全文获取类型
收费全文 | 9228篇 |
免费 | 1489篇 |
国内免费 | 893篇 |
专业分类
化学 | 4120篇 |
晶体学 | 68篇 |
力学 | 842篇 |
综合类 | 49篇 |
数学 | 363篇 |
物理学 | 6168篇 |
出版年
2024年 | 15篇 |
2023年 | 83篇 |
2022年 | 243篇 |
2021年 | 237篇 |
2020年 | 261篇 |
2019年 | 261篇 |
2018年 | 246篇 |
2017年 | 270篇 |
2016年 | 345篇 |
2015年 | 332篇 |
2014年 | 458篇 |
2013年 | 757篇 |
2012年 | 547篇 |
2011年 | 688篇 |
2010年 | 489篇 |
2009年 | 613篇 |
2008年 | 625篇 |
2007年 | 690篇 |
2006年 | 593篇 |
2005年 | 469篇 |
2004年 | 402篇 |
2003年 | 364篇 |
2002年 | 396篇 |
2001年 | 294篇 |
2000年 | 296篇 |
1999年 | 212篇 |
1998年 | 203篇 |
1997年 | 154篇 |
1996年 | 125篇 |
1995年 | 144篇 |
1994年 | 107篇 |
1993年 | 132篇 |
1992年 | 87篇 |
1991年 | 69篇 |
1990年 | 59篇 |
1989年 | 38篇 |
1988年 | 38篇 |
1987年 | 29篇 |
1986年 | 29篇 |
1985年 | 37篇 |
1984年 | 43篇 |
1983年 | 16篇 |
1982年 | 26篇 |
1981年 | 19篇 |
1980年 | 13篇 |
1979年 | 9篇 |
1978年 | 11篇 |
1977年 | 7篇 |
1976年 | 9篇 |
1973年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
221.
Gunwook Park Sung-Wook Choi Jae-Ho Kim Sung-Hoon Kim Sam-Rok Keum Kwangnak Koh 《Microchemical Journal》2005,80(2):207-211
Spiroxazine are of considerable interest as photochromic materials because of their application. On the other hand, surface plasmon resonance (SPR) is a well-known optical method for measuring optical constants of thin film. In this study, photochromic materials were used as self-assembled monolayers (SAMs) of newly synthesized spiroxazine derivatives. We used Fresnel equation (four-layer model) to determine the precise dielectric constant () of the photochromic monolayers. Structure changes of spiroxazine derivatives under UV-light irradiation resulted in the change of optical constants, the dielectric constant and thickness. The obtained results indicated that the ring opening of photochromic spiroxazine can lead to the decrease in the dielectric constant and thickness. 相似文献
222.
Low-dimensional systems are formed by planar metal dithiolene complexes which stack as columnar structures in the solid state.
Stronger interactions among units within a chain leads to highly anisotropic magnetic properties. The magnetic effects are
a manifestation of exchange interaction,J and can be studied through detailedepr techniques in conjunction with magnetic susceptibility and x-ray crystal structure. A brief review of such studies carried
out mostly in our laboratory is presented along with the relevant background materials. 相似文献
223.
A flow injection method combined with Resonance light scattering detection was developed for the determination of protein
concentration in human serum samples. This method is based on the enhanced RLS signals of protein binding with the dye acid
chrome blue K. The enhanced RLS intensities at 264 nm, in an acidic aqueous solution, were proportional to the protein concentration
over the range of 2.0–40.0 μg·mL−1 for human serum albumin (HSA) and the limit of detection (3σ) is 85 ng·mL−1. This method was successfully applied to the quantification of total proteins in human serum samples. The maximum relative
standard deviation is less than 2% and the recovery is between 97 and 103% for the standard addition method. The sample throughput
was 60 h−1. 相似文献
224.
