全文获取类型
收费全文 | 5943篇 |
免费 | 588篇 |
国内免费 | 191篇 |
专业分类
化学 | 5558篇 |
晶体学 | 3篇 |
力学 | 42篇 |
综合类 | 47篇 |
数学 | 712篇 |
物理学 | 360篇 |
出版年
2024年 | 8篇 |
2023年 | 85篇 |
2022年 | 371篇 |
2021年 | 355篇 |
2020年 | 264篇 |
2019年 | 204篇 |
2018年 | 216篇 |
2017年 | 192篇 |
2016年 | 266篇 |
2015年 | 274篇 |
2014年 | 329篇 |
2013年 | 471篇 |
2012年 | 316篇 |
2011年 | 379篇 |
2010年 | 273篇 |
2009年 | 328篇 |
2008年 | 290篇 |
2007年 | 308篇 |
2006年 | 250篇 |
2005年 | 252篇 |
2004年 | 199篇 |
2003年 | 179篇 |
2002年 | 225篇 |
2001年 | 72篇 |
2000年 | 91篇 |
1999年 | 83篇 |
1998年 | 73篇 |
1997年 | 54篇 |
1996年 | 53篇 |
1995年 | 32篇 |
1994年 | 36篇 |
1993年 | 34篇 |
1992年 | 17篇 |
1991年 | 17篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 13篇 |
1987年 | 14篇 |
1986年 | 5篇 |
1985年 | 12篇 |
1984年 | 8篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1969年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有6722条查询结果,搜索用时 8 毫秒
81.
Total synthesis of (Z) pulchellalactam, a CD protein tyrosine phosphatase inhibitor, from commercially available methallyl chloride employing ring‐closure metathesis (RCM) as a key step is described. 相似文献
82.
The title compound, neogeodin hydrate (C17H14C1208, CAS: 94540-50-8), was derived from marine fungus Aspergilhts terreus CRIM301. It was unequivocally characterized by IR, NMR spectroscopies, and single-crystal X-ray crystallography and tested for various biological activities. Neogeodin hydrate crystallizes in the triclinic space group P1 with a = 8.1159(5) A, b = 8.2472(4) A, c= 14.1278(7) A, a = 81.448(2)°, β = 84.860(2)°, γ= 70.400(2)°, V = 880.13(8) A3; Z = 2. It comprises a diphenyl ether, asterric acid skeleton and dichloro substituents. The methoxyphenoxy rings of the inversely related molecules form a ribbon-like structure that is stabilized by O-H...O hydrogen bonds through the doubly disordered carboxyl groups and by C-H...O interactions, generating the same R22(8) ring motif. The chlorinated methylbenzoate rings, making mostly a right angle, link the parallel upper and lower ribbons via bifurcated O-H...O and C-H...O hydrogen bonds, yielding endless channels. The channels formed are further sustained by C-H...O and π...π interactions Neogeodin hydrate exhibits inhibition against superoxide anion radical formation in the xanthine/xanthine oxidase (XXO) assay, but has no aromatase inhibitory activity. 相似文献
83.
Cécile Zamy Patrick Mazellier 《International journal of environmental analytical chemistry》2013,93(14-15):1059-1068
The hydrolysis of six selected pesticides has been studied in aqueous solution. Four organophosphorus pesticides (disulfoton, isofenfos, isazofos and profenfos) and two N-methylcarbamate derivatives (oxamyl and ethiofencarb) were selected. Hydrolysis was performed in purified buffered water at different pH in the range 7.0–10.0 (ionic strength?=?2.5?mM, T?=?25°C). At pH?=?8.0, isofenfos and disulfoton (t 1/2?≈?4 years, t 1/2?≈?1 year, resp.) were found to be far more stable than isazofos (t 1/2?≈?5 months), ethiofencarb and profenofos (t 1/2<1 month), themselves more stable than oxamyl (t 1/2?≈?1 day). As expected, a strong dependence on pH was observed for all pesticides: the rate of degradation increased when the pH increased. Degradation products were identified by GC–MS and/or LC–MS. Possible structures are presented in the article. 相似文献
84.
Qiuqin Zhou Florian Grundmann Marcel Kaiser Matthias Schiell Dr. Sophie Gaudriault Dr. Andreas Batzer Dr. Michael Kurz Prof. Dr. Helge B. Bode 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16772-16779
During the search for novel natural products from entomopathogenic Xenorhabdus doucetiae DSM17909 and X. mauleonii DSM17908 novel peptides named xenoamicins were identified in addition to the already known antibiotics xenocoumacin and xenorhabdin. Xenoamicins are acylated tridecadepsipeptides consisting of mainly hydrophobic amino acids. The main derivative xenoamicin A ( 1 ) was isolated from X. mauleonii DSM17908, and its structure elucidated by detailed 1 D and 2 D NMR experiments. Detailed MS experiments, also in combination with labeling experiments, confirmed the determined structure and allowed structure elucidation of additional derivatives. Moreover, the xenoamicin biosynthesis gene cluster was identified and analyzed in X. doucetiae DSM17909, and its participation in xenoamicin biosynthesis was confirmed by mutagenesis. Advanced Marfey’s analysis of 1 showed that the absolute configuration of the amino acids is in agreement with the predicted stereochemistry deduced from the nonribosomal peptide synthetase XabABCD. Biological testing revealed activity of 1 against Plasmodium falciparum and other neglected tropical diseases but no antibacterial activity. 相似文献
85.
