全文获取类型
收费全文 | 10471篇 |
免费 | 298篇 |
国内免费 | 31篇 |
专业分类
化学 | 7863篇 |
晶体学 | 31篇 |
力学 | 162篇 |
数学 | 1782篇 |
物理学 | 962篇 |
出版年
2020年 | 138篇 |
2019年 | 104篇 |
2018年 | 77篇 |
2017年 | 81篇 |
2016年 | 189篇 |
2015年 | 198篇 |
2014年 | 187篇 |
2013年 | 351篇 |
2012年 | 392篇 |
2011年 | 453篇 |
2010年 | 336篇 |
2009年 | 279篇 |
2008年 | 455篇 |
2007年 | 441篇 |
2006年 | 466篇 |
2005年 | 439篇 |
2004年 | 379篇 |
2003年 | 312篇 |
2002年 | 327篇 |
2001年 | 222篇 |
2000年 | 155篇 |
1999年 | 144篇 |
1998年 | 179篇 |
1997年 | 146篇 |
1996年 | 150篇 |
1995年 | 150篇 |
1994年 | 143篇 |
1993年 | 190篇 |
1992年 | 127篇 |
1991年 | 127篇 |
1990年 | 114篇 |
1989年 | 134篇 |
1988年 | 131篇 |
1987年 | 167篇 |
1986年 | 156篇 |
1985年 | 174篇 |
1984年 | 186篇 |
1983年 | 155篇 |
1982年 | 142篇 |
1981年 | 150篇 |
1980年 | 153篇 |
1979年 | 145篇 |
1978年 | 136篇 |
1977年 | 119篇 |
1976年 | 133篇 |
1975年 | 91篇 |
1974年 | 88篇 |
1973年 | 88篇 |
1971年 | 80篇 |
1970年 | 71篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Oliver Neudert Dmitry Germanovich Zverev Christian Bauer Peter Blümler Hans Wolfgang Spiess Dariush Hinderberger Kerstin Münnemann 《Applied magnetic resonance》2012,43(1-2):149-165
Power-dependent Overhauser dynamic nuclear polarization (DNP) enhancements and continuous-wave electron paramagnetic resonance (EPR) spectra of nitroxide radicals were measured in the magnetic field of a mobile Halbach-array permanent magnet and compared with results from a commercially available electromagnet. DNP saturation factors for varying microwave power were obtained from both measurement series and used to investigate how the increased magnetic field inhomogeneity present in the Halbach magnet affects the saturation efficiency. An EPR detection system was designed to allow continuous-wave EPR measurements at microwave power up to 20?W. Our results show that despite the lower magnetic field homogeneity, a Halbach-array magnet can be used for EPR and DNP-enhanced nuclear magnetic resonance of high quality providing almost the same performance as a more homogeneous electromagnet. 相似文献
942.
943.
E. Wolfgang Holla Manfred Schudok Angelika Weber Matthias Zulauf 《Journal of carbohydrate chemistry》2013,32(5):659-663
Abstract In 1988, MOSBACH et aL1 reported the synthesis of a-D-mannopyranosy1-L-serine and Q -D-N-acetylgalactosamino-L-serine by reversing the hydrolytic activity of a -mannosidase from jack beans and a -N-acetylgalactosaminidase from beef liver, respectively. The yields in these equilibrium-controlled syntheses2 using high concentrations of monosaccharide and serine were highly dependent on the enzyme concentration and ranged from 5 to 10 percent in both cases. 相似文献
944.