Kin-Ho Law Pui-Ling Chan Wai-Sum Lau Yin-Chung Cheng Yun-Chung Leung Wai-Hung Lo Hugh Lawford Hoi-Fu Yu 《Applied biochemistry and biotechnology》2004,114(1-3):361-372
Plastic wastes constitute a worldwide environmental problem, and the demand for biodegradable plastics has become high. One
of the most important characteristics of microbial polyesters is that they are thermoplastic with environmentally degradable
properties. In this study, pUC 19/PHA was cloned and transformed into three different Escherichia coli strains. Among the three strains that were successfully expressed in the production of polyhydroxyalkanoates (PHA), E. coli HMS174 had the highest yield in the production of poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (P[HB-HV]). The cell dry
weight and PHA content of recombinant HMS174 reached as high as 10.27 g/L and 43% (w/w), respectively, in fed-batch fermentor
culture. The copolymer of PHA, P(HB-HV), was found in the cells, and the biopolymers accumulated were identified and analyzed
by gas chromatography, proton nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. We demonstrated
clearly that the E. coli host for PHA production has to be carefully selected to obtain a high yield. The results obtained indicated that a superior
E. coli with high PHA production can be constructed with a desirable ratio of P(HB-HV), which has potential applications in industry
and medicine. 相似文献
225.
Oleg A. Raitman Andrei B. Kharitonov Maya Zayats Eugenii Katz Itamar Willner 《Analytica chimica acta》2004,504(1):101-111
Crosslinked films consisting of the acrylamide-acrylamidophenylboronic acid copolymer that are imprinted with recognition sites for β-nicotinamide adenine dinucleotide (NAD+), β-nicotinamide adenine dinucleotide phosphate NADP+, and their reduced forms (NAD(P)H), are assembled on Au-coated glass supports. The binding of the oxidized cofactors NAD+ or NADP+ or the reduced cofactors NADH or NADPH to the respective imprinted sites results in the swelling of the polymer films through the uptake of water. Surface plasmon resonance (SPR) spectroscopy is employed to follow the binding of the different cofactors to the respective imprinted sites. The imprinted recognition sites reveal selectivity towards the association of the imprinted cofactors. The method enables the analysis of the NAD(P)+ and NAD(P)H cofactors in the concentration range of 1×10−6 to 1×10−3 M. The cofactor-imprinted films associated with the Au-coated glass supports act as active interfaces for the characterization of biocatalyzed transformations that involve the cofactor-dependent enzymes. This is exemplified with the characterization of the biocatalyzed oxidation of lactate to pyruvate in the presence of NAD+ and lactate dehydrogenase using the NADH-imprinted polymer film. 相似文献
226.
We report in this study the presence of Janus particles, which are candidates for use with electronic color papers. We used negatively charged polystyrene particles (370 nm) as the core particles, and gold was then sputtered onto their packed monolayer under several conditions. The sputtered particles were next redispersed into the aqueous medium by gentle sonication. Gold nanoparticles localized on one side of the cores could also serve as seeds for subsequent shell growth by electroless gold plating. Through these treatments, a series of well-dispersed Janus particles were obtained with gold nanostructures of different size and shape only on one side. Their dispersions showed different colors originating from the surface plasmon resonance absorption of gold nanoparticles localized on the hemisphere. The particles obtained by this approach have potential applications such as in sensors and electronic color paper. 相似文献
227.
F?rster resonance energy transfer (FRET), which involves the nonradiative transfer of excitation energy from an excited donor fluorophore to a proximal ground-state acceptor fluorophore, is a well-characterized photophysical tool. It is very sensitive to nanometer-scale changes in donor-acceptor separation distance and their relative dipole orientations. It has found a wide range of applications in analytical chemistry, protein conformation studies, and biological assays. Luminescent semiconductor nanocrystals (quantum dots, QDs) are inorganic fluorophores with unique optical and spectroscopic properties that could enhance FRET as an analytical tool, due to broad excitation spectra and tunable narrow and symmetric photoemission. Recently, there have been several FRET investigations using luminescent QDs that focused on addressing basic fundamental questions, as well as developing targeted applications with potential use in biology, including sensor design and protein conformation studies. Herein, we provide a critical review of those developments. We discuss some of the basic aspects of FRET applied to QDs as both donors and acceptors, and highlight some of the advantages offered (and limitations encountered) by QDs as energy donors and acceptors compared to conventional dyes. We also review the recent developments made in using QD bioreceptor conjugates to design FRET-based assays. 相似文献
228.
