全文获取类型
收费全文 | 1759篇 |
免费 | 78篇 |
国内免费 | 7篇 |
专业分类
化学 | 1362篇 |
晶体学 | 4篇 |
力学 | 48篇 |
数学 | 232篇 |
物理学 | 198篇 |
出版年
2023年 | 13篇 |
2022年 | 31篇 |
2021年 | 87篇 |
2020年 | 43篇 |
2019年 | 41篇 |
2018年 | 13篇 |
2017年 | 33篇 |
2016年 | 61篇 |
2015年 | 56篇 |
2014年 | 73篇 |
2013年 | 96篇 |
2012年 | 115篇 |
2011年 | 145篇 |
2010年 | 76篇 |
2009年 | 88篇 |
2008年 | 122篇 |
2007年 | 117篇 |
2006年 | 107篇 |
2005年 | 100篇 |
2004年 | 80篇 |
2003年 | 72篇 |
2002年 | 67篇 |
2001年 | 19篇 |
2000年 | 15篇 |
1999年 | 16篇 |
1998年 | 16篇 |
1997年 | 13篇 |
1996年 | 16篇 |
1995年 | 9篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 7篇 |
1991年 | 6篇 |
1990年 | 5篇 |
1989年 | 12篇 |
1987年 | 2篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1971年 | 1篇 |
1964年 | 1篇 |
1963年 | 1篇 |
1911年 | 1篇 |
1909年 | 2篇 |
排序方式: 共有1844条查询结果,搜索用时 218 毫秒
91.
Paola Taddei Carla Boga Gabriele Micheletti Barbara Ballarin 《Journal of Raman spectroscopy : JRS》2015,46(1):100-108
Raman and IR spectroscopy were used to investigate the changes induced in yak hair keratin by the straightening treatment based on glyoxylic acid. The amino acidic residues that appeared involved in the reaction with glyoxylic acid were serine and lysine; the involvement of the latter was deduced by the spectroscopic detection of iminic species, resulting from the reaction between the aminic group of lysine and the carbonyl group of glyoxylic acid. The reaction with glyoxylic acid induced conformational rearrangements that mainly involved the fibre bulk rather than the cuticle. Changes in the average tyrosine environment and its hydrogen‐bonding state were detected: at increasing glyoxylic acid incorporation, the tyrosine residues appeared more exposed, probably because of H‐bond interactions with the COOH group. The distribution of the disulfide bridge conformation was also affected, although no cleavage of the S–S bond was detected, in agreement with the shiny and healthy appearance of the fibres. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
92.
Crocetti Letizia Floresta Giuseppe Nazir Shabnam Vergelli Claudia Bhogal Amrit Biancalani Claudio Cesari Nicoletta Giovannoni Maria Paola Cilibrizzi Agostino 《Structural chemistry》2022,33(3):769-793
Structural Chemistry - We report here synthetic approaches to access new classes of small molecules based on three heterocyclic scaffolds, i.e. 3,7-dihydropyrimido[4,5-d]pyridazine-4,8-dione,... 相似文献
93.
94.
Flora V. Romeo Gina Granuzzo Paola Foti Gabriele Ballistreri Cinzia Caggia Paolo Rapisarda 《Molecules (Basel, Switzerland)》2021,26(7)
Olive mill wastewater (OMW) contains valuable and interesting bioactive compounds, among which is hydroxytyrosol, which is characterized by a remarkable antioxidant activity. Due to the health claims related to olive polyphenols, the aim of this study was to obtain an extract from OMW with an increased level of hydroxytyrosol by means of microbial enzymatic activity. For this purpose, four commercial adsorbent resins were selected and tested. The beta-glucosidase and esterase activity of strains of Wickerhamomyces anomalus, Lactiplantibacillus plantarum, and Saccharomyces cerevisiae were also investigated and compared to those of a commercial enzyme and an Aspergillus niger strain. The W. anomalus strain showed the best enzymatic performances. The SP207 resin showed the best efficiency in selective recovery of hydroxytyrosol, tyrosol, oleuropein, and total phenols. The bioconversion test of the OMW extract was assessed by using both culture broths and pellets of the tested strains. The results demonstrated that the pellets of W. anomalus and L. plantarum were the most effective in hydroxytyrosol increasing in phenolic extract. The interesting results suggest the possibility to study new formulations of OMW phenolic extracts with multifunctional microorganisms. 相似文献
95.
Battistina Asproni Gabriele Murineddu Paola Corona Grard A. Pinna 《Molecules (Basel, Switzerland)》2021,26(8)
Cannabinoids comprise different classes of compounds, which aroused interest in recent years because of their several pharmacological properties. Such properties include analgesic activity, bodyweight reduction, the antiemetic effect, the reduction of intraocular pressure and many others, which appear correlated to the affinity of cannabinoids towards CB1 and/or CB2 receptors. Within the search aiming to identify novel chemical scaffolds for cannabinoid receptor interaction, the CB1 antagonist/inverse agonist pyrazole-based derivative rimonabant has been modified, giving rise to several tricyclic pyrazole-based compounds, most of which endowed of high affinity and selectivity for CB1 or CB2 receptors. The aim of this review is to present the synthesis and summarize the SAR study of such tricyclic pyrazole-based compounds, evidencing, for some derivatives, their potential in the treatment of neuropathic pain, obesity or in the management of glaucoma. 相似文献
96.
