Preparation and electrochemistry of azobenzene self-assembled monolayers on gold--long range tunneling and end-group hydrogen bonding effect

A series of thiol-functionalied azobenzene derivatives (RAzoCnSH: R=H for n=3-6, abbreviated as AzoCnSH; R=CH(3)CONH for n=4, abbreviated as aaAzoC4SH) on gold electrodes were prepared and their self-assembly and electrochemical properties were studied by cyclic voltammetry. They all formed uniform and reproducible self-assembled monolayers (SAMs) on gold and showed well-behaved voltammetric responses in aqueous solution. Both the length of the alkyl chain spacer and the H-bonding of the end acetamino group had effects on the stability and the electrochemical kinetics of the SAMs, and the effect of the H-bonding was dominant. The surface coverage of the SAMs (AzoCnSH) is gradually increased with an increase of the alkyl chain spacer length, whereas the presence of the terminal acetamino group leads to a greater increase of the surface coverage. At a low scan rate, voltammetric responses corresponding to an irreversible two-electron, two-proton reduction/oxidation of the trans-azobenzene redox center were obtained in the range of +300 mV and -800 mV, which exhibited very large peak-to-peak splitting. At a high scan rate of 500 mV/s, two steps of reversible one-electron, one-proton reduction/oxidation corresponding to the cis-isomer in azobenzene-thiol SAMs (n is odd) was clearly observed between +300 and -200 mV. The apparent electron-transfer rate is decreased with increasing distance between the azobenzene redox center and the gold electrode. The existence of the end acetamino group which restricted the conformational change during the redox process also led to a decrease of the standard rate constant, and this restriction effect is more predominant than the distance effect.     

Complexation of the Non-steroidal Anti-inflammatory Drug Nabumetone with Modified and Unmodified Cyclodextrins

The inclusion of the anti-inflammatory drug, Nabumetone, in -, - and hydroxypropyl--cyclodextrin (CDs) is studied using UV-VIS absorption and steady-state fluorescence emission. Binding constants and thermodynamic parameters of complex formation are determined by spectrofluorimetry. The inclusion phenomena of Nabumetone with the three cyclodextrins is compared with that of the well known similar anti-inflammatory drug Naproxen. In the case of Nabumetone pronounced differences are observed in the complexation process with each cyclodextrin whereas the respective Naproxen complexes are nearly identical. ¹H-NMR experiments show that the inclusion process in Nabumetone can occur either through the substituents in the -2 (butanone) or -6 (methoxy) positions in the naphthalene ring.     

双甘肽稀土配合物溶液结构的13C和1H NMR研究

~(13)C and ~1H NMR technique was used to study the interaction of Gly-Gly with heavy lanthanide cations Dy~(3+), Ho~(3+), Er~(3+), Tm~(3+) and Yb~(3+) in aqueous solution. The stability constants for the 1:1 and 1:2 complexes of Gly-Gly with Ho~(3+) and Yb~(3+) were determined from the titration curves of chemical shift versus concentration ratio of lanthanide to Gly-Gly. The solution structure of the Ln-Gly-Gly complex was analyzed based upon the ~(13)C and ~1H lanthanide-induced shifts and the results show that in the complex Gly-Gly is coordinated to the lanthanide ion through the carboxyl oxygens with the backbone of the ligand in an extended state.     

Homo-dinuclear σ-alkynyl complexes: past, present and opportunities

Homo-dinuclear alkynyl complexes with a distinct metal–metal bond constitute a rapidly growing field, where the focus is placed on compounds based on ruthenium, molybdenum, tungsten or rhodium. Interesting characteristics of these complexes include paramagnetism, intense charge-transfer absorptions, tunable bridging ligands, which may not be easily accessible in mononuclear acetylide systems. These complexes have significant potential for use in both molecular electronics and supramolecular chemistry. In this short account, previous work in this area is assessed, and each of the major groups of complexes is discussed in terms of both the synthetic strategies and structural motifs.     

Revised Robertson's test theory of special relativity: Space-time structure and dynamics

