共查询到20条相似文献,搜索用时 31 毫秒
1.
Younkee Paik Barbara Poliks Cristian C. Rusa Alan E. Tonelli Jacob Schaefer 《Journal of Polymer Science.Polymer Physics》2007,45(11):1271-1282
Molecular motions of single polycarbonate (PC) chains threaded into crystalline γ‐cyclodextrin (γ‐CD) channels were examined using solid‐state 13C NMR and molecular dynamics simulations. The location of PC within the channels was confirmed by spin diffusion from a PC 13C label to natural‐abundance 13C of the γ‐CD. Rotor‐encoded longitudinal magnetization (RELM) (under 7‐kHz magic‐angle sample‐spinning conditions) was combined with multiple‐pulse 1H‐1H dipolar decoupling to detect large‐amplitude phenyl‐ring motion in both bulk PC and polycarbonate γ‐cyclodextrin inclusion compound (PC‐γ‐CD). The RELM results indicate that the phenyl rings in PC‐γ‐CD undergo 180° flips faster than 10 kHz just as in bulk PC. The molecular dynamics simulations show that the frequency of the phenyl‐ring flips depends on the cooperative motions of PC atoms and neighboring atoms of the γ‐CD channel. The distribution of protonated aromatic‐carbon laboratory and rotating‐frame 13C spin‐lattice relaxation rates for bulk PC and PC‐γ‐CD are similar but not identical. The distributions for both systems arise from site heterogeneities. For bulk PC, the heterogeneity is attributed to variations in local chain packing, and for PC‐γ‐CD the heterogeneity arises from variations in the location of the PC phenyl rings in the γ‐CD channel. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1271–1282, 2007 相似文献
2.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(6):1532-1536
2‐Pyridylsulfone‐ and fluoroalkylated group‐activated olefins underwent highly efficient diastereo‐ and enantioselective 1,3‐dipolar cycloadditions across various aromatic and aliphatic nitrones in the presence of a chiral NiII/bis(oxazoline) catalyst. The process was tuned by 4 Å molecular sieves, chiral bis(oxazoline) ligands, reaction solvents, and temperature. A wide array of optically pure fluoroalkylated isoxazolidines were obtained, thus facilitating the asymmetric synthesis of an enantioenriched α‐trifluoromethylated γ‐amino alcohol in gram‐scale and a trifluoromethylated derivative of 1,3‐oxazinan‐2‐one with potential pharmaceutical interest. A stereochemical model, based on the absolute configuration of one adduct and some control experiments, was postulated to account for the observed endo‐ and enantioselectivity. 相似文献
3.
Jin Wang Shuo Li Lin Ye Ai‐Ying Zhang Zeng‐Guo Feng 《Macromolecular rapid communications》2012,33(13):1143-1148
A polypseudorotaxane (PPR) comprising γ‐cyclodextrin (γ‐CD) as host molecules and poly(N‐isopropylacrylamide) (PNIPAM) as a guest polymer is prepared via self‐assembly in aqueous solution. Due to the bulky pendant isopropylamide group, PNIPAM exhibits size‐selectivity toward self‐assembly with α‐, β‐, and γ‐CDs. It can fit into the cavity of γ‐CD to give rise to a PPR, but cannot pass through α‐CD and β‐CD under the same conditions. The ratio of the number of γ‐CD molecules to entrapped NIPAM repeat units is kept at 1:2.2 or 1:2.4, determined by 1H NMR spectroscopy and TGA analysis, respectively, indicating that there are more than 2 but less than 3 NIPAM repeat units included by one γ‐CD molecule. This finding opens new avenues to PPR‐based supramolecular polymers to be used as solid, stimuli‐responsive materials. 相似文献
4.
Maider Greo Antonio Salgado María Castro‐Puyana María Luisa Marina 《Electrophoresis》2019,40(15):1913-1920
The enantiomeric separation of 9‐fluorenylmethoxycarbonyl chloride (FMOC)‐homocysteine (Hcy) by CE was investigated using γ‐CD and the chiral ionic liquid (R)‐(1‐hydroxybutan‐2‐yl)(trimethyl)azanium‐bis(trifluoromethanesulfon)imidate (also called (R)‐N,N,N‐trimethyl‐2‐aminobutanol‐bis(trifluoromethane‐sulfon)imidate) (EtCholNTf2) as chiral selectors. Using 2 mM γ‐CD and 5 mM EtCholNTf2 in 50 mM borate buffer (pH 9), FMOC‐Hcy enantiomers were separated with a resolution value of 3.8. A reversal in the enantiomer migration order in comparison with the single use of γ‐CD in the separation buffer was obtained. Then, NMR experiments were carried out to elucidate the interactions taking place in the enantiomeric separation of FMOC‐Hcy. NMR analyses highlighted the formation of an inclusion complex since the hydrophobic group of FMOC‐Hcy was inserted into the γ‐CD cavity. Moreover, interactions between EtCholNTf2 and γ‐CD were also observed, suggesting that the chiral ionic liquid would also enter the cavity of the γ‐CD. 相似文献
5.