Flavio Sabatelli Jacopo Segato Leonardo Belpassi Alessandro Del Zotto Daniele Zuccaccia Paola Belanzoni 《Molecules (Basel, Switzerland)》2021,26(9)
The coordination ability of the [(ppy)Au(IPr)]2+ fragment [ppy = 2-phenylpyridine, IPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene] towards different anionic and neutral X ligands (X = Cl−, BF4−, OTf−, H2O, 2-butyne, 3-hexyne) commonly involved in the crucial pre-equilibrium step of the alkyne hydration reaction is computationally investigated to shed light on unexpected experimental observations on its catalytic activity. Experiment reveals that BF4− and OTf− have very similar coordination ability towards [(ppy)Au(IPr)]2+ and slightly less than water, whereas the alkyne complex could not be observed in solution at least at the NMR sensitivity. Due to the steric hindrance/dispersion interaction balance between X and IPr, the [(ppy)Au(IPr)]2+ fragment is computationally found to be much less selective than a model [(ppy)Au(NHC)]2+ (NHC = 1,3-dimethylimidazol-2-ylidene) fragment towards the different ligands, in particular OTf− and BF4−, in agreement with experiment. Effect of the ancillary ligand substitution demonstrates that the coordination ability of Au(III) is quantitatively strongly affected by the nature of the ligands (even more than the net charge of the complex) and that all the investigated gold fragments coordinate to alkynes more strongly than H2O. Remarkably, a stabilization of the water-coordinating species with respect to the alkyne-coordinating one can only be achieved within a microsolvation model, which reconciles theory with experiment. All the results reported here suggest that both the Au(III) fragment coordination ability and its proper computational modelling in the experimental conditions are fundamental issues for the design of efficient catalysts. 相似文献
97.
Conventional methods generally used to synthesize heterogeneous photocatalysts have some drawbacks, mainly the difficult control/preservation of catalysts’ morphology, size or structure, which strongly affect the photocatalytic activity. Supercritical carbon dioxide (scCO2)-assisted techniques have recently been shown to be a promising approach to overcome these limitations, which are still a challenge. In addition, compared to traditional methods, these innovative techniques permit the synthesis of high-performance photocatalysts by reducing the use of toxic and polluting solvents and, consequently, the environmental impact of long-term catalyst preparation. Specifically, the versatility of scCO2 allows to prepare catalysts with different structures (e.g., nanoparticles or metal-loaded supports) by several supercritical processes for the photocatalytic degradation of various compounds. This is the first updated review on the use of scCO2-assisted techniques for photocatalytic applications. We hope this review provides useful information on different approaches and future perspectives. 相似文献
98.
Kristina Westerlund Anders Myrhammar Hanna Tano Maxime Gestin Amelie Eriksson Karlstrm 《Molecules (Basel, Switzerland)》2021,26(10)
Natural backbone-cyclized proteins have an increased thermostability and resistance towards proteases, characteristics that have sparked interest in head-to-tail cyclization as a method to stability-enhance proteins used in diagnostics and therapeutic applications, for example. In this proof-of principle study, we have produced and investigated a head-to-tail cyclized and HER2-specific ZHER2:342 Affibody dimer. The sortase A-mediated cyclization reaction is highly efficient (>95%) under optimized conditions, and renders a cyclic ZHER3:342-dimer with an apparent melting temperature, Tm, of 68 °C, which is 3 °C higher than that of its linear counterpart. Circular dichroism spectra of the linear and cyclic dimers looked very similar in the far-UV range, both before and after thermal unfolding to 90 °C, which suggests that cyclization does not negatively impact the helicity or folding of the cyclic protein. The cyclic dimer had an apparent sub-nanomolar affinity (Kd ~750 pM) to the HER2-receptor, which is a ~150-fold reduction in affinity relative to the linear dimer (Kd ~5 pM), but the anti-HER2 Affibody dimer remained a high-affinity binder even after cyclization. No apparent difference in proteolytic stability was detected in an endopeptidase degradation assay for the cyclic and linear dimers. In contrast, in an exopeptidase degradation assay, the linear dimer was shown to be completely degraded after 5 min, while the cyclic dimer showed no detectable degradation even after 60 min. We further demonstrate that a site-specifically DyLight 594-labeled cyclic dimer shows specific binding to HER2-overexpressing cells. Taken together, the results presented here demonstrate that head-to-tail cyclization can be an effective strategy to increase the stability of an Affibody dimer. 相似文献
99.
Bermel W Bertini I Felli IC Matzapetakis M Pierattelli R Theil EC Turano P 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,188(2):301-310
Attempts are made to efficiently decouple (13)C nuclei without significant loss of coherence during the application of the decoupling package. Such attempts are based on the S(3)E spin-state selection method. A newly developed double S(3)E (DS(3)E) is particularly efficient for C(alpha) detection for proteins as large as 480 kDa. 相似文献
100.