全文获取类型
收费全文 | 3773篇 |
免费 | 262篇 |
国内免费 | 420篇 |
专业分类
化学 | 4033篇 |
晶体学 | 39篇 |
力学 | 5篇 |
综合类 | 20篇 |
数学 | 6篇 |
物理学 | 352篇 |
出版年
2024年 | 6篇 |
2023年 | 37篇 |
2022年 | 99篇 |
2021年 | 98篇 |
2020年 | 123篇 |
2019年 | 138篇 |
2018年 | 99篇 |
2017年 | 132篇 |
2016年 | 172篇 |
2015年 | 144篇 |
2014年 | 177篇 |
2013年 | 424篇 |
2012年 | 246篇 |
2011年 | 198篇 |
2010年 | 171篇 |
2009年 | 189篇 |
2008年 | 178篇 |
2007年 | 206篇 |
2006年 | 168篇 |
2005年 | 169篇 |
2004年 | 162篇 |
2003年 | 123篇 |
2002年 | 92篇 |
2001年 | 77篇 |
2000年 | 64篇 |
1999年 | 87篇 |
1998年 | 81篇 |
1997年 | 67篇 |
1996年 | 70篇 |
1995年 | 59篇 |
1994年 | 54篇 |
1993年 | 58篇 |
1992年 | 33篇 |
1991年 | 26篇 |
1990年 | 31篇 |
1989年 | 17篇 |
1988年 | 27篇 |
1987年 | 21篇 |
1986年 | 15篇 |
1985年 | 15篇 |
1984年 | 9篇 |
1983年 | 8篇 |
1982年 | 11篇 |
1981年 | 9篇 |
1980年 | 14篇 |
1979年 | 17篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1973年 | 3篇 |
排序方式: 共有4455条查询结果,搜索用时 15 毫秒
71.
Maryam Sarvarian Afshin Jafarpour Chinaza Godswill Awuchi Ademiku O. Adeleye Charles Odilichukwu R. Okpala 《Molecules (Basel, Switzerland)》2022,27(5)
In Iran and other parts of Western Asia, the oleaster (Elaeagnus angustifolia L.) fruit is processed in the dried powdery form, and in recent times, increasingly applied/sprinkled in fruit juices such as those made from oranges (Citrus sinensis L.). To our best knowledge, the effectiveness of oleaster fruit extract in fortifying the orange juice has not yet been reported and the knowledge of this will greatly benefit the consumers, particularly those around the Western Asia region. This current work, therefore, investigated the changes in physicochemical, free radical activity, total phenolic compounds, and sensory properties of orange juice fortified with different oleaster fruit extracts. The orange juice mix formulation comprised different concentrations (5, 10, 15, 20, and 25%) of oleaster (alcoholic, aqueous, and hydro-alcoholic) extracts. The control comprised orange concentrate (4% w/v), sugar (8.5% w/v), and citric acid (0.1% w/v) brought to the desirable volume with water. As the free radical activity depicted the antioxidant properties, the physicochemical aspects of this work involved the determinations of Brix, density, ash, pH, total acidity, sucrose, and total sugar, whereas the sensory aspects involved the determinations of color and taste. Whilst the aqueous oleaster 20 and 25% extracts produced notable physicochemical differences in the orange juice mix, both free radical activity, and phenolic compounds significantly increased (p < 0.05) after 30 days despite resembling (p > 0.05) those of control at day 1. More so, the increases in aqueous, alcoholic, and hydro-alcoholic oleaster extracts would decrease (p < 0.05) the sensory color and taste of the orange juice mix in this study. 相似文献
72.
The spectral and luminescence characteristics of water and water–ethanol solutions of dyes have been investigated. The efficiency of the process of association of dye molecules and the structure of the complexes formed depending on their concentration and the solvent composition have been established. The presence of inhomogeneities in the distribution of dissolved complex molecules in the water matrix which determine the high efficiency of the association processes in water solutions as compared with other solvents is shown. The characteristic sizes of these inhomogeneities have been estimated. 相似文献
73.
Jin Yuan Ling Wang Yitong Wang Prof. Dr. Jingcheng Hao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(16):3545-3554
Copper nanoclusters (CuNCs) as a new class of fluorescent materials have attracted a great deal of interest due to their outstanding fluorescence properties. In this work, a variety of organic solvents were used to induce self-assembly of glutathione-capped CuNCs (GSH-CuNCs) to form ordered assemblies with enhanced fluorescence properties. Assemblies with multicolor fluorescence emission were constructed on the basis of the aggregation-induced emission (AIE) of GSH-CuNCs and the solvent effect. The fluorescence emission from these GSH-CuNCs assemblies can also be tuned from yellow to purple by changing the organic solvent. A possible mechanism based on the size of the assemblies and electron transfer was explored to explain the solvent effects on GSH-CuNCs. Stimuli-responsive nanoswitches with excellent reversibility can be controlled by changing the type of organic solvent and the ratio of the organic solvent to the aqueous solution of GSH-CuNCs. As the CuNCs assemblies exhibit strong, stable, and color-tunable fluorescence, they were employed as color-conversion materials for recognizing different organic solvents. 相似文献
74.
