This dissertation presents an investigation of ordering in FCC based systems using the pair potential approximation in the ground state and mean field limits. The theoretical approach is used to explain the occurrence of observed equilibrium phases and characteristics of thermodynamic instabilities, in particular, spinodal ordering and decomposition. It is shown that the stability of non-integer domain sizes in long period superstructures such as Al{sub 3}Ti and Ag{sub 3}Mg may result from the tendency of a system to reduce the number of non-dominant ordering waves, thus producing domain sizes that have rational fraction form n/m. This conclusion is used to explain the domain size stability with respect to variations in temperature and electron concentration. The cation ordering in the precipitate phases in calcite and dolomite is analyzed by analogy with ordering in FCC based metals. The ordered phases in calcite and dolomite are shown to be consistent with pair potential minima at {l brace}100{r brace} and {l brace}1/2, 1/2, 1/2{r brace} positions in reciprocal space respectively. 32 refs., 6 figs.

Lateral changes in geology pose a serious problem in data interpretation for any surface geophysical method. Although many geophysical techniques are designed to probe vertically, the source signal invariably spreads laterally, so any lateral variations in geology will affect the measurements and interpretation. This problem is particularly acute for controlled source electromagnetic soundings because only a few techniques are available to interpret the data if lateral effects are present. In this thesis we examine the effects of geological contacts for the time domain electromagnetic sounding method (TDEM). Using two simple two-dimensional models, the truncated thin-sheet and the quarter-space, we examine the system response for several commonly used TDEM sounding configurations. For each system we determine the sensitivity to the contact, establish how to the contact anomaly may be distinguished from other anomalies and, when feasible, develop methods for interpreting the contact geometry and for stripping the contact anomaly from the observed data. Since no numerical models were available when this work was started, data were collected using scale models with a system designed at the University of California at Berkeley. The models were assembled within a table-top modeling tank from sheets or blocks of metal using air or mercury as …

Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, SUCCiOlC acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility …

Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility …

In the Standard Model (SM) of the elementary particles, the interactions among the known fundamental fermions (leptons and quarks) are mediated through gauge bosons which obey the symmetry: SU(3) {circle_times} SU(2) {circle_times} U(1). More precisely, the electroweak interaction [4-6] is described by a gauge symmetry SU(2) {circle_times} U(1) which is broken spontaneously. The electroweak symmetry breaking is implemented by the introduction of a complex scalar Higgs field which has a non-zero vacuum expectation value (vev). This way, the lagrangian of the theory remains invariant under SU(2) transformations, but quantization of the fields must start from a ground state which does not exhibit this symmetry, and therefore the full symmetry of the lagrangian is not manifest. Invariance of the theory under local SU(2) transformations implies the presence of vectorial gauge fields which mediate the electroweak interactions. The so called spontaneous symmetry breaking allows the quanta of these gauge fields, the W and Z bosons, to acquire a finite mass. The photon, the particle which mediates the electromagnetic interaction, remains massless. The Higgs boson is one of only two particles in the SM which have not yet been directly observed (the other is the {nu}{sub {tau}}, although there is indirect evidence of …

The effects of compositional gradients, are considered based on a thermodynamic analysis, referred to as the Cahn-Hillard analysis, which describes the degree to which a local surface energy is modified by the presence of a composition gradient. The analysis predicts that both ductile and brittle fracture mechanisms are enhanced by the presence of a composition gradient. Data on stress corrosion cracking and fatigue crack growth in selected FCC alloys are used to illustrate the significance of microsegregation on mechanical properties.

