Dispersion of the local parameters of quasilocalized low-frequency vibrational modes in a low-temperature glass: direct observation via single-molecule spectroscopy

Spectra of single tetra-tert-butylterrylene chromophore molecules embedded in an amorphous polyisobutylene matrix as microprobes were recorded. The individual temperature dependences of the spectral linewidths for the same single molecules (SMs) in a broad temperature interval (1.6 < T < 40 K) have been measured. This enabled us to separate the contributions of tunneling two-level systems and quasilocalized low-frequency vibrational modes (LFMs) to the observed linewidths. The analysis of the T dependences yields the values of LFM frequencies and SM-LFM coupling constants for the LFMs in the local environment of a given chromophore. Pronounced distributions of the observed parameters of LFMs were found. This result can be regarded as the first direct experimental proof of the localized nature of LFMs in glasses.     

Swallowtail porphyrins: synthesis, characterization and incorporation into porphyrin dyads

The incorporation of symmetrically branched tridecyl ("swallowtail") substituents at the meso positions of porphyrins results in highly soluble building blocks. Synthetic routes have been investigated to obtain porphyrin building blocks bearing 1-4 swallowtail groups. Porphyrin dyads have been synthesized in which the zinc or free base (Fb) porphyrins are joined by a 4,4'-diphenylethyne linker and bear swallowtail (or n-pentyl) groups at the nonlinking meso positions. The swallowtail-substituted Zn(2)- and ZnFb-dyads are readily soluble in common organic solvents. Static absorption and fluorescence spectra and electrochemical data show that the presence of the swallowtail groups slightly raises the energy level of the filled a(2u)(pi) HOMO. EPR studies of the pi-cation radicals of the swallowtail porphyrins indicate that the torsional angle between the proton on the alkyl carbon and p-orbital on the meso carbon of the porphyrin is different from that of a porphyrin bearing linear pentyl groups. Regardless, the swallowtail substituents do not significantly affect the photophysical properties of the porphyrins or the electronic interactions between the porphyrins in the dyads. In particular, time-resolved spectroscopic studies indicate that facile excited-state energy transfer occurs in the ZnFb dyad, and EPR studies of the monocation radical of the Zn(2)-dyad show that interporphyrin ground-state hole transfer is rapid.     

The effect of polymers on the phase behavior of balanced microemulsions: diblock-copolymer and comb-polymers

The effect of some amphipilic diblock-copolymers and comb-polymers on a balanced Winsor III microemulsion system is investigated with the quaternary system n-octyl-β-d-glucoside/1-octanol/n-octane/D₂O as basis system. The diblock-copolymers are polyethyleneoxide-co-polydodecenoxide (PEO _x PEDODO _y ) and polyethyleneoxide-co-polybutyleneoxide (PEO _x PEBU _y ), constituted of a straight chain hydrophilic part and a bulky hydrophobic part. Addition of the diblock-copolymer leads to an enhancement of the swelling of the middle phase by uptake of water and oil; a maximum boosting factor of 6 was obtained for PEO₁₁₁PEDODO₂₅. Nuclear magnetic resonance diffusometry yields the self-diffusion coefficients of all the components in the system. The diffusion experiments provide information on how the microstructure of the bicontinuous microemulsion changes upon addition of the polymers. The reduced self-diffusion coefficients of water and oil are sensitive to the type of polymer that is incorporated in the film. For the diblock-copolymers, as mainly used here, the reduced self-diffusion coefficient of oil and water will respond to how the polymer bends the film. When the film bends away from water, the reduced self-diffusion of the water will increase, whereas the oil diffusion will decrease due to the film acting as a barrier, hindering free diffusion. The self-diffusion coefficient of the polymer and surfactant are similar in magnitude and both decrease slightly with increasing polymer concentration.     

