全文获取类型
收费全文 | 2194篇 |
免费 | 34篇 |
国内免费 | 19篇 |
专业分类
化学 | 1283篇 |
晶体学 | 8篇 |
力学 | 34篇 |
数学 | 340篇 |
物理学 | 582篇 |
出版年
2019年 | 21篇 |
2016年 | 31篇 |
2014年 | 21篇 |
2013年 | 46篇 |
2012年 | 77篇 |
2011年 | 74篇 |
2010年 | 45篇 |
2009年 | 35篇 |
2008年 | 65篇 |
2007年 | 65篇 |
2006年 | 67篇 |
2005年 | 66篇 |
2004年 | 63篇 |
2003年 | 47篇 |
2002年 | 52篇 |
2001年 | 51篇 |
2000年 | 47篇 |
1999年 | 31篇 |
1998年 | 21篇 |
1997年 | 28篇 |
1996年 | 37篇 |
1995年 | 30篇 |
1994年 | 39篇 |
1993年 | 42篇 |
1992年 | 47篇 |
1991年 | 39篇 |
1990年 | 46篇 |
1989年 | 48篇 |
1988年 | 38篇 |
1987年 | 33篇 |
1986年 | 47篇 |
1985年 | 47篇 |
1984年 | 38篇 |
1983年 | 33篇 |
1982年 | 36篇 |
1981年 | 32篇 |
1980年 | 31篇 |
1979年 | 34篇 |
1978年 | 38篇 |
1977年 | 39篇 |
1976年 | 31篇 |
1975年 | 33篇 |
1974年 | 36篇 |
1973年 | 39篇 |
1972年 | 29篇 |
1971年 | 25篇 |
1970年 | 27篇 |
1969年 | 23篇 |
1967年 | 23篇 |
1966年 | 21篇 |
排序方式: 共有2247条查询结果,搜索用时 93 毫秒
991.
Disubstituted tetracarbonylhydridovanadium compounds (HV(CO)4L2, L2 = dppm, arphos) react with isoprene to give η3-dimethylallyl complexes of the type (η3-dimethylallyl)V(CO)3L2. The compounds have been characterized and the isomers having methyl groups in various positions of the allyl ligand identified by 1H NMR spectroscopy. 相似文献
992.
Sophie Carbonnelle Joris Van Loco Ilse Van Overmeire Isabelle Windal Nathalie Van Wouwe Stefan Van Leeuwen Leo Goeyens 《Talanta》2004,63(5):753-1259
Differences between chemical activated luciferase gene expression (CALUX) bioassay and chemoanalyses results are observed.
This paper shows that calculations of the TEQ values using REP values instead of WHO TEF values give different results. The REP values do affect the results obtained by the CALUX technique. These differences are more marked for the dioxin like PCB compounds (CALUX TEQ values are lower than WHO TEQ values) than for the dioxin compounds (CALUX TEQ values are higher than WHO TEQ values).
The CALUX results were compared with the concentrations of the congeners’ spiked into the oil. 相似文献
993.
Andre Weiss Victor Barba Hans Pritzkow Walter Siebert 《Journal of organometallic chemistry》2003,680(1-2):294-300
New macrocyclic imidazolylboranes [imidazolylB(R1)2]n, where selected carbon atoms of imidazolyl rings may bear substituents other than hydrogen, and where n=4 or 5, are obtained from 1-trimethysilylimidazoles and haloboranes XB(R1)2 by boron/silicon exchange using 2-bromoimidazole and benzimidazole. These macrocycles are formally zwitterionic and contain imidazolyl rings linked through their nitrogen atoms by BH2, B(R1)2 or BR1X units. Despite the sterical demand of these derivatives tetrameric macrocycles are formed. A new synthetic strategy to macrocyclic imidazolylboranes includes the preparation and cyclization of bis(imidazolyl)boronium chlorides. In addition dihaloboranes have been tested for cyclization to yield halogen-containing macrocycles. The new compounds are spectroscopically characterized and X-ray structure analyses of tetrameric- (2a) and pentameric 1-imidazolylborane (2a′), tetrameric 1-imidazolyldimethylborane (2b), tetrameric 1-(2-bromo)imidazolylborane (2d) and bis(2-bromoimidazolyl)boronium chloride (3d) are reported. 相似文献
994.
Ilse M. Welleman Mark W. H. Hoorens Ben L. Feringa Hendrikus H. Boersma Wiktor Szymaski 《Chemical science》2020,11(43):11672
Light-based therapeutic and imaging modalities, which emerge in clinical applications, rely on molecular tools, such as photocleavable protecting groups and photoswitches that respond to photonic stimulus and translate it into a biological effect. However, optimisation of their key parameters (activation wavelength, band separation, fatigue resistance and half-life) is necessary to enable application in the medical field. In this perspective, we describe the applications scenarios that can be envisioned in clinical practice and then we use those scenarios to explain the necessary properties that the photoresponsive tools used to control biological function should possess, highlighted by examples from medical imaging, drug delivery and photopharmacology. We then present how the (photo)chemical parameters are currently being optimized and an outlook is given on pharmacological aspects (toxicity, solubility, and stability) of light-responsive molecules. With these interdisciplinary insights, we aim to inspire the future directions for the development of photocontrolled tools that will empower clinical applications of light.This perspective article explores the current state of light-controlled molecular tools for medical therapy and imaging and offers an outlook on clinical application scenarios and optimisation strategies. 相似文献
995.
