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1.
姜垒  付阳  郭文文  郑果  王强 《波谱学杂志》2021,38(2):255-267
利用三异丁基硼氢化锂(L-selectride)试剂还原3-氧代-22-羟基何伯烷得到单一构型的3α,22-二羟基何伯烷和3β,22-二羟基何伯烷.在此基础上,通过X-射线单晶衍射实验确认了3β,22-二羟基何伯烷的绝对构型,并完整归属了该类化合物的1H和13C NMR数据.本文的方法亦可用以制备其他使用常规方法难以分离的α-和β-异构体.  相似文献   
2.
The accelerated failure time model always offers a valuable complement to the traditional Cox proportional hazards model due to its direct and meaningful interpretation. We propose a variable selection method in the context of the accelerated failure time model for survival data, which can simultaneously complete variable selection and parameter estimation. Meanwhile, the proposed method can deal with the potential outliers in survival times as well as heteroscedastic model errors, which are frequently encountered in practice. Specifically, utilizing the general nonconvex penalty, we propose the adaptive penalized weighted least absolute deviation estimator for the accelerated failure time model. Under some regularity conditions, we show that the proposed method yields consistent estimator and possesses the oracle property. In addition, we propose a new algorithm to compute the estimate in the high dimensional settings, and evaluate the practical utility of the proposed method through extensive simulation studies and two real examples.  相似文献   
3.
The most reliable method to determine the absolute configuration of chiral molecules is X‐ray crystallography, but small molecules can be difficult to crystallize. We report rapid co‐crystallization of tetraaryladamantanes with small molecules as different as n‐decane to nicotine to produce crystals for X‐ray analysis and the assignment of absolute configuration when the molecules are chiral. A screen of 52 diverse compounds gave inclusion in co‐crystals for 88 % of all cases and a high‐resolution structure in 77 % of cases. Furthermore, starting from three milligrams of analyte, a combination of NMR spectroscopy and X‐ray crystallography produced a full structure in less than three days using an adamantane crystallization chaperone that encapsulates the analyte at room temperature.  相似文献   
4.
针对光栅尺具有断电位置复位、无累计误差、高精度优点, 在光学隔振平台上分别建立开放式和封闭式绝对光栅尺实验系统, 绝对光栅尺采用图像识别原理, 以气浮直线电机ArotechABL1500为参考对象, 使用激光干涉仪RENISHAW XL-80校核精度, 研究不同结构绝对光栅尺的误码特点及原因。通过对比实验及研究分析, 表明封闭式绝对尺相对于开放式绝对尺的误码率要高, 开放式绝对式光栅尺的误码率为3%, 封闭式绝对式光栅尺的误码率为8%。  相似文献   
5.
《Physics letters. A》2019,383(27):125848
The Principle of Unattainability rules out the attainment of absolute zero temperature by any finite physical means, no matter how idealised they could be. Nevertheless, we clarify that the Third Law of Thermodynamics, as defined by Nernst's heat theorem statement, is distinct from the Principle of Unattainability in the sense that the Third Law is mathematically equivalent only to the unattainability of absolute zero temperature by quasi-static adiabatic processes. This, on the one hand, leaves open the possibility of attainability of absolute zero by non-adiabatic means, without violating the Third Law. On the other hand, we point out some apparent incompatibility between the Postulate of Projective Measurement in quantum mechanics and the Principle of Unattainability in that projective measurements of energy could result in zero temperature.  相似文献   
6.
文章首先将史瓦西黑洞场中自由下落质点的固有时(诺维科夫坐标时)公式,由自然单位制化成了国际单位制中的形式.然后,根据牛顿第二定律和万有引力定律,推导出了自由下落质点经历的绝对时间公式,进而证明了广义相对论中自由落体经历的固有时,恰好等于牛顿力学给出的绝对时间.最后,对自由下落质点在黑洞内外经历的时间进行了特例计算.  相似文献   
7.
