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71.
Dr. Lara Martinez-Fernandez Dr. Krishna Gavvala Dr. Rajans Sharma Prof. Pascal Didier Dr. Ludovic Richert Dr. Javier Segarra Martì Dr. Mattia Mori Prof. Yves Mely Dr. Roberto Improta 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7375-7386
Thienoguanosine (thG) is an isomorphic analogue of guanosine with promising potentialities as fluorescent DNA label. As a free probe in protic solvents, thG exists in two tautomeric forms, identified as the H1, being the only one observed in nonprotic solvents, and H3 keto–amino tautomers. We herein investigate the photophysics of thG in solvents of different polarity, from water to dioxane, by combining time-resolved fluorescence with PCM/TD-DFT and CASSCF calculations. Fluorescence lifetimes of 14.5–20.5 and 7–13 ns were observed for the H1 and H3 tautomers, respectively, in the tested solvents. In methanol and ethanol, an additional fluorescent decay lifetime (≈3 ns) at the blue emission side (λ≈430 nm) as well as a 0.5 ns component with negative amplitude at the red edge of the spectrum, typical of an excited-state reaction, were observed. Our computational analysis explains the solvent effects observed on the tautomeric equilibrium. The main radiative and nonradiative deactivation routes have been mapped by PCM/TD-DFT calculations in solution and CASSCF in the gas phase. The most easily accessible conical intersection, involving an out-of plane motion of the sulfur atom in the five-membered ring of thG, is separated by a sizeable energy barrier (≥0.4 eV) from the minimum of the spectroscopic state, which explains the large experimental fluorescence quantum yield. 相似文献
72.
Dr. Tatsuya Nishimaru Dr. Kohei Eto Dr. Keita Komine Prof. Dr. Jun Ishihara Prof. Dr. Susumi Hatakeyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7927-7934
The first total synthesis of lajollamycin B, a structurally novel nitro-tetraene spiro-β-lactone/γ-lactone antibiotic, is described. The convergent synthesis involves the construction of the C8′–C11′ nitrodienylstannane and its coupling with the segment prepared from the C1′–C7′ ω-iodoheptadienoic acid and the right-hand heterocyclic fragment, which has been utilized for our previous syntheses of oxazolomycin A. The revision of the geometry of the terminal Δ10′, 11′-double bond from E to Z is also described for the structure of natural lajollamycin B. 相似文献
73.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(9):1045-1052
A new tantalum phosphate, tridecasodium distrontium ditantalum nonaphosphate, Na13Sr2Ta2(PO4)9, was prepared using the high‐temperature flux method. The structure can be described as a three‐dimensional open framework containing isolated [TaV2(PO4)9]17− units that are interlocked by Na and Sr ions. Band structure studies by the first‐principles method revealed that Na13Sr2Ta2(PO4)9 is an insulator with an indirect band gap of 4.78 eV, which makes it suitable as a luminescent host matrix. A series of solid solutions, i.e. Na13Sr2–xTa2(PO4)9:xDy3+ (x = 0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.12 and 0.14), were prepared and their photoluminescence properties studied. Under 350 nm light excitation, these emit two typical emissions of the Dy3+ ion, i.e. the 4F9/2→6H15/2 transition centred at 476 nm and the 4F9/2→6H13/2 transition centred at 570 nm. 相似文献
74.
Denis Serre 《Comptes Rendus Mecanique》2018,346(3):175-183
In this review paper, we discuss helicity from a geometrical point of view and see how it applies to the motion of a perfect fluid. We discuss its relation with the Hamiltonian structure, and then its extension to arbitrary space dimensions. We also comment about the existence of additional conservation laws for the Euler equation, and its unlikely integrability in Liouville's sense. 相似文献
75.
Consider an elastic thin three-dimensional body made of a periodic distribution of elastic inclusions. When both the thickness of the beam and the size of the heterogeneities tend simultaneously to zero the authors obtain three different one-dimensional models of beam depending upon the limit of the ratio of these two small parameters. 相似文献
76.
Álvaro Santana-Mayor Ruth Rodríguez-Ramos Bárbara Socas-Rodríguez Miguel Ángel Rodríguez-Delgado Giovanni D'Orazio 《Electrophoresis》2020,41(20):1768-1775
The separation of 11 phthalic acid ester (PAEs) was carried out by nano-liquid chromatography coupled to ultraviolet and MS detection. Preliminary experiments were achieved in order to select suitable stationary phases and chromatographic conditions. The baseline separation was obtained, for all compounds, with an XBridgeTM C18 column in less than 15 min, working in step gradient mode. The sensitivity of the method was improved by on-column focusing. PAEs were extracted from alcoholic and nonalcoholic beverages using vortex-assisted emulsification dispersive liquid–liquid microextration and natural deep eutectic solvents. The whole method was validated in terms of linearity, sensitivity, precision, recovery, and repeatability. Combination of both off-line sample preparation preconcentration and large injection volume led to obtain LOQs in the range 5–47 ng/mL. The developed nano-LC-UV method was extended to MS detection to confirm the presence of PAEs in some beverages commercialized in different types of packaging. 相似文献
77.
