全文获取类型
收费全文 | 6037篇 |
免费 | 206篇 |
国内免费 | 34篇 |
专业分类
化学 | 4477篇 |
晶体学 | 36篇 |
力学 | 139篇 |
数学 | 840篇 |
物理学 | 785篇 |
出版年
2023年 | 34篇 |
2022年 | 21篇 |
2021年 | 49篇 |
2020年 | 84篇 |
2019年 | 83篇 |
2018年 | 57篇 |
2017年 | 50篇 |
2016年 | 153篇 |
2015年 | 130篇 |
2014年 | 140篇 |
2013年 | 283篇 |
2012年 | 376篇 |
2011年 | 424篇 |
2010年 | 216篇 |
2009年 | 186篇 |
2008年 | 386篇 |
2007年 | 421篇 |
2006年 | 452篇 |
2005年 | 382篇 |
2004年 | 341篇 |
2003年 | 299篇 |
2002年 | 231篇 |
2001年 | 71篇 |
2000年 | 39篇 |
1999年 | 42篇 |
1998年 | 38篇 |
1997年 | 69篇 |
1996年 | 74篇 |
1995年 | 63篇 |
1994年 | 63篇 |
1993年 | 98篇 |
1992年 | 55篇 |
1991年 | 53篇 |
1990年 | 70篇 |
1989年 | 50篇 |
1988年 | 40篇 |
1987年 | 38篇 |
1986年 | 33篇 |
1985年 | 70篇 |
1984年 | 55篇 |
1983年 | 37篇 |
1982年 | 66篇 |
1981年 | 58篇 |
1980年 | 47篇 |
1979年 | 47篇 |
1978年 | 44篇 |
1977年 | 27篇 |
1976年 | 40篇 |
1975年 | 23篇 |
1974年 | 19篇 |
排序方式: 共有6277条查询结果,搜索用时 15 毫秒
1.
Susan C. Scott Nicole M. Anders Ping He Avelina Hemingway Steven D. Gore Christine L. Hann Michelle A. Rudek 《Biomedical chromatography : BMC》2022,36(3):e5289
The Bcl-2 family small molecule inhibitor navitoclax is being clinically evaluated to treat multiple cancers including lymphoid malignancies and small cell lung cancer. A sensitive and reliable method was developed to quantitate navitoclax in human plasma using liquid chromatography with tandem mass spectrometry with which to perform detailed pharmacokinetic studies. Sample preparation involved protein precipitation using acetonitrile. Separation of navitoclax and the internal standard, navitoclax-d8, was achieved with a Waters Acquity UPLC BEH C18 column using isocratic flow over a 3 min total analytical run time. A SCIEX 4500 triple quadrupole mass spectrometer operated in positive electrospray ionization mode was used for the detection of navitoclax. The assay range was 5–5,000 ng/ml and proved to be accurate (89.5–104.9%) and precise (CV ≤ 11%). Long-term frozen plasma stability for navitoclax at −70°C was at least 43 months. The method was applied for the measurement of total plasma concentration of navitoclax in a patient receiving a 250 mg daily oral dose. 相似文献
2.
Steven Heilman 《Random Structures and Algorithms》2020,56(1):154-168
We prove the endpoint case of a conjecture of Khot and Moshkovitz related to the unique games conjecture, less a small error. Let n ≥ 2. Suppose a subset Ω of n‐dimensional Euclidean space satisfies ?Ω = Ωc and Ω + v = Ωc (up to measure zero sets) for every standard basis vector . For any and for any q ≥ 1, let and let . For any x ∈ ?Ω, let N(x) denote the exterior normal vector at x such that ‖N(x)‖2 = 1. Let . Our main result shows that B has the smallest Gaussian surface area among all such subsets Ω, less a small error: In particular, Standard arguments extend these results to a corresponding weak inequality for noise stability. Removing the factor 6 × 10?9 would prove the endpoint case of the Khot‐Moshkovitz conjecture. Lastly, we prove a Euclidean analogue of the Khot and Moshkovitz conjecture. The full conjecture of Khot and Moshkovitz provides strong evidence for the truth of the unique games conjecture, a central conjecture in theoretical computer science that is closely related to the P versus NP problem. So, our results also provide evidence for the truth of the unique games conjecture. Nevertheless, this paper does not prove any case of the unique games conjecture. 相似文献
3.
Emily K. Corlett Helen Blade Leslie P. Hughes Philip J. Sidebottom David Walker Richard I. Walton Steven P. Brown 《Magnetic resonance in chemistry : MRC》2020,58(11):1026-1035
Single-crystal X-ray diffraction structures of the 5-amino-2-methylpyridinium hydrogen fumarate salt have been solved at 150 and 300 K (CCDC 1952142 and 1952143). A base–acid–base–acid ring is formed through pyridinium-carboxylate and amine-carboxylate hydrogen bonds that hold together chains formed from hydrogen-bonded hydrogen fumarate ions. 1H and 13C chemical shifts as well as 14N shifts that additionally depend on the quadrupolar interaction are determined by experimental magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) and gauge-including projector-augmented wave (GIPAW) calculation. Two-dimensional homonuclear 1H-1H double-quantum (DQ) MAS and heteronuclear 1H-13C and 14N-1H spectra are presented. Only small differences of up to 0.1 and 0.6 ppm for 1H and 13C are observed between GIPAW calculations starting with the two structures solved at 150 and 300 K (after geometry optimisation of atomic positions, but not unit cell parameters). A comparison of GIPAW-calculated 1H chemical shifts for isolated molecules and the full crystal structures is indicative of hydrogen bonding strength. 相似文献
4.
