Electron transfer in chemically and genetically modified myoglobins

The temperature dependences of the reduction potentials (E^o') of wildtype human myoglobin (Mb) and three site-directed mutants have been measured by using thin-layer spectroelectrochemistry. Residue Val68, which is in van der Waals contact with the heme in Mb, has been replaced by Glu, Asp, and Asn. At pH 7.0, reduction of the heme iron (III) in the former two proteins is accompanied by uptake of a proton by the protein. The changes in E^o', and the standard entropy (ΔS^o') and enthalpy (ΔH^o') of reduction in the mutant proteins were determined relative to values for wild-type; the change in E^o' at 25°C was about -200 millivolts for the Glu and Asp mutants, and about -80 millivolts for the Asn mutant. Reduction of Fe(III) to Fe(II) in the Glu and Asp mutants is accompanied by uptake of a proton. These studies demonstrate that Mb can tolerate substitution of a buried hydrophobic group by potentially charged and polar residues, and that such amino acid replacements can lead to substantial changes in the redox thermodynamics of the protein.

Through analysis of the temperature dependence and shapes of NMR dispersion signals, it is determined that a water molecule is bound to the sixth coordination site of the ferric heme in the Val68Asp and in the Val68Asn recombinant proteins while the carboxyl group of the sidechain of Glu68 occupies this position in Val68Glu. The relative rhombic distortions in the ESR spectra of these mutant proteins combined with H₂¹⁷O and spin interconversion experiments performed on them confirm the conclusions of the NMRD study.

The rates of intramolecular electron transfer (ET) of (NH₃)₅Ru-His48 (Val68Asp, His81GIn, Cys110AIa)Mb and (NH₃)₅Ru-His48 (Val68GIu,His81GIn,Cys110Ala)Mb were measured to be .85(3)s^-1 and .30(2)s^-1, respectively. This data supports the hypothesis that entropy of 111 reduction and reorganization energy of ET are inversely related. The rates of forward and reverse ET for (NH₃)₅ Ru-His48 (Val68GIu, His81 GIn, Cys110AIa)ZnMb -7.2(5)•10⁴s^-1and 1.4(2)•10⁵s^-1, respectively- demonstrate that the placement of a highly polar residue nearby does not significantly change the reorganization energy of the photoactive Zn porphyrin.

The distal histidine imidazoles of (NH₃)₄isnRu-His48 SWMb and (NH₃)₅Ru-His48 SWMb were cyanated with BrCN. The intramolecular ET rates of these BrCN-modified Mb derivatives are 5.5(6)s^-1 and 3.2(5)s^-1, respectively. These respective rates are 20 and 10 times faster than those of their noncyanated counterparts after the differences in ET rate from driving force are scaled according to the Marcus equation. This increase in ET rate of the cyanated Mb derivatives is attributed to lower reorganization energy since the cyanated Mb heme is pentacoordinate in both oxidation states; whereas, the native Mb heme loses a water molecule upon reduction so that it changes from six to five coordinate. The reorganization energy from Fe-OH₂ dissociation is estimated to be .2eV. This conclusion is used to reconcile data from previous experiments in our lab. ET in photoactive porphyrin-substituted myoglobins proceed faster than predicted by Marcus Theory when it is assumed that the only difference in ET parameters between photoactive porphyrins and native heme systems is driving force. However, the data can be consistently fit to Marcus Theory if one corrects for the smaller reorganization in the photoactive porphyrin systems since they do not undergo a coordination change upon ET.

Finally, the intramolecular ET rate of (NH₃)₄isnRu-His48 SWMb was measured to be 3.0(4)s^-1. This rate is within experimental error of that for (NH₃)₄pyrRu-His48 SWMb even though the former has 80mV more driving force. One likely possibility for this observation is that the tetraamminepyridineruthenium group undergoes less reorganization upon ET than the tetraammineisonicotinamideruthenium group. Moreover, analysis of the (NH₃)₄isnRu-His48 SWMb experimental system gives a likely explanation of why ET was not observed previously in (NH₃)₄isnRu-Cytochrome C.