The molar absorptivity of the cyanide complexes [Cu(CN)(3)](2-) and [Cu(CN)(4)](3-), at their isosbestic wavelength (235 nm) is 1.13 x 10(3) l.mole(-1)mm.(-1) and can be used for the quantitative determination of micro-amounts of copper in the ppm range. The determination of 1-10 mug of Cu(2+) per g of NaCl, or 0.25-2.5 mug ml , is described in detail. The co-precipitation of copper with NaCl crystallizing from aqueous solutions has been studied by this method. 相似文献
996.
J. Weiss 《无机化学与普通化学杂志》1986,532(1):184-192
Metal Sulfur-Nitrogen Compounds. 19. Novel Complexes of CuI with the S3N? Chelate Ligand. Preparation and Structure of [Ph4As][Cu(S3N)(CN)], [(Ph3P)2N][Cu(S3N)(S7N)], and [Ph4As]2[(S3N)Cu(S2O3)Cu(S3N)] In alkaline media S7NH reacts with Cu salts to yield different products. With Cu(CN) the ion [Cu(S3N)(CN)]? is formed, which was isolated as the [Ph4As]+ salt. The crystals are monoclinic, space group P21/c, a = 10.499(5), b = 13.418(6), c = 18.032(8) Å, β = 91.84°(3), Z = 4. Besides the known complex ions [Cu(S3N)2]? and [Cu(S3N)Cl]? still some more may be obtained when CuCl2 is reacted with S7NH: Under special conditions the S7N ring is partly preserved, and [Cu(S3N)(S7N)]? is formed. Its sparingly soluble [(Ph3P)2N]+ salt is monoclinic, space group P21/n, a = 9.335(6), b = 30.984(11), c = 15.108(8) Å, β = 102.87°(4), Z = 4. Using a longer reaction time a dinuclear complex [(S3N)Cu(S2O3)Cu(S3N)]? ? results from the reaction of CuCl2 with S7NH. The two Cu atoms are bridged by an S atom of the S2O3? ? anion. The [Ph4As]+ salt of the dinuclear complex anion is triclinic, space group P1 , a = 11.226(6), b = 12.423(6), c = 19.000(10) Å, β = 76.47°(4), β = 83.98°(4), γ = 84.71°(4), Z = 2. In all these compounds the coordination of CuI is trigonal-planar, the S3N? chelate group coordinates the Cu in the usual way by two S atoms. 相似文献
997.
998.
Mansonin is the 2,3-di-O-methyl-6-deoxy-β-D-glucopyranoside of strophanthidin, and strophothevoside the corresponding 3-O-methyl-6-deoxy-β-D-glucopyranoside. 相似文献
999.
The quantum decay of a metastable system which interacts with an environment at temperatureT is considered. A general formula for the decay rate at finite temperatures is obtained by a method which is based on the framework recently described by Caldeira and Leggett. The thermal enhancement of the tunnelling rate at low temperatures is discussed for arbitrary metastable potentials, and it is found that the exponent of the rate obeys a power law in a dissipative system. The power law exponent is shown to be a characteristic feature of the dissipative mechanism. Finally, a universally valid formula for the thermal enhancement factor is given, where the form of the potential enters only through the frequency of small oscillations about the metastable minimum and the length of the zero temperature bounce trajectory. 相似文献
1000.
Leclercq L Delatour C Hoes I Brunelle F Labrique X Castro-Perez J 《Rapid communications in mass spectrometry : RCM》2005,19(12):1611-1618
Metabolism data provided with reduced cycle time has become of increasing importance for the early evaluation of DMPK properties of drugs in discovery. In this regard, quadrupole time-of-flight hybrid mass spectrometers (Q-TOF) can provide very reliable metabolite identification via accurate mass measurement of ions and the consequent access to the elemental composition of the metabolite. However, due to their cost, they are often used for drug metabolism studies on later stage drug candidates or to address challenging metabolism questions. A new prototype, consisting of a five-channel multiplexed electrospray ionization (ESI) source on a Q-TOF with one channel used for lock-mass compound infusion, was evaluated for metabolite identification. The goal was to increase the sample throughput of a single ESI-MS system by a factor of 4, while maintaining efficient metabolite separation in high-performance liquid chromatography (HPLC) as well as adequate sensitivity and mass accuracy, and ultimately improve the speed and quality of metabolism studies supporting drug discovery. The analytical performance of the system was assessed by evaluating the sensitivity and mass accuracy (using real in vitro and in vivo samples), inter-channel differences in retention times, MS/UV response, and cross-talk among channels. The sensitivity using the multiplexed ESI source was on average 2-fold lower than with single ESI, correlating well with previous literature data. The mass accuracy was comparable to that obtained using single ESI in both MS and MS/MS modes, making the metabolite identification process using the multiplexed ESI source as reliable as with single ESI. Compound-dependent differences in ionization efficiencies were observed among channels, and were minimized by analyzing related samples on the same channel. Finally, the level of cross-talk among channels was acceptable (around 0.3%) and comparable to levels previously published for quantitative applications using multiplexed ESI. The paper also focuses on the advantages and disadvantages of this new approach compared to other approaches in the literature in the field of metabolite identification. 相似文献