The reactive o-quinodimethanes, 1,2-dimethylene-1,2-dihydronaphthalene (9) and o-xylylene (1) were observed by flow {sup 1}H NMR spectroscopy at room temperature. The {sup 1}H NMR spectrum of 9 was obtained in the absence of precursor and dimers. However, the {sup 1}H NMR spectrum of the more reactive 1, generated in a similar manner from (o-((trimethylsilyl)methyl)benzyl)trimethylammonium iodide (5.) could be obtained only in the presence of its stable (4 + 2) and (4 + 4) dimers. The dimerization kinetics of 3-methyl- (5{prime}), 3,6-dimethyl- (11), 3-isopropyl- (12), and 3,6-diisoproply-1,2-xylylene (13) in acetonitrile (CH{sub 3}CN) were studied by stopped-flow UV-visible spectroscopy. Fluoride ion induced 1,2-elimination from 2-elimination from 2-trimethylsilylbenzocyclobutenyl-1 mesylate (26) was used to generate the reactive molecule benzocyclobutadiene (1{prime}) in CD{sub 3}CN, which was observed by flow {sup 1}H NMR spectroscopy at room temperature. The {sup 1}H NMR spectrum (in CD{sub 3}CN) of 1,2-dimethylene-1,2-dihydrothiophene (1{double prime}), obtained by fluoride ion induced 1,4-elimination from 3-(trimethylammoniummethyl)-2-(trimethylsilylmethyl)thiophene iodine was observed by flow {sup 1}H NMR spectroscopy at room temperature. The dimerization rate of 1{double prime} in CH{sub 3}CN, generated in the same manner, was measured by UV-visible spectroscopy. 166 refs., 7 figs., 7 tabs.

Measurements of the normal state magnetic susceptibility {chi}(T) of YBa{sub 2}Cu{sub 3}O{sub 7}, Bi{sub 1.8}Pb{sub 0.2}Sr{sub 2}CaCu{sub 2}O{sub 8+{delta}}, and Bi{sub 2{minus}x}Pb{sub x}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10+{delta}} (x = 0.2 and 0.25) were carried out. All {chi}(T) data show negative curvature below {approximately}2{Tc}. The data for YBa{sub 2}Cu{sub 3}O{sub 7} are in excellent agreement with a new calculation of the superconducting fluctuation diamagnetism. From the analysis, we infer s-wave pairing and microscopic parameters are obtained. For {chi}(T) of YBa{sub 2}Cu{sub 3}O{sub 7}, part of the negative curvature is inferred to arise from the normal state background. We find a strong temperature dependent anisotropy {delta}{chi} {equivalent to} {chi}{sub c} {minus} {chi}{sub ab} and estimate the normal state spin contributions to {chi}(T). The heat capacity C(T) of YBa{sub 2}Cu{sub 3}O{sub 7} is reported for 0.4 K < T < 400 K in zero and 70 kG magnetic fields. In addition to the feature associated with the onset of the superconductivity at {Tc}, two anomalies in C(T) were observed near 74 K and 330 K, with another possible anomaly near 102 K; the temperatures at which they occur correlate with anomalies in {chi}(T) and ultransonic measurements. The occurrence of the anomaly at {approx …

The first part of this thesis will search for the thermal isomerization of olefins to carbenes which is predicted to be a high energy process by calculations and has only been observed in a few strained olefins. The possibility of thermal isomerization of simple olefins to carbenes will be explored. Substitution of a silyl group on the double bond of an olefin allows a potential intermediate which has a {beta}-radical to the silyl group during the cis-trans isomerization. The effects of a trimethylsilyl group on this isomerization are the subject of this study. The second part of this thesis will include the generation and chemistry of intermediates containing a silicon-nitrogen double bond. The isomerization of parent silanimine to the aminosilylene was calculated to be a high energy process. New approaches to the silicon-nitrogen double bond will also be presented. 92 refs., 12 figs., 11 tabs.

As a continuation of the research on bcc Gd-Mg alloy system by Herchenroeder and Gschneidner, the metastable bcc Gd-Cd alloys were studied with the emphasis on their metallurgical and magnetic properties. An essentially single phase alloy could be retained for Cd concentrations from 15 at. % Cd to 19 at. % Cd, which is in the vicinity of the eutectoid composition of {beta}Gd in the Gd-Cd system. The lattice constants obtained for these alloys were used to determine the lattice constant of pure bcc Gd by extrapolation to 0 at. % Cd. Good agreement between this extrapolated value and that obtained from Gd-Mg alloys by using the same method suggested the validity of such extrapolation method. Thermal stability of these metastable bcc Gd-Cd alloys was examined by using differential thermal analysis (DTA).

