress reduction without a significant degradation of hardness. The stress of 0.6 GPa and the hardness of 15 GPa have been obtained for 2.0 microm thick films deposited with the optimized deposition conditions. The films are durable for the tribology test with a high load of 20 N up to more than 20,000 cycles, showing the specific wear rate and the friction coefficient were 1.2 x 10(-7) mm3/Nm and 0.04, respectively.     

Reduction of Cu2+ to Cu+ in Xerogels Prepared from (3-Aminopropyl)Trimethoxysilane

Silica gels doped with Cu²⁺ ions were prepared from the (3-aminopropyl) trimethoxysilane (APTMOS)/tetraethoxysilane (TEOS) systems. Sols showed a broad absorption peak at 640 nm, suggesting 3–5 coordination of the aminopropyl groups to Cu²⁺. For gels prepared from APTMOS and dried at room temperature, the 640 nm peak decreased and a red-shifted absorption appeared below 400 nm within a few months. The luminescence spectra of the xerogels showed emission bands at 430–470 and 510 nm. The former and latter bands are ascribed to Cu⁺ monomer and dimer emissions, respectively. These results indicate that Cu²⁺ ions are reduced to Cu⁺. When xerogels were prepared from APTMOS/TEOS = 1 (vol/vol), the color of xerogels was blue with an absorption peak at around 670 nm, indicating no reduction of Cu²⁺ ions.     

Amperometric biosensor based on reductive H2O2 detection using pentacyanoferrate-bound polymer for creatinine determination

Pentacyanoferrate-bound poly(1-vinylimidazole) (PVI[Fe(CN)₅]) was selected as a mediator for amperometric creatinine determination based on the reductive H₂O₂ detection. Creatinine amidohydrolase (CNH), creatine amidohydrolase (CRH), sarcosine oxidase (SOD), peroxidase (POD), and PVI[Fe(CN)₅] were crosslinked with poly(ethylene glycol) diglycidyl ether (PEGDGE) on a glassy carbon (GC) electrode for a creatinine biosensor fabrication. Reduction current was monitored at −0.1 V in the presence of creatinine and O₂. It is revealed that PVI[Fe(CN)₅] is suitable as a mediator for a bioelectrocatalytic reaction of POD, since PVI[Fe(CN)₅] neither reacts with reactants nor works as an electron acceptor of SOD. The amounts of PVI[Fe(CN)₅], PEGDGE, and enzymes were optimized toward creatinine detection. Nafion as a protecting film successfully prevented the enzyme layer from interferences. The detection limit and linear range in creatinine determination were 12 μM and 12–500 μM (R² = 0.993), respectively, and the sensitivity was 11 mA cm⁻² M⁻¹, which is applicable for urine creatinine tests. The results of the creatinine determination for four urine samples measured with this proposed method were compared with Jaffe method, and a good correlation was obtained between the results.