Dezhi Xu Mozhen Wang Xuewu Ge Michael Hon‐Wah Lam 《Macromolecular rapid communications》2012,33(22):1945-1951
Polystyrene (PS) microspheres coated with β‐cyclodextrin (β‐CD) were fabricated via γ‐ray‐induced emulsion polymerization in a ternary system of styrene/β‐CD/water (St/β‐CD/water). The solid inclusion complex of St and β‐CD particles formed at the St droplets–water interface can stabilize the emulsion as the surfactant. TEM and XPS results showed that β‐CD remains on the surface of PS particles. The average size of the PS particles increases from 186 to 294 nm as the weight ratio of β‐CD to St rises from 5% to 12.5%. The water contact angle (CA) of PS latex film is lower than 90°, and reduces with the β‐CD content even to 36°. Thus, this work provides a new and one‐pot strategy to surface hydrophilic modification on hydrophobic polymer particles with cyclodextrins through radiation emulsion polymerization. 相似文献
6.
Towards Truly Sustainable Polymers: A Metal‐Free Recyclable Polyester from Biorenewable Non‐Strained γ‐Butyrolactone 下载免费PDF全文
Dr. Miao Hong Prof. Dr. Eugene Y.‐X. Chen 《Angewandte Chemie (International ed. in English)》2016,55(13):4188-4193
The first effective organopolymerization of the biorenewable “non‐polymerizable” γ‐butyrolactone (γ‐BL) to a high‐molecular‐weight metal‐free recyclable polyester is reported. The superbase tert‐Bu‐P4 is found to directly initiate this polymerization through deprotonation of γ‐BL to generate reactive enolate species. When combined with a suitable alcohol, the tert‐Bu‐P4‐based system rapidly converts γ‐BL into polyesters with high monomer conversions (up to 90 %), high molecular weights (Mn up to 26.7 kg mol?1), and complete recyclability (quantitative γ‐BL recovery). 相似文献
7.
Treatment of α,β‐unsaturated ketones with an electrophilic site at the γ‐position in the presence of trimethylsilyl cyanide with bis(iodozincio)methane afforded the (Z)‐silyl enol ether of the β‐cyclopropyl substituted ketone in good yields. The reaction proceeds by 1,4‐addition to form an enolate, and its sequential intramolecular nucleophilic attack to an adjacent electrophilic site. The reaction of γ‐ethoxycarbonyl‐α,β‐unsaturated ketone and bis(iodozincio)methane in the presence of trimethylsilyl cyanide afforded 1‐ethoxy‐1‐trimethylsiloxycyclopropane derivatives, which can be regarded as the homoenolate equivalent. Additionally, reaction of the obtained homoenolate equivalents with imines give 1‐(E)‐alkenyl‐2‐(1‐aminoalkyl)alkanols diastereoselectively. 相似文献
8.
Host–guest interactions between α‐, β‐ and γ‐cyclodextrins and vanadocene dichloride (Cp2VCl2) have been investigated by a combination of thermogravimetric analysis, differential scanning calorimetry, powder X‐ray diffraction and solid‐state and solution electron paramagnetic resonance (EPR) spectroscopy. The solid‐state results demonstrated that only β‐ and γ‐cyclodextrins form 1:1 inclusion complexes, while α‐cyclodextrin does not form an inclusion complex with Cp2VCl2. The β‐ and γ‐CD–Cp2VCl2 inclusion complexes exhibited anisotropic electron‐51V (I = 7/2) hyperfine coupling constants whereas the α‐CD–Cp2VCl2 system showed only an asymmetric peak with no anisotropic hyperfine constant. On the other hand, solution EPR spectroscopy showed that α‐cyclodextrin (α‐CD) may be involved in weak host–guest interactions in equilibrium with free vanadocene species. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
9.
