The cell wall of the filamentous anoxygenic phototrophic bacterium Oscillochloris trichoides.

The filamentous anoxygenic phototrophic bacterium Oscillochloris trichoides DG-6 has been studied, and it has been shown that there are no lipopolysaccharides on the cell surface. Fatty acids hydroxylated at the C3 position, amino sugars and phosphate-containing compounds characteristic of lipid A have also not been found. The genes encoding for proteins responsible for the synthesis of lipopolysaccharides and the genes for the transport system, usually localized in the outer membrane of Gram-negative bacteria, have not been detected in the genome. The rigid layer of the cell wall contains a peptidoglycan consisting of alanine, glutamine, ornithine and glycine, in the respective ratio 1.8 : 1.5 : 1.0 : 0.6. Thus, the investigated bacterium, Osc. trichoides, is a monoderm. The cell wall also contains a branched α-1,4-d-glucan with a repeating unit consisting of glucose residues linked by α-1→4 bonds (α-1→6 at the branching sites). Such polymers have not previously been reported in phototrophic bacteria.

The design of wrinkled microcapsules for enhancement of release rate.

Thermally expandable microcapsules (TEMs) with wrinkled shells are prepared by one-step suspension polymerization, allowing for encapsulation and controlled release of cargos. Wrinkling results from concurrent crosslinking of shell copolymers and vaporization of volatile reagents along with density increase upon polymerization. Through control of the vapor pressure of the reagents and systematic variation of the suspension composition, microcapsules with different degrees of wrinkling are prepared, ranging from locally dimpled to highly crumpled morphologies. The corresponding increase of the surface-to-volume ratio results in increasing release rate of encapsulated oil red dye as a model cargo. As such, in addition to shell thickness and radius, the wrinkleness provides an effective control parameter for adjusting the release rate. The wrinkled microcapsules with a large surface-to-volume ratio may find applications in drug delivery, chemicals scavenging, and self-healing materials.

Reconstruction of bacteriochlorophyll biosynthesis pathways in the filamentous anoxygenic phototrophic bacterium Oscillochloris trichoides DG-6 and evolution of anoxygenic phototrophs of the order Chloroflexales.

It is commonly accepted that green filamentous anoxygenic phototrophic (FAP) bacteria are the most ancient representatives of phototrophic micro-organisms. Modern FAPs belonging to the order Chloroflexales are divided into two suborders: Chloroflexineae and Roseiflexineae. Representatives of Roseiflexineae lack chlorosomes and synthesize bacteriochlorophyll a, whereas those of Chloroflexineae synthesize bacteriochlorophylls a and c and utilize chlorosomes for light harvesting. Though they constitute a small number of species, FAPs are quite diverse in their physiology. This bacterial group includes autotrophs and heterotrophs, thermophiles and mesophiles, aerobes and anaerobes, occupying both freshwater and halophilic environments. The anaerobic mesophilic autotroph Oscillochloris trichoides DG-6 is still not well studied in its physiology, and its evolutionary origin remains unclear. The goals of this study included identification of the reaction centre type of O. trichoides DG-6, reconstruction of its bacteriochlorophyll biosynthesis pathways, and determination of its evolutionary relationships with other FAPs. By enzymic and genomic analysis, the presence of RCII in O. trichoides DG-6 was demonstrated and the complete gene set involved in biosynthesis of bacteriochlorophylls a and c was established. We found that the bacteriochlorophyll gene sets differed between aerobic and anaerobic FAPs. The aerobic FAP genomes code oxygen-dependent AcsF cyclases, but lack the bchQ/bchR genes, which have been associated with adaptation to low light conditions in the anaerobic FAPs. A scenario of evolution of FAPs belonging to the order Chloroflexales is proposed.

Shifting Electronic Structure by Inherent Tension in Molecular Bottlebrushes with Polythiophene Backbones.

Bottlebrush macromolecules can be regarded as molecular tensile machines, where tension is self-generated along the backbone due to steric repulsion between densely grafted side chains. This intrinsic tension is amplified upon adsorption of bottlebrush molecules onto a substrate and increases with grafting density, side chain length, and strength of adhesion to the substrate. To investigate the effects of tension on the electronic structure of polythiophene (PT), bottlebrush macromolecules were prepared by grafting poly(n-butyl acrylate) (PBA) side chains from PT macroinitiators by atom transfer radical polymerization (ATRP). The fluorescence spectra of submonolayers of PT bottlebrushes were measured on a Langmuir-Blodgett (LB) trough with the backbone tension adjusted by controlling the side-chain length, surface pressure, and chemical composition of a substrate. The wavelength of maximum emission has initially red-shifted, followed by a blue-shift as the backbone tension increases from 0 to 2.5 nN, which agrees with DFT calculations. The red-shift is ascribed to an increase in the conjugation length due to the extension of the PT backbone at lower force regime (0-1.0 nN), while the blue-shift is attributed to deformations of bond lengths and angles in the backbone at higher force regime (1.0-2.5 nN).

