全文获取类型
收费全文 | 1145篇 |
免费 | 59篇 |
国内免费 | 30篇 |
专业分类
化学 | 792篇 |
晶体学 | 7篇 |
力学 | 73篇 |
数学 | 79篇 |
物理学 | 283篇 |
出版年
2023年 | 6篇 |
2022年 | 7篇 |
2021年 | 22篇 |
2020年 | 20篇 |
2019年 | 19篇 |
2018年 | 21篇 |
2017年 | 14篇 |
2016年 | 28篇 |
2015年 | 41篇 |
2014年 | 44篇 |
2013年 | 60篇 |
2012年 | 62篇 |
2011年 | 80篇 |
2010年 | 63篇 |
2009年 | 46篇 |
2008年 | 73篇 |
2007年 | 65篇 |
2006年 | 65篇 |
2005年 | 56篇 |
2004年 | 79篇 |
2003年 | 47篇 |
2002年 | 38篇 |
2001年 | 27篇 |
2000年 | 29篇 |
1999年 | 18篇 |
1998年 | 9篇 |
1997年 | 13篇 |
1996年 | 18篇 |
1995年 | 14篇 |
1994年 | 9篇 |
1993年 | 10篇 |
1992年 | 19篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 8篇 |
1987年 | 11篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 10篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1974年 | 4篇 |
排序方式: 共有1234条查询结果,搜索用时 15 毫秒
41.
42.
Alexey P. Kostikov Joshua Chin Björn Wängler Klaus Jurkschat Ralf Schirrmacher 《Journal of fluorine chemistry》2011,132(1):27-6205
18F-labeled compounds play a major role in the development of new in vivo imaging agents for Positron Emission Tomography (PET), a non invasive imaging modality depicting the biodistribution of radioactive compounds in humans. Recently we reported a new method for the introduction of fluorine-18 into a range of organic molecules exploiting the very fast 18F-19F isotope exchange of fluorosilanes (termed SiFA compounds). Here, we wish to report the labeling of the first charged SiFA molecule N-(4-(di-tert-butylfluorosilyl)benzyl)-2-hydroxy-N,N-dimethylethylammonium bromide (SiFAN+Br−) serving as a lead compound in the development of SiFA-based prosthetic groups of reduced lipophilicity for biomolecule labeling. Mild conditions for synthesis of [18F]SiFAN+Br− and an easy purification procedure using simple C-18 solid phase cartridge have been developed yielding the [18F]SiFAN+Br− in radiochemical yields of 34% (non-decay corrected) within 40 min. A series of kinetic experiments were performed that show high isotopic exchange rate constants. Low activation energy (15.7 kcal/mol) and a large preexponential factor (7.9 × 1013 M−1 s−1) were calculated for the isotopic exchange reaction from a corresponding Arrhenius plot. For comparison, the 18F-fluorination of ethyleneglycol-di-p-tosylate via the formation of a carbon-18F bond showed a 1.3 kcal/mol higher activation energy and a much lower preexponential factor of 2.9 × 109 M−1 s−1. Moderate hydrophilicity (log D = 0.44), stability in aqueous media at pH up to 7.4 and a high specific activity of [18F]SiFAN+Br− (SA = 20.4 GBq/μmol, 0.55 Ci/μmol) make this charged SiFA compound useful for the development of novel SiFA-based 18F-labeling synthons. 相似文献
43.
Fatty acid methyl ester (FAME) profiling in complex fish oil and milk fat samples was studied using integrated comprehensive 2D GC (GC × GC) and multidimensional GC (MDGC). Using GC × GC, FAME compounds – cis‐ and trans‐isomers, and essential fatty acid isomers – ranging from C18 to C22 in fish oil and C18 in milk fat were clearly displayed in contour plot format according to structural properties and patterns, further identified based on authentic standards. Incompletely resolved regions were subjected to MDGC, with Cn (n = 18, 20) zones transferred to a 2D column. Elution behavior of C18 FAME on various 2D column phases (ionic liquids IL111, IL100, IL76, and modified PEG) was evaluated. Individual isolated Cn zones demonstrated about four‐fold increased peak capacities. The IL100 provided superior separation, good peak shape, and utilization of elution space. For milk fat‐derived FAME, the 2D chromatogram revealed at least three peaks corresponding to C18:1, more than six peaks for cis/trans‐C18:2 isomers, and two peaks for C18:3. More than 17 peaks were obtained for the C20 region of fish oil‐derived FAMEs using MDGC, compared with ten peaks using GC × GC. The MDGC strategy is useful for improved FAME isomer separation and confirmation. 相似文献
44.
