全文获取类型
收费全文 | 1693篇 |
免费 | 48篇 |
国内免费 | 7篇 |
专业分类
化学 | 1370篇 |
晶体学 | 13篇 |
力学 | 25篇 |
数学 | 210篇 |
物理学 | 130篇 |
出版年
2023年 | 15篇 |
2022年 | 36篇 |
2021年 | 41篇 |
2020年 | 44篇 |
2019年 | 33篇 |
2018年 | 28篇 |
2017年 | 19篇 |
2016年 | 58篇 |
2015年 | 44篇 |
2014年 | 48篇 |
2013年 | 92篇 |
2012年 | 135篇 |
2011年 | 111篇 |
2010年 | 64篇 |
2009年 | 44篇 |
2008年 | 122篇 |
2007年 | 137篇 |
2006年 | 106篇 |
2005年 | 107篇 |
2004年 | 84篇 |
2003年 | 75篇 |
2002年 | 70篇 |
2001年 | 19篇 |
2000年 | 14篇 |
1999年 | 12篇 |
1998年 | 18篇 |
1997年 | 18篇 |
1996年 | 22篇 |
1995年 | 6篇 |
1994年 | 8篇 |
1993年 | 11篇 |
1992年 | 12篇 |
1991年 | 8篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 11篇 |
1984年 | 13篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 6篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 7篇 |
1972年 | 1篇 |
1968年 | 1篇 |
1937年 | 1篇 |
排序方式: 共有1748条查询结果,搜索用时 15 毫秒
81.
Gaetano Isola Alessandro Polizzi Vincenzo Ronsivalle Angela Alibrandi Giuseppe Palazzo Antonino Lo Giudice 《Molecules (Basel, Switzerland)》2021,26(6)
Matrix metalloproteinase-9 (MMP-9) has been shown to play a key role in endothelial function and perhaps pivotal in the correlation between periodontal disease and cardiovascular disease (CVD). For the study, the impact of MMP-9 of periodontitis and CVD on serum and saliva concentrations was analyzed. For the study patients with periodontitis (n = 31), CVD (n = 31), periodontitis + CVD (n = 31), and healthy patients (n = 31) were enrolled. Clinical and demographic characteristics as well as serum and salivary MMP-9 were evaluated. MMP-9 concentrations in serum and saliva were statistically elevated in patients with CVD (p < 0.01) and in patients with periodontitis plus CVD (p < 0.001) compared to patients with periodontitis and healthy subjects. Multivariate regression analysis showed that c-reactive protein (hs-CRP) was the only significant predictor for MMP-9 serum (p < 0.001), whereas hs-CRP (p < 0.001) and total cholesterol (p = 0.029) were the statistically significant salivary MMP-9 predictors. This study evidenced that patients with CVD and periodontitis + CVD presented elevated MMP-9 concentrations in serum and saliva compared to patients with periodontitis and healthy subjects. Furthermore, hs-CRP was a negative predictor of serum and salivary MMP-9. 相似文献
82.
Electrodes modified by liquid films or plasticized polymeric membranes containing a redox species offer valuable alternatives for the study of ion transfers and bimolecular electron transfers at liquid–liquid interfaces with conventional electrode arrangements and stable interfaces. The ion-to-electron (or electron-to-electron) transducer affects the electrochemical signal, complicating the accurate analysis of experimental data. This can be reduced through the use of an electrode surface-attached redox species of well-defined electrochemical behaviour. As will be demonstrated, the voltammetry of these systems show significant deviations with respect to individual charge transfers, which must be considered for appropriate diagnosis and quantitative analysis. For this, a simple analytical theory is presented here, deducing mathematical expressions for the current–potential response, as well as for the potential difference at the two polarized interfaces, the surface excess of the redox species and the ion interfacial concentrations. 相似文献
83.