Synthesis and characterization of polymer linked copper(I) bis(N‐heterocyclic carbene) mechanocatalysts 下载免费PDF全文
Philipp Michael Shima Khazraee Sheidaee Mehr Wolfgang H. Binder 《Journal of polymer science. Part A, Polymer chemistry》2017,55(23):3893-3907
In this paper, the synthesis and characterization of a series of latent polymeric bis(N‐heterocyclic carbene) (NHC) copper(I) complexes is reported, which can be activated for the copper(I)‐catalyzed azide/alkyne cycloaddition (CuAAC) via ultrasound. To prove the influence of chain length and nature of the polymer towards the activation, poly(isobutylene) (PIB), poly(styrene) (PS) and poly(tetrahydrofuran) (PTHF) are synthesized via living polymerization techniques (LCCP, ATRP, CROP) obtaining different chain lengths (from 2500 to 9000 g/mol), followed by quaternization with N‐methylimidazole, generating the corresponding N‐methylimidazolium‐telechelic polymers. The deprotonation of these macroligands via strong bases like sodium tert‐butoxide (NaOtBu) or potassium hexamethyldisilazide (KHMDS) yields the free N‐heterocyclic carbenes (NHCs), which are used to coordinate to tetrakis(acetonitrile)copper(I) hexafluorophosphate, forming the final polymer‐based mono‐ and bis(N‐methylimidazole‐2‐ylidene) copper(I)X complexes. The structural proof of these complexes is accomplished via 1H‐NMR spectroscopy, MALDI‐TOF‐MS and GPC‐techniques. The activation of the copper(I) biscarbene catalysts by ultrasound is studied by GPC, revealing the cleavage of one shielding NHC‐ligand. The initial catalytic latency and the via ultrasound introduced catalytic activation is successfully demonstrated monitoring a CuAAC “click” reaction of benzyl azide and phenylacetylene by in situ 1H‐NMR spectroscopy introducing thus “click” conversions up to 97%. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3893–3907 相似文献
945.
Dr. Michael Jäger Dr. Helmar Görls Dr. Wolfgang Günther Prof. Dr. Ulrich S. Schubert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(6):2150-2157
A new modular approach based on Pd‐catalyzed C? C bond formation is presented for the assembly of a benzannulated azocine scaffold, the key intermediate in the synthesis of functionalized azadibenzocyclooctynes (aza‐DIBOs). The intramolecular ring‐closing Heck coupling was investigated by variation of the C? X bond. The reaction rate is limited by the initial oxidative addition step and the regiochemistry strongly depends on the auxiliary phosphine. Under optimized conditions, the 8‐endo regioisomer was obtained in 71 % yield over two steps (with no protecting group chemistry) or in one pot, inclusive of C? N bond formation. The practical generation of the octyne triple bond of a prototypical N‐benzoyl aza‐DIBO, without the need for chromatographic purification, is also described. The structural features, including those of the ring‐strained cyclic octyne, were elucidated by NMR spectroscopy and X‐ray crystallographic analysis. The high reactivity of the N‐benzoyl aza‐DIBO synthesized is demonstrated in a strain‐promoted azide–alkyne cycloaddition reaction with an alkyl azide (k=0.38 M ?1 s?1). 相似文献
946.
947.
948.
949.
Valerie Huemer Gernot A. Eller Wolfgang Holzer 《Magnetic resonance in chemistry : MRC》2010,48(6):476-482
Various [5,6]pyrano[2,3‐c]pyrazol‐4(1H)‐thiones were synthesized in high yields by treatment of the corresponding [5,6]pyrano[2,3‐c]pyrazol‐4(1H)‐ones with Lawesson's reagent. Detailed NMR spectroscopic studies were undertaken of the title compounds. Complete and unambiguous assignment of chemical shifts (1H, 13C, 15N) and coupling constants (1H,1H; 13C,1H) was achieved by the combined application of various one‐ and two‐dimensional (1D and 2D) NMR spectroscopic techniques. Unequivocal mapping of most 13C,1H spin coupling constants is accomplished by 2D (δ, J) long‐range INEPT spectra with selective excitation. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
950.
A blue light-inducible phosphodiesterase (PDE) activity, specific for the hydrolysis of cyclic di-GMP (c-di-GMP), has been identified in a recombinant protein from Synechococcus elongatus. Blue light (BL) activation is accomplished by a light, oxygen, voltage (LOV) domain, found in plant phototropins and bacterial BL photoreceptors. The genome of S. elongatus contains two genes coding for proteins with LOV domains fused to EAL domains (SL1 and SL2). In both cases, a GGDEF motif is placed in between the LOV and the EAL motifs. Such arrangement is frequently found with diguanylate-cyclase (DGC) functions that form c-di-GMP. Cyclic di-GMP acts as a second messenger molecule regulating biofilm formation in many microbial species. Both enzyme activities modulate the intracellular level of this second messenger, although in most proteins only one of the two enzyme functions is active. Both S. elongatus LOV-GGDEF-EAL proteins were expressed in full length or as truncated proteins. Only the SL2 protein, expressed as a LOV-GGDEF-EAL construct, showed an increase of PDE activity upon BL irradiation, demonstrating this activity for the first time in a LOV-domain protein. Addition of GTP or c-di-GMP did not affect the observed enzymatic activity. In none of the full-length or truncated proteins was a DGC activity detected. 相似文献