Determination of the activity of nitrifying bacteria in surface waters by a modified BOD-test. [Translation from: Zentbl.Bakt.Parasitkde 156(1) 414-421, 1972. ]

A modified method of the Biochemical oxygen demand (BOD)test was applied in order to find out the seasonal changing activity of the nitrifying bacteria in surface waters. Samples were taken from the River Elbe near Teufelsbrueck.

MODIFIED DIRECT TWOS-COMPLEMENT PARALLEL ARRAY MULTIPLICATION ALGORITHM FOR COMPLEX MATRIX OPERATION

A direct twos-complement parallel array multiplication algorithm is introduced and modified for digital optical numerical computation. The modified version overcomes the problems encountered in the conventional optical twos-complement algorithm. In the array, all the summands are generated in parallel, and the relevant summands having the same weights are added simultaneously without carries, resulting in the product expressed in a mixed twos-complement system. In a two-stage array, complex multiplication is possible with using four real subarrays. Furthermore, with a three-stage array architecture, complex matrix operation is straightforwardly accomplished. In the experiment, parallel two-stage array complex multiplication with liquid-crystal panels is demonstrated.

MODIFIED ENGAGEMENT METHOD FOR MATRIX OPERATION

We describe a modified engagement method for matrix operation based on a two-dimensional crossed-ring interconnection network, Our method incorporates fewer steps than that reported by Bocker et al. [Appl. Opt. 22, 804 (1983)], and its performance is found to be the most efficient (minimum steps) in comparison with other systolic and/or engagement methods for matrix operation. Thus, it may be helpful for other optical and electronic implementations of matrix operations. One compact optoelectronic integrity approach for implementing the modified engagement method is briefly described. (C) 1995 Optical Society of America

Compact parallel optical modified-signed-digit arithmetic-logic array processor with electron-trapping device

A compact two-step modified-signed-digit arithmetic-logic array processor is proposed. When the reference digits are programmed, both addition and subtraction can be performed by the same binary logic operations regardless of the sign of the input digits. The optical implementation and experimental demonstration with an electron-trapping device are shown. Each digit is encoded by a single pixel, and no polarization is included. Any combinational logic can be easily performed without optoelectronic and electro-optic conversions of the intermediate results. The system is compact, general purpose, simple to align, and has a high signal-to-noise ratio. (C) 1999 Optical Society of America.

Two-step digit-set-restricted modified signed-digit addition-subtraction algorithm and its optoelectronic implementation

A novel, to our knowledge, two-step digit-set-restricted modified signed-digit (MSD) addition-subtraction algorithm is proposed. With the introduction of the reference digits, the operand words are mapped into an intermediate carry word with all digits restricted to the set {(1) over bar, 0} and an intermediate sum word with all digits restricted to the set {0, 1}, which can be summed to form the final result without carry generation. The operation can be performed in parallel by use of binary logic. An optical system that utilizes an electron-trapping device is suggested for accomplishing the required binary logic operations. By programming of the illumination of data arrays, any complex logic operations of multiple variables can be realized without additional temporal latency of the intermediate results. This technique has a high space-bandwidth product and signal-to-noise ratio. The main structure can be stacked to construct a compact optoelectronic MSD adder-subtracter. (C) 1999 Optical Society of America.

Classified one-step modified signed-digit arithmetic and its optical implementation

Based on the two-step modified signed-digit (MSD) algorithm, we present a one-step algorithm for the parallel addition and subtraction of two MSD numbers. This algorithm is reached by classifying the three neighboring digit pairs into 10 groups and then making a decision on the groups. It has only a look-up truth table, and can be further formulated by eight computation rules. A joint spatial encoding technique is developed to represent both the input data and the computation rules. Furthermore, an optical correlation architecture is suggested to implement the MSD adder in parallel. An experimental demonstration is also given. (C) 1996 Society of Photo-Optical instrumentation Engineers.

