997 resultados para ELECTRON INJECTION


Relevância:

20.00% 20.00%

Publicador:

Resumo:

A description is given of experimental work on the damping of a second order electron plasma wave echo due to velocity space diffusion in a low temperature magnetoplasma. Sufficient precision was obtained to verify the theoretically predicted cubic rather than quadratic or quartic dependence of the damping on exciter separation. Compared to the damping predicted for Coulomb collisions in a thermal plasma in an infinite magnetic field, the magnitude of the damping was approximately as predicted, while the velocity dependence of the damping was weaker than predicted. The discrepancy is consistent with the actual non-Maxwellian electron distribution of the plasma.

In conjunction with the damping work, echo amplitude saturation was measured as a function of the velocity of the electrons contributing to the echo. Good agreement was obtained with the predicted J1 Bessel function amplitude dependence, as well as a demonstration that saturation did not influence the damping results.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Viruses possess very specific methods of targeting and entering cells. These methods would be extremely useful if they could also be applied to drug delivery, but little is known about the molecular mechanisms of the viral entry process. In order to gain further insight into mechanisms of viral entry, chemical and spectroscopic studies in two systems were conducted, examining hydrophobic protein-lipid interactions during Sendai virus membrane fusion, and the kinetics of bacteriophage λ DNA injection.

Sendai virus glycoprotein interactions with target membranes during the early stages of fusion were examined using time-resolved hydrophobic photoaffinity labeling with the lipid-soluble carbene generator3-(trifluoromethyl)-3-(m-^(125 )I] iodophenyl)diazirine (TID). The probe was incorporated in target membranes prior to virus addition and photolysis. During Sendai virus fusion with liposomes composed of cardiolipin (CL) or phosphatidylserine (PS), the viral fusion (F) protein is preferentially labeled at early time points, supporting the hypothesis that hydrophobic interaction of the fusion peptide at the N-terminus of the F_1 subunit with the target membrane is an initiating event in fusion. Correlation of the hydrophobic interactions with independently monitored fusion kinetics further supports this conclusion. Separation of proteins after labeling shows that the F_1 subunit, containing the putative hydrophobic fusion sequence, is exclusively labeled, and that the F_2 subunit does not participate in fusion. Labeling shows temperature and pH dependence consistent with a need for protein conformational mobility and fusion at neutral pH. Higher amounts of labeling during fusion with CL vesicles than during virus-PS vesicle fusion reflects membrane packing regulation of peptide insertion into target membranes. Labeling of the viral hemagglutinin/neuraminidase (HN) at low pH indicates that HN-mediated fusion is triggered by hydrophobic interactions, after titration of acidic amino acids. HN labeling under nonfusogenic conditions reveals that viral binding may involve hydrophobic as well as electrostatic interactions. Controls for diffusional labeling exclude a major contribution from this source. Labeling during reconstituted Sendai virus envelope-liposome fusion shows that functional reconstitution involves protein retention of the ability to undergo hydrophobic interactions.

Examination of Sendai virus fusion with erythrocyte membranes indicates that hydrophobic interactions also trigger fusion between biological membranes, and that HN binding may involve hydrophobic interactions as well. Labeling of the erythrocyte membranes revealed close membrane association of spectrin, which may play a role in regulating membrane fusion. The data show that hydrophobic fusion protein interaction with both artificial and biological membranes is a triggering event in fusion. Correlation of these results with earlier studies of membrane hydration and fusion kinetics provides a more detailed view of the mechanism of fusion.

The kinetics of DNA injection by bacteriophage λ. into liposomes bearing reconstituted receptors were measured using fluorescence spectroscopy. LamB, the bacteriophage receptor, was extracted from bacteria and reconstituted into liposomes by detergent removal dialysis. The DNA binding fluorophore ethidium bromide was encapsulated in the liposomes during dialysis. Enhanced fluorescence of ethidium bromide upon binding to injected DNA was monitored, and showed that injection is a rapid, one-step process. The bimolecular rate law, determined by the method of initial rates, revealed that injection occurs several times faster than indicated by earlier studies employing indirect assays.

