Spectroscopic studies, lead

In the near-infrared, Al Ga As and In Ga As P lasers, and in the far-infrared lead compound semiconductor lasers are tunable by varying temperature and operating current. Many exceUent spectroscopic studies have been performed using them. However, they do have relatively limited tuning ranges for any one device. 

Whereas most 3-amino-l,2,4-triazoles prefer the amino form 60 [76AHC (SI), p. 439,445 80KGS1414], strong electron withdrawing substituents can lead to the predominance of the imino form, as is the case of the compound 65 (R = C3F7) (80KGS1414) or to 5-amino tautomer 61 (R = H, R = CF3) [98AX(C)442]. This conclusion was based on gas-phase IR and mass-spectroscopic studies. 

It has been reported recently83 that the spectroscopic study of methylacetylene leads to the value 1.462 0.005 A. for the carbon-carbon single-bond distance in this substance. This is 0.08 A. less than the value 1.54 A. which we expect on the basis of the argument that constancy of the single-bond distance should be retained in the presence of an adjacent triple as well as of an adjacent double bond or aromatic nucleus. An electron-diffraction investigation of this substance is under way in these Laboratories. 

Consequently, due to preferred cis-cis orientation a dimeric structure is observed for the indium complex and an unprecedented cis-trans arrangement in the thallium structure leads to a polymeric aggregate. Further N-NMR spectroscopic studies show that the aluminum and gallium complexes are stable contact ion pairs even in solution whereas the indium and thallium compounds are solvent-separated ion pairs in THE solution. 

Iron is the most abundant, useful, and important of all metals. For example, in the 70-kg human, there is approximately 4.2 g of iron. It can exist in the 0, I, II, III, and IV oxidation states, although the II and III ions are most common. Numerous complexes of the ferrous and ferric states are available. The Fe(II) and Fe(III) aquo complexes have vastly different pAa values of 9.5 and 2.2, respectively. Iron is found predominantly as Fe (92%) with smaller abundances of Fe (6%), Fe (2.2%), and Fe (0.3%). Fe is highly useful for spectroscopic studies because it has a nuclear spin of. There has been speculation that life originated at the surface of iron-sulfide precipitants such as pyrite or greigite that could have caused autocatalytic reactions leading to the first metabolic pathways (2, 3). 

Vibrational spectroscopic studies of heterogeneously catalyzed reactions refer to experiments with low area metals in ultra high vacuum (UHV) as well as experiments with high area, supported metal oxides over wide ranges of pressure, temperature and composition [1]. There is clearly a need for this experimental diversity. UHV studies lead to a better understanding of the fundamental structure and chemistry of the surface-adsorbate system. Supported metals and metal oxides are utilized in a variety of reactions. Their study leads to a better understanding of the chemistry, kinetics and mechanisms in the reaction. Unfortunately, the most widely used technique for determining adsorbate molecular structure in UHV,... 

Hoshi N, Bae IT, Scherson DA. 2000. In situ infrared reflection absorption spectroscopic studies of coadsorption of CO with underpotential-deposited lead on Pt(lll) in an aqueous acidic solution. J Phys Chem B 104 6049-6052. 

Stabilization of quinone methides by coordination to transition metals might have various applications, beyond the important structural and spectroscopic studies of these coordinated compounds. For example, it is possible to manipulate their structure while coordinated to the metal center and affect their controlled release and trapping, leading to new synthetic procedures. 

Our latest results in this field stem from a matrix-spectroscopic study of the isomerization of nitrosyl halides (152) and isonitrosyl halides (153).201 Irradiation of nitrosyl bromide (152 X = Br) and nitrosyl chloride (152 X = Cl) leads to the corresponding isomers isonitrosyl bromide (153 X = Br) and isonitrosyl chloride (153 X = Cl). Both compounds, NOBr and NOC1,202 have again been identified by comparison of the experimental and calculated (BLYP/6-311+G ) IR spectra. The back-reactions 153 - 152 can be initiated by UV, visible or IR light. Astonishingly, this retransformation also occurs spontaneously even in the matrix at 10 K under exclusion of any UV/VIS or IR radiation. 

Sealants obtained by curing polysulfide liquid polymers with aryl bis(nitrile oxides) possess stmctural feature of thiohydroximic acid ester. These materials exhibit poor thermal stability when heated at 60°C they soften within days and liquefy in 3 weeks. Products obtained with excess nitrile oxide degrade faster than those produced with equimolar amounts of reagents. Spectroscopic studies demonstrate that, after an initial rapid addition between nitrile oxide and thiol, a second slower reaction occurs which consumes additional nitrile oxide. Thiohydroximic acid derivatives have been shown to react with nitrile oxides at ambient temperature to form 1,2,4-oxadiazole 4-oxides and alkyl thiol. In the case of a polysulfide sealant, the rupture of a C-S bond to form the thiol involves cleavage of the polymer backbone. Continuation of the process leads to degradation of the sealant. These observations have been supported by thermal analysis studies on the poly sulfide sealants and model polymers (511). 

Acetonitrile is another participating solvent, which in many cases leads to the formation of an equatorially linked glycoside [125-131], It has been proposed that these reactions proceed via an a-nitrilium ion intermediate. It is not well understood why the nitrilium ion adopts an axial orientation however, spectroscopic studies support the proposed anomeric configuration [130,131], It is known that nucleophilic substitution of the a-nitrilium ion by an alcohol leads to P-glycosidic bonds and the best P-selectivities are obtained when reactive alcohols at low reaction temperatures are employed. Unfortunately, mannosides give poor anomeric selec-tivities under these conditions. 

SiH3)2C6H4 (H2L) leads to the nickel(iv) complex Ni(dmpe-P,.f, )(L-6V,6V )2. 31P NMR spectroscopic studies of the reaction indicate the presence of the intermediates Ni(dmpe-.P,.P )(dmpe-P)(L-Structural data have confirmed the unusual Ni2Si2 core. Starting from Ni(depe)2 (depe = l,2-bis(diethylphosphino)ethane), reaction with... 

Proteins having one chromophore per molecule are the simplest and most convenient in studies of fluorescence decay kinetics as well as in other spectroscopic studies of proteins. These were historically the first proteins for which the tryptophan fluorescence decay was analyzed. It was natural to expect that, for these proteins at least, the decay curves would be singleexponential. However, a more complex time dependence of the emission was observed. To describe the experimental data for almost all of the proteins studied, it was necessary to use a set of two or more exponents.(2) The decay is single-exponential only in the case of apoazurin.(41) Several authors(41,42) explained the biexponentiality of the decay by the existence of two protein conformers in equilibrium. Such an explanation is difficult to accept without additional analysis, since there are many other mechanisms leading to nonexponential decay and in view of the fact that deconvolution into exponential components is no more than a formal procedure for treatment of nonexponential curves. 

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