全文获取类型
收费全文 | 1350篇 |
免费 | 70篇 |
国内免费 | 3篇 |
专业分类
化学 | 1129篇 |
晶体学 | 9篇 |
力学 | 17篇 |
数学 | 92篇 |
物理学 | 176篇 |
出版年
2024年 | 1篇 |
2023年 | 17篇 |
2022年 | 19篇 |
2021年 | 24篇 |
2020年 | 34篇 |
2019年 | 44篇 |
2018年 | 26篇 |
2017年 | 28篇 |
2016年 | 45篇 |
2015年 | 46篇 |
2014年 | 60篇 |
2013年 | 106篇 |
2012年 | 125篇 |
2011年 | 136篇 |
2010年 | 82篇 |
2009年 | 68篇 |
2008年 | 89篇 |
2007年 | 75篇 |
2006年 | 65篇 |
2005年 | 69篇 |
2004年 | 57篇 |
2003年 | 45篇 |
2002年 | 47篇 |
2001年 | 19篇 |
2000年 | 13篇 |
1999年 | 7篇 |
1998年 | 8篇 |
1997年 | 10篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 6篇 |
1989年 | 4篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 2篇 |
排序方式: 共有1423条查询结果,搜索用时 15 毫秒
51.
Kim In S. Barrow Kevin D. Rogers Peter L. 《Applied biochemistry and biotechnology》2000,84(1-9):357-370
The fermentation characteristics and effects of lignocelulosic toxic compounds on recombinant Zymomonas mobilis ZM4(pZB5), which is capable of converting both glucose and xylose to ethanol, and its parental strain, ZM4, were characterized
using 13C and 31P nuclear magnetic resonance (NMR) in vivo. From the 31P NMR data, the levels of nucleoside triphosphates (NTP) of ZM(pZB5) using xylose were lower than those of glucose. This can
be related to the intrinsically slower assimilation and/or metabolism of xylose compared to glucose and is evidence of a less
energized state of ZM4(pZB5) cells during xylose fermentation. Acetic acid was shown to be strongly inhibitory to ZM4(pZB5)
on xylose medium, with xylose utilization being completely inhibited at pH 5.0 or lower in the presence of 10.9 g/L of sodium
acetate. From the 31P NMR results, the addition of sodium acetate caused decreased NTP and sugar phosphates, together with acidification of the
cytoplasm. Intracellular deenergization and acidification appear to be the major mechanisms by which acetic acid exerts its
toxic effects on this recombinant strain. 相似文献
52.
Cheikhousman R Zude M Bouveresse DJ Léger CL Rutledge DN Birlouez-Aragon I 《Analytical and bioanalytical chemistry》2005,382(6):1438-1443
The potential of fluorescence spectroscopy for characterizing the deterioration of extra virgin olive oil (EVOO) during heating was investigated. Two commercial EVOO were analysed by HPLC to determine changes in EVOO vitamin E and polyphenols as a result of heating at 170°C for 3 h. This thermal oxidation of EVOO caused an exponential decrease in hydroxytyrosol and vitamin E (R2=0.90 and 0.93, respectively) whereas the tyrosol content was relatively stable. At the same time, amounts of preformed hydroperoxides (ROOH), analysed by an indirect colorimetric method, decreased exponentially during the heating process (R2=0.94), as a result of their degradation into secondary peroxidation products. Fluorescence excitation spectra with emission at 330 and 450 nm were recorded to monitor polyphenols and vitamin E evolution and ROOH degradation, respectively. Partial least-squares calibration models were built to predict these indicators of EVOO quality from oil fluorescence spectra. A global approach was then proposed to monitor the heat charge from the overall fluorescence fingerprint. Different data pretreatment methods were tested. This study indicates that fluorescence spectroscopy is a promising, rapid, and cost-effective approach for evaluating the quality of heat-treated EVOO, and is an alternative to time-consuming conventional analyses. In future work, calibration models will be developed using a wide range of EVOO samples. 相似文献
53.