A second polymorph of the hydrochloride salt of the recreational drug ethylone, C12H16NO3+·Cl, is reported [systematic name: (±)‐2‐ethylammonio‐1‐(3,4‐methylenedioxyphenyl)propane‐1‐one chloride]. This polymorph, denoted form (A), appears in crystallizations performed above 308 K. The originally reported form (B) [Wood et al. (2015). Acta Cryst. C 71 , 32–38] crystallizes preferentially at room temperature. The conformations of the cations in the two forms differ by a 180° rotation about the C—C bond linking the side chain to the aromatic ring. Hydrogen bonding links the cations and anions in both forms into similar extended chains in which any one chain contains only a single enantiomer of the chiral cation, but the packing of the ions is different. In form (A), the aromatic rings of adjacent chains interleave, but pack equally well if neighbouring chains contain the same or opposite enantiomorph of the cation. The consequence of this is then near perfect inversion twinning in the structure. In form (B), neighbouring chains are always inverted, leading to a centrosymmetric space group. The question as to why the polymorphs crystallize at slightly different temperatures has been examined by density functional theory (DFT) and lattice energy calculations and a consideration of packing compactness. The free energy (ΔG) of the crystal lattice for polymorph (A) lies some 52 kJ mol−1 above that of polymorph (B).  相似文献   
8.
Methionine (Met) oxidation is an important biological redox node, with hundreds if not thousands of protein targets. The process yields methionine oxide (MetO). It renders the sulfur chiral, producing two distinct, diastereomerically related products. Despite the biological significance of Met oxidation, a reliable protocol to separate the resultant MetO diastereomers is currently lacking. This hampers our ability to make peptides and proteins that contain stereochemically defined MetO to then study their structural and functional properties. We have developed a facile method that uses supercritical CO2 chromatography and allows obtaining both diastereomers in purities exceeding 99 %. 1H NMR spectra were correlated with X-ray structural information. The stereochemical interconversion barrier at sulfur was calculated as 45.2 kcal mol−1, highlighting the remarkable stereochemical stability of MetO sulfur chirality. Our protocol should open the road to synthesis and study of a wide variety of stereochemically defined MetO-containing proteins and peptides.  相似文献   
9.
Despite slow ongoing progress in increasing the representation of women in academia, women remain significantly under-represented at senior levels, in particular in the natural sciences and engineering. Not infrequently, this is downplayed by bringing forth arguments such as inherent biological differences between genders, that current policies are adequate to address the issue, or by deflecting this as being “not my problem” among other examples. In this piece we present scientific evidence that counters these claims, as well as a best-practice example, Genie, from Chalmers University of Technology, where one of the authors is currently employed. We also highlight particular challenges caused by the current COVID-19 pandemic. Finally, we conclude by proposing some possible solutions to the situation and emphasize that we need to all do our part, to ensure that the next generation of academics experience a more diverse, inclusive, and equitable working environment.  相似文献   
10.
We emphasize that it is extremely important for future neutrinoless double-beta(0νββ)decay experiments to reach the sensitivity to the effective neutrino mass|mββ|≈1 meV.With such a sensitivity,it is highly possible to discover the signals of 0νββ decays.If no signal is observed at this sensitivity level,then either neutrinos are Dirac particles or stringent constraints can be placed on their Majorana masses.In this paper,assuming the sensitivity of|mββ|≈1 meV for future 0νββ decay experiments and the precisions on neutrion oscillation parameters after the JUNO experiment,we fully explore the constrained regions of the lightest neutrino mass m1 and two Majorana-type CP-violating phases{ρ,σ}.Several important conclusions in the case of normal neutrino mass ordering can be made.First,the lightest neutrino mass is severely constrained to a narrow range m1∈[0.7,8]meV,which together with the precision measurements of neutrino mass-squared differences from oscillation experiments completely determines the neutrino mass spectrum m2∈[8.6,11.7]meV ing phases is limited to ρ∈[130°,230°],which cannot be obtained from any other realistic experiments.Third,the sum of three neutrino masses is found to beΣ≡m1+m2+m3∈[59.2,72.6]meV,while the effective neutrino mass for beta decays turns out to be mβ≡(|Ue1|2m1^2+|Ue2|2m2^2+|Ue3|2m3^2)1/2∈[8.9,12.6]meV.These observations clearly set up the roadmap for future non-oscillation neutrino experiments aiming to solve the fundamental problems in neutrino physics.  相似文献   
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