全文获取类型
收费全文 | 4314篇 |
免费 | 96篇 |
国内免费 | 29篇 |
专业分类
化学 | 2258篇 |
晶体学 | 31篇 |
力学 | 126篇 |
数学 | 668篇 |
物理学 | 762篇 |
无线电 | 594篇 |
出版年
2021年 | 37篇 |
2020年 | 48篇 |
2019年 | 59篇 |
2018年 | 41篇 |
2017年 | 35篇 |
2016年 | 63篇 |
2015年 | 63篇 |
2014年 | 57篇 |
2013年 | 177篇 |
2012年 | 137篇 |
2011年 | 160篇 |
2010年 | 93篇 |
2009年 | 85篇 |
2008年 | 136篇 |
2007年 | 170篇 |
2006年 | 183篇 |
2005年 | 177篇 |
2004年 | 143篇 |
2003年 | 146篇 |
2002年 | 149篇 |
2001年 | 105篇 |
2000年 | 86篇 |
1999年 | 57篇 |
1998年 | 68篇 |
1997年 | 73篇 |
1996年 | 67篇 |
1995年 | 69篇 |
1994年 | 72篇 |
1993年 | 71篇 |
1992年 | 76篇 |
1991年 | 64篇 |
1990年 | 64篇 |
1989年 | 59篇 |
1988年 | 67篇 |
1987年 | 58篇 |
1986年 | 59篇 |
1985年 | 92篇 |
1984年 | 74篇 |
1983年 | 59篇 |
1982年 | 76篇 |
1981年 | 54篇 |
1980年 | 61篇 |
1979年 | 51篇 |
1978年 | 57篇 |
1977年 | 44篇 |
1976年 | 62篇 |
1975年 | 59篇 |
1974年 | 71篇 |
1973年 | 65篇 |
1972年 | 37篇 |
排序方式: 共有4439条查询结果,搜索用时 15 毫秒
201.
Tau protein undergoes complex biochemical processes involved in normal and diseased cellular functions; specifically, tau pathology has been linked to neurodegeneration. At the heart of tau biochemistry are three pillars: microtubules, phosphorylation, and aggregation. However, these three processes are also regulated through other biomolecules in the biological setting, such as metal ions and small and larger ligands, including proteins and nucleic acids. This review describes the latest electrochemical approaches toward greater understanding of tau biochemistry, early disease diagnosis, and drug inhibitor screening. 相似文献
202.
Tvaskis V Christy ME Arrington J Asaturyan R Baker OK Blok HP Bosted P Boswell M Bruell A Cochran A Cole L Crowder J Dunne J Ent R Fenker HC Filippone BW Garrow K Gasparian A Gomez J Jackson HE Keppel CE Kinney E Lapikás L Liang Y Lorenzon W Lung A Mack DJ Martin JW McIlhany K Meekins D Milner RG Mitchell JH Mkrtchyan H Moreland B Nazaryan V Niculescu I Opper A Piercey RB Potterveld DH Rose B Sato Y Seo W Smith G Spurlock K van der Steenhoven G Stepanyan S Tadevosian V Uzzle A Vulcan WF Wood SA 《Physical review letters》2007,98(14):142301
We report on a study of the longitudinal to transverse cross section ratio, R=sigmaL/sigmaT, at low values of x and Q2, as determined from inclusive inelastic electron-hydrogen and electron-deuterium scattering data from Jefferson Laboratory Hall C spanning the four-momentum transfer range 0.06相似文献
203.
Pfeifer P Aston L Banks M Barker S Burress J Carter S Coleman J Crockett S Faulhaber C Flavin J Gordon M Hardcastle L Kallenborn Z Kemiki M Lapilli C Pobst J Schott R Shah P Spellerberg S Suppes G Taylor D Tekeei A Wexler C Wood M Buckley P Breier T Downing J Eastman S Freeze P Graham S Grinter S Howard A Martinez J Radke D Vassalli T Ilavsky J 《Chaos (Woodbury, N.Y.)》2007,17(4):041108
204.
