全文获取类型
收费全文 | 2075篇 |
免费 | 83篇 |
国内免费 | 9篇 |
专业分类
化学 | 1668篇 |
晶体学 | 8篇 |
力学 | 21篇 |
数学 | 170篇 |
物理学 | 300篇 |
出版年
2023年 | 29篇 |
2022年 | 41篇 |
2021年 | 52篇 |
2020年 | 75篇 |
2019年 | 64篇 |
2018年 | 47篇 |
2017年 | 26篇 |
2016年 | 73篇 |
2015年 | 57篇 |
2014年 | 65篇 |
2013年 | 93篇 |
2012年 | 175篇 |
2011年 | 202篇 |
2010年 | 80篇 |
2009年 | 59篇 |
2008年 | 114篇 |
2007年 | 137篇 |
2006年 | 110篇 |
2005年 | 110篇 |
2004年 | 91篇 |
2003年 | 69篇 |
2002年 | 52篇 |
2001年 | 19篇 |
2000年 | 14篇 |
1999年 | 11篇 |
1998年 | 12篇 |
1997年 | 15篇 |
1996年 | 8篇 |
1994年 | 9篇 |
1993年 | 10篇 |
1992年 | 9篇 |
1991年 | 10篇 |
1987年 | 5篇 |
1985年 | 11篇 |
1984年 | 18篇 |
1982年 | 11篇 |
1981年 | 23篇 |
1980年 | 20篇 |
1979年 | 5篇 |
1978年 | 11篇 |
1977年 | 11篇 |
1976年 | 8篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 11篇 |
1972年 | 5篇 |
1971年 | 6篇 |
1970年 | 6篇 |
1969年 | 6篇 |
1967年 | 6篇 |
排序方式: 共有2167条查询结果,搜索用时 0 毫秒
991.
Zhou M Kuralay F Windmiller JR Wang J 《Chemical communications (Cambridge, England)》2012,48(32):3815-3817
The integration of a biosensor employing a DNAzyme logic system within a biofuel cell is presented. The self-powered DNAzyme logic biosensor conforms with INH logic operation and generates power output in accordance with a truth table. The new concept of logic-activated DNAzyme by the input signals has wide-ranging implications in the self-powered diagnostics domain. 相似文献
992.
The activation of the P=C bond of phosphaalkenes with electrophiles is investigated as a means to prepare and characterize unusual organophosphorus compounds. Treatment of RP=CHtBu (1a: R=tBu; 1b: R=1-adamantyl) with HOTf (0.5 equiv) affords diphosphiranium salts [RP-CHtBu-PR (CH(2)tBu)]OTf ([2a]OTf and [2b]OTf), each containing a three-membered P(2)C ring. In contrast, the addition of MeOTf (0.5 equiv) to either 1a or 1b affords diphosphetanium salts [RP-CHtBu-P(Me)R-CHtBu]OTf ([3a]OTf and [3b]OTf) containing four-membered P(2)C(2) heterocycles. The phosphenium triflate [tBuP(CH(2)tBu)]OTf ([5a]OTf) and methylenephosphonium triflate [tBu(Me)P=CHtBu]OTf ([7a]OTf) are identified spectroscopically as intermediates in the formation of [2a](+) and [3a](+), respectively. The phosphenium triflate intermediate can be trapped with 2-butyne to afford phosphirenium salt [MeC=CMe-tBuPCH(2)tBu]OTf ([6a]OTf). Treatment of diphosphetanium [3a]OTf with an excess MeOTf affords [Me(2)P-CHtBu-PMetBu-CHtBu](OTf)(2) ([4a](OTf)(2)), a compound containing a diphosphetanium dication. The molecular structures are reported for [2a]OTf, [2b][H(OTf)(2)], [3a]I, [3b]I, [4a](OTf)(2), and [6a]OTf. 相似文献
993.
