Longer polyenyl cations in relation to soliton theory

The carotene-like polyenes decapreno-beta-carotene (C50), C54-beta-carotene (C54, first synthesis) and dodecapreno-beta-carotene (C60) with 15, 17 and 19 conjugated double bonds, respectively, were synthesized by double Wittig reactions. Introduction of a leaving group in allylic position failed, and cations were obtained by hydride elimination effected by i) triphenylcarbenium tetrafluoroborate-d15, prepared by a new method, or ii) treatment with trifluoroacetic acid-d. Deuterated reagents were employed for product analysis by 1H NMR. Parallel experiments were performed with beta,beta-carotene (C40). NIR spectra at room temperature and at -15 degrees C were employed for characterisation and stability studies of the cationic products. In CH2Cl2lambdamax in the 900-1350 nm region was recorded. NMR data for the cationic product of beta,beta-carotene obtained by the two new preparation methods were consistent with the two monocations previously characterised. The cationic products of the longer polyenes provided downfield-shifted, broadened signals, compatible with C50-monocation, mixed C54-mono- and dication and C60-dication. Combined NIR and NMR data suggest that the extent of charge delocalisation is limited by the maximum soliton width for cations obtained from linear polyenes with more than ca. 20 sp2-hybridized carbon atoms.     

Identification of an additional low-lying excited state of carotenoid radical cations

Carotenoids are the crucial pigments involved in photoprotection and in scavenging harmful free radicals in all living organisms. The underlying chemical processes are charge transfer and free radical reactions, both of them leading to carotenoid radical cation (Car*+) formation. Accurate knowledge of the molecular properties of Car*+ is thus a prerequisite for understanding of their function as photoprotective and antioxidant agents. Despite their fundamental importance in nonphotochemical quenching in green plants, only little is known about the Car*+ excited states and their dynamics. Our combined experimental and theoretical investigation employing femtosecond time-resolved pump-probe spectroscopy and quantum chemical calculations proves the existence of a second low-lying pipi* excited-state energetically below the well-known strongly allowed excited-state responsible for the intense absorption of Car*+ in the near-IR region. Hence, we suggest denoting the latter state as D3 state in the future. Our findings have also implications for nonphotochemical quenching in green plants, since direct quenching of chlorophyll excited states by Forster energy transfer to Car*+ is possible and efficient.     

“Delocalized model” in CNDO/2 framework. Application to reduction of 2-cyclohexenone

An attempts is made to develop the “delocalized model” in the CNDO/2 framework. This treatment is able to reproduce the results concerning the study of the factors influencing the 2-cyclohexenone reduction by hydride ions.     

Characterisation of carotenoid radical cations in liposomal environments: interaction with vitamin C

Pulse radiolysis was used to generate the radical cations of beta-carotene and two xanthophylls, zeaxanthin and lutein, in unilamellar vesicles of dipalmitoylphosphatidyl choline. The rate constants for the reaction (repair) of these carotenoid radical cations with the water-soluble vitamin C were found to be similar (approximately 1x10(7) M(-1) s(-1)) for beta-carotene and zeaxanthin and somewhat lower (approximately 0.5x10(7) M(-1) s(-1)) for lutein. The results are discussed in terms of the microenvironment of the carotenoids and suggest that for beta-carotene, a hydrocarbon carotenoid, the radical cation is able to interact with a water-soluble species even though the parent hydrocarbon carotenoid is probably entirely in the non-polar region of the liposome.     

Sorption properties of natural sorbent silica clay in relation to nickel cations

Sorption of nickel cations on natural sorbent silica clay was studied. The sorption isotherms were constructed and the quantitative characteristics of the process of sorption on a sorbent were determined.     