It is hoped that these studies will increase the understanding of the mechanisms of virus entry into cells, and to facilitate the development of virus-mimetic drug delivery strategies.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

The subject of this thesis is electronic coupling in donor-bridge-acceptor systems. In Chapter 2, ET properties of cyanide-bridged dinuclear ruthenium complexes were investigated. The strong interaction between the mixed-valent ruthenium centers leads to intense metal-to-metal charge transfer bands (MMCT). Hush analysis of the MMCT absorption bands yields the electronic-coupling strength between the metal centers (H_(AB)) and the total reorganization energy (λ). Comparison of ET kinetics to calculated rates shows that classical ET models fail to account for the observed kinetics and nuclear tunneling must be considered.

In Chapter 3, ET rates were measured in four ruthenium-modified highpotential iron-sulfur proteins (HiPIP), which were modified at position His50, His81, His42 and His18, respectively. ET kinetics for the His50 and His81 mutants are a factor of 300 different, while the donor-acceptor separation is nearly identical. PATHWAY calculations corroborate these measurements and highlight the importance of structural detail of the intervening protein matrix.

In Chapter 4, the distance dependence of ET through water bridges was measured. Photoinduced ET measurements in aqueous glasses at 77 K show that water is a poor medium for ET. Luminescence decay and quantum yield data were analyzed in the context of a quenching model that accounts for the exponential distance dependence of ET, the distance distribution of donors and acceptors embedded in the glass and the excluded volumes generated by the finite sizes of the donors and acceptors.

In Chapter 5, the pH-dependent excited state dynamics of ruthenium-modified amino acids were measured. The [Ru(bpy)_(3)] ^(2+) chromophore was linked to amino acids via an amide linkage. Protonation of the amide oxygen effectively quenches the excited state. In addition. time-resolved and steady-state luminescence data reveal that nonradiative rates are very sensitive to the protonation state and the structure of the amino acid moiety.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

The quality of a thermoelectric material is judged by the size of its temperature de- pendent thermoeletric-figure-of-merit (zT ). Superionic materials, particularly Zn4Sb3 and Cu2Se, are of current interest for the high zT and low thermal conductivity of their disordered, superionic phase. In this work it is reported that the super-ionic materials Ag2Se, Cu2Se and Cu1.97Ag0.03Se show enhanced zT in their ordered, normal ion-conducting phases. The zT of Ag2Se is increased by 30% in its ordered phase as compared to its disordered phase, as measured just below and above its first order phase transition. The zT ’s of Cu2Se and Cu1.97Ag0.03Se both increase by more than 100% over a 30 K temperatures range just below their super-ionic phase transitions. The peak zT of Cu2Se is 0.7 at 406 K and of Cu1.97Ag0.03Se is 1.0 at 400 K. In all three materials these enhancements are due to anomalous increases in their Seebeck coefficients, beyond that predicted by carrier concentration measurements and band structure modeling. As the Seebeck coefficient is the entropy transported per carrier, this suggests that there is an additional quantity of entropy co-transported with charge carriers. Such co-transport has been previously observed via co-transport of vibrational entropy in bipolaron conductors and spin-state entropy in NaxCo2O4. The correlation of the temperature profile of the increases in each material with the nature of their phase transitions indicates that the entropy is associated with the thermodynamcis of ion-ordering. This suggests a new mechanism by which high thermoelectric performance may be understood and engineered.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Semiconductor technology scaling has enabled drastic growth in the computational capacity of integrated circuits (ICs). This constant growth drives an increasing demand for high bandwidth communication between ICs. Electrical channel bandwidth has not been able to keep up with this demand, making I/O link design more challenging. Interconnects which employ optical channels have negligible frequency dependent loss and provide a potential solution to this I/O bandwidth problem. Apart from the type of channel, efficient high-speed communication also relies on generation and distribution of multi-phase, high-speed, and high-quality clock signals. In the multi-gigahertz frequency range, conventional clocking techniques have encountered several design challenges in terms of power consumption, skew and jitter. Injection-locking is a promising technique to address these design challenges for gigahertz clocking. However, its small locking range has been a major contributor in preventing its ubiquitous acceptance.

