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排序方式: 共有357条查询结果,搜索用时 31 毫秒
61.
Minkyu Kim Moon Jong Han Hansol Lee Paraskevi Flouda Daria Bukharina Kellina J. Pierce Katarina M. Adstedt Madeline L. Buxton Young Hee Yoon William T. Heller Srikanth Singamaneni Vladimir V. Tsukruk 《Angewandte Chemie (International ed. in English)》2023,62(30):e202305646
Chiral metal–organic frameworks (MOFs) have gained rising attention as ordered nanoporous materials for enantiomer separations, chiral catalysis, and sensing. Among those, chiral MOFs are generally obtained through complex synthetic routes by using a limited choice of reactive chiral organic precursors as the primary linkers or auxiliary ligands. Here, we report a template-controlled synthesis of chiral MOFs from achiral precursors grown on chiral nematic cellulose-derived nanostructured bio-templates. We demonstrate that chiral MOFs, specifically, zeolitic imidazolate framework (ZIF), unc -[Zn(2-MeIm)2, 2-MeIm=2-methylimidazole], can be grown from regular precursors within nanoporous organized chiral nematic nanocelluloses via directed assembly on twisted bundles of cellulose nanocrystals. The template-grown chiral ZIF possesses tetragonal crystal structure with chiral space group of P41, which is different from traditional cubic crystal structure of I-43 m for freely grown conventional ZIF-8. The uniaxially compressed dimensions of the unit cell of templated ZIF and crystalline dimensions are signatures of this structure. We observe that the templated chiral ZIF can facilitate the enantiotropic sensing. It shows enantioselective recognition and chiral sensing abilities with a low limit of detection of 39 μM and the corresponding limit of chiral detection of 300 μM for representative chiral amino acid, D- and L- alanine. 相似文献
62.
We investigated the effect of several computational variables, including the choice of the basis set, application of symmetry constraints, and zero-point energy (ZPE) corrections, on the structural parameters and predicted ground electronic state of model 5-coordinate hemes (iron(II) porphines axially coordinated by a single imidazole or 2-methylimidazole). We studied the performance of B3LYP and B3PW91 with eight Pople-style basis sets (up to 6-311+G*) and B97-1, OLYP, and TPSS functionals with 6-31G and 6-31G* basis sets. Only hybrid functionals B3LYP, B3PW91, and B97-1 reproduced the quintet ground state of the model hemes. With a given functional, the choice of the basis set caused up to 2.7 kcal/mol variation of the quintet-triplet electronic energy gap (DeltaEel), in several cases, resulting in the inversion of the sign of DeltaEel. Single-point energy calculations with triple-zeta basis sets of the Pople (up to 6-311G++(2d,2p)), Ahlrichs (TZVP and TZVPP), and Dunning (cc-pVTZ) families showed the same trend. The zero-point energy of the quintet state was approximately 1 kcal/mol lower than that of the triplet, and accounting for ZPE corrections was crucial for establishing the ground state if the electronic energy of the triplet state was approximately 1 kcal/mol less than that of the quintet. Within a given model chemistry, effects of symmetry constraints and of a "tense" structure of the iron porphine fragment coordinated to 2-methylimidazole on DeltaEel were limited to 0.3 kcal/mol. For both model hemes the best agreement with crystallographic structural data was achieved with small 6-31G and 6-31G* basis sets. Deviation of the computed frequency of the Fe-Im stretching mode from the experimental value with the basis set decreased in the order: nonaugmented basis sets, basis sets with polarization functions, and basis sets with polarization and diffuse functions. Contraction of Pople-style basis sets (double-zeta or triple-zeta) affected the results insignificantly for iron(II) porphyrin coordinated with imidazole. Poor performance of a "locally dense" basis set with a large number of basis functions on the Fe center was observed in calculation of quintet-triplet gaps. Our results lead to a series of suggestions for density functional theory calculations of quintet-triplet energy gaps in ferrohemes with a single axial imidazole; these suggestions are potentially applicable for other transition-metal complexes. 相似文献
63.
Maris A Giuliano BM Bonazzi D Caminati W 《Journal of the American Chemical Society》2008,130(42):13860-13861
Two homochiral dimers of glycidol, deriving from two different conformers, have been characterized by rotational spectroscopy in a supersonic expansion. 相似文献
64.
The Bioluminescence Resonance Energy Transfer from Firefly Luciferase to a Synthetic Dye and its Application for the Rapid Homogeneous Immunoassay of Progesterone
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Daria V. Smirnova Jeanne V. Samsonova Natalia N. Ugarova 《Photochemistry and photobiology》2016,92(1):158-165
The sensitive BRET system for the homogeneous immunoassay of a low‐molecular weight antigen was developed using progesterone as an example. Two thermostable mutants of the Luciola mingrelica firefly luciferase (Luc)—the “red” mutant with λmax.em = 590 nm (RedLuc) and the “green” mutant with λmax.em = 550 nm (GreenLuc)—were tested as the donors. The water‐soluble Alexa Fluor 610× (AF) dye was selected as the acceptor because its two absorption maxima, located at 550 and 610 nm, are close to the bioluminescence maxima of the GreenLuc and RedLuc, respectively. The methods for the synthesis of the luciferase–progesterone (Luc–Pg) conjugate and the conjugate of the dye and the polyclonal antiprogesterone antibody (AF–Ab) were developed. Both conjugates retained their functional properties, had high antigen–antibody binding activity, and demonstrated a high BRET signal. The homogeneous immunoassay system based on the BRET from the firefly luciferase to the synthetic dye was established to assay progesterone as a model antigen. Optimization of the assay conditions, the composition of the reaction mixture, and the concentrations of the donor and the acceptor made it possible to reach the minimum detectable progesterone concentration of 0.5 ng mL?1. 相似文献
65.