Optoelectronic quotient-selected modified signed-digit division

A novel optoelectronic quotient-selected modified signed-digit division technique is proposed. This division method generates one quotient digit per iteration involving only one shift operation, one quotient selection operation and one addition/subtraction operation. The quotient digit can be selected by observing three most significant digits of the partial remainder independent of the divisor. Two algorithms based on truth-table look-up and binary logic operations are derived. For optoelectronic implementation, an efficient shared content-addressable memory based architecture as well as compact logic array processor based architecture with an electron-trapping device is proposed. Performance evaluation of the proposed optoelectronic quotient-selected division shows that it is faster than the previously reported convergence division approach. Finally, proof-of-principle experimental results are presented to verify the effectiveness of the proposed technique. (C) 2001 Society of Photo-Optical Instrumentation Engineers.

One-step digit-set-restricted modified signed-digit adder using an incoherent correlator based on a shared content-addressable memory

An efficient one-step digit-set-restricted modified signed-digit (MSD) adder based on symbolic substitution is presented. In this technique, carry propagation is avoided by introducing reference digits to restrict the intermediate carry and sum digits to {1,0} and {0,1}, respectively. The proposed technique requires significantly fewer minterms and simplifies system complexity compared to the reported one-step MSD addition techniques. An incoherent correlator based on an optoelectronic shared content-addressable memory processor is suggested to perform the addition operation. In this technique, only one set of minterms needs to be stored, independent of the operand length. (C) 2002 society or Photo-Optical Instrumentation Engineers.

Electrocatalytic reduction of dioxygen at chemically modified electrodes

The kinetics of the reduction of O₂ by Ru(NH₃)₆⁺² as catalyzed by cobalt(II) tetrakis(4-N-methylpyridyl)porphyrin are described both in homogeneous solution and when the reactants are confined to Nafion coatings on graphite electrodes. The catalytic mechanism is determined and the factors that can control the total reduction currents at Nafion-coated electrodes are specified. A kinetic zone diagram for analyzing the behavior of catalyst-mediator-substrate systems at polymer coated electrodes is presented and utilized in identifying the current-limiting processes. Good agreement is demonstrated between calculated and measured reduction currents at rotating disk electrodes. The experimental conditions that will yield the optimum performance of coated electrodes are discussed, and a relationship is derived for the optimal coating thickness.

The relation between the reduction potentials of adsorbed and unadsorbed cobalt(III) tetrakis(4-N-methylpyridyl)porphyrin and those where it catalyzes the electroreduction of dioxygen is described. There is an unusually large change in the formal potential of the Co(III) couple upon the adsorption of the porphyrin on the graphite electrode surface. The mechanism in which the (inevitably) adsorbed porphyrin catalyzes the reduction of O₂ is in accord with a general mechanistic scheme proposed for most monomeric cobalt porphyrins.

Four new dimeric metalloporphyrins (prepared in the laboratory of Professor C. K. Chang) have the two porphyrin rings linked by an anthracene bridge attached to meso positions. The electrocatalytic behavior of the diporphyrins towards the reduction of O₂ at graphite electrodes has been examined for the following combination of metal centers: Co-Cu, Co-Fe, Fe-Fe, Fe-H₂. The Co-Cu diporphyrin catalyzes the reduction of O₂ to H₂O₂ but no further. The other three catalysts all exhibit mixed reduction pathways leading to both H₂O₂ and H₂O. However, the pathways that lead to H₂O do not involve H₂O₂ as an intermediate. A possible mechanistic scheme is offered to account for the observed behavior.

Efficient two-step digit-set-restricted modified signed-digit algorithm based on optoelectronic shared content-addressable memory

A two-step digit-set-restricted modified signed-digit (MSD) adder based on symbolic substitution is presented. In the proposed addition algorithm, carry propagation is avoided by using reference digits to restrict the intermediate MSD carry and sum digits into {(1) over bar ,0} and {0, 1}, respectively. The algorithm requires only 12 minterms to generate the final results, and no complementarity operations for nonzero outputs are involved, which simplifies the system complexity significantly. An optoelectronic shared content-addressable memory based on an incoherent correlator is used for experimental demonstration. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Remoção de compostos sulfurados e nitrogenados de diesel hidrotratado por adsorção em argila, alumina e sílica-alumina, impregnadas com metais de transição

