全文获取类型
收费全文 | 2430篇 |
免费 | 50篇 |
国内免费 | 8篇 |
专业分类
化学 | 1584篇 |
晶体学 | 42篇 |
力学 | 86篇 |
数学 | 567篇 |
物理学 | 209篇 |
出版年
2023年 | 12篇 |
2022年 | 44篇 |
2021年 | 61篇 |
2020年 | 40篇 |
2019年 | 43篇 |
2018年 | 30篇 |
2017年 | 21篇 |
2016年 | 62篇 |
2015年 | 66篇 |
2014年 | 51篇 |
2013年 | 118篇 |
2012年 | 106篇 |
2011年 | 145篇 |
2010年 | 91篇 |
2009年 | 81篇 |
2008年 | 123篇 |
2007年 | 102篇 |
2006年 | 131篇 |
2005年 | 122篇 |
2004年 | 107篇 |
2003年 | 89篇 |
2002年 | 78篇 |
2001年 | 31篇 |
2000年 | 18篇 |
1999年 | 25篇 |
1998年 | 20篇 |
1997年 | 20篇 |
1996年 | 42篇 |
1995年 | 25篇 |
1994年 | 30篇 |
1993年 | 25篇 |
1992年 | 20篇 |
1991年 | 21篇 |
1990年 | 21篇 |
1989年 | 11篇 |
1988年 | 17篇 |
1987年 | 14篇 |
1986年 | 8篇 |
1985年 | 25篇 |
1984年 | 15篇 |
1983年 | 19篇 |
1982年 | 22篇 |
1981年 | 20篇 |
1980年 | 31篇 |
1979年 | 26篇 |
1978年 | 17篇 |
1976年 | 16篇 |
1975年 | 13篇 |
1915年 | 9篇 |
1906年 | 7篇 |
排序方式: 共有2488条查询结果,搜索用时 15 毫秒
121.
The methodology of J-based analysis applied to 1,3-methylcarboamido systems allowed us to deduce the relative configurations of the two leucine-like fragments of a new tetrachloro amino acid derivative dysithiazolamide, which was isolated from an unidentified sponge of the genus Dysidea. Furthermore, the absolute configuration was also proposed by comparison with analogous systems. 相似文献
122.
Synthesis and Biological Evaluation of Several Dephosphonated Analogues of CMP‐Neu5Ac as Inhibitors of GM3‐Synthase 下载免费PDF全文
Dr. Paola Rota Dr. Federica Cirillo Dr. Marco Piccoli Dr. Antonio Gregorio Prof. Guido Tettamanti Prof. Pietro Allevi Prof. Luigi Anastasia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(41):14614-14629
Previous studies demonstrated that reducing the GM3 content in myoblasts increased the cell resistance to hypoxic stress, suggesting that a pharmacological inhibition of the GM3 synthesis could be instrumental for the development of new treatments for ischemic diseases. Herein, the synthesis of several dephosphonated CMP‐Neu5Ac congeners and their anti ‐ GM3‐synthase activity is reported. Biological activity testes revealed that some inhibitors almost completely blocked the GM3‐synthase activity in vitro and reduced the GM3 content in living embryonic kidney 293A cells, eventually activating the epidermal growth factor receptor (EGFR) signaling cascade. 相似文献
123.
Danilo Sciarrone Luisa Schipilliti Carla Ragonese Peter Quinto Tranchida Paola Dugo Giovanni Dugo Luigi Mondello 《Journal of chromatography. A》2010,1217(7):1101-1105
The present research is focused on the determination of the enantiomeric distribution of chiral compounds, contained in mandarin essential oils, by means of conventional chiral gas chromatography with flame ionization detection (enantio-GC-FID); the results attained were compared with those derived from heart-cutting multidimensional GC-mass spectrometry (MDGC/MS), to evaluate the reliability of the monodimensional technique as a tool for quality control. The Deans-switch MDGC system was equipped with two GC ovens, which were connected via a heated transfer line, a flame ionization detector (FID1) in the first dimension and a quadrupole MS as second-dimension detector. The a priori knowledge of potential co-elutions concerning target compounds (an enantiomer and an interfering compound), when using enantio-GC-FID, could enable the use of corrected enantiomer excess values. Correction factors could be calculated through a preliminary GC-FID analysis (using an apolar column), considering the peak areas of the known interferences. The method used for the calculation of a so-called “coelution correction factor” is described, along with some examples. 相似文献
124.
In this work, it is shown how to implement both hard and soft computing by means of two structurally related heterocyclic compounds: flindersine (FL) and 6(5H)-phenanthridinone (PH). Since FL and PH have a carbonyl group in their molecular skeletons, they exhibit Proximity Effects in their photophysics. In other words, they have an emission power that can be modulated through external inputs such as temperature (T) and hydrogen-bonding donation (HBD) ability of solvents. This phenomenology can be exploited to implement both crisp and fuzzy logic. Fuzzy Logic Systems (FLSs) wherein the antecedents of the rules are connected through the AND operator, are built by both the Mamdani’s and Sugeno’s models. Finally, they are adopted as approximators of the proximity effect phenomenon and tested for their prediction capabilities. Moreover, FL as photochromic compound is also a multiply configurable crisp logic molecular element. 相似文献
125.
[structure: see text] An approach relying on quantum mechanical calculations of proton-proton and proton-carbon J coupling values is proposed as a tool for assigning the relative configuration on chiral organic compounds. The method is suitable for carbon frameworks containing several adjacent stereogenic centers and may allow significant advances in the extensive use of spin-spin couplings in structural elucidation. 相似文献
126.