Location of the charge and geometric components of soliton waves in cations of unsymmetrical conjugated systems

A quantum-chemical investigation into the location and form of solitons in the cations of unsymmetrical polymethine systems was undertaken. It was shown that the introduction of one terminal group (electron-donating or electron-accepting) with intrinsic level outside the energy gap of the main chromophore leads to displacement of the charge and geometric waves without substantial distortion of their form; the introduction of an amino group with a high level for the unshared electron pair is accompanied by displacement of the solitons to the end of the conjugation chain, so that half of the soliton wave projects onto the molecule. In unsymmetrical polymethine cations with two nitrous groups the geometric soliton is closer to the less basic residue; replacement of one terminal residue by a methoxy group moves the position of the soliton to the end of the chromophore. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 4, pp. 221–227, July–August, 2008.     

Delocalized TCNQ stacks in nickel and copper tetraazamacrocyclic systems

New derivatives of formula [M(dieneN4)](TCNQ)3, M = Ni or Cu and dieneN4 = cis- or trans-hexamethyltetraazacyclotetradecadiene, have been obtained. The TCNQ units show electronic delocalization and formation of 1D stacks, with no direct interactions with the metal cations. The stack is not uniform and can be seen as formed by trimeric dianions (TCNQ)3(2-). The electronic delocalization favors the conductivity in these materials, which behave as good semiconductors. The crystal structures of the trans derivatives have been solved: [Ni(transdieneN4)](TCNQ)3, triclinic, P-1, a = 8.809(2) A, b = 10.896(2) A, c = 13.727(2) A, alpha = 103.04(1) degrees, beta = 101.23(2) degrees, gamma = 109.37(2) degrees, Z = 1; [Cu(trans-dieneN4)](TCNQ)3: triclinic, P-1, a = 7.872(1) A, b = 9.840(1) A, c = 14.819(1) A, alpha = 92.32(1) degrees, beta = 95.05(1) degrees, gamma = 95.66(1) degrees, Z = 1.     

Activity of a cationic carotenoid derivative in a mouse model of protoporphyria

Prior work using cell culture has shown that certain synthetic carotenoid derivatives are more effective than natural carotenoids in preventing photosensitized cell killing. These carotenoid derivatives are either cationic or are weak bases. We have now found that of one of these derivatives, the Girard's reagent T derivative of beta-apo-8'-carotenal (GRT-carotenal) decreases acute photosensitivity in a mouse model of protoporphyria. When GRT-carotenal was added to the diet of SKH1 mice, both GRT-carotenal and its metabolites accumulated in the skin of the mice. Protoporphyria was induced in SKH1 mice by adding collidine to their diet. When the porphyric mice were exposed to 400 nm light (2.6+/-0.1 mW cm(-2)) for a period of 2h, the skin on the backs of these animals increased in thickness. Increased vascularity also developed in the skin of the mouse ears. Animals, that were fed a diet containing both collidine and GRT-carotenal and then exposed to light, had significantly smaller increases in skin thickness and less prominent increases in the vascular pattern on their ears.     

Lipid binding to the carotenoid binding site in photosynthetic reaction centers

Lipid binding to the carotenoid binding site near the inactive bacteriochlorophyll monomer was probed in the reaction centers of carotenoid-less mutant, R-26 from Rhodobacter sphaeroides. Recently, a marked light-induced change of the local dielectric constant in the vicinity of the inactive bacteriochlorophyll monomer was reported in wild type that was attributed to structural changes that ultimately lengthened the lifetime of the charge-separated state by 3 orders of magnitude (Deshmukh, S. S.; Williams, J. C.; Allen, J. P.; Kalman, L. Biochemistry 2011, 50, 340). Here in the R-26 reaction centers, the combination of light-induced structural changes and lipid binding resulted in a 5 orders of magnitude increase in the lifetime of the charge-separated state involving the oxidized dimer and the reduced primary quinone in proteoliposomes. Only saturated phospholipids with fatty acid chains of 12 and 14 carbon atoms long were bound successfully at 8 °C by cooling the reaction center protein slowly from room temperature. In addition to reporting a dramatic increase of the lifetime of the charge-separated state at physiologically relevant temperatures, this study reveals a novel lipid binding site in photosynthetic reaction center. These results shed light on a new potential application of the reaction center in energy storage as a light-driven biocapacitor since the charges separated by ～30 ? in a low-dielectric medium can be prevented from recombination for hours.     