Synthese und Charakterisierung neuer intramolekular stickstoffstabilisierter Organoaluminium‐ und Organogalliumalkoxide

Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me₂Al{μ‐O(CH₂)₃NMe₂}]₂ ( 1a ), Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6 ( 2a ), [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]₂ ( 3a ) and [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]₂ ( 4 ) are formed by reacting equimolar amounts of AlMe₃ and Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH₂OH, or (S)‐PhCH₂NHCH(i‐Pr)CH₂OH, respectively. An excess of AlMe₃ reacts with Me₂N(CH₂)₂OH, Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH₂OH producing the “pick‐a‐back” complexes [Me₂AlO(CH₂)₂NMe₂](AlMe₃) ( 5 ), [Me₂AlO(CH₂)₃NMe₂](AlMe₃) ( 1b ), [Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6](AlMe₃)₂ ( 2b ), and [(S)‐Me₂AlOCH₂CH(i‐Pr)NH‐i‐Pr](AlMe₃) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 6 ) and [{CH₂=C(CH₃)}(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 8 ) are to obtain from Me₂AlCl and Me₂N(CH₂)₂OH and from [Cl₂Al{μ‐O(CH₂)₂NMe₂}]₂ ( 7 ) and CH₂=C(CH₃)MgBr, respectively. The analogous dimethylgallium alkoxides [Me₂Ga{μ‐O(CH₂)₃NMe₂}]₂ ( 9 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]_n ( 10 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]_n ( 11 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)N(Me)CH₂Ph}]_n ( 12 ) and [(S)‐Me₂Ga{μ‐OCH₂(C₄H₇NHCH₂Ph)}]_n ( 13 ) result from the equimolar reactions of GaMe₃ with the corresponding alcohols. The new compounds were characterized by elemental analyses, ¹H‐, ¹³C‐ and ²⁷Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction.     

P840-Reaction Centers from Chlorobium tepidum–Quinone Analysis and Functional Reconstitution into Lipid Vesicles

Membranes of Chlorobium tepidum contain about 35, 45 and2–10 molecules of menaquinone-7, chlorobium quinone (1′-oxo-menaquinone-7) and of the polar menaquinone (probably 1′-OH-menaquinone-7) per reaction center, respectively. None of these quinones was retained during the isolation of P840-reaction centers beyond the detection limit of about 0.2 quinones per reaction center, neither in the core complex nor in functionally intact reaction center preparations. The latter is shown to catalyze the formation of an electrochemical proton gradient in the presence of ascorbate and phenazinium methosulfate, when it is incorporated into lipid vesicles.     

Different modes of aggregation in organoaluminium and -gallium hydroxylamides

The organoaluminium and -gallium hydroxylamides (Me2GaONMe2)2, (tBu2AlONMe2)2, (tBu2GaONMe2)2 and (Me2AlONiPr2)2 have been prepared by the reaction of the hydroxylamines Me2NOH and iPr2NOH with the trialkylmetal compounds trimethylgallium, tri-tbutylaluminium and tri-tbutylgallium, respectively. All compounds have been characterised by NMR spectroscopy (1H, 13C, 15N, 17O and 27Al), by mass spectrometry and elemental analyses. The crystal structures of the four compounds have been determined, showing that they all form dimers but with different modes of aggregation: (Me2GaONMe2)2 has a Ga2O2N2 six-membered ring, (tBu2AlONMe2)2 and (Me2AlONiPr2)2 have Al2O2 four-membered rings, (tBu2GaONMe2)2 forms a Ga2O2N five-membered ring.     

Chemo- and periselectivity in the addition of [OsO2(CH2)2] to ethylene: a theoretical study

Quantum chemical calculations by using density functional theory at the B3LYP level have been carried out to elucidate the reaction course for the addition of ethylene to [OsO2(CH2)2] (1). The calculations predict that the kinetically most favorable reaction proceeds with an activation barrier of 8.1 kcal mol(-1) via [3+2] addition across the O=Os=CH2 moiety. This reaction is -42.4 kcal mol(-1) exothermic. Alternatively, the [3+2] addition to the H2C=Os=CH2 fragment of 1 leads to the most stable addition product 4 (-72.7 kcal mol(-1)), yet this process has a higher activation barrier (13.0 kcal mol(-1)). The [3+2] addition to the O=Os=O fragment yielding 2 is kinetically (27.5 kcal mol(-1)) and thermodynamically (-7.0 kcal mol(-1)) the least favorable [3+2] reaction. The formal [2+2] addition to the Os=O and Os=CH2 double bonds proceeds by initial rearrangement of 1 to the metallaoxirane 1 a. The rearrangement 1-->1 a and the following [2+2] additions have significantly higher activation barriers (>30 kcal mol(-1)) than the [3+2] reactions. Another isomer of 1 is the dioxoosmacyclopropane 1 b, which is 56.2 kcal mol(-1) lower in energy than 1. The activation barrier for the 1-->1 b isomerization is 15.7 kcal mol(-1). The calculations predict that there are no energetically favorable addition reactions of ethylene with 1 b. The isomeric form 1 c containing a peroxo group is too high in energy to be relevant for the reaction course. The accuracy of the B3LYP results is corroborated by high level post-HF CCSD(T) calculations for a subset of species.     