In the first part of this dissertation we describe a wideband injection locking scheme in an LC oscillator. Phase locked loop (PLL) and injection locking elements are combined symbiotically to achieve wide locking range while retaining the simplicity of the latter. This method does not require a phase frequency detector or a loop filter to achieve phase lock. A mathematical analysis of the system is presented and the expression for new locking range is derived. A locking range of 13.4 GHz–17.2 GHz (25%) and an average jitter tracking bandwidth of up to 400 MHz are measured in a high-Q LC oscillator. This architecture is used to generate quadrature phases from a single clock without any frequency division. It also provides high frequency jitter filtering while retaining the low frequency correlated jitter essential for forwarded clock receivers.

To improve the locking range of an injection locked ring oscillator; QLL (Quadrature locked loop) is introduced. The inherent dynamics of injection locked quadrature ring oscillator are used to improve its locking range from 5% (7-7.4GHz) to 90% (4-11GHz). The QLL is used to generate accurate clock phases for a four channel optical receiver using a forwarded clock at quarter-rate. The QLL drives an injection locked oscillator (ILO) at each channel without any repeaters for local quadrature clock generation. Each local ILO has deskew capability for phase alignment. The optical-receiver uses the inherent frequency to voltage conversion provided by the QLL to dynamically body bias its devices. A wide locking range of the QLL helps to achieve a reliable data-rate of 16-32Gb/s and adaptive body biasing aids in maintaining an ultra-low power consumption of 153pJ/bit.

From the optical receiver we move on to discussing a non-linear equalization technique for a vertical-cavity surface-emitting laser (VCSEL) based optical transmitter, to enable low-power, high-speed optical transmission. A non-linear time domain optical model of the VCSEL is built and evaluated for accuracy. The modelling shows that, while conventional FIR-based pre-emphasis works well for LTI electrical channels, it is not optimum for the non-linear optical frequency response of the VCSEL. Based on the simulations of the model an optimum equalization methodology is derived. The equalization technique is used to achieve a data-rate of 20Gb/s with power efficiency of 0.77pJ/bit.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Proton-coupled electron transfer (PCET) reactions are ubiquitous throughout chemistry and biology. However, challenges arise in both the the experimental and theoretical investigation of PCET reactions; the rare-event nature of the reactions and the coupling between quantum mechanical electron- and proton-transfer with the slower classical dynamics of the surrounding environment necessitates the development of robust simulation methodology. In the following dissertation, novel path-integral based methods are developed and employed for the direct simulation of the reaction dynamics and mechanisms of condensed-phase PCET.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