Dr. Lewis C. H. Maddock Rebekka Morton Dr. Alan R. Kennedy Prof. Dr. Eva Hevia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(61):15181-15187
Alkali-metal ferrates containing amide groups have emerged as regioselective bases capable of promoting Fe−H exchanges of aromatic substrates. Advancing this area of heterobimetallic chemistry, a new series of sodium ferrates is introduced incorporating the bulky arylsilyl amido ligand N(SiMe3)(Dipp) (Dipp=2,6-iPr2-C6H3). Influenced by the large steric demands imposed by this amide, transamination of [NaFe(HMDS)3] (HMDS=N(SiMe3)2) with an excess of HN(SiMe3)(Dipp) led to the isolation of heteroleptic [Na(HMDS)2Fe{N(SiMe3)Dipp}]∞ ( 1 ) resulting from the exchange of just one HMDS group. An alternative co-complexation approach, combining the homometallic metal amides [NaN(SiMe3)Dipp] and [Fe{N(SiMe3)Dipp}2] induces lateral metallation of one Me arm from the SiMe3 group in the iron amide furnishing tetrameric [NaFe{N(SiCH2Me2)Dipp}{N(SiMe3)Dipp}]4 ( 2 ). Reactivity studies support that this deprotonation is driven by the steric incompatibility of the single metal amides rather than the basic capability of the sodium reagent. Displaying synergistic reactivity, heteroleptic sodium ferrate 1 can selectively promote ferration of pentafluorobenzene using one of its HMDS arms to give heterotrileptic [Na{N(SiMe3)Dipp}(HMDS)Fe(C6F5)]∞ ( 4 ). Attempts to deprotonate less activated pyridine led to the isolation of NaHMDS and heteroleptic Fe(II) amide [(py)Fe{N(SiMe3)Dipp}(HMDS)] ( 5 ), resulting from an alternative redistribution process which is favoured by the Lewis donor ability of this substrate. 相似文献
205.
Let T f be a Toeplitz operator on the Segal–Bargmann space or the standard weighted Bergman space over a bounded symmetric domain \({\Omega \subset {\bf C}^n}\) with possibly unbounded symbol f. Combining recent results in Bauer et al. (J. Funct. Anal. 259:57–78, 2010), Bauer et al. (J. reine angew. Math. doi: 10.1515/crelle-2015-0016), Issa (Integr. Equ. Oper. Theory 70:569–582, 2011) we show that in the case of uniformly continuous symbols f with respect to the Euclidean metric on C n and the Bergman metric on \({\Omega}\), respectively, the operator T f is bounded if and only if f is bounded. Moreover, T f is compact if and only if f vanishes at the boundary of \({\Omega.}\) This observation substantially extends a result in Coburn (Indiana Univ. Math. J. 23:433–439, 1973). 相似文献
206.
Ewelina Lipiec Dr. Ryo Sekine Dr. Jakub Bielecki Prof. Dr. Wojciech M. Kwiatek Assoc. Prof. Bayden R. Wood 《Angewandte Chemie (International ed. in English)》2014,53(1):169-172
DNA double strand breaks (DSBs) are deadly lesions that can lead to genetic defects and cell apoptosis. Techniques that directly detect DNA DSBs include scanning electron microscopy, atomic force microscopy (AFM), and fluorescence based approaches. While these techniques can be used to identify DSBs they provide no information on the molecular events occurring at the break. Tip‐enhanced Raman scattering (TERS) can provide molecular information from DNA at the nanoscale and in combination with AFM provides a new way to visualize and characterize the molecular structure of DSBs. DSBs result from cleavage at the 3’‐ and 5’‐bonds of deoxyribose upon exposure to UVC radiation based on the observation of P? O? H and methyl/methylene deformation modes enhanced in the TERS spectra. It is hypothesized that strand fragments are hydrogen‐terminated at the lesion, indicating the action of free radicals during photon exposure. 相似文献
207.
