全文获取类型
收费全文 | 942篇 |
免费 | 54篇 |
国内免费 | 11篇 |
专业分类
化学 | 616篇 |
力学 | 24篇 |
数学 | 202篇 |
物理学 | 165篇 |
出版年
2024年 | 1篇 |
2023年 | 17篇 |
2022年 | 19篇 |
2021年 | 43篇 |
2020年 | 22篇 |
2019年 | 21篇 |
2018年 | 22篇 |
2017年 | 24篇 |
2016年 | 46篇 |
2015年 | 44篇 |
2014年 | 46篇 |
2013年 | 80篇 |
2012年 | 73篇 |
2011年 | 76篇 |
2010年 | 54篇 |
2009年 | 47篇 |
2008年 | 54篇 |
2007年 | 72篇 |
2006年 | 48篇 |
2005年 | 59篇 |
2004年 | 40篇 |
2003年 | 17篇 |
2002年 | 18篇 |
2001年 | 7篇 |
2000年 | 12篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1997年 | 9篇 |
1996年 | 5篇 |
1995年 | 6篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1987年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1976年 | 1篇 |
排序方式: 共有1007条查询结果,搜索用时 15 毫秒
991.
Changes in the intrinsic protein fluorescence with the additive concentration provide one of the most employed methodologies for the evaluation of the binding constant and the number of binding sites. In the last years, more than 175 studies have been published where the double logarithmic plot shown below is used toward determining the number of equivalent binding sites ( n ). Log [( F ° ? F ) /F] = log K + n log [Q 0 ]. However, the value of n evaluated by this procedure is unrelated to the number of equivalent binding sites; rather it represents the stoichiometry of the binding step. The confusion on the meaning of n arises upon assuming that the binding process is represented by the forward and backward elementary steps shown below, implying that binding of the n solutes takes place simultaneously, i.e. there are no intermediate species. n Q + P ? Q n P. The conclusion that n is unrelated to the number of equivalent binding sites is supported by the fact that in all the systems considered (99% of them) n values are close to one and much smaller than those obtained by ultrafiltration. It is then remarkable, the profusion of publications in peer‐reviewed, specialized journals including a conceptual error that confuses Hill′s coefficient and/or the stoichiometry of the binding step with the number of independent binding sites. Here, we discuss the origin of this common misconception and provide alternative methods to determine the number of binding sites. 相似文献
992.
Robert M. Moriarty Neena Rani Cristian Condeiu Michael P. Duncan Om Prakash # 《合成通讯》2013,43(18):3273-3277
Hypervalent iodine oxidation of trimethylsilyl ketene acetals of esters and lactones using iodosobenzene in methanol affords the corresponding α-methoxylated carbonyl compounds in good yields. 相似文献
993.
Under very mild reaction conditions, iron or copper nanoparticles efficiently promoted the homocoupling of different Grignard reagents in tetrahydrofuran at room temperature. The nanosized iron or copper particles were generated in situ in a simple and economical way from commercially available FeCl2 or CuCl2, respectively, an excess of lithium powder, and a catalytic amount (5 mol%) of 4,4′-di-tert-butylbiphenyl (DTBB) as electron carrier. The reaction of a series of aryl, heteroaryl, benzyl, and alkenyl Grignard reagents in the presence of a substoichiometric amount of the iron or copper nanoparticles led to the formation of the corresponding homocoupling products in good yield. 相似文献
994.