The Use of Bridging Ligand Substituents to Bias the Population of Localized and Delocalized Mixed-Valence Conformers in Solution

The electronic structure and associated spectroscopic properties of ligand-bridged, bimetallic ‘mixed-valence’ complexes of the general form {M}(μ-B){M⁺} are dictated by the electronic couplings, and hence orbital overlaps, between the metal centers mediated by the bridge. In the case of complexes such as [{Cp*(dppe)Ru}(μ-C≡CC₆H₄C≡C){Ru(dppe)Cp*}]⁺, the low barrier to rotation of the half-sandwich metal fragments and the arylene bridge around the acetylene moieties results in population of many energy minima across the conformational energy landscape. Since orbital overlap is also sensitive to the particular mutual orientations of the metal fragment(s) and arylene bridge through a Karplus-like relationship, the different members of the population range exemplify electronic structures ranging from strongly localized (weakly coupled Robin-Day Class II) to completely delocalized (Robin-Day Class III). Here, we use electronic structure calculations with the hybrid density functional BLYP35-D3 and a continuum solvent model in combination with UV-vis-NIR and IR spectroelectrochemical studies to show that the conformational population in complexes [{Cp*(dppe)Ru}(μ-C≡CArC≡C){Ru(dppe)Cp*]⁺, and hence the dominant electronic structure, can be biased through the steric and electronic properties of the diethynylarylene (Ar) moiety (Ar=1,4-C₆H₄, 1,4-C₆F₄, 1,4-C₆H₂-2,5-Me₂, 1,4-C₆H₂-2,5-(CF₃)₂, 1,4-C₆H₂-2,5-ⁱPr₂).     

Tetrafluoroborate Selective Electrodes on the Basis of Cations with Delocalized Charge

Screening of active substances based on styryl and trimethine cyanine dyes was carried out to prepare tetrafluoroborate ion‐selective electrodes. Correlations between the nature of the organic cation (pK_a) and working pH ranges of the sensors were studied. New tetrafluoroborate‐selective PVC membrane electrodes based on an active substance formed by the ion pair of 2‐(n‐ethylcarbazol‐3)‐ethenyl‐1,3,3‐trimethyl‐3H‐indolium and 2‐[3‐(5,6‐dimethyl‐3‐nonyl‐1,3‐benzothiazol‐2(3H)‐ylidene)propenyl]‐5,6‐dimethyl‐3‐nonyl‐1,3‐benzothiazolium with tetrafluoroborate ion were developed. The electrodes are non‐sensitive to pH in the range of 2–8 and can be used for boron determination in acidic media of 6–7 mol L^?1 H₂SO₄. The developed sensor was successfully applied for the determination of B₂O₃ in CdS(Se) nanocrystal‐doped glasses.     

Laboratory spectra of cold gas phase polycyclic aromatic hydrocarbon cations, and their possible relation to the diffuse interstellar bands

A novel laboratory technique is described, combining the use of supersonic expansion, laser excitation and small aromatic-rare gas van der Waals (vdW) clusters properties, which was developed to access the electronic absorption spectra of the polycyclic aromatic hydrocarbon (PAH) cations in the visible. It consists in preparing vdW complexes of the PAH molecule with a rare gas in a molecular beam, to photoionize it by resonant selective two-photon ionization, then to photodissociate this ionic complex by means of a delayed laser pulse in a time-of-flight mass spectrometer. The method is illustrated by presenting the visible spectra of the Naphthalene, Phenanthrene, Fluorene and Phenylacetylene cations. Such spectra can be unambiguously compared to the astronomical spectra of reddened stars, which exhibit the so-called diffuse interstellar bands (DIBs) in absorption. An interesting feature of the technique is its ability to measure the absolute absorption cross-sections. The large values of the oscillator strengths of the transitions, which are derived, are discussed in the astrophysical context which consists in considering that the PAH cations could be carriers for some of the DIBs.     