This contribution provides a new approach for single blood cell analysis in cerebrospinal fluid (CSF) with the possibility of utilizing simultaneously on the same sample the unique capabilities of the two methods fluorescence staining and Raman spectroscopy. By doing so this technique enables the potential of accurate and rapid cell identification in order to determine cell parameters immediately (e.g. the study of the level of activation or phagocytosis activity of single blood cells). Fluorescence labeling of blood cells offers the great possibility of differentiating easily between the subtypes of white blood cells, while Raman spectroscopy reveals molecular fingerprint information with a spatial resolution down to the diffraction limit. Compared to an unstained cell, the presented results nicely demonstrate that the selected fluorescence dye does not influence the Raman spectrum of a labeled blood cell notably. By the combined application of Raman spectroscopy and statistical data analysis a distinction between white blood cell substructures could be performed. Since several blood cell types also differ in the amount of their cell components, differentiation between several blood cell types is also possible when one blood cell is described in the database by several Raman spectra according their presented sub-microscopic structures. This capability with the possibility of accurate and rapid blood cell identification in cerebrospinal fluid is extremely promising for implementation in clinical diagnostics. 相似文献
994.
Pascal Poc Vanessa A. Gutzeit Julia Ast Joon Lee Ben J. Jones Elisa D'Este Bettina Mathes Martin Lehmann David J. Hodson Joshua Levitz Johannes Broichhagen 《Chemical science》2020,11(30):7871
Employing self-labelling protein tags for the attachment of fluorescent dyes has become a routine and powerful technique in optical microscopy to visualize and track fused proteins. However, membrane permeability of the dyes and the associated background signals can interfere with the analysis of extracellular labelling sites. Here we describe a novel approach to improve extracellular labelling by functionalizing the SNAP-tag substrate benzyl guanine (“BG”) with a charged sulfonate (“SBG”). This chemical manipulation can be applied to any SNAP-tag substrate, improves solubility, reduces non-specific staining and renders the bioconjugation handle impermeable while leaving its cargo untouched. We report SBG-conjugated fluorophores across the visible spectrum, which cleanly label SNAP-fused proteins in the plasma membrane of living cells. We demonstrate the utility of SBG-conjugated fluorophores to interrogate class A, B and C G protein-coupled receptors (GPCRs) using a range of imaging approaches including nanoscopic superresolution imaging, analysis of GPCR trafficking from intra- and extracellular pools, in vivo labelling in mouse brain and analysis of receptor stoichiometry using single molecule pull down.Impermeable SNAP-tag substrates allow exclusive labelling of receptors on the cell membrane for nanoscopy, SiMPull and in vivo use. 相似文献
995.
Siavosh Mahboobi Stella Eluwa Markus Koller Alfred Popp Dieter Schollmeyer 《Journal of heterocyclic chemistry》2000,37(5):1177-1185
3‐Amino‐4‐(3‐indolyl)pyrrolin‐2,5‐diones are condensed with various aldehydes and ketones to the cor responding imines. Under Pictet‐Spengler conditions, the latter do not cyclize to pyrrolo‐β‐carbolines, but readily yield pyrrolo[3′,4′:2,3]azepino[4,5,6‐cd]indole‐8,10‐diones. 相似文献
996.
Joshua D. Gilbert Christine M. Fisher Jiexun Bu Boone M. Prentice James G. Redwine Scott A. McLuckey 《Journal of mass spectrometry : JMS》2015,50(2):418-426
Several approaches for the generation of peptide radical cations using ion/ion reactions coupled with either collision induced dissociation (CID) or ultraviolet photo dissociation (UVPD) are described here. Ion/ion reactions are used to generate electrostatic or covalent complexes comprised of a peptide and a radical reagent. The radical site of the reagent can be generated multiple ways. Reagents containing a carbon–iodine (C―I) bond are subjected to UVPD with 266‐nm photons, which selectively cleaves the C―I bond homolytically. Alternatively, reagents containing azo functionalities are collisionally activated to yield radical sites on either side of the azo group. Both of these methods generate an initial radical site on the reagent, which then abstracts a hydrogen from the peptide while the peptide and reagent are held together by either electrostatic interactions or a covalent linkage. These methods are demonstrated via ion/ion reactions between the model peptide RARARAA (doubly protonated) and various distonic anionic radical reagents. The radical site abstracts a hydrogen atom from the peptide, while the charge site abstracts a proton. The net result is the conversion of a doubly protonated peptide to a peptide radical cation. The peptide radical cations have been fragmented via CID and the resulting product ion mass spectra are compared to the control CID spectrum of the singly protonated, even‐electron species. This work is then extended to bradykinin, a more broadly studied peptide, for comparison with other radical peptide generation methods. The work presented here provides novel methods for generating peptide radical cations in the gas phase through ion/ion reaction complexes that do not require modification of the peptide in solution or generation of non‐covalent complexes in the electrospray process. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
997.