Dr. Julie Bouckaert Dr. Zhaoli Li Dr. Catarina Xavier Dr. Mehdi Almant Dr. Vicky Caveliers Prof. Tony Lahoutte Dr. Stephen D. Weeks Prof. José Kovensky Dr. Sébastien G. Gouin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(24):7847-7855
n‐Heptyl α‐D ‐mannoside (HM) has previously been identified as a nanomolar FimH antagonist able to prevent Escherichia coli adhesion. We have designed mono‐ and heptavalent glycoconjugates in which HM is tethered to β‐cyclodextrin (β‐CD) through short and long spacers. One‐pot click or co‐clicking procedures were developed to directly obtain the glycoconjugates from unprotected HM and β‐CD precursors. These FimH antagonists were examined biophysically and in vivo. Reverse titrations by isothermal calorimetry led to trapping of the short‐tethered heptavalent β‐CD in a complex with three FimH lectins. Combined dynamic light scattering and small‐angle X‐ray solution scattering data allowed the construction of a model of the FimH trimer. The heptavalent β‐CDs were shown to capture and aggregate living bacteria in solution and are therefore also able to aggregate FimH when attached to different bacteria pili. The first in vivo evaluation of multivalent FimH inhibitors has been performed. The heptavalent β‐CDs proved to be much more effective anti‐adhesive agents than monovalent references with doses of around 2 μg instilled in the mouse bladder leading to a significantly decreased E. coli load. Intravenously injected radiolabeled glycoconjugates can rapidly reach the mouse bladder and >2 μg concentrations can easily be retained over 24 h to prevent fluxing bacteria from rebinding. 相似文献
10.
Rajkumar Misra Gijo George Abhijith Saseendran Srinivasarao Raghothama Hosahudya N. Gopi 《化学:亚洲杂志》2019,14(23):4408-4414
Molecular chirality is ubiquitous in nature. The natural biopolymers, proteins and DNA, preferred a right‐handed helical bias due to the inherent stereochemistry of the monomer building blocks. Here, we are reporting a rare co‐existence of left‐ and right‐handed helical conformations and helix‐terminating property at the C‐terminus within a single molecule of α,γ‐hybrid peptide foldamers composed of achiral Aib (α‐aminoisobutyric acid) and 3,3‐dimethyl‐substituted γ‐amino acid (Adb; 4‐amino‐3,3‐dimethylbutanoic acid). At the molecular level, the left‐ and right‐handed helical screw sense of α,γ‐hybrid peptides are representing a macroscopic tendril perversion. The pronounced helix‐terminating behaviour of C‐terminal Adb residues was further explored to design helix–Schellman loop mimetics and to study their conformations in solution and single crystals. The stereochemical constraints of dialkyl substitutions on γ‐amino acids showed a marked impact on the folding behaviour of α,γ‐hybrid peptides. 相似文献
11.
Telma Costa J. S. Seixas de Melo 《Journal of polymer science. Part A, Polymer chemistry》2008,46(4):1402-1415
The interaction between poly(acrylic acid) polymers (PAA) of low‐ (2000 g/mol) and high‐ (450,000 g/mol) molecular weight (Mw) hydrophobically modified with pyrene (PAAMePy) and β‐ and γ‐cyclodextrins (β‐CD, γ‐CD) was investigated with fluorescent techniques. The interaction with β‐CD promotes little variation in the spectral and photophysical behavior of the polymer, whereas significant changes are observed upon addition of γ‐CD. The degree of inclusion (between the pyrene groups of the polymer and the cyclodextrins) is followed through the observation of the changes in the absorption, excitation (collected in the monomer and excimer emission regions) and emission (IE/IM ratio) spectra and from time‐resolved data. Within the studied range of γ‐CD concentration, the fluorescence decays of the long chain (high Mw) PAAMePy polymers were found tri‐exponential in the monomer and excimer emission regions in agreement with previous studies. In the case of the low Mw PAAMePy polymers, tri‐exponential decays were observed at the monomer and excimer emission wavelengths. However, when a γ‐CD concentration of 0.01 and 0.03 M is reached for, respectively, the low‐ and high‐labeled pyrene short chain (low Mw) polymers, the fluorescence decays in the excimer region become biexponential (two excimers) with no rising component, thus showing that all pyrene groups are encapsulated (and preassociated) into the γ‐CD cavity. In the case of the high Mw polymers, the addition of γ‐CD has been found to change the level of polymer interaction from pure intramolecular (water in the absence of cyclodextrin) to a coexistence of intra‐ with intermolecular interactions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1402–1415, 2008 相似文献
12.