The temperature dependences of the reduction potentials (Eo') 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 Eo', and the standard entropy (ΔSo') and enthalpy (ΔHo') of reduction in the mutant proteins were determined relative to values for wild-type; the change in Eo' 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.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Enquanto os métodos tradicionais de processamento de restaurações cerâmicas tornaram-se notórios por sua complexidade, as técnicas mais modernas vêm privilegiando a simplicidade de execução e a automação. Dentre estas, destaca-se a injeção em moldes, que recentemente, foi associada a métodos CAD-CAM. Estudos anteriores demonstraram a viabilidade de utilização de um vidro feldspático de baixa expansão térmica, Alpha (Vita Zahnfabrik), para injeção, porém, faltam informações quanto às propriedades mecânicas e a microestrutura deste material quando submetido à injeção. Os objetivos deste estudo são: produzir pastilhas vidrocerâmicas para injeção a quente a partir de Alpha e da mistura deste vidro com partículas de alumina e zircônia; avaliar a resistência à flexão dos materiais processados, e compará-la a um material compatível existente no mercado (PM9 - Vita Zahnfabrik); estudar a estrutura microscópica dos materiais e correlacioná-la com suas propriedades mecânicas; identificar por meio de difração de raios X a formação de fases cristalinas durante as diferentes etapas de processamento. A injeção aumentou a resistência do vidro Alpha devido à redução na quantidade e tamanho dos defeitos internos, principalmente porosidades. Apesar de ter sido observada nucleação de cristais nos dois materiais, durante o processamento, não foi possível determinar de que forma este fenômeno afetou as propriedades mecânicas dos materiais. Não foi detectada alteração no padrão de distribuição das fases cristalinas observadas em microscópio eletrônico de varredura antes e depois da injeção. Não foi verificada diferença estatística significante entre a resistência à flexão de Alpha injetado e PM9. A adição de partículas de alumina e zirconia ao vidro Alpha provocou redução da resistência, devido à formação de aglomerados durante a confecção das pastilhas e a incapacidade da injeção em dispersá-los. Tais aglomerados funcionaram como concentradores de tensões, enfraquecendo o material.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Description of a simple method for counting bacteria with active electron transport systems in water and sediment samples. Sodium succinate, NADH and NADPH served as electron donors. It is possible to see several sites of electron transport in the larger cells. Especially impressive are the plankton-algae, protozoa, and small metazoa. This is a partial translation of the ”method” section only.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

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.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Techniques are described for mounting and visualizing biological macromolecules for high resolution electron microscopy. Standard techniques are included in a discussion of new methods designed to provide the highest structural resolution. Methods are also discussed for handling samples on the grid, for making accurate size measurements at the 20 Å level, and for photographically enhancing image contrast.

The application of these techniques to the study of the binding of DNA polymerase to DNA is described. It is shown that the electron micrographs of this material are in agreement with the model proposed by Dr. Arthur Kornberg. A model is described which locates several active sites on the enzyme.

The chromosomal material of the protozoan tetrahymena has been isolated and characterized by biochemical techniques and by electron microscopy. This material is shown to be typical of chromatin of higher creatures.

Comparison with other chromatins discloses that the genome of tetrahymena is highly template active and has a relatively simple genetic construction.

High resolution electron microscope procedures developed in this work have been combined with standard biochemical techniques to give a comprehensive picture of the structure of interphase chromosome fibers. The distribution of the chromosomal proteins along its DNA is discussed.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Magnetic resonance techniques have given us a powerful means for investigating dynamical processes in gases, liquids and solids. Dynamical effects manifest themselves in both resonance line shifts and linewidths, and, accordingly, require detailed analyses to extract desired information. The success of a magnetic resonance experiment depends critically on relaxation mechanisms to maintain thermal equilibrium between spin states. Consequently, there must be an interaction between the excited spin states and their immediate molecular environment which promote changes in spin orientation while excess magnetic energy is coupled into other degrees of freedom by non-radiative processes. This is well known as spin-lattice relaxation. Certain dynamical processes cause fluctuations in the spin state energy levels leading to spin-spin relaxation and, here again, the environment at the molecular level plays a significant role in the magnitude of interaction. Relatively few electron spin relaxation studies of solutions have been conducted and the present work is addressed toward the extension of our knowledge in this area and the retrieval of dynamical information from line shape analyses on a time scale comparable to diffusion controlled phenomena.

Specifically, the electron spin relaxation of three Mn+23d5 complexes, Mn(CH3CN)6+2, MnCl4-2 in acetonitrile has been studied in considerable detail. The effective spin Hamiltonian constants were carefully evaluated under a wide range of experimental conditions. Resonance widths of these Mn+2 complexes were studied in the presence of various excess ligand ions and as a function of concentration, viscosity, temperature and frequency (X-band, ~9.5 Ԍ Hz and K-band, ~35 Ԍ Hz).

A number of interesting conclusions were drawn from these studies. For the Et4NCl-4-2 system several relaxation mechanisms leading to resonance broadening were observed. One source appears to arise through spin-orbit interactions caused by modulation of the ligand field resulting from transient distortions of the complex imparted by solvent fluctuations in the immediate surroundings of the paramagnetic ion. An additional spin relaxation was assigned to the formation of ion pairs [Et4N+…MnCl4-2] and it was possible to estimate the dissociation constant for this specie in acetonitrile.