A Novel Bismuth‐Based Metal–Organic Framework for High Volumetric Methane and Carbon Dioxide Adsorption 下载免费PDF全文
Mathew Savage Dr. Sihai Yang Dr. Mikhail Suyetin Prof. Dr. Elena Bichoutskaia Dr. William Lewis Prof. Dr. Alexander J. Blake Sarah A. Barnett Prof. Dr. Martin Schröder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(26):8024-8029
Solvothermal reaction of H4L (L=biphenyl‐3,3′,5,5′‐tetracarboxylate) and Bi(NO3)3 ? (H2O)5 in a mixture of DMF/MeCN/H2O in the presence of piperazine and nitric acid at 100 °C for 10 h affords the solvated metal–organic polymer [Bi2(L)1.5(H2O)2] ? (DMF)3.5 ? (H2O)3 (NOTT‐220‐solv). A single crystal X‐ray structure determination confirms that it crystallises in space group P2/c and has a neutral and non‐interpenetrated structure comprising binuclear {Bi2} centres bridged by tetracarboxylate ligands. NOTT‐220‐solv shows a 3,6‐connected network having a framework topology with a {4 ? 62}2{42 ? 65 ? 88}{62 ? 8} point symbol. The desolvated material NOTT‐220a shows exceptionally high adsorption uptakes for CH4 and CO2 on a volumetric basis at moderate pressures and temperatures with a CO2 uptake of 553 g L?1 (20 bar, 293 K) with a saturation uptake of 688 g L?1 (1 bar, 195 K). The corresponding CH4 uptake was measured as 165 V(STP)/V (20 bar, 293 K) and 189 V(STP/V) (35 bar, 293 K) with a maximum CH4 uptake for NOTT‐220a recorded at 20 bar and 195 K to be 287 V(STP)/V, while H2 uptake of NOTT‐220a at 20 bar, 77 K is 42 g L?1. These gas uptakes have been modelled by grand canonical Monte Carlo (GCMC) and density functional theory (DFT) calculations, which confirm the experimental data and give insights into the nature of the binding sites of CH4 and CO2 in this porous hybrid material. 相似文献
208.
The Ketimide Ligand is Not Just an Inert Spectator: Heteroallene Insertion Reactivity of an Actinide–Ketimide Linkage in a Thorium Carbene Amide Ketimide Complex 下载免费PDF全文
Dr. Erli Lu Dr. William Lewis Prof. Alexander J. Blake Prof. Stephen T. Liddle 《Angewandte Chemie (International ed. in English)》2014,53(35):9356-9359
The ketimide anion R2C?N? is an important class of chemically robust ligand that binds strongly to metal ions and is considered ideal for supporting reactive metal fragments due to its inert spectator nature; this contrasts with R2N? amides that exhibit a wide range of reactivities. Here, we report the synthesis and characterization of a rare example of an actinide ketimide complex [Th(BIPMTMS){N(SiMe3)2}(N?CPh2)] [ 2 , BIPMTMS=C(PPh2NSiMe3)2]. Complex 2 contains Th?Ccarbene, Th? Namide and Th? Nketimide linkages, thereby presenting the opportunity to probe the preferential reactivity of these linkages. Importantly, reactivity studies of 2 with unsaturated substrates shows that insertion reactions occur preferentially at the Th? Nketimide bond rather than at the Th?Ccarbene or Th? Namide bonds. This overturns the established view that metal‐ketimide linkages are purely inert spectators. 相似文献
209.
Dr. Cheng‐Chung Lee Dr. Manuel Maestre‐Reyna Dr. Kai‐Cheng Hsu Prof. Dr. Hao‐Ching Wang Prof. Dr. Chia‐I Liu Prof. Dr. Wen‐Yih Jeng Li‐Ling Lin Richard Wood Dr. Chia‐Cheng Chou Prof. Dr. Jinn‐Moon Yang Prof. Dr. Andrew H.‐J. Wang 《Angewandte Chemie (International ed. in English)》2014,53(48):13054-13058
Crown ethers are small, cyclic polyethers that have found wide‐spread use in phase‐transfer catalysis and, to a certain degree, in protein chemistry. Crown ethers readily bind metallic and organic cations, including positively charged amino acid side chains. We elucidated the crystal structures of several protein‐crown ether co‐crystals grown in the presence of 18‐crown‐6. We then employed biophysical methods and molecular dynamics simulations to compare these complexes with the corresponding apoproteins and with similar complexes with ring‐shaped low‐molecular‐weight polyethylene glycols. Our studies show that crown ethers can modify protein surface behavior dramatically by stabilizing either intra‐ or intermolecular interactions. Consequently, we propose that crown ethers can be used to modulate a wide variety of protein surface behaviors, such as oligomerization, domain–domain interactions, stabilization in organic solvents, and crystallization. 相似文献
210.
Frontispiece: NMR Fingerprints of the Drug‐like Natural‐Product Space Identify Iotrochotazine A: A Chemical Probe to Study Parkinson’s Disease 下载免费PDF全文