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Spectral hole burning studies of photosystem II

Description: Low temperature absorption and hole burning spectroscopies were applied to the D1-D2-cyt b{sub 559} and the CP47 and CP43 antenna protein complexes of Photosystem H from higher plants. Low temperature transient and persistent hole-burning data and theoretical calculations on the kinetics and temperature dependence of the P680 hole profile are presented and provide convincing support for the linker model. Implicit in the linker model is that the 684-nm-absorbing Chl a serve to shuttle energy from the proximal antenna complex to reaction center. The stoichiometry of isolated Photosystem H Reaction Center (PSII RC) in several different preparations is also discussed. The additional Chl a are due to 684-nm-absorbing Chl a, some contamination by the CP47 complex, and non-native Chl a absorbing near 670 nm. In the CP47 protein complex, attention is focused on the lower energy chlorophyll a Q{sub y}-states. High pressure hole-burning studies of PSII RC revealed for the first time a strong pressure effect on the primary electron transfer dynamics. The 4.2 K lifetime of P680*, the primary donor state, increases from 2.0 ps to 7.0 ps as pressure increases from 0.1 to 267 MPa. Importantly, this effect is irreversible (plastic) while the pressure induced effect on the low temperature absorption and non-line narrowed P680 hole spectra are reversible (elastic). Nonadiabatic rate expressions, which take into account the distribution of energy gap values, are used to estimate the linear pressure shift of the acceptor state energy for both the superexchange and two-step mechanisms for primary charge separation. It was found that the pressure dependence could be explained with a linear pressure shift of {approximately} 1 cm{sup -1}/MPa in magnitude for the acceptor state. The results point to the marriage of hole burning and high pressures as having considerable potential for the study of primary transport dynamics in reaction centers ...
Date: November 1, 1995
Creator: Chang, H.C.
Partner: UNT Libraries Government Documents Department

Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

Description: In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl{sub 2} (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph){sub 2}C(Ph){sub 2}O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and {alpha}-hydroxy ketones to benzaldehyde and {alpha}-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono-, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation ...
Date: December 19, 2004
Creator: Du, Guodong
Partner: UNT Libraries Government Documents Department

Investigation of the phase equilibria and phase transformations associated with the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub y} superconductor

Description: The solid solution region and reaction kinetics of the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub y} (2212) superconductor were examined as a function of temperature and oxygen partial pressure. Crystallization studies from the glassy and molten states were undertaken to determine the phase transformation and kinetics associated with the formation of 2212 and other competing phases. Crystallization of nominal 2212 glasses was found to proceed in two steps with the formation of Bi{sub 2}Sr{sub 2{minus}x}Ca{sub x}CuO{sub y} (2201) and Cu{sub 2}O followed by Bi{sub 2}Sr{sub 3{minus}x}Ca{sub x}O{sub y}, CaO, and SrO. The 2212 phase converts from the 2201 phase with increasing temperatures. However, its formation below 800 C was kinetically limited. At 800 C and above, a nearly full conversion to the 2212 phase was achieved after only one minute although considerably longer anneal times were necessary for the system to reach equilibrium. In low oxygen partial pressures, the solidus is reduced to approximately 750 C. Solidification studies revealed an eutectic structure separating the incongruently melting 2212/2201 phases at high oxygen partial pressures from the congruently melting Bi{sub 2}Sr{sub 3{minus}x}Ca{sub x}O{sub y} (23x) and Bi{sub 2}Sr{sub 2{minus}x}Ca{sub x}O{sub y} (22x) phases present at low oxygen partial pressures. During solidification in various oxygen partial pressures, the separation of CaO in the melt and the initial crystallization of alkaline-earth cuprates leaves behind a Bi-rich liquid from which it is impossible to form single-phase 2212. Hence, significant amounts of 2201 were also present in these samples. These problems could be reduced by melt processing in inert atmospheres. Bulk 2212 material produced in this manner was found to possess high transition temperatures, high intergranular critical current densities below 20K, and modest critical current densities at 77K.
Date: December 9, 1993
Creator: Holesinger, T.
Partner: UNT Libraries Government Documents Department

Stoichiometry and Deposition Temperature Dependence of the Microstructural and Electrical Properties of Barium Strontium Titanate Thin Films

Description: Barium Strontium Titanate (BST) was deposited on Pt/ZrO2 / SiO2/Si substrates using liquid source metal organic chemical vapor deposition. A stoichiometry series was deposited with various GrII/Ti ratios (0.658 to 1.022) and a temperature series was deposited at 550 to 700°C. The thin films were characterized using transmission electron microscopy. Both series of samples contained cubic perovskite BST and an amorphous phase. The grain size increased and the volume fraction of amorphous phase decreased with increasing deposition temperature. The electrical and microstructural properties improved as the GrII/Ti ratio approached 1 and deteriorated beyond 1. This research demonstrates that BST thin films are a strong candidate for future MOS transistor gate insulator applications.
Date: May 1998
Creator: Pena, Piedad
Partner: UNT Libraries