Na matriz energética brasileira, o óleo diesel tem lugar de destaque, porém ainda é comercializado com teores de compostos sulfurados e nitrogenados considerados altos para as legislações ambientais que entrarão em vigor nos próximos anos. Tradicionalmente, a remoção desses compostos de enxofre de correntes de petróleo é realizada por processos de hidrotratamento (HDT). No entanto, devido as características do diesel brasileiro, se faz necessária maior severidade para atingir as novas especificações dos combustíveis. Isto implica em investimentos e custos operacionais crescentes para atender a demanda que se instala. Neste contexto, a adsorção está sendo estudada para a purificação da corrente de óleo diesel oriunda da etapa de hidrotratamento como polimento final para alcançar as especificações mais exigentes. Sabe-se que os adsorventes comerciais apresentam limitações na remoção destes contaminantes e uma alternativa que tem se mostrado promissora é a incorporação de metais de transição na estrutura do sólido. No presente trabalho foram modificados adsorventes comerciais, tais como aluminas, sílica-aluminas e argilas pela introdução dos elementos níquel, colbalto e molibdênio e testado o desempenho dessas modificações frente à adsorção de compostos sulfurados e nitrogenados presentes em um diesel hidrotratado. Foram feitas caracterizações químicas, físicas, texturais e morfológicas dos sólidos com e sem incorporação de metais de transição na estrutura original. Os experimentos de adsorção foram realizados a 40C. Avaliando todos os sólidos, o adsorvente que mostrou o melhor desempenho na remoção de compostos sulfurados e nitrogenados por massa de adsorvente foi a sílica-alumina sem modificações, que foi capaz de remover em torno de 90% de compostos nitrogenados e 55 % de sulfurados para 2 g de sólido / 10 mL de diesel. Para os materiais modificados, observou-se que a incorporação dos metais de transição ocasionou redução da sua área superficial e do volume total de poros. Desta maneira, os efeitos esperados pelas interações entre o sítios metálicos e os compostos de nitrogênio e enxofre foram reduzidos

Efficient two-step digit-set-restricted modified signed-digit algorithm based on optoelectronic shared content-addressable memory

A two-step digit-set-restricted modified signed-digit (MSD) adder based on symbolic substitution is presented. In the proposed addition algorithm, carry propagation is avoided by using reference digits to restrict the intermediate MSD carry and sum digits into {(1) over bar ,0} and {0, 1}, respectively. The algorithm requires only 12 minterms to generate the final results, and no complementarity operations for nonzero outputs are involved, which simplifies the system complexity significantly. An optoelectronic shared content-addressable memory based on an incoherent correlator is used for experimental demonstration. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Optimized condition for etching fused-silica phase gratings with inductively coupled plasma technology

Polymer deposition is a serious problem associated with the etching of fused silica by use of inductively coupled plasma (ICP) technology, and it usually prevents further etching. We report an optimized etching condition under which no polymer deposition will occur for etching fused silica with ICP technology. Under the optimized etching condition, surfaces of the fabricated fused silica gratings are smooth and clean. Etch rate of fused silica is relatively high, and it demonstrates a linear relation between etched depth and working time. Results of the diffraction of gratings fabricated under the optimized etching condition match theoretical results well. (c) 2005 Optical Society of America.

High-efficiency reflective diffraction gratings in fused silica as (de)multiplexers at 1.55 mu m for dense wavelength division multiplexing application

We describe high-efficiency, high-dispersion reflection gratings fabricated in bulk fused Silica illuminated by incident lights in the C + L bands as (de)multiplexers for dense wavelength division multiplexing (DWDM) application. Based on the phenomenon of total internal reflection, gratings with optimized profile parameters exhibit diffraction efficiencies of more than 90% under TM- and TE-polarized incident lights for 101-nm spectral bandwidths (1520-1620 nm) and can reach an efficiency of greater than 97% for both polarizations at a wavelength of 1550 nm. Without loss of metal absorption, without coating of dielectric film layers, and independent of tooth shape, this new kind of grating should be of great interest for DWDM application. (C) 2005 Optical Society of America.