全文获取类型
收费全文 | 6708篇 |
免费 | 341篇 |
国内免费 | 122篇 |
专业分类
化学 | 4937篇 |
晶体学 | 31篇 |
力学 | 217篇 |
综合类 | 2篇 |
数学 | 953篇 |
物理学 | 1031篇 |
出版年
2023年 | 68篇 |
2022年 | 93篇 |
2021年 | 134篇 |
2020年 | 125篇 |
2019年 | 160篇 |
2018年 | 104篇 |
2017年 | 93篇 |
2016年 | 209篇 |
2015年 | 173篇 |
2014年 | 213篇 |
2013年 | 380篇 |
2012年 | 485篇 |
2011年 | 524篇 |
2010年 | 288篇 |
2009年 | 253篇 |
2008年 | 446篇 |
2007年 | 453篇 |
2006年 | 400篇 |
2005年 | 378篇 |
2004年 | 343篇 |
2003年 | 304篇 |
2002年 | 257篇 |
2001年 | 99篇 |
2000年 | 99篇 |
1999年 | 76篇 |
1998年 | 64篇 |
1997年 | 69篇 |
1996年 | 81篇 |
1995年 | 58篇 |
1994年 | 44篇 |
1993年 | 32篇 |
1992年 | 35篇 |
1991年 | 39篇 |
1990年 | 36篇 |
1989年 | 30篇 |
1988年 | 21篇 |
1987年 | 18篇 |
1986年 | 29篇 |
1985年 | 28篇 |
1984年 | 39篇 |
1983年 | 31篇 |
1982年 | 41篇 |
1981年 | 30篇 |
1980年 | 40篇 |
1979年 | 27篇 |
1978年 | 30篇 |
1977年 | 38篇 |
1976年 | 28篇 |
1975年 | 28篇 |
1973年 | 18篇 |
排序方式: 共有7171条查询结果,搜索用时 15 毫秒
81.
James A. Phillips Anna R. Ley Patrick W. Treacy Benjamin M. Wahl Brittany C. Zehner Kelling J. Donald Samuel Gillespie 《International journal of quantum chemistry》2020,120(20):e26383
We have explored the structural and energetic properties of a series of RMX3-NH3 (M=Si, Ge; X=F, Cl; R=CH3, C6H5) complexes using density functional theory and low-temperature infrared spectroscopy. In the minimum-energy structures, the NH3 binds axially to the metal, opposite a halogen, while the organic group resides in an equatorial site. Remarkably, the primary mode of interaction in several of these systems seems to be hydrogen bonding (C-H--N) rather than a tetrel (N→M) interaction. This is particularly clear for the RMCl3-NH3 complexes, and analyses of the charge distributions of the acid fragment corroborate this assessment. We also identified a set of metastable geometries in which the ammonia binds opposite the organic substituent in an axial orientation. Acid fragment charge analyses also provide a clear rationale as to why these configurations are less stable than the minimum-energy structures. Matrix-isolation infrared spectra provide clear evidence for the occurrence of the minimum-energy form of CH3SiCl3–NH3, but analogous results for CH3GeCl3–NH3 are less conclusive. Computational scans of the M-N distance potentials for CH3SiCl3–NH3 and CH3GeCl3–NH3, both in the gas phase and bulk dielectric media, reveal a great deal of anharmonicity and a propensity for condensed-phase structural change. 相似文献
82.
Coupled Hartree-Fock theory is used to compute and map the current density induced in planar hydrocarbons by an external magnetic field. Results of useful accuracy can be obtained with modest (6-31G**) basis sets by employing a continuous gauge transformation. Maps are presented and discussed for benzene, naphthalene, anthracene, tetracene, pentacene, heptacene, and biphenylene. © 1996 John Wiley & Sons, Inc. 相似文献
83.
Thierry Boxus Michle Deldime-Rubbens Patrick Mougenot Yves-Jacques Schneider Jacqueline Marchand-Brynaert 《先进技术聚合物》1996,7(7):589-598
Poly(ethylene terephthalate) (PET) films and track-etched microporous membranes naturally display, on their surfaces, reactive chain-ends, i.e. carboxyl and hydroxyl functions. These were assayed by suitable activation (reaction with carbodiimide and tosyl chloride, respectively), followed by coupling with 3H-lysine and liquid scintillation counting of the sample-associated radioactivity. Values ranging between 5 and 30 pmol/cm2 (open surface) of labeled end-groups were obtained, depending on the physico-chemical nature of the samples. Basic hydrolysis enriched the PET films with both types of endings (15–25 pmol/cm2). Reduction of films with the NaBH4-catechol complex in tetrahydrofuran enriched their surfaces with hydroxyl groups. However, this procedure was not readily applicable to the surface modification of membranes; we observed an erosion effect that was confirmed by scanning electron microscope analyses. In contrast with the reduction process, the oxidation with KMnO4 in 1.2N H2SO4 could be easily applied to the modification of either films or membranes; their surfaces were significantly enriched with carboxyl groups (15–50 pmol/cm2). This surface modification strategy has been used for the covalent coupling of adhesive proteins on PET membranes developed as supports for cell cultivation. 相似文献
84.