A method for determining the location and possible existence of symmetry elements in Patterson superposition maps has been developed. A comparison of the original superposition map and a superposition map operated on by the symmetry element gives possible translations to the location of the symmetry element. A reciprocal space approach using structure factor-like quantities obtained from the Fourier transform of the superposition function is then used to determine the best'' location of the symmetry element. Constraints based upon the space group requirements are also used as a check on the locations. The locations of the symmetry elements are used to modify the Fourier transform coefficients of the superposition function to give an approximation of the structure factors, which are then refined using the EG relation. The analysis of several compounds using this method is presented. Reciprocal space techniques for locating multiple images in the superposition function are also presented, along with methods to remove the effect of multiple images in the Fourier transform coefficients of the superposition map. In addition, crystallographic studies of the extended chain structure of (NHC{sub 5}H{sub 5})SbI{sub 4} and of the twinning method of the orthorhombic form of the high-{Tc} superconductor YBa{sub 2}Cu{sub 3}O{sub 7-x} are …

Optical properties and electronic structures of disordered Ag{sub 1- x}In{sub x}(x = 0.0, 0.04, 0.08, 0.12) and Ni{sub 1-x}Cu{sub x} (x = 0.0, 0.1, 0.3, 0.4) alloys and ordered AuGa{sub 2}, PtGa{sub 2}, {beta}{prime}-NiAl, {beta}{prime}-CoAl, CeSn{sub 3}, and LaSn{sub 3} have been studied. The complex dielectric functions have been determined for Ag{sub 1-x}In{sub x}, Ni{sub 1-x}Cu{sub x}, AuGa{sub 2}, and PtGa{sub 2} in the 1.2--5.5 eV region and for CeSn{sub 3} and LaSn{sub 3} in the 1.5--4.5 eV region using spectroscopic ellipsometry. Self-consistent relativistic band calculations using the linearized-augmented-plane-wave method have been performed for AuGa{sub 2}, PtGa{sub 2}, {beta}{prime}-NiAl, {beta}{prime}-CoAl, CeSn{sub 3}, and LaSn{sub 3} to interpret the experimental optical spectra.

Resistivity measurements have been performed for electric characterization of the compounds Ba{sub 5}Sb{sub 3} and Ba{sub 5}Sb{sub 3}Cl, both with the Mn{sub 5}Si{sub 3} structure type, along with Ca{sub 5}Bi{sub 3} and Ca{sub 5}Bi{sub 3}F, both with the {beta}-Yb{sub 5}Sb{sub 3} structure type. These measurements were taken as a function of temperature using the four probe method on pressed polycrystalline pellets of the compounds. A sealed apparatus was developed for containing these air-sensitive compounds throughout the experiments. By a simple electron count, one extra electron in both Ba{sub 5}Sb{sub 3} and Ca{sub 5}Bi{sub 3} should occupy a conduction band, giving these compounds a metallic character. In the cases of Ba{sub 5}Sb{sub 3}Cl and Ca{sub 5}Bi{sub 3}F, the extra electron should bond to the halide, both filling the valence band and giving rise to semiconducting character. Ca{sub 5}Bi{sub 3}, Ca{sub 5}Bi{sub 3}F, and Ba{sub 5}Sb{sub 3}Cl were found to comply with the electron count prediction. Ba{sub 5}Sb{sub 3}, however, was found to be a semiconductor (E{sub g} = 0.30 eV) with a larger band gap than its corresponding chloride (E{sub g} = 0.09 eV).