Oribatid mites (Acari, Oribatida) of plain area of the Southern European Russia.

The paper is devoted to the fauna of oribatid mites (Acari: Oribatida) mostly of a plain area of the Southern European Russia. The most updated taxonomic list of oribatid mite taxa compiled from the original authors' data collected after sam- pling soil, nests and plumage of birds, as well as published sources is presented. It includes 256 species of oribatid mites belonging to 72 families. Twenty species and one family of oribatid mites are recorded for the first time at the research territory. The abundance of mites in the soil is also provided for selected species.

Anti-Arrhenius cleavage of covalent bonds in bottlebrush macromolecules on substrate.

Spontaneous degradation of bottlebrush macromolecules on aqueous substrates was monitored by atomic force microscopy. Scission of C ─ C covalent bonds in the brush backbone occurred due to steric repulsion between the adsorbed side chains, which generated bond tension on the order of several nano-Newtons. Unlike conventional chemical reactions, the rate of bond scission was shown to decrease with temperature. This apparent anti-Arrhenius behavior was caused by a decrease in the surface energy of the underlying substrate upon heating, which results in a corresponding decrease of bond tension in the adsorbed macromolecules. Even though the tension dropped minimally from 2.16 to 1.89 nN, this was sufficient to overpower the increase in the thermal energy (k(B)T) in the Arrhenius equation. The rate constant of the bond-scission reaction was measured as a function of temperature and surface energy. Fitting the experimental data by a perturbed Morse potential V = V(0)(1 - e(-ßx))(2) - fx, we determined the depth and width of the potential to be V(0) = 141 ± 19 kJ/mol and ß(-1) = 0.18 ± 0.03 Å, respectively. Whereas the V(0) value is in reasonable agreement with the activation energy E(a) = 80-220 kJ/mol of mechanical and thermal degradation of organic polymers, it is significantly lower than the dissociation energy of a C ─ C bond D(e) = 350 kJ/mol. Moreover, the force constant K(x) = 2ß(2)V(0) = 1.45 ± 0.36 kN/m of a strained bottlebrush along its backbone is markedly larger than the force constant of a C ─ C bond K(l) = 0.44 kN/m, which is attributed to additional stiffness due to deformation of the side chains.

Molecular tensile machines: intrinsic acceleration of disulfide reduction by dithiothreitol.

Significant tension on the order of 1 nN is self-generated along the backbone of bottlebrush macromolecules due to steric repulsion between densely grafted side chains. The intrinsic tension is amplified upon adsorption of bottlebrush molecules onto a substrate and increases with grafting density, side chain length, and strength of adhesion to the substrate. These molecules were employed as miniature tensile machines to study the effect of mechanical force on the kinetics of disulfide reduction by dithiothreitol (DTT). For this purpose, bottlebrush macromolecules containing a disulfide linker in the middle of the backbone were synthesized by atom transfer radical polymerization (ATRP). The scission reaction was monitored through molecular imaging by atomic force microscopy (AFM). The scission rate constant increases linearly with the concentration of DTT and exponentially with mechanical tension along the disulfide bond. Moreover, the rate constant at zero force is found to be significantly lower than the reduction rate constant in bulk solution, which suggests an acidic composition of the water surface with pH = 3.7. This work demonstrates the ability of branched macromolecules to accelerate chemical reactions at specific covalent bonds without applying an external force.

Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes.

The simultaneous, concerted transfer of electrons and protons--electron-proton transfer (EPT)--is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4'-biphenylphenol. Femtosecond transient absorption spectral measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H(+) is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck-Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated (+)H ─ B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state.

Electrostatic control of spin exchange between mobile spin-correlated radical pairs created in micellar solutions.

A series of photoinduced H-atom abstraction reactions between anthraquinone-2,6,-disulfonate, disodium salt (AQDS) and differently charged micellar substrates is presented. After a 248 nm excimer laser flash, the first excited triplet state of AQDS is rapidly formed and then quenched by abstraction of a hydrogen atom from the alkyl chain of the micelle surfactant, leading to a spin-correlated radical pair (SCRP). The SCRP is detected 500 ns after the laser flash using time-resolved (direct detection) electron paramagnetic resonance (TREPR) spectroscopy at X-band (9.5 GHz). By changing the charge on the surfactant headgroup from negative (sodium dodecyl sulfate, SDS) to positive (dodecyltrimethylammonium chloride, DTAC), TREPR spectra with different degrees of antiphase structure (APS) in their line shape were observed. The first derivative-like APS line shape is the signature of an SCRP experiencing an electron spin exchange interaction between the radical centers, which was clearly observable in DTAC micelles and absent in SDS micellar solutions. Solutions with surfactant concentrations well below the critical micelle concentration (cmc) or solutions where micellar formation had been disrupted (1:1 v/v CH(3)CN/H(2)O) also showed no APS line shapes in their TREPR spectra. These results support the conclusion that electrostatic forces between the sensitizer (AQDS) charge and the substrate (surfactant) headgroup charge are responsible for the observed effects. The results represent a new example of electrostatic control of a spin exchange interaction in mobile radical pairs.