The Bu4NBr-MnBr4-2 study was considerably more interesting. As in the former case, solvent fluctuations and ion-pairing of the paramagnetic complex [Bu4N+…MnBr4-2] provide significant relaxation for the electronic spin system. Most interesting, without doubt, is the onset of a new relaxation mechanism leading to resonance broadening which is best interpreted as chemical exchange. Thus, assuming that resonance widths were simply governed by electron spin state lifetimes, we were able to extract dynamical information from an interaction in which the initial and final states are the same

MnBr4-2 + Br- = MnBr4-2 + Br-.

The bimolecular rate constants were obtained at six different temperatures and their magnitudes suggested that the exchange is probably diffusion controlled with essentially a zero energy of activation. The most important source of spin relaxation in this system stems directly from dipolar interactions between the manganese 3d5 electrons. Moreover, the dipolar broadening is strongly frequency dependent indicating a deviation between the transverse and longitudinal relaxation times. We are led to the conclusion that the 3d5 spin states of ion-paired MnBr4-2 are significantly correlated so that dynamical processes are also entering the picture. It was possible to estimate the correlation time, Td, characterizing this dynamical process.

In Part II we study nuclear magnetic relaxation of bromine ions in the MnBr4-2-Bu4NBr-acetonitrile system. Essentially we monitor the 79Br and 81Br linewidths in response to the [MnBr4-2]/[Br-] ratio with the express purpose of supporting our contention that exchange is occurring between "free" bromine ions in the solvent and bromine in the first coordination sphere of the paramagnetic anion. The complexity of the system elicited a two-part study: (1) the linewidth behavior of Bu4NBr in anhydrous CH3CN in the absence of MnBr4-2 and (2) in the presence of MnBr4-2. It was concluded in study (1) that dynamical association, Bu4NBr k1= Bu4N+ + Br-, was modulating field-gradient interactions at frequencies high enough to provide an estimation of the unimolecular rate constant, k1. A comparison of the two isotopic bromine linewidth-mole fraction results led to the conclusion that quadrupole interactions provided the dominant relaxation mechanism. In study (2) the "residual" bromine linewidths for both 79Br and 81Br are clearly controlled by quadrupole interactions which appear to be modulated by very rapid dynamical processes other than molecular reorientation. We conclude that the "residual" linewidth has its origin in chemical exchange and that bromine nuclei exchange rapidly between a "free" solvated ion and the paramagnetic complex, MnBr4-2.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

O aumento nos rejeitos industriais e a contínua produção de resíduos causam muitas preocupações no âmbito ambiental. Neste contexto, o descarte de pneus usados tem se tornado um grande problema por conta da pequena atenção que se dá à sua destinação final. Assim sendo, essa pesquisa propõe a produção de uma mistura polimérica com polipropileno (PP), a borracha de etileno-propileno-dieno (EPDM) e o pó de pneu (SRT). A Metodologia de Superfície de Resposta (MSR), coleção de técnicas estatísticas e matemáticas úteis para desenvolver, melhorar e optimizar processos, foi aplicada à investigação das misturas ternárias. Após o processamento adequado em extrusora de dupla rosca e a moldagem por injeção, as propriedades mecânicas de resistência à tração e resistência ao impacto foram determinadas e utilizadas como variáveis resposta. Ao mesmo tempo, a microscopia eletrônica de varredura (MEV) foi usada para a investigação da morfologia das diferentes misturas e melhor interpretação dos resultados. Com as ferramentas estatísticas específicas e um número mínimo de experimentos foi possível o desenvolvimento de modelos de superfícies de resposta e a otimização das concentrações dos diferentes componentes da mistura em função do desempenho mecânico e além disso com a modificação da granulometria conseguimos um aumento ainda mais significativo deste desempenho mecânico.