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71.
Jacob Powell Domenic Valenti Harley Bobnar Erika Drain Blaine Elliott Sydney Frank Tyler McCullough Sean Moore Andrew Kettring Robbie Iuliucci James K. Harper 《Magnetic resonance in chemistry : MRC》2017,55(11):979-989
This study explores the feasibility of using a combination of experimental and theoretical 1‐bond 13C─13C scalar couplings (1JCC) to establish structure in organic compounds, including unknowns. Historically, nJCC and nJCH studies have emphasized 2 and 3‐bond couplings, yet 1JCC couplings exhibit significantly larger variations. Moreover, recent improvements in experimental measurement and data processing methods have made 1JCC data more available. Herein, an approach is evaluated in which a collection of theoretical structures is created from a partial nuclear magnetic resonance structural characterization. Computed 1JCC values are compared to experimental data to identify candidates giving the best agreement. This process requires knowledge of the error in theoretical methods, thus the B3LYP, B3PW91, and PBE0 functionals are evaluated by comparing to 27 experimental values from INADEQUATE. Respective errors of ±1.2, ±3.8, and ±2.3 Hz are observed. An initial test of this methodology involves the natural product 5‐methylmellein. In this case, only a single candidate matches experimental data with high statistical confidence. This analysis establishes the intramolecular hydrogen‐bonding arrangement, ring heteroatom identity, and conformation at one position. This approach is then extended to hydroheptelidic acid, a natural product not fully characterized in prior studies. The experimental/theoretical approach proposed herein identifies a single best‐fit structure from among 26 candidates and establishes, for the first time, 1 configuration and 3 conformations to complete the characterization. These results suggest that accurate and complete structural characterizations of many moderately sized organic structures (<800 Da) may be possible using only 1JCC data. 相似文献
72.
Chong Han Sean M. Kelly Theresa Cravillion Scott J. Savage Tina Nguyen Francis Gosselin 《Tetrahedron》2019,75(32):4351-4357
An efficient synthesis of PI3K inhibitor GDC-0077, featuring two consecutive Cu-catalyzed CN coupling reactions, is reported. The described synthetic route involves a chemoselective Ullmann-type coupling of a chiral difluoromethyl-substituted oxazolidinone, a Cu-catalyzed N-arylation of l-alanine with high stereochemical integrity, and a high-yielding final amide bond formation step to produce GDC-0077 in >99.5 area % HPLC purity. 相似文献
73.
Wenhao Ren Xin Tan Wanfeng Yang Chen Jia Shumao Xu Kaixue Wang Sean C. Smith Chuan Zhao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(21):7046-7050
Polynary single‐atom structures can combine the advantages of homogeneous and heterogeneous catalysts while providing synergistic functions based on different molecules and their interfaces. However, the fabrication and identification of such an active‐site prototype remain elusive. Here we report isolated diatomic Ni‐Fe sites anchored on nitrogenated carbon as an efficient electrocatalyst for CO2 reduction. The catalyst exhibits high selectivity with CO Faradaic efficiency above 90 % over a wide potential range from ?0.5 to ?0.9 V (98 % at ?0.7 V), and robust durability, retaining 99 % of its initial selectivity after 30 hours of electrolysis. Density functional theory studies reveal that the neighboring Ni‐Fe centers not only function in synergy to decrease the reaction barrier for the formation of COOH* and desorption of CO, but also undergo distinct structural evolution into a CO‐adsorbed moiety upon CO2 uptake. 相似文献
74.
A Multi‐Stimuli‐Responsive Oxazine Molecular Switch: A Strategy for the Design of Electrochromic Materials 下载免费PDF全文
Xiaojun Wang Chang Gu Hongzhi Zheng Dr. Yu‐Mo Zhang Prof. Sean Xiao‐An Zhang 《化学:亚洲杂志》2018,13(9):1206-1212
A multi‐state and multi‐stimuli‐responsive oxazine molecular switch that combines an electro‐base property and sensitive base/acid‐responsive properties was designed and synthesized. The multi‐state structures of the molecular switch, with different colors, were predicted by comparing the optical properties with reference molecules and confirmed by using NMR spectroscopy. The color‐switching mechanism under stimulation with acids and bases was investigated by using DFT calculations. Three single states can be obtained and the switching is unidirectional under acid and base stimulation. The electrochromic phenomenon of the molecular switch, which combines its electro‐base and base‐sensitive properties, was demonstrated. An electrochromic device that exhibited good electrochromic properties with excellent reversibility (2000 cycles) and high coloration efficiency (804 cm2 C?1) was successfully constructed. 相似文献
75.