Structural and pH dependence of excited state PCET reactions involving reductive quenching of the MLCT excited state of [RuII(bpy)2(bpz)]2+ by hydroquinones.

The proton-coupled electron transfer (PCET) reaction between the bpz-based photoexcited (3)MLCT state of [Ru(II)(bpy)(2)(bpz)](2+) (bpy = 2,2'-bipyridine, bpz = 2,2'-bipyrazine) and a series of substituted hydroquinones (H(2)Q) has been studied by transient absorption (TA) and time-resolved electron paramagnetic resonance (TREPR) spectroscopy at X-band. When the reaction is carried out in a CH(3)CN/H(2)O mixed solvent system with unsubstituted hydroquinone, the neutral semiquinone radical (4a) and its conjugate base, the semiquinone radical anion (4b), are both observed. Variation of the acid strength in the solvent mixture allows the acid/base dependence of the PCET reaction to be investigated. In solutions with very low acid concentrations, TREPR spectra exclusively derived from radical anion 4b are observed, while at very high acid concentrations, the spectrum is assigned to the protonated structure 4a. At intermediate acid concentrations, either a superposition of spectra is observed (slow exchange between 4a and 4b) or substantial broadening in the TREPR spectrum is observed (fast exchange between 4a and 4b). Variation of substituents on the H(2)Q ring substantially alter this acid/base dependence and provide a means to investigate electronic effects on both the ET and PT components of the PCET process. The TA results suggest a change in mechanism from PCET to direct ET quenching in strongly basic solutions and with electron withdrawing groups on the H(2)Q ring system. Changing the ligand on the Ru complex also alters the acid/base dependence of the TREPR spectra through a series of complex equilibria between protonated and deprotonated hydroquinone radicals and anions. The relative intensities of the signals from radical 4a versus 4b can be rationalized quantitatively in terms of these equilibria and the relevant pK(a) values. An observed equilibrium deuterium isotope effect supports the conclusion that the post-PCET HQ(•)/Q(•-) equilibrium is the most important in determining the 4a/4b ratio at early delay times.

Supramolecular photochemistry in beta-cyclodextrin hosts: a TREPR, NMR, and CIDNP investigation.

A systematic investigation of the photochemistry and ensuing radical chemistry of three guest ketones encapsulated in randomly methylated beta-cyclodextrin (beta-CD) hosts is reported. Dibenzyl ketone (DBK), deoxybenzoin (DOB), and benzophenone (BP) triplet states are rapidly formed after photolysis at 308 nm. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy, steady-state NMR spectroscopy, and time-resolved chemically induced nuclear polarization (TR-CIDNP) experiments were performed on the ketone/CD complexes and on the ketones in free solution for comparison. The major reactivity pathways available from these excited states are either Norrish I alpha-cleavage or H-atom abstraction from the interior of the CD capsule or the solvent. The DOB triplet state undergoes both reactions, whereas the DBK triplet shows exclusively alpha-cleavage and the BP triplet shows exclusively H-atom abstraction. Radical pairs are observed in beta-CDs by TREPR, consisting of either DOB or BP ketyl radicals with sugar radicals from the CD interior. The TREPR spectra acquired in CDs are substantially broadened due to strong spin exchange. The electron spin polarization mechanism is mostly due to S-T(0) radical pair mechanism (RPM) in solution but changes to S-T(-) RPM in the CDs due to the large exchange interaction. The TR-CIDNP results confirm the reactivity patterns of all three ketones, and DOB shows strong nuclear spin polarization from a novel rearrangement product resulting from the alpha-cleavage reaction.

The missing link between molecular triplets and spin-polarized free radicals: room temperature triplet states of nanocrystalline radical pairs.