Won Sohn Jonghwa Kim So Hee Kang Se Ra Yang Ju-Yeon Cho Hyun Chin Cho Sang Goon Shim Yong-Han Paik 《Experimental & molecular medicine》2015,47(9):e184
Recent studies have shown that circulating microRNAs are a potential biomarker in various types of malignancies. The aim of this study was to investigate the feasibility of using serum exosomal microRNAs as novel serological biomarkers for hepatocellular carcinoma (HCC) in patients with chronic hepatitis B (CHB). We measured the serum exosomal microRNAs and serum circulating microRNAs in patients with CHB (n=20), liver cirrhosis (LC) (n=20) and HCC (n=20). Serum exosomal microRNA was extracted from 500 μl of serum using an Exosome RNA Isolation kit. The expression levels of microRNAs were quantified by real-time PCR. The expression levels of selected microRNAs were normalized to Caenorhabditis elegans microRNA (Cel-miR-39). The serum levels of exosomal miR-18a, miR-221, miR-222 and miR-224 were significantly higher in patients with HCC than those with CHB or LC (P<0.05). Further, the serum levels of exosomal miR-101, miR-106b, miR-122 and miR-195 were lower in patients with HCC than in patients with CHB (P=0.014, P<0.001, P<0.001 and P<0.001, respectively). There was no significant difference in the levels of miR-21 and miR-93 among the three groups. Additionally, the serum levels of circulating microRNAs showed a smaller difference between HCC and either CHB or LC. This study suggests that serum exosomal microRNAs may be used as novel serological biomarkers for HCC. 相似文献
45.
Polymersomes Prepared from Thermoresponsive Fluorescent Protein–Polymer Bioconjugates: Capture of and Report on Drug and Protein Payloads 下载免费PDF全文
Chin Ken Wong Alistair J. Laos Dr. Alexander H. Soeriyadi Prof. Jörg Wiedenmann Prof. Paul M. G. Curmi Prof. J. Justin Gooding Dr. Christopher P. Marquis Prof. Martina H. Stenzel Assoc. Prof. Pall Thordarson 《Angewandte Chemie (International ed. in English)》2015,54(18):5317-5322
Polymersomes provide a good platform for targeted drug delivery and the creation of complex (bio)catalytically active systems for research in synthetic biology. To realize these applications requires both spatial control over the encapsulation components in these polymersomes and a means to report where the components are in the polymersomes. To address these twin challenges, we synthesized the protein–polymer bioconjugate PNIPAM‐b‐amilFP497 composed of thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM) and a green‐fluorescent protein variant (amilFP497). Above 37 °C, this bioconjugate forms polymersomes that can (co‐)encapsulate the fluorescent drug doxorubicin and the fluorescent light‐harvesting protein phycoerythrin 545 (PE545). Using fluorescence lifetime imaging microscopy and Förster resonance energy transfer (FLIM‐FRET), we can distinguish the co‐encapsulated PE545 protein inside the polymersome membrane while doxorubicin is found both in the polymersome core and membrane. 相似文献
46.
Kimia Moozeh Dr. Soon Mog So Prof. Jik Chin 《Angewandte Chemie (International ed. in English)》2015,54(32):9381-9385
A combination of an achiral pyridoxal analogue and a chiral base has been developed for catalytic deuteration of L ‐alanine with inversion of stereochemistry to give deuterated D ‐alanine under mild conditions (neutral pD and 25 °C) without the use of any protecting groups. This system can also be used for catalytic deuteration of D ‐alanine with retention of stereochemistry to give deuterated D ‐alanine. Thus a racemic mixture of alanine can be catalytically deuterated to give an enantiomeric excess of deuterated D ‐alanine. While catalytic deracemization of alanine is forbidden by the second law of thermodynamics, this system can be used for catalytic deracemization of alanine with deuteration. Such green and biomimetic approach to catalytic stereocontrol provides insights into efficient amino acid transformations. 相似文献
47.