High temperature vaporization and thermodynamic study of the scandium-- sulfur system

Description: Results of studies on the stoichiometry, structure, vaporization behavior, and thermodynamic properties of the Sc--S system are reported. The thermodynamic results for the stability of ScS(s) are compared with reported results for other transition-metal and rare-earth monosulfides. Various models are discussed in regard to their ability to describe the bonding in these refractory solids. (JRD)
Date: January 1, 1976
Creator: Tuenge, R.T.
Partner: UNT Libraries Government Documents Department

Self-diffusion of Co$sup 60$ in crystals of Co$nu$sub 1-x/O

Description: Tracer self-diffusion coefficients were measured as functions of temperature and deviations from stoichiometry. The arc-transfer technique of crystal growth was found to produce crystal of Co/sub 1-x/O of essentially the same purity as the starting Co rod, and the quality was comparable to commercially available crystals grown by Verneuil process. Measurements at x = 0.005 in Co/sub 1-x/O showed the Co tracer self-diffusion coefficient to be D = 3.88 x 10$sup -4$ exp (--31600 +- 2400/RT) cm$sup 2$/s between 1037 and 1350$sup 0$C. This activation energy is in agreement with measurements made in air, if proper compensation is made for the effect of variation in stoichiometry. Measurements on crystals having deviations between 0.002 and 0.008 at 1150$sup 0$C showed the diffusion coefficient to depend on p/sub O$sub 2$/ as D = 9.74 x 10$sup -9$ p/sub O$sub 2$//sup 1/(3.59)/ cm$sup 2$/s, where p/sub O$sub 2$/ varied between 10$sup -2$.$sup 5$ and 10$sup -0$.$sup 25$ atm. Comparison with thermogravimetric and electrical conductivity measurements confirms that the defects responsible for Co diffusion in the range of temperature and p/sub O$sub 2$/ of this investigation are singly ionized cobalt vacancies. The Co tracer self-diffusion coefficients in single crystals are nearly identical to those in polycrystalline Co/sub 1-x/O. 53 references, 29 fig, 6 tables (DLC)
Date: January 1, 1976
Creator: Rahman, S. F.
Partner: UNT Libraries Government Documents Department

Studies of the structure and function of Mms6, a bacterial protein that promotes the formation of magnetic nanoparticles

Description: Here we report structural and functional studies of Mms6, a biomineralization protein that can promote the formation in vitro of magnetic nanoparticles with sizes and morphologies similar to the magnetites synthesized by magnetotactic bacteria. We found the binding pattern of Mms6 to ferric ion to be two-phase and multivalent. We quantatively determined that Mms6 binds one Fe{sup 3+} with a very high affinity (K{sub d} = 10{sup -16} M). The second phase of iron binding is multivalent and cooperative with respect to iron with a K{sub d} in the {mu}M range and a stoichiometry of about 20 ferric ion per protein molecule. We found that Mms6 exists in large particles of two sizes, one consisting of 20-40 monomeric units and the other of 200 units. From proteolytic digestion, ultracentrifugation and liposome fusion studies, we found that Mms6 forms a large micellar quaternary structure with the N-terminal domain self-assembling into a uniformly sized micelle and the C-terminal domain on the surface. The two-phase iron-binding pattern may be relevant to iron crystal formation. We propose that the first high affinity phase may stabilize a new conformation of the C-terminal domain that allows interaction with other C-terminal domains leading to a structural change in the multimeric protein complex that enables the second low affinity iron binding phase to organize iron and initiate crystal formation. We also observed a dimeric apparent molecular mass of the Mms6 C-terminal peptide (C21Mms6). We speculate that the C-terminal domain may form higher order quaternary arrangements on the surface of the micelle or when anchored to a membrane by the N-terminal domain. The change in fluorescence quenching in the N-terminal domain with iron binding suggests a structural integrity between the C- and N-terminal domains. The slow change in trp fluorescence as a function of time after adding iron suggests ...
Date: May 15, 2011
Creator: Wang, Lijun
Partner: UNT Libraries Government Documents Department