Fabrication of Defined Polydopamine Nanostructures by DNA Origami‐Templated Polymerization 下载免费PDF全文
Yu Tokura Sean Harvey Chaojian Chen Prof. Dr. Yuzhou Wu Dr. David Y. W. Ng Prof. Dr. Tanja Weil 《Angewandte Chemie (International ed. in English)》2018,57(6):1587-1591
A versatile, bottom‐up approach allows the controlled fabrication of polydopamine (PD) nanostructures on DNA origami. PD is a biosynthetic polymer that has been investigated as an adhesive and promising surface coating material. However, the control of dopamine polymerization is challenged by the multistage‐mediated reaction mechanism and diverse chemical structures in PD. DNA origami decorated with multiple horseradish peroxidase‐mimicking DNAzyme motifs was used to control the shape and size of PD formation with nanometer resolution. These fabricated PD nanostructures can serve as “supramolecular glue” for controlling DNA origami conformations. Facile liberation of the PD nanostructures from the DNA origami templates has been achieved in acidic medium. This presented DNA origami‐controlled polymerization of a highly crosslinked polymer provides a unique access towards anisotropic PD architectures with distinct shapes that were retained even in the absence of the DNA origami template. 相似文献
76.
High‐Frequency Fe–H Vibrations in a Bridging Hydride Complex Characterized by NRVS and DFT 下载免费PDF全文
Dr. Vladimir Pelmenschikov Dr. Leland B. Gee Dr. Hongxin Wang Dr. K. Cory MacLeod Sean F. McWilliams Dr. Kazimer L. Skubi Prof. Dr. Stephen P. Cramer Prof. Dr. Patrick L. Holland 《Angewandte Chemie (International ed. in English)》2018,57(30):9367-9371
High‐spin iron species with bridging hydrides have been detected in species trapped during nitrogenase catalysis, but there are few general methods of evaluating Fe?H bonds in high‐spin multinuclear iron systems. An 57Fe nuclear resonance vibrational spectroscopy (NRVS) study on an Fe(μ‐H)2Fe model complex reveals Fe?H stretching vibrations for bridging hydrides at frequencies greater than 1200 cm?1. These isotope‐sensitive vibrational bands are not evident in infrared (IR) spectra, showing the power of NRVS for identifying hydrides in this high‐spin iron system. Complementary density functional theory (DFT) calculations elucidate the normal modes of the rhomboidal iron hydride core. 相似文献
77.
Sean P. Cleary Huilin Li Dhanashri Bagal Joseph A. Loo Iain D. G. Campuzano James S. Prell 《Journal of the American Society for Mass Spectrometry》2018,29(10):2067-2080
Native mass spectra of large, polydisperse biomolecules with repeated subunits, such as lipoprotein Nanodiscs, can often be challenging to analyze by conventional methods. The presence of tens of closely spaced, overlapping peaks in these mass spectra can make charge state, total mass, or subunit mass determinations difficult to measure by traditional methods. Recently, we introduced a Fourier Transform-based algorithm that can be used to deconvolve highly congested mass spectra for polydisperse ion populations with repeated subunits and facilitate identification of the charge states, subunit mass, charge-state-specific, and total mass distributions present in the ion population. Here, we extend this method by investigating the advantages of using overtone peaks in the Fourier spectrum, particularly for mass spectra with low signal-to-noise and poor resolution. This method is illustrated for lipoprotein Nanodisc mass spectra acquired on three common platforms, including the first reported native mass spectrum of empty “large” Nanodiscs assembled with MSP1E3D1 and over 300 noncovalently associated lipids. It is shown that overtone peaks contain nearly identical stoichiometry and charge state information to fundamental peaks but can be significantly better resolved, resulting in more reliable reconstruction of charge-state-specific mass spectra and peak width characterization. We further demonstrate how these parameters can be used to improve results from Bayesian spectral fitting algorithms, such as UniDec. 相似文献
78.
79.
Lars Winther Christensen Sean Sather-Wagstaff 《Journal of Pure and Applied Algebra》2010,214(6):982-989
A central problem in the theory of Gorenstein dimensions over commutative noetherian rings is to find resolution-free characterizations of the modules for which these invariants are finite. Over local rings, this problem was recently solved for the Gorenstein flat and the Gorenstein projective dimensions; here we give a solution for the Gorenstein injective dimension. Moreover, we establish two formulas for the Gorenstein injective dimension of modules in terms of the depth invariant; they extend formulas for the injective dimension due to Bass and Chouinard. 相似文献
80.