A simple method has been developed for the simultaneous determination of N-butylscopolamine bromide and oxazepam in pharmaceutical formulations using first-order digital derivative spectrophotometry. Acetonitrile was selected as the solvent in which both compounds showed well-defined bands. Both analytes showed good stability in this solvent when solutions of the analytes were exposed to light and temperatures between 20 degrees and 80 degrees C. The simultaneous determination of both drugs was performed by the zero-crossing method at 226.0 and 257.0 nm for N-butylscopolamine and oxazepam, respectively. The linear range of determination was found to be 2.5 x 10(-7) to 8.0 x 10(-5) mol/L for N-butylscopolamine and 7.1 x 10(-8) to 8.0 x 10(-5) mol/L for oxazepam. A very good level of repeatability (relative standard deviation) of 0.2% was observed for N-butylscopolamine and oxazepam. The ingredients commonly found in pharmaceutical formulations do not interfere. The proposed method was applied to the determination of these drugs in pharmaceutical formulations (capsules). 相似文献
54.
Dr. Christophe Ansiaux Inès N'Go Prof. Stéphane P. Vincent 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(46):14860-14866
A series of UDP‐galactitols were designed as analogues of high‐energy intermediates of the UDP‐galactopyranose mutase (UGM) catalyzed furanose/pyranose interconversion, an essential step of Mycobacterium tuberculosis cell wall biosynthesis. The final compounds structurally share the UDP and the galactitol substructures that were connected by four distinct electrophilic connections (epoxide, lactone and Michael acceptors). All molecules were synthesized from a common perbenzylated acyclic galactose precursor that was derivatized by alkenylation, alkynylation and cyclopropanation. The inhibition study against UGM could clearly show that slight changes in the relative orientation of the UDP and the galactitol moieties resulted in dramatic variations of binding properties. Compared to known inhibitors, the epoxide derivative displayed a very tight, reversible, inhibition profile. Moreover, a time‐dependent inactivation study showed that none of these electrophilic structures could react with UGM, or its FAD cofactor, the catalytic nucleophile of this still intriguing reaction. 相似文献
55.
Sayaka Taji Takeshi Yamada Yasuko In Shun‐ichi Wada Yoshihide Usami Kazuo Sakuma Reiko Tanaka 《Helvetica chimica acta》2007,90(11):2047-2057
Three new lanostane‐type triterpenoids, inonotsulides A, B, and C ( 1 – 3 , resp.) were isolated from the sclerotia of Inonotus obliquus (Pers .: Fr.) (Japanese name: Kabanoanatake; Russian name: Chaga). Their structures were determined to be (20R,24S)‐3β,25‐dihydroxylanost‐8‐en‐20,24‐olide ( 1 ), (20R,24R)‐3β,25‐dihydroxylanost‐8‐en‐20,24‐olide ( 2 ), and (20R,24S)‐3β,25‐dihydroxylanosta‐7,9(11)‐dien‐20,24‐olide ( 3 ) on the basis of chemical transformation, NMR spectroscopy including 1D and 2D (1H,1H‐COSY, NOESY, HMQC, HMBC), EI‐MS, and single‐crystal X‐ray analysis. 相似文献
56.
Ronaldo Santos da Silva Maria Inês Basso Bernardi Antonio Carlos Hernandes 《Journal of Sol-Gel Science and Technology》2007,42(2):173-179
In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba0.77Ca0.23TiO3 nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis,
morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through
thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy.
In summary, Ba0.77Ca0.23TiO3 nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity
and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions
with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution
(30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the
chelation in higher pHs. 相似文献
57.