When trypsin reacts with Herring sperm DNA (hsDNA), Salmon sperm DNA (sDNA), and Calf thymus DNA (ctDNA) to form a complex,
the resonance Rayleigh scattering (RRS) was remarkably enhanced and new RRS spectra appear. These new spectra have similar
characteristics of RRS spectra. The maximum RRS peaks are at 307 nm (hsDNA, sDNA) and 290 nm (ctDNA), and other peaks are
at 350 nm. The scattering intensity is proportional to the concentration of DNA or trypsin; so this intereaction can be used
to determine trypsin using DNA or DNA using trypsin. In the determination of DNA using trypsin, the linear ranges for hsDNA,
sDNA, and ctDNA are 0–2.3, 0–2.5, and 0–1.9 μg·mL−1, and the detection limits are 0.4, 0.7, and 1.1 ng·mL−1, respectively. In the determination of trypsin using hsDNA, the linear range is 0–30.0 μg·mL−1, and the detection limit is 39.0 ng·mL−1. In this paper, the intereaction conditions were optimized. The affecting factors, chemical properties of the complex, and
the composition ratio of trypsin with DNA were investigated. Using trypsin as RRS probe, a sensitive method for the determination
of trace amounts of DNA was developed.
Translated from Chemical Journal of Chinese Universities, 2006, 27(3) (in Chinese) 相似文献
229.
Pablo A. Molina R. Steven Sikorski Jan H. Jensen 《Theoretical chemistry accounts》2003,109(3):100-107
The relationship between hydrogen bonding and NMR chemical shifts in the catalytic triad of low-pH α-chymotrypsin is investigated
by combined use of the effective fragment potential [(2001) J Phys Chem A 105:293] and ONIOM–NMR [(2000) Chem Phys Lett 317:589] methods. Our study shows that while the His57 Nδ1−H bond is stretched by a relatively modest amount (to about 1.060 ?) this lengthening, combined with the polarization due
to the molecular environment, is sufficient to explain the experimentally observed chemical shifts of 18.2 ppm. Furthermore,
the unusual down-field shift of Hɛ1 (9.2 ppm) observed experimentally is reproduced and shown to be induced by interactions with the C=O group of Ser214 as previously
postulated. The free-energy cost of moving Hδ1 from His57 to Asp102 is predicted to be 5.5 kcal/mol.
Received: 26 September 2001 / Accepted: 6 September 2002 / Published online: 21 January 2003
Contribution to the Proceedings of the Symposium on Combined QM/MM Methods at the 222nd National Meeting of the American
Chemical Society, 2001
Correspondence to: J. H. Jensen e-mail: jan-jensen@uiowa.edu
Acknowledgements. This work was supported by a Research Innovation Award from the Research Corporation and a type G starter grant from the
Petroleum Research Fund. The calculations were performed on IBM RS/6000 workstations obtained through a CRIF grant from the
NSF (CHE-9974502) and on supercomputers at the National Center for Supercomputer Applications at Urbana-Champaign. The authors
are indebted to Visvaldas Kairys for help with the CHARMM program, and to Daniel Quinn for many helpful discussions. 相似文献
230.
本文探讨了计算机断层扫描(CT)、磁共振成像(MRI)对良恶性甲状腺结节的鉴别价值。方法:选取2015年3月至2018年3月本院收治的甲状腺结节患者150例,依据病理结果分为恶性48例、良性102例,所有患者均给予CT、MRI检查,分析CT、MRI对良恶性甲状腺结节的鉴别价值。结果发现,MRI总病灶、形态不规则、边界不清/毛糙、信号/密度不均检出率明显高于CT,MRI钙化灶检出率明显低于CT,差异有统计学意义(P<0.05),CT、MRI淋巴结转移检出率比较,差异无统计学意义(P>0.05);在鉴别良恶性甲状腺结节的敏感度、特异度、准确度中,CT为79.17%、74.51%、76.00%,MRI为83.33%、80.39%、81.33%,CT联合MRI为95.83%、96.08%、96.00%,CT联合MRI明显高于CT、MRI,差异有统计学意义(P<0.05)。说明CT、MRI可作为鉴别良恶性甲状腺结节的重要方法,CT对钙化灶有较高的分辨能力,MRI对软组织及小病灶有较高的分辨能力,CT联合MRI可有效提高其鉴别价值。 相似文献