Donahue NM Tischuk JE Marquis BJ Huff Hartz KE 《Physical chemistry chemical physics : PCCP》2007,9(23):2991-2998
Limona ketone was synthesized to explore the secondary organic aerosol (SOA) formation mechanism from limonene ozonolysis and also to test group-additivity concepts describing the volatility distribution of ozonolysis products from similar precursors. Limona ketone SOA production is indistinguishable from alpha-pinene, confirming the expected similarity. However, limona ketone SOA production is significantly less intense than limonene SOA production. The very low vapor pressure of limonene ozonolysis products is consistent with full oxidation of both double bonds in limonene and furthermore with production of products other than ketones after oxidation of the exo double bond in limonene. Mass-balance constraints confirm that ketone products from exo double-bond ozonolysis have a minimal contribution to the ultimate product yield. These results serve as the foundation for an emerging framework to describe the effect on volatility of successive generations of organic compounds in the atmosphere. 相似文献
998.
Wang G Zhang B Wayment JR Harris JM White HS 《Journal of the American Chemical Society》2006,128(23):7679-7686
Electrostatic-gated transport in chemically modified glass nanopore electrodes with orifice radii as small as 15 nm is reported. A single conical-shaped nanopore in glass, with a approximately 1 microm radius Pt disk located at the pore base, is prepared by etching the exposed surface of a glass-sealed Pt nanodisk. The electrochemical response of the nanopore electrode corresponds to diffusion of redox-active species through the nanopore orifice to the Pt microdisk. Silanization of the exterior glass surface with Cl(Me)(2)Si(CH(2))(3)CN and the interior pore surface with EtO(Me)(2)Si(CH(2))(3)NH(2) introduces pH-dependent ion selectivity at the pore orifice, a consequence of the electrostatic interactions between the redox ions and protonated surface amines. Nanopore electrodes with very small pore orifice radii (< approximately 50 nm) display anion permselectively at pH < 4, as demonstrated by electrochemical measurement of transport through the pore orifice. Ion selective transport vanishes at pH > 6 or when the pore radius is significantly larger than the Debye screening length, consistent with the observed ion selectivity resulting from electrostatic interactions. The ability to introduce different surface functionalities to the interior and exterior surfaces of glass nanopores is demonstrated using fluorescence microscopy to monitor the localized covalent attachment of 5- (and 6)-carboxytetramethylrhodamine succinimidyl ester to interior pore surfaces previously silanized with EtO(Me)(2)Si(CH(2))(3)NH(2). 相似文献
999.
SERS: a versatile tool in chemical and biochemical diagnostics 总被引:1,自引:0,他引:1
Hering K Cialla D Ackermann K Dörfer T Möller R Schneidewind H Mattheis R Fritzsche W Rösch P Popp J 《Analytical and bioanalytical chemistry》2008,390(1):113-124
Raman spectroscopy is a valuable tool in various research fields. The technique yields structural information from all kind
of samples often without the need for extensive sample preparation. Since the Raman signals are inherently weak and therefore
do not allow one to investigate substances in low concentrations, one possible approach is surface-enhanced (resonance) Raman
spectroscopy. Here, rough coin metal surfaces enhance the Raman signal by a factor of 104–1015, depending on the applied method. In this review we discuss recent developments in SERS spectroscopy and their impact on
different research fields. 相似文献
1000.
Joshua D. Thomas 《Tetrahedron letters》2006,47(49):8785-8787
Evidence is presented that contradicts an earlier finding that, in the absence of steric hindrance, the coupling reaction of alkylcarbonyloxymethyl (ACOM) halides with phenols favors acylated product. A one-step synthesis is used to generate sterically unhindered ACOM iodides, which are then reacted with several phenols to give mainly alkylated phenol. 相似文献