The effects of molecular reorientation on the absorption of intense light by organic-dye solutions

Equations are presented for the spectral and orientational distribution of unexcited dye molecules in the field of an intense giant laser pulse. The solute dye molecules are linear oscillators that may be broadened either homogeneously or inhomogeneously, and may reorient by sudden jumps over large angles or by small angular steps (brownian rotational motion). The equations are employed to analyze the intensity dependence of fluorescence polarization observed by Mourou and Denariez-Roberge for the system cryptocyanine-glycerin. Their data are consistent with an excited-state deactivation time T₁ = 0.4 ± 1.0 ns and a rotational diffusion constant D = 20/T₁ = 5.0 × 10⁹ s⁻¹     

Are dipolar liquids ferroelectric?

VH and HV depolarized hyper-Rayleigh scattering spectra were measured for liquid solutions of dipolar CH3CN in nondipolar C2Cl4 at T=300 K. The VH spectrum contains a strong narrow peak due to a slowly relaxing longitudinal orientation mode. This peak is absent in the HV spectrum, and it disappears from the VH spectrum when the CH3CN concentration is reduced to 8%. This observation is consistent with a ferroelectric phase transition predicted to occur when rho mu0(2)=9epsilon0kT=49 D2 M.     

High accuracy ab initio studies of Li6+, Li6-, and three isomers of Li6

The structures and energetics of Li(6) (+), Li(6) (-) and three isomers of Li(6) are investigated using the coupled-cluster singles, doubles and perturbative triples [CCSD(T)] method with valence and core-valence correlation consistent basis sets of double- to quadruple-zeta quality (cc-pVXZ and cc-pCVXZ, where X=D-Q). These results are compared with qualitatively different predictions by less reliable methods. Our results conclusively show that the D(4h) isomer is the global minimum structure for Li(6). It is energetically favored over the C(5v) and D(3h) structures by about 5.1 and 7.1 kcal mol(-1), respectively, after the inclusion of the zero-point vibrational energy (ZPVE) correction. Our most accurate total atomization energies are 123.2, 117.6, and 115.7 kcal mol(-1) for the D(4h), C(5v), and D(3h) isomers, respectively. Comparison of experimental optical absorption spectra with our computed electronic spectra also indicate that the D(4h) isomer is indeed the most stable structure. The cation, anion, and some higher spin states are investigated using the less expensive cc-pCVDZ basis set. Adiabatic ionization energies and electron affinities are reported and compared with experimental values. Predictions of molecular properties are found to be sensitive to the basis set used and to the treatment of electron correlation.     

SN2 reactions in the gas phase. Structure of the transition state

The alkylhalide-halide association ions, [RX₂]^? that are observed in the negative chemical ionization mass spectra of alkyl halides appear to be directly related to the corresponding S_N2 transition states in solution. ‘Frontside’ association of halide ions with bridgehead alkyl halides does not occur in our system. The Change in heats and entropies of association for the chloromethane series is consistent with delocalization in the [RX]₂^? ions.     

Diverse redox-active molecules bearing O-, S-, or Se-terminated tethers for attachment to silicon in studies of molecular information storage

A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols.     

Water-Soluble imide-amide copolymers. II. Preparation and characterization of poly (acrylamide-co-p-maleimidobenzoic acid)

The comonomer required, p-maleimidobenzoic acid (MBA) was first prepared in good yield by refinements of published methods. p-Carboxysuccinanilic acid (CSA), and p-succinimidobenzoic acid (SBA), were also prepared to provide models useful for IR and NMR for spectroscopic assignments of the new copolymers. Polymerization of MBA with acrylamide in glacial acetic acid at 60°C gave copolymers with estimated viscosity average molecular weights of 60,000 to 90,000. Yields and viscosity average molecular weights decreased as the MBA to acrylamide monomer feed ratio was increased. The rate of incorporation of MBA into the copolymer rose from 7 to 23% when the mole ratio in the feed was raised from 5 to 20%. Decreasing the initiator concentration increased molecular weights by less than predicted and reduced the yield of copolymer for any given feed ratio of MBA to acrylamide. In all cases about 30–40% of the MBA units in the purified copolymers were hydrolyzed. A change to dimethyl sulfoxide solvent gave good, and poor yields of copolymer at 5 and 10 mol % MBA, respectively, and no copolymer at 20 mol % MBA. Viscosity average molecular weights of the copolymer products prepared in DMSO were somewhat lower than obtained for the copolymers prepared in acetic acid. Polymerization in a DMSO-water mixture gave a negligible yield of polymeric product. Instead, only hydrolysates of MBA precipitated when the coloured polymerization solutions were added to methanol.     

UV photoelectron spectra of 5- and 6-azauracil

The He(I) photoelectron spectra of 5-azauracil (1,3,5-triazine-2,4(1H,3H)-dione) and 6-azauracil (1,2,4-triazine-3, 5(2H,4H)-dione) are presented. The spectra are assigned by using INDO/S calculations and comparison arguments with uracil. The first ionization energy in the title compounds is higher than in the usual nucleic acid bases.     

Hybrid Ia antigens: genetic, serologic, and biochemical analyses

Ia specificities 22 and 23 were found to be determinants on hybrid Ia molecules, formed by the noncovalent binding of a 26,000--28,000 dalton beta polypeptide chain (Ae) coded by the I-A subregion and a 32,000--35,000 dalton alpha chain (E alpha) coded by the I-E subregion. For expression of Ia.23 the Ae chain, coded by the I-A subregion, must be derived from the H-2d haplotype, while Ab, As, or Ak can provide the complementing beta chain for the expression of Ia.22. For expression of Ia.22 and Ia.23, most Ia.7 positive strains can provide the complementing alpha chain (E alpha), with the one exception of B10.PL (Eu), which is Ia.7 positive but will not complement with Ad to express Ia.23. Antisera were also produced against hybrid Ia antigens by immunizing with F1 cells expressing Ia.22 or Ia.23 generated by generated by trans-complementation. These antisera detect the same specificities as conventional anti-Ia.22 and anti-Ia.23 sera produced against cis-complementing Ia antigens. It is postulated that hybrid Ia determinants are involved in recognition and generation of immune response to antigens under dual Ir gene control. It is also suggested that there are 2 types of Ia specificities: 1) allotypic Ia specificities expressed on the alpha or beta chains (for example, Ia.7 on the E alpha chain) and 2) hybrid Ia specificities, which are unique interaction determinants formed by the association of alpha and beta chains (for example, Ia.22 and Ia.23). These interaction gene products may be involved in antigen recognition and presentation.     

PROBING THE STRUCTURE OF HPD BY FLUORESCENCE SPECTROSCOPY

Fluorescence emission spectra indicate that oligomers containing both hematoporphyrin and its dehydration products (vinyl porphyrins) comprise the tumor-localizing fraction of HPD. In the relatively polar solvent methanol, the vinyl porphyrins exhibit reduced fluorescence yields while the hematoporphyrin residues are relatively resistant to fluorescence quenching by Fe+3. In the less polar solvent tetrahydrofuran, fluorescence from oligomeric vinyl porphyrins was enhanced, and Fe+3-induced quenching of oligomeric hematoporphyrin promoted. These, together with other studies in biological systems, suggest a substantial degree of interaction among the porphyrin units contained in these oligomers, as a function of the polarity of the environment.     

Synthesis of a tetraazacyclotetradecadiene and a pentaazacyclotetradecatriene

Useful procedures for preparing a novel tetraazacyclotetradecadiene and a pentaazacyclotetradecatriene are reported. J. Heterocyclic Chem., 14, 1097 (1977)