Choi I Song HD Lee S Yang YI Kang T Yi J 《Journal of the American Chemical Society》2012,134(29):12083-12090
We report core-satellites (Au-Ag) coupled plasmonic nanoassemblies based on bottom-up, high-density assembly of molecular-scale silver nanoparticles on a single gold nanoparticle surface, and demonstrate direct observation and quantification of enhanced plasmon coupling (i.e., intensity amplification and apparent spectra shift) in a single particle level. We also explore metal ion sensing capability based on our coupled plasmonic core-satellites, which enabled at least 1000 times better detection limit as compared to that of a single plasmonic nanoparticle. Our results demonstrate and suggest substantial promise for the development of coupled plasmonic nanostructures for ultrasensitive detection of various biological and chemical analytes. 相似文献
58.
Photo‐ and pH‐Tunable Multicolor Fluorescent Nanoparticle‐Based Spiropyran‐ and BODIPY‐Conjugated Polymer with Graphene Oxide 下载免费PDF全文
Shazid Md. Sharker Chan Jin Jeong Sung Min Kim Jung‐Eun Lee Prof. Ji Hoon Jeong Prof. Insik In Prof. Haeshin Lee Prof. Sung Young Park 《化学:亚洲杂志》2014,9(10):2921-2927
We report a stimuli‐responsive fluorescent nanomaterial, based on graphene oxide coupled with a polymer conjugated with photochromic spiropyran (SP) dye and hydrophobic boron dipyrromethane (BODIPY) dye, for application in triggered target multicolor bioimaging. Graphene oxide (GO) was reduced by catechol‐conjugated polymers under mildly alkaline conditions, which enabled to formation of functionalized multicolor graphene nanoparticles that can be induced by irradiation with UV light and by changing the pH from acidic to neutral. Investigation of these nanoparticles by using AFM, fluorescence emission, and in vitro cell and in vivo imaging revealed that they show different tunable colors in bioimaging applications and, more specifically, in cancer‐cell detection. The stability, biocompatibility, and quenching efficacy of this nanocomposite open a different perspective for cell imaging in different independent colors, sequentially and simultaneously. 相似文献
59.
Biswas K Zhang Q Chung I Song JH Androulakis J Freeman AJ Kanatzidis MG 《Journal of the American Chemical Society》2010,132(42):14760-14762
The Lewis acidic ionic liquid EMIMBr-AlCl(3) (EMIM = 1-ethyl-3-methylimidazolium) allows a novel synthetic route to the semiconducting layered metal chalcogenides halide [Bi(2)Te(2)Br](AlCl(4)) and its Sb analogue. [Bi(2)Te(2)Br](AlCl(4)) is a direct band gap, strongly anisotropic semiconductor and consists of cationic infinite layers of [Bi(2)Te(2)Br](+) and [AlCl(4)](-) anions inserted between the layers. 相似文献
60.
Jae Chul Cheong Sung Ill Suh Beom Jun Ko Jin Young Kim Moon Kyo In Won Jo Cheong 《Journal of separation science》2010,33(12):1767-1778
A simple and rapid GC‐MS method has been developed for the screening and quantification of many illicit drugs and their metabolites in human urine by using automatic SPE and trimethylsilylation. Sixty illicit drugs, including parent drugs and their metabolites that are possibly abused in Korea, can be monitored by this method. Among them, 24 popularly abused illicit drugs were selected for quantification. Very delicate optimizations were carried out in SPE, trimethylsilylation derivatization, and GC/MS to enable such remarkable achievements. Trimethylsilylated analytes were well separated within 21 min by GC‐MS. In the validation results, the LOD of all the analytes were in the range of 2–75 ng/mL. The LOQ of the quantified analytes were in the range of 5–98 ng/mL. The linearity (r2) of the quantified analytes ranged 0.990–1.000 in each concentration range between 10 and 1000 ng/mL. The mean recoveries ranged from 62 to 126% at three different concentrations of each analyte. The inter‐day and inter‐person accuracies were within ?13.3~14.9%, and ?10.1~13.0%, respectively, and the inter‐day and inter‐person precisions were less than 12.9%. The method was reliable and efficient for the screening and quantification of abused illicit drugs in routine urine analysis. 相似文献