Monica Dan Adriana Vulcu Sebastian A. Porav Cristian Leostean Gheorghe Borodi Oana Cadar Camelia Berghian-Grosan 《Molecules (Basel, Switzerland)》2021,26(13)
Four N-doped graphene materials with a nitrogen content ranging from 8.34 to 13.1 wt.% are prepared by the ball milling method. This method represents an eco-friendly mechanochemical process that can be easily adapted for industrial-scale productivity and allows both the exfoliation of graphite and the synthesis of large quantities of functionalized graphene. These materials are characterized by transmission and scanning electron microscopy, thermogravimetry measurements, X-ray powder diffraction, X-ray photoelectron and Raman spectroscopy, and then, are tested towards the oxygen reduction reaction by cyclic voltammetry and rotating disk electrode methods. Their responses towards ORR are analysed in correlation with their properties and use for the best ORR catalyst identification. However, even though the mechanochemical procedure and the characterization techniques are clean and green methods (i.e., water is the only solvent used for these syntheses and investigations), they are time consuming and, generally, a low number of materials can be prepared, characterized and tested. In order to eliminate some of these limitations, the use of regression learner and reverse engineering methods are proposed for facilitating the optimization of the synthesis conditions and the materials’ design. Thus, the machine learning algorithms are applied to data containing the synthesis parameters, the results obtained from different characterization techniques and the materials response towards ORR to quickly provide predictions that allow the best synthesis conditions or the best electrocatalysts’ identification. 相似文献
995.
Alexandru C. Razus Liviu Birzan Mihaela Cristea Victorita Tecuceanu Anamaria Hanganu Cristian Enache 《Journal of heterocyclic chemistry》2011,48(5):1019-1027
Pyranylium perchlorates with azulen‐1‐yl moiety in 4‐position and thiophen‐2‐yl or furan‐2‐yl in 2 and 6‐positions were obtained by the substitution of 4‐chloro corresponding salts with azulenes. The pyranylium salts are used as starting materials for the synthesis of pyridine and pyridinium salts. The products were characterized and for pyridines pKa was spectroscopically determined. Several attempts were made for pyridine complexation with metal cations as Hg2+ or Ag+. J. Heterocyclic Chem., (2011). 相似文献
996.
997.
Ilie A Raţ CI Scheutzow S Kiske C Lux K Klapötke TM Silvestru C Karaghiosoff K 《Inorganic chemistry》2011,50(6):2675-2684
Gold(I) and silver(I) complexes of 1-methyl-5-thio-tetrazole (1) have been prepared and the coordination chemistry of this ligand toward metal-phosphine frameworks has been explored. As indicated by IR and Raman data, ligand 1 is deprotonated and the resulted anion acts as a bidentate (S,N)-tetrazole-5-thiolato unit in the new gold(I) complexes, [Au(SCN(4)Me)(PPh(3))] (2), [{Au(SCN(4)Me)}(2)(μ-dppm)] (3), and [{Au(SCN(4)Me)}(2)(μ-dppe)] (4), while it is coordinated only through the sulfur atom as its neutral tetrazole-5-thione form in the silver(I) derivative, [Ag(HSCN(4)Me)(PPh(3))](2)(OTf)(2) (5). Further characterization of the new compounds was performed using multinuclear ((1)H, (13)C, (31)P, (19)F) NMR spectroscopy, mass spectrometry, and DSC measurements. Single-crystal X-ray diffraction studies revealed basically linear P-M-S arrangements in complexes 3-5. The bidentate (S,N) coordination pattern results in a T-shaped (S,N)PAu core in 3 and 4, whereas, in 5, a similar coordination geometry is achieved in the dimer association based on S-bridging ligand 1. Herein, weak (C)H···Au and (C)H···Ag agostic interactions were observed. An intramolecular Au···Au contact occurs in 3, while in 4 intermolecular aurophilic bonds lead to formation of a chain polymer. An intermolecular Ag···Ag contact is also present in the dimer unit of 5. Low-temperature (31)P NMR data for 5 evidenced the presence of monomer and dimer units in solution. Theoretical calculations on model of the complexes 2 and 4 are consistent with the geometries found by X-ray diffraction studies. 相似文献
998.