The experimental testing of the Lorentz transformations is based on a family of sets of coordinate transformations that do not comply in general with the principle of equivalence of the inertial frames. The Lorentz and Galilean sets of transformations are the only member sets of the family that satisfy this principle. In the neighborhood of regular points of space-time, all members in the family are assumed to comply with local homogeneity of space-time and isotropy of space in at least one free-falling elevator, to be denoted as Robertson'sab initio rest frame [H. P. Robertson,Rev. Mod. Phys. 21, 378 (1949)].Without any further assumptions, it is shown that Robertson's rest frame becomes a preferred frame for all member sets of the Robertson family except for, again, Galilean and Einstein's relativities. If one now assumes the validity of Maxwell-Lorentz electrodynamics in the preferred frame, a different electrodynamics spontaneously emerges for each set of transformations. The flat space-time of relativity retains its relevance, which permits an obvious generalization, in a Robertson context, of Dirac's theory of the electron and Einstein's gravitation. The family of theories thus obtained constitutes a covering theory of relativistic physics.A technique is developed to move back and forth between Einstein's relativity and the different members of the family of theories. It permits great simplifications in the analysis of relativistic experiments with relevant Robertson's subfamilies. It is shown how to adapt the Clifford algebra version of standard physics for use with the covering theory and, in particular, with the covering Dirac theory.Part of this work was done at the Department of Physics, Utah State University, Logan, Utah 84322.     

The spherical-model limit in a random field

The spherical-model limitn of then-vector model in a random field, with either a statistically independent distribution or with long-range correlated random fields, is studied to demonstrate the correctness of the replica method in which then and replica limits limits are interchanged, provided the replica and thermodynamic limits are taken in the right order, in the case of long-range correlated random fields. A scaling form for the two-point correlation function relevant to the first-order phase transition below the lower critical dimensionality of the random system is also obtained.     

Amphiphilic cyclodextrin carriers embedding porphyrins: charge and size modulation of colloidal stability in heterotopic aggregates

The interaction between the anionic 5,10,15,20-tetrakis(4-sulfonatophenyl)-21H,23H-porphyrin (TPPS) and cationic vesicles formed by heptakis(2-omega-amino-O-oligo(ethylene oxide)-6-hexylthio)-beta-cyclodextrin (SC6CDNH2) has been investigated in detail through a combination of elastic light scattering (ELS), quasi-elastic light scattering (QELS), zeta potential measurements, and time-resolved fluorescence anisotropy. ELS experiments provided the first structural characterization of these cationic vesicles both in the absence and in the presence of TPPS porphyrin, modeling the system as a spherical particle described by a single thin shell form factor. The structure of mixed hetero-aggregates is modulated by charge and size of the two components as function of different porphyrin/cyclodextrin (CD) molar ratios. At the limiting molar ratio studied, the absolute value of zeta potential (/zeta/ = 12.5 mV) seems to be a reference value for the formation of stable colloidal CD vesicular aggregates at thermodynamic equilibrium. New insights on the structure of these heterotopic colloids have been obtained by analysis of rotational correlation times at different molar ratios exploiting time-resolved fluorescence anisotropy experiments. At high porphyrin loads, the anisotropy decays behave as monoexponentials and the rotational correlation times (1-2 ns) together with the r(0) values close to zero suggest the presence of small amounts of TPPS embedded in a hydrophobic environment either in monomeric or in aggregated form. At the lower porphyrin/CD molar ratios, the anisotropy decays exhibit a double-exponential behavior showing a predominant component with a slow rotational correlation time (20-25 ns) and limiting anisotropy values of approximately 0.15. This component has been assigned to molecules that are more stabilized onto the CD vesicles, that is, porphyrins embedded into the oligo-ethylene "wall" of the CD vesicles. Scanning near-field optical microscopy of the samples evaporated on glass surfaces gave further insights on the morphology and optical properties of these systems, confirming the embedding of TPPS on the vesicles and evidencing the role of the solvent.     

Molecular shape effects and quantum theory

Certain features of the chemist's molecular structure model, viz. size and shape, are retrieved even in the best non-adiabatic variational calculations thus far carried out for ground states of H ₂ ⁺ and H₂. Those features do not conflict with the full symmetry of exact molecular eigenstates, once they are properly understood as correlation effects.     

Potentiometric studies on the complexation of copper(II) by phenolic acids as discrete ligand models of humic substances

Studies on the complexation of copper(II) by phenolic acids, as ligand models of humic substances were done by potentiometry. The acids under study were: 3,4-dihydroxyhydrocinnamic acid or hydrocaffeic acid (1), 3,4-dihydroxyphenylacetic acid (2) and 3,4-dihydroxybenzoic acid or protocatechuic acid (3). Acidity constants of the ligands and the formation constants of metal-ligand complexes were evaluated by computer programs. The carboxylic group of the phenolic acids has different pK_a1 values, being the dissociation constants intrinsically related with the distance between the function and the aromatic nucleus. The results obtained allow concluding that acidity constants of the catechol moiety of the compounds are similar with pK_a2 and pK_a3 values between 9.47-9.41 and 11.55-11.70. The complexation properties of the three ligands towards copper(II) ion are quite similar, being the species found not different either in nature or stability. Although the model ligands have some structural differences no significant differences were found in their complexation properties towards copper(II). So, it can be postulated that complexation process is intrinsically related with the presence of a catechol group.