全文获取类型
收费全文 | 3079篇 |
免费 | 97篇 |
国内免费 | 10篇 |
专业分类
化学 | 2248篇 |
晶体学 | 30篇 |
力学 | 52篇 |
数学 | 405篇 |
物理学 | 451篇 |
出版年
2022年 | 18篇 |
2021年 | 31篇 |
2020年 | 47篇 |
2019年 | 48篇 |
2018年 | 24篇 |
2017年 | 32篇 |
2016年 | 66篇 |
2015年 | 59篇 |
2014年 | 67篇 |
2013年 | 116篇 |
2012年 | 166篇 |
2011年 | 161篇 |
2010年 | 100篇 |
2009年 | 81篇 |
2008年 | 115篇 |
2007年 | 144篇 |
2006年 | 164篇 |
2005年 | 158篇 |
2004年 | 131篇 |
2003年 | 109篇 |
2002年 | 112篇 |
2001年 | 43篇 |
2000年 | 19篇 |
1998年 | 31篇 |
1997年 | 38篇 |
1996年 | 39篇 |
1995年 | 26篇 |
1994年 | 30篇 |
1993年 | 42篇 |
1992年 | 43篇 |
1991年 | 32篇 |
1990年 | 34篇 |
1989年 | 42篇 |
1988年 | 37篇 |
1987年 | 23篇 |
1986年 | 30篇 |
1985年 | 57篇 |
1984年 | 39篇 |
1983年 | 38篇 |
1982年 | 50篇 |
1981年 | 54篇 |
1980年 | 52篇 |
1979年 | 57篇 |
1978年 | 65篇 |
1977年 | 34篇 |
1976年 | 56篇 |
1975年 | 33篇 |
1974年 | 28篇 |
1973年 | 35篇 |
1967年 | 17篇 |
排序方式: 共有3186条查询结果,搜索用时 15 毫秒
111.
The regioselectivity of the metal-catalyzed ring opening of unsymmetrical 1,2-dioxines to cis-gamma-hydroxyenones was investigated using two different Co(II) salen complexes. Regioselectivity was determined by direct examination of the enone ratios and by derivitization with a stabilized phosphorus ylide. The steric influence of the substituents on the 1,2-dioxine was the primary influence on regioselectivity. Temperature played little role; however, solvent and selection of Co(II) complex could be used to mildly influence the outcome of the rearrangement for selected substrates. The origins of the selectivity for the reaction are discussed. 相似文献
112.
The first examples of manipulating stereocontrol solely by reaction topography in radical cyclizations starting from acyclic precursors are reported. The kinetic model for acyclic compound stereoselection is verified experimentally by conducting a series of radical cyclizations of 1,3-dihalo-2-(1-phenyl-3-butynyl)propanes with triphenyltin hydride and measuring the ratios of the products. Monohalide intermediates are observed for the first time, and evidence that bromide- and iodide-substituted radicals have different cyclization rate constants is provided. 相似文献
113.
van de Waterbeemd H Smith DA Jones BC 《Journal of computer-aided molecular design》2001,15(3):273-286
Lipophilicity, often expressed as distribution coefficients (log D) in octanol/water, is an important physicochemical parameter influencing processes such as oral absorption, brain uptake and various pharmacokinetic (PK) properties. Increasing log D values increases oral absorption, plasma protein binding and volume of distribution. However, more lipophilic compounds also become more vulnerable to P450 metabolism, leading to higher clearance. Molecular size and hydrogen bonding capacity are two other properties often considered as important for membrane permeation and pharmacokinetics. Interrelationships among these physicochemical properties are discussed. Increasing size (molecular weight) often gives higher potency, but inevitably also leads to either higher lipophilicity, and hence poorer dissolution/solubility, or to more hydrogen bonding capacity, which limits oral absorption. Differences in optimal properties between gastrointestinal absorption and uptake into the brain are addressed. Special attention is given to the desired lipophilicity of CNS drugs. In examples using -blockers, Ca channel antagonists and peptidic renin inhibitors we will demonstrate how potency and pharmacokinetic properties need to be balanced. 相似文献
114.
Kanai M Porfyrakis K Briggs GA Dennis TJ 《Chemical communications (Cambridge, England)》2004,(2):210-211
We report the purification of the nitrogen-containing incar-fullerenes iNC(60) and iNC(70), and their characterisation by UV-Vis absorption spectroscopy. 相似文献
115.
The 444 nm 2 0 (1) bands of the A 2A'-X 2A" transition of the jet-cooled HP 35Cl and HP 37Cl radicals have been studied at high resolution using the pulsed electric discharge technique with a precursor mixture of PCl3 and H2. Spectra recorded with linewidths of approximately 360 MHz revealed resolved hyperfine structure in both isotopomers arising from the excited state Fermi contact interaction of the unpaired electron with the magnetic moment of the 31P nucleus, with aF'=0.0641(10) cm(-1) and 0.0636(31) cm(-1) for HP 35Cl and HP 37Cl, respectively. No contribution from the ground state, or excited state contributions from the hydrogen or chlorine nuclei were resolved, confirming ab initio predictions that HPCl is a p pi radical in the X state, and an s sigma radical with a substantial contribution from the phosphorus 3s atomic orbital in the A state. The free atom comparison method has been used to estimate that the singly occupied molecular orbital in the excited state has 14% phosphorus 3s character. 相似文献
116.