Adriana Cecilia Csakvari Cristian Moisa Dana G. Radu Leonard M. Olariu Andreea I. Lupitu Anca Ofelia Panda Georgeta Pop Dorina Chambre Vlad Socoliuc Lucian Copolovici Dana Maria Copolovici 《Molecules (Basel, Switzerland)》2021,26(13)
Cannabis sativa L. (hemp) is a plant used in the textile industry and green building material industry, as well as for the phytoremediation of soil, medical treatments, and supplementary food products. The synergistic effect of terpenes, flavonoids, and cannabinoids in hemp extracts may mediate the biogenic synthesis of metal nanoparticles. In this study, the chemical composition of aqueous leaf extracts of three varieties of Romanian hemp (two monoecious, and one dioecious) have been determined by Fourier-Transformed Infrared spectroscopy (FT-IR), high-performance liquid chromatography, and mass spectrometry (UHPLC-DAD-MS). Then, their capability to mediate the green synthesis of silver nanoparticles (AgNPs) and their pottential antibacterial applications were evaluated. The average antioxidant capacity of the extracts had 18.4 ± 3.9% inhibition determined by 2,2-diphenyl-1-picrylhydrazyl (DPPH•) and 78.2 ± 4.1% determined by 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS™) assays. The total polyphenolic content of the extracts was 1642 ± 32 mg gallic acid equivalent (GAE) L−1. After this, these extracts were reacted with an aqueous solution of AgNO3 resulting in AgNPs, which were characterized by UV−VIS spectroscopy, FT-IR, scanning electron microscopy (SEM-EDX), and dynamic light scattering (DLS). The results demonstrated obtaining spherical, stable AgNPs with a diameter of less than 69 nm and an absorbance peak at 435 nm. The mixture of extracts and AgNPs showed a superior antioxidant capacity of 2.3 ± 0.4% inhibition determined by the DPPH• assay, 88.5 ± 0.9% inhibition as determined by the ABTS•+ assay, and a good antibacterial activity against several human pathogens: Escherichia coli, Klebsiella pneumoniae, Pseudomonas fluorescens, and Staphylococcus aureus. 相似文献
999.
Victor I. Afonso Gonzalo J. Olmo Emanuele Orazi Diego Rubiera-Garcia 《The European Physical Journal C - Particles and Fields》2018,78(10):866
We show that families of nonlinear gravity theories formulated in a metric-affine approach and coupled to a nonlinear theory of electrodynamics can be mapped into general relativity (GR) coupled to another nonlinear theory of electrodynamics. This allows to generate solutions of the former from those of the latter using purely algebraic transformations. This correspondence is explicitly illustrated with the Eddington-inspired Born–Infeld theory of gravity, for which we consider a family of nonlinear electrodynamics and show that, under the map, preserve their algebraic structure. For the particular case of Maxwell electrodynamics coupled to Born–Infeld gravity we find, via this correspondence, a Born–Infeld-type nonlinear electrodynamics on the GR side. Solving the spherically symmetric electrovacuum case for the latter, we show how the map provides directly the right solutions for the former. This procedure opens a new door to explore astrophysical and cosmological scenarios in nonlinear gravity theories by exploiting the full power of the analytical and numerical methods developed within the framework of GR. 相似文献
1000.
Chiara Franceschini Cristian Giardinà Wolter Groenevelt 《Mathematical Physics, Analysis and Geometry》2018,21(4):29
We present a theorem which elucidates the connection between self-duality of Markov processes and representation theory of Lie algebras. In particular, we identify sufficient conditions such that the intertwining function between two representations of a certain Lie algebra is the self-duality function of a (Markov) operator. In concrete terms, the two representations are associated to two operators in interwining relation. The self-dual operator, which arise from an appropriate symmetric linear combination of them, is the generator of a Markov process. The theorem is applied to a series of examples, including Markov processes with a discrete state space (e.g. interacting particle systems) and Markov processes with continuous state space (e.g. diffusion processes). In the examples we use explicit representations of Lie algebras that are unitarily equivalent. As a consequence, in the discrete setting self-duality functions are given by orthogonal polynomials whereas in the continuous context they are Bessel functions. 相似文献