This paper is our attempt, on the basis of physical theory, to bring more clarification on the question “What is life?” formulated in the well-known book of Schrödinger in 1944. According to Schrödinger, the main distinguishing feature of a biosystem’s functioning is the ability to preserve its order structure or, in mathematical terms, to prevent increasing of entropy. However, Schrödinger’s analysis shows that the classical theory is not able to adequately describe the order-stability in a biosystem. Schrödinger also appealed to the ambiguous notion of negative entropy. We apply quantum theory. As is well-known, behaviour of the quantum von Neumann entropy crucially differs from behaviour of classical entropy. We consider a complex biosystem S composed of many subsystems, say proteins, cells, or neural networks in the brain, that is, We study the following problem: whether the compound system S can maintain “global order” in the situation of an increase of local disorder and if S can preserve the low entropy while other increase their entropies (may be essentially). We show that the entropy of a system as a whole can be constant, while the entropies of its parts rising. For classical systems, this is impossible, because the entropy of S cannot be less than the entropy of its subsystem . And if a subsystems’s entropy increases, then a system’s entropy should also increase, by at least the same amount. However, within the quantum information theory, the answer is positive. The significant role is played by the entanglement of a subsystems’ states. In the absence of entanglement, the increasing of local disorder implies an increasing disorder in the compound system S (as in the classical regime). In this note, we proceed within a quantum-like approach to mathematical modeling of information processing by biosystems—respecting the quantum laws need not be based on genuine quantum physical processes in biosystems. Recently, such modeling found numerous applications in molecular biology, genetics, evolution theory, cognition, psychology and decision making. The quantum-like model of order stability can be applied not only in biology, but also in social science and artificial intelligence. 相似文献
78.
79.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(5):608-617
The two single‐enantiomer phosphoric triamides N‐(2,6‐difluorobenzoyl)‐N′,N′′‐bis[(S)‐(−)‐α‐methylbenzyl]phosphoric triamide, [2,6‐F2‐C6H3C(O)NH][(S)‐(−)‐(C6H5)CH(CH3)NH]2P(O), denoted L‐1 , and N‐(2,6‐difluorobenzoyl)‐N′,N′′‐bis[(R)‐(+)‐α‐methylbenzyl]phosphoric triamide, [2,6‐F2‐C6H3C(O)NH][(R)‐(+)‐(C6H5)CH(CH3)NH]2P(O), denoted D‐1 , both C23H24F2N3O2P, have been investigated. In their structures, chiral one‐dimensional hydrogen‐bonded architectures are formed along [100], mediated by relatively strong N—H…O(P) and N—H…O(C) hydrogen bonds. Both assemblies include the noncentrosymmetric graph‐set motifs R22(10), R21(6) and C22(8), and the compounds crystallize in the chiral space group P1. Due to the data collection of L‐1 at 120 K and of D‐1 at 95 K, the unit‐cell dimensions and volume show a slight difference; the contraction in the volume of D‐1 with respect to that in L‐1 is about 0.3%. The asymmetric units of both structures consist of two independent phosphoric triamide molecules, with the main difference being seen in one of the torsion angles in the OPNHCH(CH3)(C6H5) part. The Hirshfeld surface maps of these levo and dextro isomers are very similar; however, they are near mirror images of each other. For both structures, the full fingerprint plot of each symmetry‐independent molecule shows an almost asymmetric shape as a result of its different environment in the crystal packing. It is notable that NMR spectroscopy could distinguish between compounds L‐1 and D‐1 that have different relative stereocentres; however, the differences in chemical shifts between them were found to be about 0.02 to 0.001 ppm under calibrated temperature conditions. In each molecule, the two chiral parts are also different in NMR media, in which chemical shifts and P–H and P–C couplings have been studied. 相似文献
80.
S. V. Partsevskaya T. B. Zheltonozhskaya D. O. Klymchuk 《Molecular Crystals and Liquid Crystals》2018,671(1):128-139
AbstractA series of amphiphilic MOPEO-b-PCL copolymers (DBCs), based on biocompatible methoxypoly(ethylene oxide) with Mn=4.5?kDa and poly(ε-caprolactone) of a variable chain length, was synthesized by an anionic ring-opening block copolymerization. The structural investigations, performed by DSC and WAXS methods, revealed the microphase separation in DBC bulk structure and the existence of separate amorphous regions and microcrystalline domains of MOPEO and PCL blocks. Spectrophotometry and SLS were used to study the self-assembling of DBC macromolecules in selective dioxane/aqueous solution and to determine the main micellization parameters (CMC and -ΔG°). The DBC micelles morphology and their specific aggregation in mixed solvent were shown. 相似文献