Description: The use of high rate anodic dissolution (electrochemical machining) for shaping titanium carbide, zirconium carbide, titanium boride and zirconium boride has been investigated in 2N potassium nitrate and 3N sodium chloride under current densities ranging from 20 to 120 A/cm{sup 2} (corresponding to cutting rates of 0.3 to 1.8 mm/min). The dissolution stoichiometry for all these materials is independent of the current density in the range 20 to 120 A/cm{sup 2}. Both titanium and zirconium appear to dissolve in the +4 state, boron in the +3 state and the weight loss measurements indicate that carbon is oxidized to CO and CO{sub 2}. The current voltage curves permit to establish that, over the entire current density and flow range investigated, dissolution occurs in the transpassive state. The surface roughness obtained on TiC and ZrC is within 3-5 {micro}m and is independent of current density, applied voltage or flow rate.
Date: July 1, 1978
Creator: Dissaux, Bernard Antoine; Muller, Rolf H. & Tobias, Charles W.
Partner: UNT Libraries Government Documents Department

Structural and Electronic Investigations of Complex Intermetallic Compounds

Description: In solid state chemistry, numerous investigations have been attempted to address the relationships between chemical structure and physical properties. Such questions include: (1) How can we understand the driving forces of the atomic arrangements in complex solids that exhibit interesting chemical and physical properties? (2) How do different elements distribute themselves in a solid-state structure? (3) Can we develop a chemical understanding to predict the effects of valence electron concentration on the structures and magnetic ordering of systems by both experimental and theoretical means? Although these issues are relevant to various compound classes, intermetallic compounds are especially interesting and well suited for a joint experimental and theoretical effort. For intermetallic compounds, the questions listed above are difficult to answer since many of the constituent atoms simply do not crystallize in the same manner as in their separate, elemental structures. Also, theoretical studies suggest that the energy differences between various structural alternatives are small. For example, Al and Ga both belong in the same group on the Periodic Table of Elements and share many similar chemical properties. Al crystallizes in the fcc lattice with 4 atoms per unit cell and Ga crystallizes in an orthorhombic unit cell lattice with 8 atoms per unit cell, which are both fairly simple structures (Figure 1). However, when combined with Mn, which itself has a very complex cubic crystal structure with 58 atoms per unit cell, the resulting intermetallic compounds crystallize in a completely different fashion. At the 1:1 stoichiometry, MnAl forms a very simple tetragonal lattice with two atoms per primitive unit cell, while MnGa crystallizes in a complicated rhombohedral unit cell with 26 atoms within the primitive unit cell. The mechanisms influencing the arrangements of atoms in numerous crystal structures have been studied theoretically by calculating electronic structures of these and related materials. ...
Date: August 18, 2008
Creator: Ko, Hyunjin
Partner: UNT Libraries Government Documents Department

Structural and Magnetothermal Properties of Compounds: Yb5SixGe4-x,Sm5SixGe4-x, EuO, and Eu3O4

Description: The family of R{sub 5}Si{sub x}Ge{sub 4-x} alloys demonstrates a variety of unique physical phenomena related to magneto-structural transitions associated with reversible breaking and reforming of specific bonds that can be controlled by numerous external parameters such as chemical composition, magnetic field, temperature, and pressure. Therefore, R{sub 5}Si{sub x}Ge{sub 4-x} systems have been extensively studied to uncover the mechanism of the extraordinary magneto-responsive properties including the giant magnetoresistance (GMR) and colossal magnetostriction, as well as giant magnetocaloric effect (GMCE). Until now, more than a half of possible R{sub 5}Si{sub x}Ge{sub 4-x} pseudobinary systems have been completely or partially investigated with respect to their crystallography and phase relationships (R = La, Pr, Nd, Gd, Tb, Dy, Er, Lu, Y). Still, there are other R{sub 5}Si{sub x}Ge{sub 4-x} systems (R = Ce, Sm, Ho, Tm, and Yb) that are not studied yet. Here, we report on phase relationships and structural, magnetic, and thermodynamic properties in the Yb{sub 5}Si{sub x}Ge{sub 4-x} and Sm{sub 5}Si{sub x}Ge{sub 4-x} pseudobinary systems, which may exhibit mixed valence states. The crystallography, phase relationships, and physical properties of Yb{sub 5}Si{sub x}Ge{sub 4-x} alloys with 0 {le} x {le} 4 have been examined by using single crystal and powder x-ray diffraction at room temperature, and dc magnetization and heat capacity measurements between 1.8 K and 400 K in magnetic fields ranging from 0 to 7 T. Unlike the majority of R{sub 5}Si{sub x}Ge{sub 4-x} systems studied to date, where R is the rare earth metal, all Yb-based germanide-silicides with the 5:4 stoichiometry crystallize in the same Gd{sub 5}Si{sub 4}-type structure. The magnetic properties of Yb{sub 5}Si{sub x}Ge{sub 4-x} materials are nearly composition-independent, reflecting the persistence of the same crystal structure over the whole range of x from 0 to 4. Both the crystallographic and magnetic property data indicate that Yb{sub ...
Date: May 9, 2007
Creator: Ahn, Kyunghan
Partner: UNT Libraries Government Documents Department