This paper develops the theory of Dirac reduction by symmetry for nonholonomic systems on Lie groups with broken symmetry. The reduction is carried out for the Dirac structures, as well as for the associated Lagrange–Dirac and Hamilton–Dirac dynamical systems. This reduction procedure is accompanied by reduction of the associated variational structures on both Lagrangian and Hamiltonian sides. The reduced dynamical systems obtained are called the implicit Euler–Poincaré–Suslov equations with advected parameters and the implicit Lie–Poisson–Suslov equations with advected parameters. The theory is illustrated with the help of finite and infinite dimensional examples. It is shown that equations of motion for second order Rivlin–Ericksen fluids can be formulated as an infinite dimensional nonholonomic system in the framework of the present paper. 相似文献
86.
Efforts toward the synthesis of the decalin ring system common to the hibarimicin shunt metabolite HMP-Y1 and parent aglycone hibarimicinone are reported herein. An intramolecular Diels–Alder cyclization rapidly generated the decalin framework. Two approaches toward completion of the AB decalin were vetted. Incorporation of a phenylsulfonyl leaving group β- to both a ketone and a γ-lactone followed by base-induced elimination of sulfinate led to the undesired α,β-unsaturated lactone. Methanolysis of the γ-lactone followed by elimination produced the unexpected bridged cyclic ether by way of an intramolecular oxy-Michael addition of the endo oriented C13 alcohol. 相似文献
87.
Natural products (NPs) are evolutionarily optimized as drug-like molecules and remain the most consistently successful source of drugs and drug leads. They offer major opportunities for finding novel lead structures that are active against a broad spectrum of assay targets, particularly those from secondary metabolites of microbial origin. Due to traditional discovery approaches’ limitations relying on untargeted screening methods, there is a growing trend to employ unconventional secondary metabolomics techniques. Aided by the more in-depth understanding of different biosynthetic pathways and the technological advancement in analytical instrumentation, the development of new methodologies provides an alternative that can accelerate discoveries of new lead-structures of natural origin. This present mini-review briefly discusses selected examples regarding advancements in bioinformatics and genomics (focusing on genome mining and metagenomics approaches), as well as bioanalytics (mass-spectrometry) towards the microbial NPs-based drug discovery and development. The selected recent discoveries from 2015 to 2020 are featured herein. 相似文献
88.
Clostridium botulinum type E is a cold-tolerant, neurotoxigenic, endospore-forming organism, primarily associated with aquatic environments. High pressure thermal (HPT) processing presents a promising tool to enhance food safety and stability. The effect of fat on HPT inactivation of C. botulinum type E spores was investigated using an emulsion model system. The distribution of spores in oil-in-water (O/W) emulsions and their HPT (300–750?MPa, 45–75?°C, 10?min) inactivation was determined as a function of emulsion fat content (30–70% (v/v) soybean oil in buffer). Approximately 26% and 74% of the spores were located at the oil–buffer interface and the continuous phase, respectively. Spore inactivation in emulsion systems decreased with increasing oil contents, which suggests that the fat content of food plays an important role in the protection of C. botulinum type E endospores against HPT treatments. These results can be helpful for future safety considerations. 相似文献
89.
Quinones as Dienophiles in the Diels–Alder Reaction: History and Applications in Total Synthesis 下载免费PDF全文
Dr. Christopher C. Nawrat Prof. Dr. Christopher J. Moody 《Angewandte Chemie (International ed. in English)》2014,53(8):2056-2077
In the canon of reactions available to the organic chemist engaged in total synthesis, the Diels–Alder reaction is among the most powerful and well understood. Its ability to rapidly generate molecular complexity through the simultaneous formation of two carbon? carbon bonds is almost unrivalled, and this is reflected in the great number of reported applications of this reaction. Historically, the use of quinones as dienophiles is highly significant, being the very first example investigated by Diels and Alder. Herein, we review the application of the Diels–Alder reaction of quinones in the total synthesis of natural products. The highlighted examples span some 60 years from the landmark syntheses of morphine (1952) and reserpine (1956) by Gates and Woodward, respectively, through to the present day examples, such as the tetracyclines. 相似文献
90.
Shujun Cai Zheming Xiao Yingbo Shi Prof. Dr. Shuanhu Gao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(28):8677-8681
The reaction conditions and scope of the photo‐Nazarov reaction of aryl vinyl ketones were investigated. In contrast to the conventional acid‐catalyzed methods, this photolytic electrocyclization proceeds in the neutral or basic conditions. Irradiating substrates bearing various aromatic rings, acid‐sensitive groups, cyclohexenyl, cycloheptenyl, and unsaturated pyran with UV‐light (254 nm) smoothly yielded hexahydrofluorenones and related structures. This photo‐Nazarov reaction could also be applicable to the substrates carrying β‐alkyl groups on the enone, which gave corresponding polycyclic rings containing quaternary centers. These photo‐electrocyclized products may prove useful for synthesizing a variety of natural products and their derivatives. Further application of this mild photo‐Nazarov reaction in the synthesis of taiwaniaquinol B was achieved. 相似文献