An angle-resolved photoemission study of the normal and superconducting states in Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} was performed. Measurements in the normal state show bands dispersing through the Fermi level from at least 350 meV below E{sub F}. The Fermi level crossings are consistant with local-density band calculation, including a point calculated to be of Bi-O character. Additional measurements were made where bands crossed the Fermi level between 100 and 250K, along with measurements on an adjacent Pt foil. The Fermi edges of both materials agree to within the noise. Below the Fermi level, the spectra show correlation effects on the form of an increased effective mass. The shape of the spectra can be explained by a lifetime-broadened photohole and secondary electrons. The effective inverse photohole lifetime is linear in energy. A superconducting gap has been measured at a number of points where there is density at the Fermi level in the normal state. By proper modeling, a gap of 24 meV was obtained for all these points, including points of Cu-O and Bi-O character respectively, according to band calculation. The lack of gap anisotropy in the basal plane suggests that pinning in this material is not d-wave pairing.

There has been much recent interest in the photochemistry and photophysics of transition metal polypyridine complexes due to the possibility of their use in solar energy conversion systems. The excited state of these compounds are known to undergo useful electron transfer and energy transfer reactions. This work attempts to elucidate the mechanism of the quenching of *CrL{sub 3}{sup 3+} (where L = 2,2{prime}-bipyridine, 4,4{prime}-dimethyl-2,2{prime}-bipyridine, 1,10-phenanthroline, 5-chloro-1,10-phenanthroline, 5-methyl-1,10-phenanthroline) by oxalate ions in neutral pH. Evidence suggests an ion-pairing pre-equilibrium followed by rate limiting electron transfer to produce CrL{sub 3}{sup 2+} and CO{sub 2}{sup {minus}} can then react with ground state chromium(III) species to produce another mole of the reduced product or it can produce a secondary transient as in the case of phenanthroline and substituted phenanthroline complexes. The secondary transient reacts to produce CrL{sub 3}{sup 2+} in a subsequent reaction. 85 refs., 24 figs., 7 tabs.

Proton magnetic resonance spectroscopy, or nuclear magnetic resonance (NMR) of hydrogen, has been applied to investigate silica-supported Group VIII monometallic and Group VIII-Group IB bimetallic catalysts and alumina- and silica-supported platinum-rhenium bimetallic catalysts. Two adsorbed states of hydrogen, i.e., irreversible and reversible hydrogen, on the surfaces of monometallic Ru, Pt, and Cu particles and bimetallic Ru-Group Ib, Pt-Group Ib, and Pt-Re particles were observed directly via proton NMR. The same amounts of the irreversible hydrogen adsorbed on pure Ru catalysts were measured by both proton NMR and the volumetric technique. The electronic environments on surfaces of monometallic catalysts are sensitive to changes in metal dispersion, state of adsorbed hydrogen, and residual chlorine. Surface compositions for the Ru--Cu and Pt--Cu bimetallic catalysts were determined by NMR of adsorbed hydrogen. 297 refs., 96 figs., 19 tabs.

The electrocatalysis of oxygen-transfer reactions is discussed in two parts. In Part I, the reduction of iodate (IO{sub 3}{sup {minus}}) is examined as an example of cathodic oxygen transfer. On oxide-covered Pt electrodes (PtO), a large cathodic current is observed in the presence of IO{sub 3}{sup {minus}} to coincide with the reduction of PtO. The total cathodic charge exceeds the amount required for reduction of PtO and IO{sub 3}{sup {minus}} to produce an adsorbed product. An electrocatalytic link between reduction of IO{sub 3}{sup {minus}} and reduction of PtO is indicated. In addition, on oxide-free Pt electrodes, the reduction of IO{sub 3}{sup {minus}} is determined to be sensitive to surface treatment. The electrocatalytic oxidation of CN{sup {minus}} is presented as an example of anodic oxygen transfer in Part II. The voltametric response of CN{sup {minus}} is virtually nonexistent at PbO{sub 2} electrodes. The response is significantly improved by doping PbO{sub 2} with Cu. Cyanide is also oxidized effectively at CuO-film electrodes. Copper is concluded to serve as an adsorption site for CN{sup {minus}}. It is proposed that an oxygen tunneling mechanism comparable to electron tunneling does not occur at the electrode-solution interface. The adsorption of CN{sup {minus}} is therefore considered to …