Michel Boulouard Patrick Dallemagne Abdellah Alsaïdi Sylvain Rault 《Journal of heterocyclic chemistry》1996,33(6):1743-1749
Treatment of 3-(2-formyl-1H-pyrrol-1-yl)-2-thiophenecarboxamide by various nucleophiles like methyl ketones, amines, alcohols, thiols or acetates led to new 5,6-dihydro-4H-pyrrolo[1,2-a]thieno-[2,3-f][1,4]diazepines. 相似文献
85.
Philippe Savarino Emmanuel Colson Guillaume Caulier Igor Eeckhaut Patrick Flammang Pascal Gerbaux 《Molecules (Basel, Switzerland)》2022,27(2)
Saponins are plant and marine animal specific metabolites that are commonly considered as molecular vectors for chemical defenses against unicellular and pluricellular organisms. Their toxicity is attributed to their membranolytic properties. Modifying the molecular structures of saponins by quantitative and selective chemical reactions is increasingly considered to tune the biological properties of these molecules (i) to prepare congeners with specific activities for biomedical applications and (ii) to afford experimental data related to their structure–activity relationship. In the present study, we focused on the sulfated saponins contained in the viscera of Holothuria scabra, a sea cucumber present in the Indian Ocean and abundantly consumed on the Asian food market. Using mass spectrometry, we first qualitatively and quantitatively assessed the saponin content within the viscera of H. scabra. We detected 26 sulfated saponins presenting 5 different elemental compositions. Microwave activation under alkaline conditions in aqueous solutions was developed and optimized to quantitatively and specifically induce the desulfation of the natural saponins, by a specific loss of H2SO4. By comparing the hemolytic activities of the natural and desulfated extracts, we clearly identified the sulfate function as highly responsible for the saponin toxicity. 相似文献
86.
Xiao-Nan Zhang Albert T. Lam Qinqin Cheng Valentine V. Courouble Timothy S. Strutzenberg Jiawei Li Yiling Wang Hua Pei Bangyan L. Stiles Stan G. Louie Patrick R. Griffin Yong Zhang 《Chemical science》2022,13(7):1982
Among various protein posttranslational modifiers, poly-ADP-ribose polymerase 1 (PARP1) is a key player for regulating numerous cellular processes and events through enzymatic attachments of target proteins with ADP-ribose units donated by nicotinamide adenine dinucleotide (NAD+). Human PARP1 is involved in the pathogenesis and progression of many diseases. PARP1 inhibitors have received approvals for cancer treatment. Despite these successes, our understanding about PARP1 remains limited, partially due to the presence of various ADP-ribosylation reactions catalyzed by other PARPs and their overlapped cellular functions. Here we report a synthetic NAD+ featuring an adenosyl 3′-azido substitution. Acting as an ADP-ribose donor with high activity and specificity for human PARP1, this compound enables labelling and profiling of possible protein substrates of endogenous PARP1. It provides a unique and valuable tool for studying PARP1 in biology and pathology and may shed light on the development of PARP isoform-specific modulators.An analogue of nicotinamide adenine dinucleotide (NAD+) featuring an azido group at 3′-OH of adenosine moiety is found to possess high specificity for human PARP1-catalyzed protein poly-ADP-ribosylation. 相似文献
87.
Jérôme Deprince Manuel Bautista Stephan Fritzsche Javier García Timothy Kallman Claudio Mendoza Patrick Palmeri Pascal Quinet 《X射线光谱测定》2020,49(1):29-32
In the present work, we report an investigation of plasma environment effects on the atomic parameters associated with the K-vacancy states in highly charged iron ions within the astrophysical context of accretion disks around black holes. More particularly, the sensitivity of K-line X-ray fluorescence parameters (wavelengths, radiative transition probabilities, and Auger rates) in Fe XVII–Fe XXV ions has been estimated for plasma conditions characterized by an electron temperature ranging from 105 to 107 K and an electron density ranging from 1018 to 1022 cm−3. In order to do this, relativistic multiconfiguration Dirac-Fock atomic structure calculations have been carried out by considering a time averaged Debye-Hückel potential for both the electron–nucleus and electron–electron interactions. 相似文献
88.
Gabriela HuelgasLynne K. LaRochelle Lucrecia RivasYekaterina Luchinina Rubén A. ToscanoPatrick J. Carroll Patrick J. WalshCecilia Anaya de Parrodi 《Tetrahedron》2011,67(24):4467-4474
The catalytic asymmetric addition of alkyl groups to ketones has received considerable attention. Outlined herein is the synthesis of two new ligands based on the C2-symmetric 11,12-diamino-9,10-dihydro-9,10-ethanoanthracene. The scope of the new ligands has been evaluated in the catalytic asymmetric addition of diethylzinc to a variety of ketones. Enantioselectivities as high as 99% have been achieved. The structures of two of these ligands have been determined by X-ray crystallography and are compared with related structures. Additionally, the structure of a titanium complex bound to a bis(sulfonamide) diol ligand is reported. 相似文献
89.
回收率依赖回收产品质量的再制造EOQ模型 总被引:1,自引:0,他引:1
研究回收率依赖回收产品质量情况下制造/再制造混合系统的EOQ模型.该模型假设顾客的需求可通过新产品的制造和回收产品的再制造两种方式满足,且这两种产品无质量差异;需求率是确定的、连续的;总成本包括制造和再制造的固定启动成本,可销售产品和回收品的库存成本,以及缺货成本.当假设缺货成本无限大时给出不允许缺货情况下的模型.给出算例验证模型的有效性. 相似文献
90.