Gian Luigi Bendazzoli 《Theoretical chemistry accounts》2007,118(1):135-142
We present and discuss a variational single-product approximation to the van der Waals dispersion interaction leading to a
simple formula for C
6 that seems capable to give more than 99% of the ‘exact’ value. The formula is derived from Hylleraas’ variational principle
in the tensor product space of the interacting molecules and therefore enjoys bounding properties. The formula has been tested
by computing the C
6 dispersion constants of H–H, and, at Full CI level, of the following systems: He–He, He–Li, Li–Li, LiH–LiH, HF–HF. Connections
with the London formula are discussed.
Contribution to the Fernando Bernardi Memorial Issue. 相似文献
127.
Boiocchi M Fabbrizzi L Foti F Vazquez M 《Dalton transactions (Cambridge, England : 2003)》2004,(17):2616-2620
The spin interconversion equilibrium involving the [Ni(II)(cyclam)]2+ complex has been investigated in a variety of polar solvents, at varying temperatures. The greater the donor tendencies of the solvent, the higher the endothermicity of the high-to-low-spin conversion. In particular, a positive linear relationship exists between DeltaHdegrees and Gutmann's Donor Number (DN). In the same way, higher donor tendencies of the solvent favour the occurrence of the Ni(II)-to-Ni(III) oxidation process and negative linear relationship has been found between the E1/2(Ni(III)/Ni(II)) and DN. General behaviour is related to the intensity of the metal-solvent axial bonds in the octahedrally elongated cyclam complexes (of both Ni(II) and Ni(III)). 相似文献
128.
Gallo P Nasi A Vinci F Guadagnuolo G Brambilla G Fiori M Serpe L 《Rapid communications in mass spectrometry : RCM》2005,19(4):574-579
In this work we present a method for confirmatory analysis of chloramphenicol (CAP) in bovine and buffalo raw milk. CAP is extracted in acetonitrile and purified by affinity chromatography on an alpha-1-acid glycoprotein (AAG) column, then is identified and determined by ion-trap liquid chromatography/electrospray ionisation tandem mass spectrometry (LC/ESI-MS/MS) analysis in the negative ion mode. CAP was identified at the minimum required performance limit (MRPL) of 0.30 ppb, by monitoring the [M-H]- ion and at least two product ions, meeting the qualitative and quantitative criteria set by the European Commission in Decision 2002/657/EC for confirmation of prohibited veterinary drugs. The trueness and within-day and between-day repeatability data are also reported. Moreover, the loading capacity of affinity columns towards CAP was tested. This method, based on the molecular recognition between drug and AAG during the purification step to improve sample cleanup, represents a quantitative and repeatable procedure for confirmatory analysis, and fits the requirements for the routine official control of CAP residues in raw milk. 相似文献
129.
Daniela Metro Mattia Papa Luigi Manasseri Teresa Gervasi Luca Campone Vito Pellizzeri 《Natural product research》2020,34(16):2255-2261
Abstract Breakfast habits affect the nutritional status and health of people, in particular children and adolescents. This is the second part a previous study about the adherence to the Mediterranean diet in a Sicilian (Italy) student population. The investigation analysed both normal weight and overweight subjects in order to understand how eating habits, number of meals and daily calorie intakes could affect their body mass indexes (BMI). The aim of this second part was to analyse the breakfast nutritional profiles of this student population. The results highlighted that breakfast was regularly consumed by a percentage ranging from a maximum of 84% (in normal subjects) to a minimum value of 57.4% (in overweight/obese students). Milk, yoghurt, sugar, bread/rusk and tea contributed as main foods to the breakfast composition. The results highlighted that subjects who consumed breakfast showed lower BMI values with significant differences between normal and overweight/obese students. 相似文献
130.
Silvestro L Gheorghe M Iordachescu A Ciuca V Tudoroniu A Rizea Savu S Tarcomnicu I 《Analytical and bioanalytical chemistry》2011,401(3):1023-1034
A new sensitive and fast quantitative analytical method for the simultaneous determination of clopidogrel, its main metabolite
clopidogrel carboxylic acid, and the newly described acyl glucuronide metabolite, in human plasma samples, is presented. The
analytical procedures (plasma storage, handling, and extract storage in the autosampler) were optimized in order to avoid
back-conversion; a known drawback in measurements of clopidogrel. Clopidogrel acyl glucuronide was confirmed as a major source
of back-conversion to the parent drug in the presence of methanol, and thorough stability experiments were carried out to
find the most appropriate conditions for an accurate analysis of clopidogrel and the two metabolites. The method was validated
by assessing selectivity, sensitivity, linearity, accuracy, and precision for all three analytes, in accordance to Food and
Drug Administration guidelines. Spiked quality controls in plasma as well as incurred samples were used to verify back-conversion
in the selected conditions, with results meeting European Medicines Agency acceptance criteria (concentrations within 80–120%
of the first reading). The method was then applied to a pharmacokinetic study, and for the first time, a pharmacokinetic curve
of clopidogrel acyl glucuronide in human plasma is presented. The concentrations ranged up to 1,048.684 ng/mL, with a mean
of 470.268 ng/mL, while clopidogrel had a mean C
max of 1.348 ng/mL; these orders of magnitude show how much the back-conversion of this metabolite may influence clopidogrel
quantification if it is not properly controlled. 相似文献