Synthesis of β‐Substituted γ‐Aminobutyric Acid Derivatives through Enantioselective Photoredox Catalysis 下载免费PDF全文
Jiajia Ma Jiahui Lin Lifang Zhao Dr. Klaus Harms Michael Marsch Dr. Xiulan Xie Prof. Dr. Eric Meggers 《Angewandte Chemie (International ed. in English)》2018,57(35):11193-11197
β‐Substituted chiral γ‐aminobutyric acids feature important biological activities and are valuable intermediates for the synthesis of pharmaceuticals. Herein, an efficient catalytic enantioselective approach for the synthesis of β‐substituted γ‐aminobutyric acid derivatives through visible‐light‐induced photocatalyst‐free asymmetric radical conjugate additions is reported. Various β‐substituted γ‐aminobutyric acid analogues, including previously inaccessible derivatives containing fluorinated quaternary stereocenters, were obtained in good yields (42–89 %) and with excellent enantioselectivity (90–97 % ee). Synthetically valuable applications were demonstrated by providing straightforward synthetic access to the pharmaceuticals or related bioactive compounds (S)‐pregabalin, (R)‐baclofen, (R)‐rolipram, and (S)‐nebracetam. 相似文献
13.
Dr. Tanveer Hussain Dr. Tuhina Adit Maark Dr. Sudip Chakraborty Prof. Rajeev Ahuja 《Chemphyschem》2015,16(12):2557-2561
A thorough study of the structural, electronic, and hydrogen‐desorption properties of β‐ and γ‐MgH2 phases substituted by selected transition metals (TMs) is performed through first‐principles calculations based on density functional theory (DFT). The TMs considered herein include Sc, V, Fe, Co, Ni, Cu, Y, Zr, and Nb, which substitute for Mg at a doping concentration of 3.125 % in both the hydrides. This insertion of TMs causes a variation in the cell volumes of β‐ and γ‐MgH2. The majority of the TM dopants decrease the lattice constants, with Ni resulting in the largest reduction. From the formation‐energy calculations, it is predicted that except for Cu and Ni, the mixing of all the selected TM dopants with the MgH2 phases is exothermic. The selected TMs also influence the stability of both β‐ and γ‐MgH2 and cause destabilization by weakening the Mg?H bonds. Our results show that doping with certain TMs can facilitate desorption of hydrogen from β‐ and γ‐MgH2 at much lower temperatures than from their pure forms. The hydrogen adsorption strengths are also studied by density‐of‐states analysis. 相似文献
14.
Physicochemical characterization of α‐chitin, β‐chitin,and γ‐chitin separated from natural resources
Mi‐Kyeong Jang Byeong‐Gi Kong Young‐Il Jeong Chang Hyung Lee Jae‐Woon Nah 《Journal of polymer science. Part A, Polymer chemistry》2004,42(14):3423-3432
We isolated α‐chitin, β‐chitin, and γ‐chitin from natural resources by a chemical method to investigate the crystalline structure of chitin. Its characteristics were identified with Fourier transform infrared (FTIR) and solid‐state cross‐polarization/magic‐angle‐spinning (CP–MAS) 13C NMR spectrophotometers. The average molecular weights of α‐chitin, β‐chitin, and γ‐chitin, calculated with the relative viscosity, were about 701, 612, and 524 kDa, respectively. In the FTIR spectra, α‐chitin, β‐chitin, and γ‐chitin showed a doublet, a singlet, and a semidoublet at the amide I band, respectively. The solid‐state CP–MAS 13C NMR spectra revealed that α‐chitin was sharply resolved around 73 and 75 ppm and that β‐chitin had a singlet around 74 ppm. For γ‐chitin, two signals appeared around 73 and 75 ppm. From the X‐ray diffraction results, α‐chitin was observed to have four crystalline reflections at 9.6, 19.6, 21.1, and 23.7 by the crystalline structure. Also, β‐chitin was observed to have two crystalline reflections at 9.1 and 20.3 by the crystalline structure. γ‐Chitin, having an antiparallel and parallel structure, was similar in its X‐ray diffraction patterns to α‐chitin. The exothermic peaks of α‐chitin, β‐chitin, and γ‐chitin appeared at 330, 230, and 310, respectively. The thermal decomposition activation energies of α‐chitin, β‐chitin, and γ‐chitin, calculated by thermogravimetric analysis, were 60.56, 58.16, and 59.26 kJ mol?1, respectively. With the Arrhenius law, ln β was plotted against the reciprocal of the maximum decomposition temperature as a straight line; there was a large slope for large activation energies and a small slope for small activation energies. α‐Chitin with high activation energies was very temperature‐sensitive; β‐Chitin with low activation energies was relatively temperature‐insensitive. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3423–3432, 2004 相似文献
15.