Effect of non-planarity on the spin distribution in the radical anions containing the stilbene or the azobenzene π-system: An ESR and ENDOR Study

The radical anions of 5H-dibenzo[a,d]cycloheptene ( 9 ), 5 H-dibenzo[c,f][1,2]diazepine ( 10 ), 5,6-dihydrodibenzo[a,e]cyclooctene ( 11 ), 5,6-dihydrodibenzo[c,g][1,2]diazocine ( 12 ), and (E)-2,2,5,5-tetramethyl-3,4-diphenylhex-3-ene ( 13 ) were characterized by ESR and ENDOR spectroscopy. Their hyperfine data were compared with those previously reported for radical anions also containing the stilbene or the azobenzene π-system. Whereas the π-spin distribution in the radical anions of the stilbene series is only moderately sensitive to deviations of the π-system from planarity, the radical anions of the azobenzene series respond to steric strain by shifting the π-spin population from the benzene rings to the azo group. This finding is impressively demonstrated by the similar hyperfine data for 9 ^{· ?} and 11 ^{· ?} which contrast with the strongly highly hindered 13 ^{· ?}. A. plausible interpretation is readily provided by the electron affinities of the constituent π-moieties in stilbene and azobenzene. While those of benzene and ethene are both comparatively low, the azo group has a considerably higher electron affinity.     

Macrophage-targeting oligopeptides from Mortierella alpina

The realm of natural products of early diverging fungi such as Mortierella species is largely unexplored. Herein, the nonribosomal peptide synthetase (NRPS) MalA catalysing the biosynthesis of the surface-active biosurfactants, malpinins, has been identified and biochemically characterised. The investigation of the substrate specificity of respective adenylation (A) domains indicated a substrate-tolerant enzyme with an unusual, inactive C-terminal NRPS module. Specificity-based precursor-directed biosynthesis yielded 20 new congeners produced by a single enzyme. Moreover, MalA incorporates artificial, click-functionalised amino acids which allowed postbiosynthetic coupling to a fluorophore. The fluorescent malpinin conjugate penetrates mammalian cell membranes via an phagocytosis-mediated mechanism, suggesting Mortierella oligopeptides as carrier peptides for directed cell targeting. The current study demonstrates substrate-specificity testing as a powerful tool to identify flexible NRPS modules and highlights basal fungi as reservoir for chemically tractable compounds in pharmaceutical applications.

Specificity profiling of a nonribosomal peptide synthetase of an early diverging fungus revealed high substrate flexibility. Feeding studies with click-functionalised amino acids enabled the production of fluorescent peptides targeting macrophages.     

A Polyclonal Selex Aptamer Library Directly Allows Specific Labelling of the Human Gut Bacterium Blautia producta without Isolating Individual Aptamers

Recent studies have demonstrated that changes in the abundance of the intestinal bacterium Blautia producta, a potential probiotic, are closely associated with the development of various diseases such as obesity, diabetes, some neurodegenerative diseases, and certain cancers. However, there is still a lack of an effective method to detect the abundance of B. producta in the gut rapidly. Especially, DNA aptamers are now widely used as biometric components for medical testing due to their unique characteristics, including high chemical stability, low production cost, ease of chemical modification, low immunogenicity, and fast reproducibility. We successfully obtained a high-affinity nucleic acid aptamer library (B.p-R14) after 14 SELEX rounds, which efficiently discriminates B. producta in different analysis techniques including fluorometric suspension assays or fluorescence microscopy from other major gut bacteria in complex mixtures and even in human stool samples. These preliminary findings will be the basis towards aptamer-based biosensing applications for the fast and reliable monitoring of B. producta in the human gut microbiome.