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51.
Joanna Bojarska Milan Remko Izabela D. Madura Krzysztof Kaczmarek Janusz Zabrocki Wojciech M. Wolf 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(4):328-345
Recently, fluorenylmethoxycarbonyl (Fmoc) amino acids (e.g. Fmoc–tyrosine or Fmoc–phenylalanine) have attracted growing interest in biomedical research and industry, with special emphasis directed towards the design and development of novel effective hydrogelators, biomaterials or therapeutics. With this in mind, a systematic knowledge of the structural and supramolecular features in recognition of those properties is essential. This work is the first comprehensive summary of noncovalent interactions combined with a library of supramolecular synthon patterns in all crystal structures of amino acids with the Fmoc moiety reported so far. Moreover, a new Fmoc‐protected amino acid, namely, 2‐{[(9H‐fluoren‐9‐ylmethoxy)carbonyl](methyl)amino}‐3‐{4‐[(2‐hydroxypropan‐2‐yl)oxy]phenyl}propanoic acid or N‐fluorenylmethoxycarbonyl‐O‐tert‐butyl‐N‐methyltyrosine, Fmoc‐N‐Me‐Tyr(t‐Bu)‐OH, C29H31NO5, was successfully synthesized and the structure of its unsolvated form was determined by single‐crystal X‐ray diffraction. The structural, conformational and energy landscape was investigated in detail by combined experimental and in silico approaches, and further compared to N‐Fmoc‐phenylalanine [Draper et al. (2015). CrystEngComm, 42 , 8047–8057]. Geometries were optimized by the density functional theory (DFT) method either in vacuo or in solutio. The polarizable conductor calculation model was exploited for the evaluation of the hydration effect. Hirshfeld surface analysis revealed that H…H, C…H/H…C and O…H/H…O interactions constitute the major contributions to the total Hirshfeld surface area in all the investigated systems. The molecular electrostatic potentials mapped over the surfaces identified the electrostatic complementarities in the crystal packing. The prediction of weak hydrogen‐bonded patterns via Full Interaction Maps was computed. Supramolecular motifs formed via C—H…O, C—H…π, (fluorenyl)C—H…Cl(I), C—Br…π(fluorenyl) and C—I…π(fluorenyl) interactions are observed. Basic synthons, in combination with the Long‐Range Synthon Aufbau Modules, further supported by energy‐framework calculations, are discussed. Furthermore, the relevance of Fmoc‐based supramolecular hydrogen‐bonding patterns in biocomplexes are emphasized, for the first time. 相似文献
52.
Ewa esawska Izabela Korona-Gowniak Wojciech Nitek Waldemar Tejchman 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(4):359-366
Derivatives of pyrimidine‐2(1H)‐selenone are a group of compounds with very strong antimicrobial activity. In order to study the effect of the position of the methoxy substituent on biological activity, molecular geometry and intermolecular interactions in the crystal, three derivatives were prepared and evaluated with respect to their antimicrobial activities, and their crystal structures were determined by X‐ray diffraction. The investigated compounds, namely, 1‐(X‐methoxyphenyl)‐4‐methyl‐6‐phenylpyrimidine‐2(1H)‐selenones (X = 2, 3 and 4 for 1 , 2 and 3 , respectively), C18H16N2OSe, showed very strong activity against selected strains of Gram‐positive bacteria and fungi. Two compounds, 1 and 2 , crystallize in the monoclinic space group P21/c, while 3 crystallizes in the space group P21/n; 1 has two molecules in the asymmetric unit and the other two ( 2 and 3 ) have one molecule. The geometries of the investigated compounds differ slightly in the mutual orientations of the aromatic and pyrimidineselenone rings. The O atom in 1 stabilizes the conformation of the molecules via intramolecular C—H…O hydrogen bonding. The packing of molecules is determined by weak C—H…N and C—H…Se intermolecular interactions and additionally in 1 and 2 by C—H…O intermolecular interactions. The introduction of the methoxy substituent results in greater selectivity of the investigated compounds. 相似文献
53.
A novel method is presented for generating periodic surfaces. Such periodic surfaces appear in all systems which are characterized by internal interfaces and which additionally exhibit ordering. One example are systems of AB diblock copolymers, where the internal interfaces are formed by the chemical bonds between the A and B blocks. In these systems at least two bicontinuous phases are formed: the ordered bicontinuous double diamond phase and the gyroid phase. In these phases the ordered domains of A monomers and B monomers are separated by a periodic interface of the same symmetry as the phases themselves. Here we present a novel method for the generation of such periodic surfaces based on the simple Landau-Ginzburg model of microemulsions. We test the method on four known minimal periodic surfaces, find two new surfaces of cubic symmetry, and show how to obtain periodic surfaces of high genus and n-tuply continuous phases (n > 2). So far only bicontinuous (n = 2) phases have been known. We point out that the Landau model used here should be generic for all systems characterized by internal interfaces, including the diblock copolymer systems. 相似文献
54.