Enantioselective Synthesis of Quaternary Carbon Stereocenters: Addition of 3‐Substituted Oxindoles to Vinyl Sulfone Catalyzed by Pentanidiums 下载免费PDF全文
Dr. Lili Zong Shubo Du Kek Foo Chin Dr. Chao Wang Prof. Dr. Choon‐Hong Tan 《Angewandte Chemie (International ed. in English)》2015,54(32):9390-9393
A pentanidium‐catalyzed highly enantioselective conjugate addition of 3‐alkyloxindoles to phenyl vinyl sulfone has been demonstrated. This approach allows the construction of 3,3‐dialkyl‐substituted oxindole frameworks with high yield and excellent enantioselectivity (up to 99 %) under simple phase‐transfer conditions. A variety of oxindoles bearing all‐carbon quaternary stereogenic centers were obtained in the presence of 0.25 mol % pentanidium. Meanwhile, practicality was illustrated by a gram‐scale asymmetric synthesis of two 3,3‐dialkyl‐substituted oxindoles. The resulting adduct can be smoothly transformed to the natural product analogue in a short synthetic route. 相似文献
48.
Chin PT Donega Cde M van Bavel SS Meskers SC Sommerdijk NA Janssen RA 《Journal of the American Chemical Society》2007,129(48):14880-14886
In this work we present the preparation of highly luminescent anisotropic CdTe/CdSe colloidal heteronanocrystals. The reaction conditions used (low temperature, slow precursor addition, and surfactant composition) resulted in a tunable shape from prolate to branched CdTe/CdSe nanocrystals. Upon CdSe shell growth the heteronanocrystals show a gradual evolution from type-I to type-II optical behavior. These heteronanocrystals show a remarkably high photoluminescence quantum yield (up to 82%) and negligible thermally induced quenching up to temperatures as high as 373 K. 相似文献
49.
Shura Hayryan Chin‐Kun Hu Shun‐Yun Hu Rung‐Ji Shang 《Journal of computational chemistry》2001,22(12):1287-1296
The determination of the three‐dimensional (3D) structure of a protein or peptide is a very important research problem in biological and medical sciences. Anfinsen's experiments (Science 1973, 181, 223) on renaturation of denatured proteins have shown that the native 3D structure of a (small) protein at low (room) temperatures is uniquely determined by its amino acid sequence, which suggests that it might be possible to determine the 3D structure of a protein from its amino acid sequence by pure computations. As a step toward that goal, in this article we present a simple approach for parallelization of multicanonical Monte Carlo simulations of proteins with continuous potentials. Our method is based on the parallel calculation of the protein energy function. The algorithm is tested by simulated annealing and multicanonical simulations of two small peptides, and known results are reproduced accurately. An acceptable degree of parallelization can be achieved in the simulation of Protein L using up to 30 PCs. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1287–1296, 2001 相似文献
50.
The potential energy surface for the decomposition of HXSiS (X = H, F, and Cl) on the singlet state has been explored by B3LYP and CCSD(T) calculations. Five different types of reaction are proposed: (A) 1,1‐HX elimination, (B) 1,2‐H shift, (C) 1,2‐X shift, (D) H · and XSiS · radical formation, and (E) X · and HSiS · radical formation. These results show interesting trends for the HXSiS isomers. Our theoretical investigations suggest that the doubly bonded species HXSiS should be the lowest energy structure among the isomers from both kinetic and thermodynamic viewpoints. We also report theoretical predictions of molecular parameters and vibrational infrared (IR) spectra of the monohalogen‐substituted silanethione, which should be useful for future experimental observations. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 14–25, 2001 相似文献