Ruben Elvas-Leito Filomena Martins Leonor Borbinha Catarina Marranita Angela Martins Nelson Nunes 《Molecules (Basel, Switzerland)》2020,25(23)
Attempts to optimize heterogeneous catalysis often lack quantitative comparative analysis. The use of kinetic modelling leads to rate (k) and relative sorption equilibrium constants (K), which can be further rationalized using Quantitative Structure-Property Relationships (QSPR) based on Multiple Linear Regressions (MLR). Friedel-Crafts acylation using commercial and hierarchical BEA zeolites as heterogeneous catalysts, acetic anhydride as the acylating agent, and a set of seven substrates with different sizes and chemical functionalities were herein studied. Catalytic results were correlated with the physicochemical properties of substrates and catalysts. From this analysis, a robust set of equations was obtained allowing inferences about the dominant factors governing the processes. Not entirely surprising, the rate and sorption equilibrium constants were found to be explained in part by common factors but of opposite signs: higher and stronger adsorption forces increase reaction rates, but they also make the zeolite active sites less accessible to new reactant molecules. The most relevant parameters are related to the substrates’ molecular size, which can be associated with different reaction steps, namely accessibility to micropores, diffusion capacity, and polarizability of molecules. The relatively large set of substrates used here reinforces previous findings and brings further insights into the factors that hamper/speed up Friedel-Crafts reactions in heterogeneous media. 相似文献
84.
Sen Ye Nir Hananya Ori Green Hansen Chen Angela Qian Zhao Jiangang Shen Doron Shabat Dan Yang 《Angewandte Chemie (International ed. in English)》2020,59(34):14326-14330
Selective and sensitive molecular probes for hydrogen peroxide (H2O2), which plays diverse roles in oxidative stress and redox signaling, are urgently needed to investigate the physiological and pathological effects of H2O2. A lack of reliable tools for in vivo imaging has hampered the development of H2O2 mediated therapeutics. By combining a specific tandem Payne/Dakin reaction with a chemiluminescent scaffold, H2O2‐CL‐510 was developed as a highly selective and sensitive probe for detection of H2O2 both in vitro and in vivo. A rapid 430‐fold enhancement of chemiluminescence was triggered directly by H2O2 without any laser excitation. Arsenic trioxide induced oxidative damage in leukemia was successfully detected. In particular, cerebral ischemia‐reperfusion injury‐induced H2O2 fluxes were visualized in rat brains using H2O2‐CL‐510 , providing a new chemical tool for real‐time monitoring of H2O2 dynamics in living animals. 相似文献
85.
Angela Giorgia Potortì Alessia Tropea Vito Pellizzeri Asma Belfita Giacomo Dugo 《Natural product research》2020,34(1):167-171
AbstractSpices and aromatic herbs can be contaminated with mycotoxins, since of their preharvest, postharvest, and storage conditions. In this study, 112 samples of different spices and aromatic herbs were evaluated for their mycotoxins content by HPLC-MS/MS in order to highlight their possible risk linked with human use. The results showed that mycotoxins were occasionally detected only in samples of coriander, laurel, mint, rosemary, and verbena. In both geographical origins a different contamination was detected. Among the investigated mycotoxins, AFB2, AFG1, AFG2, T2 and HT2 were detected, whereas none of the samples contained AFB1 and FB1. The co-occurrence of two toxins were observed for some samples of rosemary and verbena. This study indicates that it is essential minimize the toxins in agriculture, industry, and food-product manufacturing for the consumer health protection. 相似文献
86.
87.