This paper reports two subjects. It describes LC-GC transfer by partially concurrent eluent evaporation at a greatly accelerated rate, as required for optimal compatibility with 2–3 mm i.d. LC columns and LC flow rates up to some 500 μl/min. Evaporation rates around 200 μl/min were obtained using a 0.53 mm. i.d. uncoated pre-column and an early vapor exit. A stationary-phasecoated “retaining” pre-column was used for preventing escape of volatile solutes through the vapor exit. The technique was used for the detection of food irradiation by analyzing selected radiolysis products of triglycerides, namely alkanes/alkanes and aldehydes. Extracted fat of chicken, hazel-nuts, and soup mixes was injected in LO and the relevant fractions were transferred on-line to GC. For chicken and nuts, detection of irradiation was possible down to doses below 0.5 kGy. Detection limits were higher for soup mixes due to interfering peaks. 相似文献
117.
Addition of stabilized Horner-Wadsworth-Emmons (HWE) phosphonates to substituted 1,2-dioxines leads to diastereomerically pure di- and trisubstituted cyclopropanes in high yields and represents a viable alternative to ylides in the cyclopropanation reaction involving 1,2-dioxines. While yields are comparable, reaction times with these stabilized phosphonates were accelerated and the diastereoselectivity for this cyclopropanation reaction was significantly greater than for the previously reported examples employing ylides. 相似文献
118.
The classical simplex method is extended into the Semiglobal Simplex (SGS) algorithm. Although SGS does not guarantee finding the global minimum, it affords a much more thorough exploration of the local minima than any traditional minimization method. The basic idea of SGS is to perform a local minimization in each step of the simplex algorithm, and thus, similarly to the Convex Global Underestimator (CGU) method, the search is carried out on a surface spanned by local minima. The SGS and CGU methods are compared by minimizing a set of test functions of increasing complexity, each with a known global minimum and many local minima. Although CGU delivers substantially better success rates in simple problems, the two methods become comparable as the complexity of the problems increases. Because SGS is generally faster than CGU, it is the method of choice for solving optimization problems in which function evaluation is computationally inexpensive and the search region is large. The extreme simplicity of the method is also a factor. The SGS method is applied here to the problem of finding the most preferred (i.e., minimum free energy) solvation sites on a streptavidin monomer. It is shown that the SGS method locates the same lowest free energy positions as an exhaustive multistart Simplex search of the protein surface, with less than one-tenth the number of minizations. The combination of the two methods, i.e.. multistart simplex and SGS, provides a reliable procedure for predicting all potential solvation sites of a protein. 相似文献
119.
The structure of p,p'-dibenzene (PDB) has been investigated by full geometry optimizations using the empirical force field (EFF) and MINDO/3 methods. While other structural parameters are in good agreement, the central bond length calculated by MINDO/3 (1.595 Å), as confirmed by an ab initio (STO-3G basis set) optimization (1.596 Å), is in striking contrast to the corresponding length calculated by EFF (1.543 Å). A detailed analysis of the electronic structure of PDB based on a quantitative perturbational molecular orbital treatment reveals that through-bond coupling of the four π systems is responsible for an elongation of the σ bond which mediates this interaction. Further studies using the EFF and MINDO/3 approaches demonstrate that extended C-C single bonds can arise even in structures with fewer than four π systems. The effect of substituents on the central bond length in PDB has been briefly investigated. (MINDO/3). A variety of other structures have been identified in which bond lengthening may result from through-bond coupling. 相似文献
120.
Edgar Heilbronner Evi Honegger Jacques Lecoultre Cyril A. Grob Raymond Houriet Eric Rolli 《Helvetica chimica acta》1986,69(8):2114-2126
The n ionization energies I and the gas-phase basicities GB of CH3-, Cl-, or CN-substituted quinuclidines have been measured by PE and ICR spectroscopy. The dependence of the shifts ΔI and ΔGB (relative to the values of the parent molecule) allow conclusions about the charge dispersal accompanying the n ionization or the protonation of quinuclidine in the gas phase. The agreement with the results of a minimal basis set ab initio calculation is excellent. Comparison of the solution pKa values with either I or GB reveals that 2-substituted quinuclidines exhibit sizeable solvent-induced proximity effects, i.e. that the corresponding quinuclidinium ions are more acidic in solution than expected on the basis of the gas-phase basicities. This agrees with earlier results concerning 2-substituted pyridines. 相似文献