The data engineers and scientists use to determine if the groundwater supply is contaminated are derived from analysis of samples taken largely from monitoring wells. For these data to be reliable several factors must be considered. One factor is the integrity of the monitoring well. In this project, emphasis has been placed on the potential impact on water quality caused by diffusion across the threaded joints of PVC pipe. In this study, the diffusion of trichloroethylene across several common types of threaded joints (i.e., square flush, modified ACME, modified ACME stub, and ACME) has been measured. Samples were obtained from the water inside the pipe sections and analyzed for trichloroethylene by gas chromatography. Breakthrough occurs within days of the samples being placed in the baths. The softened PVC joints of the pipes in the pure trichloroethylene split before the first sample interval of 1.5 weeks. The data show great variability in casting joints from the same manufacturer, and indicate a need for increased precision in the manufacturing of the PVC pipe joints. A one-dimensional diffusion model is used to determine an equivalent gap size through which the diffusion occurs. Flow rates through the threaded joints are calculated by using the …

Data are presented for the first time on exclusive Pomeron-Pomeron interactions which produce a neutral strange and neutral antistrange particle pair in a central system X. In this paper, the system, X, is identified as one of the following neutral combinations; K{sub s}{sup 0}K{sub s}{sup 0}, K{sub s}{sup 0}K{sup {plus minus}}{pi}{sup {minus plus}}, {Lambda}{sup 0}{bar {Lambda}}{sup 0}, {Lambda}{sup 0}{bar {Lambda}}{sup 0}*. These data were obtained in proton-proton collisions at {radical}s = 62 GeV at the CERN ISR. The triggering systems used to obtain these data are described, followed by a description of the data. The central system mass distributions are presented along with differential mass cross section estimates. A broad enhancement is seen in the K{sub s}{sup 0}K{sub s}{sup 0} system at a mass of 1.2 GeV, and is likely to have the quantum numbers J{sup PC} = 0{sup ++}. Total cross section estimates of 1.3 {plus minus} .64 {mu}b in the K{sub 2}{sup 0}K{sub s}{sup 0} system, . 44 {plus minus} .14 {mu}b in the K{sub s}{sup 0}K{sup {plus minus}}{pi}{sup {minus plus}} system, .20 {plus minus} .14 {mu}b in the {Lambda}{sup 0}{bar {Lambda}}{sup 0} system, and .13 {plus minus} .06 {mu}b in the {Lambda}{sup 0}{bar {Lambda}}{sup 0}* system are …

The kinetics of the reactions of C{sub 2}H{sub 5} radical with Co(NH{sub 3}){sub 5}X{sup 2+}, Ru(NH{sub 3}){sub 5}X{sup 2+}, and Co(dmgH){sub 2} (X) (Y) (X = Br, Cl, N{sub 3}, SCN; Y = H{sub 2}O, CH{sub 3}CN) complexes were studied using laser flash photolysis of ethylcobalt complexes. The kinetics were obtained by the kinetic probe method. Some relative rate constants were also determined by a competition method based on ethyl halide product ratios. The kinetics of colligation reactions of a series of alkyl radicals with {beta}-Ni(cyclam){sup 2+} were studied using flaser flash photolysis of alkylcobalt complexes. Again, the kinetics were obtained by employing the kinetic probe competition method. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H{sub 2}O{sup 2+} were studied. Activation parameters were obtained for the unimolecular homolysis of C{sub 2}H{sub 5}Ni(cyclam)H{sub 2}O{sup 2+}. Kinetic and thermodynamic data obtained from these reactions were compared with those for the {sigma}-bonded organometallic complexes. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H{sub 2}O{sup 2+} complexes were studied by monitoring the formation of the oxygen insertion product RO{sub 2}Ni(cyclam)H{sub 2}O{sup 2+}. The higher rate constants for the reactions of alkyl radicals with oxygen in solution, as compared with …