α‐Aminoxy‐Acid‐Auxiliary‐Enabled Intermolecular Radical γ‐C(sp3)−H Functionalization of Ketones 下载免费PDF全文
Dr. Heng Jiang Prof. Dr. Armido Studer 《Angewandte Chemie (International ed. in English)》2018,57(6):1692-1696
A method for site‐specific intermolecular γ‐C(sp3)?H functionalization of ketones has been developed using an α‐aminoxy acid auxiliary applying photoredox catalysis. Regioselective activation of an inert C?H bond is achieved by 1,5‐hydrogen atom abstraction by an oxidatively generated iminyl radical. Tertiary and secondary C‐radicals thus formed at the γ‐position of the imine functionality undergo radical conjugate addition to various Michael acceptors to provide, after reduction and imine hydrolysis, the corresponding γ‐functionalized ketones. 相似文献
16.
The title compounds were synthesized by the microwave‐assisted, mostly solvent‐free bis Kabachnik–Fields condensation of β‐alanine and γ‐aminobutyric acid or their esters with formaldehyde and >P(O)H species, such as dialkyl phosphites and diphenylphosphine oxide. 相似文献
17.
Feten Béji Sonia Taktouk Jihène Ben Kraïem Salem S. Al‐Deyab Hassen Amri 《Journal of heterocyclic chemistry》2015,52(5):1576-1579
We present herein an efficient and rapid method for the synthesis of N,1‐dialkyl‐4‐(2‐hydroxyethyl)‐5‐oxopyrrolidine‐3‐carboxamides based on the conversion of γ‐lactone to γ‐lactam via the conjugate addition of primary amines to an ethyl α‐functionalized acrylate followed by intramolecular cyclization. 相似文献
18.
One‐Pot Synthesis of Polysubstituted Benzenes through a N,N‐dimethyl‐4‐aminopyridine (DMAP)‐Catalyzed [4+2] Benzannulation of 1,3‐Bis(sulfonyl)butadienes and γ‐Substituted Allenoates 下载免费PDF全文
A new strategy for the one‐pot synthesis of polysubstituted benzenes through a N,N‐dimethyl‐4‐aminopyridine (DMAP)‐catalyzed [4+2] benzannulation from readily prepared 1,3‐bis(sulfonyl)butadienes and γ‐substituted allenoates is described. This method provides a facile, metal‐free and general route to highly substituted benzenes under mild conditions in moderate‐to‐good yields with complete regioselectivity. 相似文献
19.
Rajkumar Misra Sanjit Dey Rahi M. Reja Prof. Dr. Hosahudya N. Gopi 《Angewandte Chemie (International ed. in English)》2018,57(4):1057-1061
Double helices are not common in polypeptides and proteins except in the peptide antibiotic gramicidin A and analogous l,d ‐peptides. In contrast to natural polypeptides, remarkable β‐double‐helical structures from achiral γ‐peptides built from α,β‐unsaturated γ‐amino acids have been observed. The crystal structures suggest that they adopted parallel β‐double helical structures and these structures are stabilized by the interstrand backbone amide H‐bonds. Furthermore, both NMR spectroscopy and fluorescence studies support the existence of double‐helical conformations in solution. Although a variety of folded architectures featuring distinct H‐bonds have been discovered from the β‐ and γ‐peptide foldamers, this is the first report to show that achiral γ‐peptides can spontaneously intertwine into β‐double helical structures. 相似文献
20.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(35):10554-10558
We adopted a spirocyclization‐based strategy to design γ‐glutamyl hydroxymethyl selenorhodamine green (gGlu‐HMSeR) as a photo‐inactive compound that would be specifically cleaved by the tumor‐associated enzyme γ‐glutamyltranspeptidase (GGT) to generate the potent photosensitizer HMSeR. gGlu‐HMSeR has a spirocyclic structure and is colorless and does not show marked phototoxicity toward low‐GGT‐expressing cells or normal tissues upon irradiation with visible light. In contrast, HMSeR predominantly takes an open structure, is colored, and generates reactive oxygen species upon irradiation. The γ‐glutamyl group thus serves as a tumor‐targeting moiety for photodynamic therapy (PDT), switching on tumor‐cell‐specific phototoxicity. To validate this system, we employed chick chorioallantoic membrane (CAM), a widely used model for preliminary evaluation of drug toxicity. Photoirradiation after gGlu‐HMSeR treatment resulted in selective ablation of implanted tumor spheroids without damage to healthy tissue. 相似文献