Photochemical reactions of organic molecules in the solid state have an excellent potential in green chemistry technologies as they often proceed in high yields to give a single product without generating volatile organic solvent waste. While recent synthetic applications highlight the need for a better understanding of reaction mechanisms and kinetics, spectroscopic observations of excited states and short-lived intermediates in single crystals and powdered samples have been extremely challenging due to the high optical density and scattering power of single crystals and powdered samples. In this communication, we report the first direct observation of a radical pair triplet state by time-resolved electron paramagnetic resonance (TREPR) with nanocrystals of 4,4'-dimethoxy-dicumyl ketone (1OMe) suspended in water. Steady state irradiation of 1OMe had previously shown that reactions in dry powders and nanocrystalline suspensions proceed with high efficiency and chemoselectivity to generate 4,4'-dimethoxy-dicumene 2OMe by decarbonylation and radical coupling. The nanocrystalline suspensions were excited with an 25 ns laser pulse at 308 nm using a flow system within the cavity of a time-resolved EPR spectrometer. The resulting TREPR spectra showed strong spin polarization with enhanced absorption A and emission E signals in an AAAEEE pattern characteristic of a randomly oriented triplet with zero-field splitting parameters D = 243 G and E = 11 G as well as an isotropic exchange integral J = -45,000 G. The assignment of this spectrum to a radical pair triplet state was supported by measurements carried out in fluid solution and in frozen glasses, which allowed for the characterization of the free radical and the triplet excited molecular state of the starting ketone 1OMe.

Radical reactions with double memory of chirality (2MOC) for the enantiospecific synthesis of adjacent stereogenic quaternary centers in solution: cleavage and bonding faster than radical rotation.

The solution photochemistry of bis(phenylpyrrolidinonyl)ketones (R,R)-1b and (S,S)-1b exhibited a remarkably high memory of chirality. Stereospecific decarbonylation to products (R,R)-3b and (S,S)-3b, respectively, occurred with an ee of ca. 80%. The reaction is thought to occur along the single state manifold by sequential Norrish type-I alpha-cleavage, decarbonylation, and radical-radical combination in a time scale that is comparable to that required for the radical intermediate to expose its other enantiotopic face by rotation about an axis perpendicular to that of the p orbital (ca. 3-7 ps). The absolute configuration of a key intermediate and that of ketone (R,R)-1b were determined by single-crystal X-ray diffraction and the ee values of the photochemical products with the help of chiral shift reagent (+)-Eu(tfc)(3) and chiral LC-MS/MS. On the basis of the ee and de values at 25 degrees C, it could be determined that ca. 70% of the bond forming events occur with double memory of chirality, ca. 21% occur after rotation of one radical to form the meso product (R,S)-3b, and only 9% occur after double rotation to form the opposite enantiomer. This report represents the first example of a doubly enantiospecific Norrish type-I and decarbonylation reaction in solution and illustrates potentially efficient ways to obtain compounds with adjacent stereogenic quaternary centers.

Time-resolved EPR investigation of potential model systems for acrylate polymer main chain radicals based on esters of Kemp's tri-acid.

Methyl esters of Kemp's tri-acid and cyclohexanetricarboxylic acid are structurally similar to acrylate polymers, having the same functionalities and stereoregularities as poly(methylmethacrylate) and poly(methylacrylate), respectively. The photochemistry and free radicals from these model systems have been studied using time-resolved electron paramagnetic resonance spectroscopy with laser flash photolysis at 248 nm. Chemically induced electron spin polarization from the triplet mechanism (net emission) is observed. Well-resolved spectra are obtained at all temperatures for the model system radicals, which are determined to be in the slow motion condition, that is, there is no interconversion of chair conformations. The temperature dependence of the spectra is minimal; some hyperfine lines shift as the temperature increases, but without much broadening. Density functional theory calculations are presented and discussed in support of the experimental data.

Model systems for poly(acrylic acid) main-chain radicals based on the Kemp's triacid framework.

Kemp's triacid (KTA) and cyclohexane tricarboxylic acid (CTA) are small-molecule model systems for acrylic acid polymers, having the same functionalities and stereoregularities as isotactic poly(methacrylic acid) (PMAA) and poly(acrylic acid) (PAA), respectively. As part of an ongoing investigation of radicals produced by photolysis of acrylic polymers, the photochemistry and free radicals from the model systems have been studied using time-resolved EPR spectroscopy as a function of temperature and pH. Radicals are created by direct photolysis of the acids at 248 nm or by sensitized photo-oxidation using quinone triplet states at 308 nm. The two methods of radical production lead to different chemically induced electron spin polarization (CIDEP) patterns in the ensuing radicals, which are simulated and discussed. Well-resolved spectra are obtained at all temperatures for the model system radicals, which are determined to be in the slow motion condition. DFT calculations of the model system radicals are presented and discussed in support of the experimental data.

"Fatal adsorption" of brushlike macromolecules: high sensitivity of C-C bond cleavage rates to substrate surface energy.

Adsorption-induced degradation of brushlike macromolecules was monitored through molecular imaging by atomic force microscopy. The rate constant for C-C bond cleavage was shown to be extremely sensitive to the substrate surface energy. A few percent increase in the surface energy from 69.2 to 71.2 mN/m led to an order of magnitude increase of the scission rate. The absolute values of the rupture forces ranging from 2.57 to 2.47 nN are in agreement with previously calculated and measured values for stretching surface-tethered molecules.