We use the Mark II detector to study Z decays into bottom quark-anti-quark pairs, leading to the production of bottom hadrons. The Z bosons are formed in e{sup +}e{sup {minus}} annihilation at the SLC at center-of-mass energies between 89 and 93 GeV. We identify events containing semileptonic decays of bottom hadrons by detecting isolated leptons, i.e leptons with high transverse momenta relative to the nearest hadronic jet. Using isolated electrons and muons, we measure the B-hadron semileptonic branching ratio times the fraction of hadronic Z decays which contain bottom hadrons, B(B {yields} X{ell}{nu}){center dot}{Gamma}(Z {yields} b{bar b})/{Gamma}(Z {yields} had) = 0.025 {sub {minus}0.009}{sup +0.100} {plus minus} 0.005, where we have listed the statistical errors followed by the systematic error. Assuming B(B {yields} X(ell){nu}) = 11% {plus minus} 1%, we measure {Gamma}(Z {yields} b{bar b})/{Gamma}(Z {yields} had) = 0.23 {sub {minus}0.09}{sup +0.11}, in good agreement with the standard-model prediction of 0.22. We find {Gamma}(Z {yields} b{bar b}) = 0.40 {sub {minus}0.16}{sup +0.19} GeV. 83 refs., 34 figs., 19 tabs.

This thesis is divided into two sections, which describe portions of the data acquisition system and online software for the Cherenkov Ring Imaging Detector (CRID) for the SLD, and analyses of several low cross section strangeonium channels in data from the LASS spectrometer. The CRID section includes a description of the data acquisition system, determination of the preamplifier gain, and development of an online pulse finding algorithm based on deconvolution. Deconvolution uses knowledge of the preamplifier impulse response to aid in pulse finding. The algorithm is fast and shows good single pulse resolution and excellent double pulse resolution in preliminary tests. The strangeonium analyses are based on data from a 4.1 event/nanobarn exposure of the LASS spectrometer in K{sup {minus}}p interactions at 11 GeV/c, and include studies of {Lambda}{eta}{pi}{sup {plus}}{pi}{sup {minus}}, {Lambda}{Kappa}*{Kappa}*, and {Lambda}{phi}{phi}.

Ultrasonic techniques have recently been applied to the texture characterization in polycrystalline aggregates of hexagonal crystals. The basis of this application lies in the relations between the elastic constants {bar C}{sub ij} of the aggregates, which can be inferred from ultrasonic wave velocity measurements, and the orientation distribution coefficients. This communication present such relations for aggregates which possess orthotopic material symmetry and hexagonal crystal symmetry for Voigt, Reuss, and Hill averaging methods in a unified and concise representation.

The use of platinum(II) complexes as tags and probes for biomolecules is indeed advantageous for their reactivities can be selective for certain purposes through an interplay of mild reaction conditions and of the ligands bound to the platinum. The use of {sup 195}Pt NMR as a method of detecting platinum and its interactions with biomolecules was carried out with the simplest model of platinum(II) tagging to proteins. Variable-temperature {sup 195}Pt NMR spectroscopy proved useful in studying the stereodynamics of complex thioethers like methionine. The complex, Pt(trpy)Cl{sup +}, with its chromophore has a greater potential for probing proteins. It is a noninvasive and selective tag for histidine and cysteine residues on the surface of cytochrome c at pH 5. The protein derivatives obtained are separable, and the tags are easily quantitated and differentiated through the metal-to-ligand charge transfer bands which are sensitive to the environment of the tag. Increasing the pH to 7.0 led to the modification by Pt(trpy)Cl{sup +}of Arg 91 in cytochrome c. Further studies with guanidine-containing ligands as models for arginine modification by Pt(trpy)Cl{sup +} showed that guanidine can act as a terminal ligand and as a bridging ligand. Owing to the potential utility of Pt(trpy)L{sup n+} as …