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801.
802.
803.
M. Reisinger D. A. Lightner 《Journal of inclusion phenomena and macrocyclic chemistry》1985,3(4):479-485
Intramolecularly hydrogen-bonded, bichromophoric tetrapyrrole pigments, bilirubin-IX and mesobilirubin-XIII, adopt either of two enantiomeric conformations which are in dynamic equilibrium in solution. InpH 8 aqueous sodium deoxycholate solutions, chiral micelles preferentially select one conformational enantiomer, and the solutions exhibit a bisignate circular dichroism Cotton effect in the vicinity of the bilirubin long wavelength electronic transition. Exciton coupling theory indicates a predominance of the left-handed (or negative) chirality bilirubin conformational enantiomer. 相似文献
804.
Dr. Fan Xie Dr. Wenhao Sun Dr. Pablo Pinacho Prof. Dr. Melanie Schnell 《Angewandte Chemie (International ed. in English)》2023,62(14):e202218539
The initial stages of the gas-phase nucleation between CO2 and monoethanolamine were investigated via broadband rotational spectroscopy with the aid of extensive theoretical structure sampling. Sub-nanometer-scale aggregation patterns of monoethanolamine-(CO2)n, n=1–4, were identified. An interesting competition between the monoethanolamine intramolecular hydrogen bond and the intermolecular interactions between monoethanolamine and CO2 upon cluster growth was discovered, revealing an intriguing CO2 binding priority to the hydroxyl group over the amine group. These findings are in sharp contrast to the general results for aqueous solutions. In the quinary complex, a cap-like CO2 tetramer was observed cooperatively surrounding the monoethanolamine. As the cluster approaches the critical size of new particle formation, the contribution of CO2 self-assembly to the overall stability increases. 相似文献
805.
Nathan Downs Nawin Raj Jennifer Vanos Alfio V. Parisi Harry Butler Ravinesh Deo Damien Igoe Benjamin Dexter Melanie Beckman-Downs Joanna Turner Stijn Dekeyser 《Photochemistry and photobiology》2023,99(4):1193-1207
Current shading strategies used to protect outdoor playgrounds from harmful solar radiation include the placement of artificial cloth weaves or permanent roofing over a playground site, planting trees in proximity to playground equipment, and using vegetation or surface texture variations to cool playground surfaces. How and where an artificial shade structure is placed or a tree is planted to maximize the shade protection over specific playground areas, requires careful assessment of local seasonal sun exposure patterns. The Playground Shade Index (PSI) is introduced here as a design metric to enable shade and solar ultraviolet exposure patterns to be derived in an outdoor space using conventional aerial views of suburban park maps. The implementation of the PSI is demonstrated by incorporating a machine learning design tool to classify the position of trees from an aerial image, thus enabling the mapping of seasonal shade and ultraviolet exposure patterns within an existing 7180 m2 parkland. This is achieved by modeling the relative position of the sun with respect to nearby buildings, shade structures, and the identified evergreen and deciduous tree species surrounding an outdoor playground. 相似文献
806.
Walter Alabiso Bernhard Sölle David Reisinger Dr. Gema Guedes de la Cruz Dr. Max Schmallegger Dr. Thomas Griesser Dr. Elisabeth Rossegger Priv.-Doz. Dr. Sandra Schlögl 《Angewandte Chemie (International ed. in English)》2023,62(45):e202311341
Chemical amplification is a well-established concept in photoresist technology, wherein one photochemical event leads to a cascade of follow-up reactions that facilitate a controlled change in the solubility of a polymer. Herein, we transfer this concept to dynamic polymer networks to liberate both catalyst and functional groups required for bond exchange reactions under UV irradiation. For this, we exploit a photochemically generated acid to catalyse a deprotection reaction of an acid-labile tert-butoxycarbonyl group, which is employed to mask the hydroxy groups of a vinyl monomer. At the same time, the released acid serves as a catalyst for thermo-activated transesterifications between the deprotected hydroxy and ester moieties. Introduced in an orthogonally cured (450 nm) thiol-click photopolymer, this approach allows for a spatio-temporally controlled activation of bond exchange reactions, which is crucial in light of the creep resistance versus reflow ability trade-off of dynamic polymer networks. 相似文献
807.
F. Kurth T. Gudjons B. Hilbert T. Reisinger G. Werth A. -M. Mårtensson-Pendrill 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1995,34(4):227-232
We have observed dark resonances in theA-type level structure, formed by the 4S1/2 ground state, the 4P1/2 excited state and the low lying metastable 3D3/2 state in the Calcium ion, confined in a Paul radio-frequency trap. These Doppler-free and potentially very narrow resonances were used to determine the magnetic dipole hyperfine interaction constant A for the 4P1/2 and 3D3/2 state of43Ca+, giving –142(8) MHz and –48.3(1.6) MHz, respectively. From measurements of the P-D (E1) and S-D (E2) transition wavelength in a mixture of43Ca+ and40Ca+ we determined the isotope shifts of these lines. 相似文献
808.
We have proposed that DNA-mediated charge transport (CT) is gated by base motions, with only certain base conformations being CT-active; a CT-active conformation can be described as a domain, a transiently extended pi-orbital defined dynamically by DNA sequence. Here, to explore these CT-active conformations, we examine the yield of base-base CT between photoexcited 2-aminopurine (Ap*) and guanine in DNA in rigid LiCl glasses at 77 K, where conformational rearrangement is effectively eliminated. Duplex DNA assemblies (35-mers) were constructed containing adenine bridges Ap(A)nG (n = 0-4). The yield of CT was monitored through fluorescence quenching of Ap* by G. We find, first, that the emission intensity of Ap* in all DNA duplexes increases dramatically upon cooling and becomes comparable to free Ap*. This indicates that all quenching of Ap* in duplex DNA is a dynamic process that requires conformational motion of the DNA bases. Second, DNA-mediated CT between Ap* and G is not observed at 77 K; rather than hindering the ability of DNA to transport charge, conformational motion is required. Moreover, the lack of DNA-mediated CT at 77 K, even through the shortest bridge, suggests that the static structures adopted upon cooling do not represent optimum CT-active conformations. These observations are consistent with our model of conformationally gated CT. Through conformational motion of the DNA bases, CT-active domains form and break-up transiently, both facilitating and limiting CT. 相似文献
809.
A convenient large-scale preparation of bilirubin-XIIIα from IXα via acid-catalyzed isomerization is described. 相似文献
810.
Love JA Sanford MS Day MW Grubbs RH 《Journal of the American Chemical Society》2003,125(33):10103-10109
A series of ruthenium olefin metathesis catalysts of the general structure (H(2)IMes)(PR(3))(Cl)(2)Ru=CHPh (H(2)IMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) have been prepared; these complexes are readily accessible in two steps from commercially available (H(2)IMes)(PCy(3))(Cl)(2)Ru=CHPh. Their phosphine dissociation rate constants (k(1)), relative rates of phosphine reassociation, and relative reaction rates in ring-opening metathesis polymerization (ROMP) and ring-closing metathesis (RCM) have been investigated. The rates of phosphine dissociation (initiation) from these complexes increase with decreasing phosphine donor strength. Complexes containing a triarylphosphine exhibit dramatically improved initiation relative to (H(2)IMes)(PCy(3))(Cl)(2)Ru=CHPh. Conversely, phosphine reassociation shows no direct correlation with phosphine electronics. In general, increased phosphine dissociation leads to faster olefin metathesis reaction rates, which is of direct significance to both organic and polymer metathesis processes. 相似文献