Physical aging in amorphous poly(ethylene furanoate): Enthalpic recovery,density, and oxygen transport considerations 下载免费PDF全文
Steven K. Burgess Christopher R. Mubarak Robert M. Kriegel William J. Koros 《Journal of Polymer Science.Polymer Physics》2015,53(6):389-399
The current work utilizes three separate techniques to study the physical aging process in amorphous poly(ethylene furanoate) (PEF), which is a recently introduced engineering thermoplastic with enhanced properties compared to petroleum‐sourced poly(ethylene terephthalate). Differential scanning calorimetry aging experiments were conducted at multiple aging temperatures and times, and the resultant enthalpic recovery values compared to the theoretical maximum enthalpy loss evaluated from calculations involving extrapolation of the equilibrium liquid line. Density measurements reveal densification of the matrix for the aged versus unaged samples, and provide an estimate for the reduction in free volume for the aged samples. Complementary oxygen permeation and pressure‐decay sorption experiments provide independent verification of the free volume reduction mechanism for physical aging in glassy polymers. The current work provides the first detailed aging study for PEF. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 389–399 相似文献
5.
6.
7.
Crosslinked poly(ethylene oxide) containing siloxanes fabricated through thiol‐ene photochemistry 下载免费PDF全文
Victor A. Kusuma Elliot A. Roth William P. Clafshenkel Steven S. Klara Xu Zhou Surendar R. Venna Erik Albenze David R. Luebke Meagan S. Mauter Richard R. Koepsel Alan J. Russell David Hopkinson Hunaid B. Nulwala 《Journal of polymer science. Part A, Polymer chemistry》2015,53(13):1548-1557
Homogenous amphiphilic crosslinked polymer films comprising of poly(ethylene oxide) and polysiloxane were synthesized utilizing thiol‐ene “ click ” photochemistry. A systematic variation in polymer composition was Carried out to obtain high quality films with varied amount of siloxane and poly(ethylene oxide). These films showed improved gas separation performance with high gas permeabilities with good CO2/N2 selectivity. Furthermore, the resulting films were also tested for its biocompatibility, as a carrier media which allow human adult mesenchymal stem cells to retain their capacity for osteoblastic differentiation after transplantation. The obtained crosslinked films were characterized using differential scanning calorimetry, dynamic mechanical analysis, thermogravimetric analysis, FTIR, Raman‐IR , and small angle X‐ray scattering. The synthesis ease and commercial availability of the starting materials suggests that these new crosslinked polymer networks could find applications in wide range of applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1548–1557 相似文献
8.
Hui Li Jian Liu Juan Zhao Huiting He Dr. Dabo Jiang Prof. Steven Robert Kirk Prof. Qiong Xu Dr. Xianxiang Liu Prof. Dulin Yin 《ChemistryOpen》2021,10(4):477-485
A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of β-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO3]4 under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss. 相似文献
9.
Georgia Englezou Kristoffer Kortsen Ana A. C. Pacheco Robert Cavanagh Joachim C. Lentz Eduards Krumins Carlos Sanders-Velez Steven M. Howdle Alisyn J. Nedoma Vincenzo Taresco 《Journal of polymer science. Part A, Polymer chemistry》2020,58(11):1571-1581
2-methyltetrahydrofuran (2-MeTHF) is a readily available, inexpensive, neoteric, bio-based solvent. It has been adopted across a wide range of chemical processes including the batch manufacture of fine chemicals, enzymatic polycondensations and ring opening polymerizations. To reduce the environmental burden related to the synthesis of pharmaceutical-grade polymers based on lactide and caprolactone, we envisaged the use of 2-MeTHF. For the first time, we combined a series of metal-free and enzymatic ROPs with free radical and controlled RAFT polymerizations (carried out separately and in tandem) in 2-MeTHF, in order to easily tune the chemistry and the architecture of the final polymers. After a simple purification, the amphiphilic polymers were formulated into nanoparticles and tested for their cytocompatibility in three model cell lines, to assess their application as potential polymeric excipients for nanomedicines. 相似文献
10.
Nikolaos V. Tzouras Dr. Fady Nahra Dr. Laura Falivene Prof. Dr. Luigi Cavallo Marina Saab Prof. Dr. Kristof Van Hecke Dr. Alba Collado Dr. Christopher J. Collett Prof. Dr. Andrew D. Smith Prof. Dr. Catherine S. J. Cazin Prof. Dr. Steven P. Nolan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(20):4515-4519
We have been puzzled by the involvement of weak organic and inorganic bases in the synthesis of metal–N-heterocyclic carbene (NHC) complexes. Such bases are insufficiently strong to permit the presumed required deprotonation of the azolium salt (the carbene precursor) prior to metal binding. Experimental and computational studies provide support for a base-assisted concerted process that does not require free NHC formation. The synthetic protocol was found applicable to a number of transition-metal- and main-group-centered NHC compounds and could become the synthetic route of choice to form M–NHC bonds. 相似文献