Skarpos H Osipov SN Vorob'eva DV Odinets IL Lork E Röschenthaler GV 《Organic & biomolecular chemistry》2007,5(15):2361-2367
An efficient general synthetic approach giving the possibility for facile, rapid and cheap access to a wide range of novel nitrogen-bisphosphonates (N-BPs) as potent drug candidates, based on the reaction of mono- and bis-propargyl-substituted bisphosphonates with a variety of azides under Cu(i) catalysis ("click" methodology), has been developed. The method allows the incorporation of two functionalities into the N-BP molecule simultaneously, as well as to ligate in situ two N-BPs to one another via the one-pot reaction of organic dibromides with propargyl-substituted bisphosphonates, generating both the diazide and Cu(I) moieties. 相似文献
66.
Nina Kasyanenko Daria Afanasieva Boris Dribinsky Dmitry Mukhin Olga Nazarova Evgeny Panarin 《Structural chemistry》2007,18(4):519-525
DNA complexes with cationic polymers (polyvinylamine (PVA), polyallylamine (PAA), polydimethylaminoethylmethacrylate (PDMAEM),
poly-(N,N,N-trimethylammonio)ethyl methacrylate chloride (PTMAEM), poly-l-lysine (PLL)) were investigated. It was shown that volume and persistent length of DNA do not change essentially at low cationic
polymer concentration in a solution. DNA packaging in 0.005 M NaCl was observed at charge ratio N/P ≈ 1. Secondary DNA structure
in complexes was not disrupted, and DNA was protected from protonation. The comparison between DNA packaging in complexes
with polycations and DNA condensation induced by trivalent ions was made. 相似文献
67.
T. N. Zavaritskaya N. N. Melnik F. A. Pudonin O. S. Talarico I. A. Sherstnev 《Bulletin of the Russian Academy of Sciences: Physics》2017,81(3):301-304
A new method is proposed that allows an integrated technology to be used for the synthesis of carbon planar structures with predetermined properties. The method is based on the avalanche annealing of amorphous short-period superlattices. The synthesized samples are investigated by Raman spectroscopy and photoluminescence. The possibility of synthesizing carbon layers with diamond-like, graphite-like, graphene, or other structures is demonstrated experimentally using the example of a C/SiC superlattice. 相似文献
68.
Magorzata Szultka-Myska Daria Janiszewska Pawe Pomastowski Micha Zoch Wojciech Kupczyk Bogusaw Buszewski 《Molecules (Basel, Switzerland)》2021,26(16)
The bacterial infection of post-operative wounds is a common health problem. Therefore, it is important to investigate fast and accurate methods of identifying bacteria in clinical samples. The aim of the study was to analyse the use of the MALDI-TOF MS technique to identify microorganism wounds that are difficult to heal. The most common bacteria are Escherichia coli, Staphylococcus spp., and Enterococcus spp. We also demonstrate the effect of culture conditions, such as the used growth medium (solid: Brain Heart Infusion Agar, Mueller Hilton Agar, Glucose Bromocresol Purple Agar, and Vancomycin Resistance Enterococci Agar Base and liquid: Tryptic Soy Broth and BACTEC Lytic/10 Anaerobic/F), the incubation time (4, 6, and 24h), and the method of the preparation of bacterial protein extracts (the standard method based on the Bruker guideline, the Sepsityper method) to identify factors and the quality of the obtained mass spectra. By comparing the protein profiles of bacteria from patients not treated with antibiotics to those treated with antibiotics based on the presence/absence of specific signals and using the UniProt platform, it was possible to predict the probable mechanism of the action of the antibiotic used and the mechanism of drug resistance. 相似文献
69.
Daria A. Smirnova Ilya V. Shadrivov Alexander I. Smirnov Yuri S. Kivshar 《Laser \u0026amp; Photonics Reviews》2014,8(2):291-296
Nonlinear properties of a multi‐layer stack of graphene sheets are studied. It is predicted that such a structure may support dissipative plasmon‐solitons generated and supported by an external laser radiation. Novel nonlinear equations describing spatial dynamics of the nonlinear plasmons driven by a plane wave in the Otto configuration are derived and the existence of single and multi‐hump dissipative solitons in the graphene structure is predicted. 相似文献
70.
Gephart RT Huang DL Aguila MJ Schmidt G Shahu A Warren TH 《Angewandte Chemie (International ed. in English)》2012,51(26):6488-6492
Aniline joins the club: A β-diketiminato copper(I) catalyst enables C-H amination of anilines employing low catalyst loadings to preclude oxidation to the diazene ArN=NAr. Electron-poor anilines are particularly resistant towards diazene formation and participate in the amination of strong and unactivated C-H bonds. N-alkyl anilines also take part in C-H amination. 相似文献