Isabel V. L. Wilkinson Kelly J. Perkins Hannah Dugdale Lee Moir Aini Vuorinen Maria Chatzopoulou Sarah E. Squire Sebastian Monecke Alexander Lomow Marcus Geese Philip D. Charles Peter Burch Jonathan M. Tinsley Graham M. Wynne Stephen G. Davies Francis X. Wilson Fraydoon Rastinejad Shabaz Mohammed Kay E. Davies Angela J. Russell 《Angewandte Chemie (International ed. in English)》2020,59(6):2420-2428
Duchenne muscular dystrophy (DMD) is a fatal muscle‐wasting disease arising from mutations in the dystrophin gene. Upregulation of utrophin to compensate for the missing dystrophin offers a potential therapy independent of patient genotype. The first‐in‐class utrophin modulator ezutromid/SMT C1100 was developed from a phenotypic screen through to a Phase 2 clinical trial. Promising efficacy and evidence of target engagement was observed in DMD patients after 24 weeks of treatment, however trial endpoints were not met after 48 weeks. The objective of this study was to understand the mechanism of action of ezutromid which could explain the lack of sustained efficacy and help development of new generations of utrophin modulators. Using chemical proteomics and phenotypic profiling we show that the aryl hydrocarbon receptor (AhR) is a target of ezutromid. Several lines of evidence demonstrate that ezutromid binds AhR with an apparent KD of 50 nm and behaves as an AhR antagonist. Furthermore, other reported AhR antagonists also upregulate utrophin, showing that this pathway, which is currently being explored in other clinical applications including oncology and rheumatoid arthritis, could also be exploited in future DMD therapies. 相似文献
88.
A simple and rapid method for the preparation of a series of novel quinoxaline derivatives in the presence of Ag+ is reported. 相似文献
89.
Racemic 1-acetyl-2-methoxymethylferrocene, (±)-1 was subjected to asymmetric reduction with two different methodologies and complementary results were obtained. When the reduction of (±)-1 was carried out in the presence of CBS-oxazaborolidine catalyst and BH3·Me2S as the hydrogen source, both enantiomers of the substrate were converted with comparable reaction rates and selectivities. The corresponding diastereoisomeric ferrocenylalcohols 3a and 3b were obtained in a 1:1 ratio and >90% enantiomeric excess; this reaction profile being related with a parallel kinetic resolution with high ds1 and ds2 diastereofacial selectivities. On the contrary, the transfer hydrogenation of (±)-1 with HCOOH/triethylamine in the presence of (R,R)-Noyori’s catalyst proceeded via classical kinetic resolution, so that the formed (?)-3b or unreacted (+)-1 could be obtained in highly enantiopure form before or beyond 50% of the substrate conversion, respectively. Alcohol 3b with an (1Rp,S)- or (1Sp,R)-configuration is not easily accessible by the diastereoselective metallation/electrophilic quenching sequence routinely applied in the synthesis of planar chiral ferrocenes. As a result, the described procedures provide a valuable access to this useful starting material for the synthesis of homochiral related derivatives. 相似文献
90.
Andrea Petrella Pinalysa Cosma M. Lucia Curri Sergio Rochira Angela Agostiano 《Journal of nanoparticle research》2011,13(12):6467-6481
Heterostructures formed of films of organic-capped ZnO and TiO2 nanocrystals (both with the size of ca. 6 nm) and photosynthetic pigments were prepared and characterized. The surface of
optically transparent electrodes (Indium Tin Oxide) was modified with nanocrystals and prepared by colloidal synthetic routes.
The nanostructured electrodes were sensitized by a mixture of chlorophyll a and carotenoids. The characterization of the hybrid
structures, carried out by means of steady-state optical measurements, demonstrated such class of dyes able to extend the
photoresponse of the large band-gap semiconductors. The charge-transfer processes between the components of the heterojunction
were investigated, and photoelectrochemical measurements taken on the sensitized ZnO and TiO2 nanocrystals electrodes elucidated the photoactivity of the heterojunctions as a function of the dyes and of the red–ox mediator
used in solution. The effect of methyl viologen as different red–ox mediator was also evaluated in order to show its effect
on the heterojunction photoactivity. The overall results contributed to describe the photoelectrochemical potential of the
investigated heterojunctions, highlighting a higher response of the dye-sensitized ZnO nanocrystals, and then provided the
TiO2-modified counterparts. 相似文献