Wojciech Krzysztof Czerwinski 《Macromolecular theory and simulations》1993,2(4):577-585
A new so-called reactant-solvent complex model is proposed to describe the effect of solvent on chain propagation in homopolymerization. It takes into account complex formation of both monomer and radical with solvent by equilibria. Evaluation methods presented permit to estimate the complex equilibrium constant K which is assumed to be nearly the same for both monomer and radical complexation and the relative reactivity ratio r11, for complexed monomer. Measured reaction rates as function of monomer concentration are needed for calculations. 相似文献
55.
The stereochemical course of the epoxide-induced oxidative rearrangement of ribonucleoside cyclic 3′,5′-phosphorothioates into the corresponding 2′,3′-phosphates has been determined using styrene [18O] oxide and (Sp)-uridine cyclic 3′,5′-phosphorothioate. The evidence of full stereoselectivity of this reaction is presented and mechanistic implications of the presence of the nucleoside 2′-hydroxyl group are discussed in terms of a classical Hamer Mechanism. 相似文献
56.
Radunsky AS Williams EM Walmsley IA Wasylczyk P Wasilewski W U'Ren AB Anderson ME 《Optics letters》2006,31(7):1008-1010
We propose and demonstrate a novel implementation of spectral-shearing interferometry (SSI) for reconstructing the electric field of ultrashort pulses by utilizing asymmetric group velocity matching in a long nonlinear crystal. The proposed configuration eliminates the requirement for a linearly chirped auxiliary pulse that is in common in all existing SSI methods, relying on nonlinear conversion to produce a spectral shear. 相似文献
57.
The miscibility-immiscibility phase transition in binary Bose-Einstein condensates (BECs) can be controlled by a coupling between the two components. Here we propose a new scheme that uses coupling-induced pattern formation to test the Kibble-Zurek mechanism (KZM) of topological-defect formation in a quantum phase transition. For a binary BEC in a ring trap we find that the number of domains forming the pattern scales as a function of the coupling quench rate with an exponent as predicted by the KZM. For a binary BEC in an elongated harmonic trap we find a different scaling law due to the transition being spatially inhomogeneous. We perform a "quantum simulation" of the harmonically trapped system in a ring trap to verify the scaling exponent. 相似文献
58.
Krauter H Muschik CA Jensen K Wasilewski W Petersen JM Cirac JI Polzik ES 《Physical review letters》2011,107(8):080503
Entanglement is a striking feature of quantum mechanics and an essential ingredient in most applications in quantum information. Typically, coupling of a system to an environment inhibits entanglement, particularly in macroscopic systems. Here we report on an experiment where dissipation continuously generates entanglement between two macroscopic objects. This is achieved by engineering the dissipation using laser and magnetic fields, and leads to robust event-ready entanglement maintained for 0.04 s at room temperature. Our system consists of two ensembles containing about 10(12) atoms and separated by 0.5 m coupled to the environment composed of the vacuum modes of the electromagnetic field. By combining the dissipative mechanism with a continuous measurement, steady state entanglement is continuously generated and observed for up to 1 h. 相似文献
59.
Mariusz Michalec Wojciech Florkowski Wojciech Broniowski 《Physics letters. [Part B]》2001,520(3-4):213-216
By means of a simple rescaling, modifications of hadron masses and widths are incorporated into the thermal analysis of particle ratios in ultrarelativistic heavy-ion collisions. We find that moderate, up to 20%, changes of hadron masses do not spoil the quality of the fits, which remain as good as those obtained without modifications. Larger changes are not likely. The fits with the modified masses yield modified values of the optimal temperature and baryon chemical potential. In particular, with decreasing masses of all hadrons (except for pseudo-Goldstone bosons) the fitted values of the temperature and the baryon chemical potential are lowered, with the change approximately proportional to the scaling of masses. In addition, we find that the broadening of the hadron widths by less than a factor of two practically does not affect the fits. 相似文献
60.
The idea that the parton system created in relativistic heavy-ion collisions (i) emerges in a state with transverse momenta close to thermodynamic equilibrium and (ii) its evolution at early times is dominated by the 2-dimensional (transverse) hydrodynamics of the ideal fluid is investigated. It is argued that this mechanism may help to solve the problem of early equilibration. 相似文献