Paradigms and paradoxes: revisiting the relation of oxidation state and acidity of polyhydride cations

Structural Chemistry - Nearly four decades ago, we published a simple chemical regularity: the proton affinity of MHa is higher than that of MHb when “a” is greater than...     

Luminescence from thermally oxidized model amides in relation to nylon 66 degradation

Fluorescence and phosphorescence are observed following the mild thermal oxidation of two model compounds for nylon 66. Both emissions are remarkably similar in structure and in wavelength location to the corresponding emissions normally observed from the commercial polymer. Although the fluorescence could not be characterized, the phosphorescence exhibits several features which are clearly consistent with that of a nπ* carbonyl emission. The role of carbonyl groups in the thermal and photochemical oxidation of nylon 66 is discussed.     

Thioglycolic acid grafted onto silica gel and its properties in relation to extracting cations from ethanolic solution determined by calorimetric technique

Thioglycolic acid was immobilized onto silica gel surface using 3-aminopropyltrimethoxysilane as precursor silylating agent to yield silica. The amount of thioglycolic acid immobilized was 1.03 mmol per gram of silica. This new surface displayed a chelating moiety containing nitrogen, sulfur, and oxygen basic centers which are potentially capable of extracting cations from ethanolic solution, such as MCl3 ( M=Fe, Cr, and Mo). This process of extraction was carried out by the batch method when similar chemisorption isotherms were observed for all cations. The data were adjusted to a modified Langmuir equation. The sequence of the maximum retention capacity was Cr(III) > Mo(III) > Fe(III). The same adsorption was determined by calorimetric titration and the enthalpic values of -35.75 +/- 0.02, 32.90 +/- 0.15, and -84.08 +/- 0.12 kJmol(-1) for chromium, molybdenum, and iron, respectively, were obtained. From the calculated Gibbs free energy -23.4 +/- 0.2, -27.2 +/- 0.2, and -32.7 +/- 0.3 kJmol(-1), the variations in entropy obtained were 42 +/- 1, 201 +/- 1, 172 +/- 1 JK(-1)mol(-1) for the same sequence. All thermodynamic values are in agreement with the spontaneity of the proposed cation-basic center interactions for these chelating processes.     

Delocalized electronic behavior observed in transition metal oxide clusters under strong-field excitation

Heterogeneously composed clusters are exposed to intensity resolved, 100 fs laser pulses to reveal the energy requirements for the production of the high charge states of both metal and nonmetal ions. The ionization and fragmentation of group V transition metal oxide clusters are here examined with laser intensities ranging nearly four orders in magnitude (～3 × 10(11) W/cm(2) to ～2 × 10(15) W/cm(2)) at 624 nm. The ionization potentials of the metal atoms are measured using both multiphoton ionization and tunneling ionization models. We demonstrate that the intensity selective scanning method can be utilized to measure the low ionization potentials of transition metals (～7 eV). The high charge states demonstrate an enhancement in ionization that is three orders of magnitude lower in laser intensity than predicted for the atomic counterparts. Finally, the response from the various metals and the oxygen is compared to elucidate the mechanism of enhanced ionization that is observed. Specifically, the sequence of ion appearances demonstrates delocalized electron behavior over the entire cluster.     

掺杂剂对聚乙炔中孤子的影响

本文用半经验CNDO/2量子化学计算方法研究了各种掺杂剂对聚乙炔中孤子性质的影响。掺杂剂的存在使孤子的宽度变小, 且p型掺杂剂比n型掺杂剂的影响更大, 这主要是由于掺杂剂与聚乙炔链之间的电荷转移量不同造成的。