Leah B. Casabianca 《Magnetic resonance in chemistry : MRC》2020,58(7):611-624
The nuclear magnetic resonance (NMR) chemical shift is extremely sensitive to molecular geometry, hydrogen bonding, solvent, temperature, pH, and concentration. Calculated magnetic shielding constants, converted to chemical shifts, can be valuable aids in NMR peak assignment and can also give detailed information about molecular geometry and intermolecular effects. Calculating chemical shifts in solution is complicated by the need to include solvent effects and conformational averaging. Here, we review the current state of NMR chemical shift calculations in solution, beginning with an introduction to the theory of calculating magnetic shielding in general, then covering methods for inclusion of solvent effects and conformational averaging, and finally discussing examples of applications using calculated chemical shifts to gain detailed structural information. 相似文献
75.
Atika Muhammad Dr. Graziano Di Carmine Luke Forster Dr. Carmine D'Agostino 《Chemphyschem》2020,21(11):1101-1106
Solvent effects in homogeneous catalysis are known to affect catalytic activity. Whilst these effects are often described using qualitative features, such as Kamlet-Taft parameters, experimental tools able to quantify and reveal in more depth such effects have remained unexplored. In this work, PFG NMR diffusion and T1 relaxation measurements have been carried out to probe solvent effects in the homogeneous catalytic reduction of propionaldehyde to 1-propanol in the presence of aluminium isopropoxide catalyst. Using data on diffusion coefficients it was possible to estimate trends in aggregation of different solvents. The results show that solvents with a high hydrogen-bond accepting ability, such as ethers, tend to form larger aggregates, which slow down the molecular dynamics of aldehyde molecules, as also suggested by T1 measurements, and preventing their access to the catalytic sites, which results in the observed decrease of catalytic activity. Conversely, weakly interacting solvents, such as alkanes, do not lead to the formation of such aggregates, hence allowing easy access of the aldehyde molecules to the catalytic sites, resulting in higher catalytic activity. The work reported here is a clear example on how combining traditional catalyst screening in homogeneous catalysis with NMR diffusion and relaxation time measurements can lead to new physico-chemical insights into such systems by providing data able to quantify aggregation phenomena and molecular dynamics. 相似文献
76.
S. Harris 《Journal of statistical physics》1970,2(4):379-385
A model Liouville equation is proposed for a system composed of an ion moving in a solvent fluid. Using this model, explicit results are obtained for the Ohmic conductivityL and the Hall conductivityh. These results are then used to calculate the Hall coefficientR = ehL–2, which is a measure of the effect of non-Brownian motion, for several charge carriers of interest. Our results are in agreement with earlier findings based on a stochastic model which predictR > 1 for H+(aq). Our results also indicate thatR 1 for charge carriers such as Na+, Cl–, and K+ which have a mass greater than that of a solvent molecule (here taken as 18 amu).This research was supported in part by grants from the National Science Foundation and by the Research Foundation of the State University of New York. 相似文献
77.
Danuta Wróbel Izabela Hanyż Renata Bartkowiak Rodica M. Ion 《Journal of fluorescence》1998,8(3):191-198
Porphyrin dyes fulfill an essential function in photosynthesis and are important in photodynamic therapy and in a range of electronic devices. Their spectroscopic characteristics may play a crucial role in these processes. The spectral properties of two porphyrin dyes: tetraphenylporphyrin and tetraphenysulfporphyrin in organic solvents (acetone, chloroform, methyl alcohol, and dimethyl-sulfoxide) and in polyvinyl alcohol and poly(methylmethacrylate) films have been investigated. Absorption, fluorescence, and microsecond time-resolved delayed luminescence spectra have been measured at room temperature. The existence of different aggregated dye forms in the ground and excited states has been demonstrated. The manifold of dye species depends on the solvent/polymer. In the case of the polymers, it also depends on the solvent used to coat the polymer film. Delayed luminescence spectra and decay times of the two porphyrins in the different solutions and in polymeric matrices suggest that different mechanisms of deexcitation of the singlet excited states may be responsible for their generation in these and other porphyrin dyes. 相似文献
78.
Paulo A. R. Pires Muhammad Imran Carina Loffredo Paulo M. Donate Daniel Previdi Omar A. El Seoud 《Journal of Physical Organic Chemistry》2013,26(3):280-285
The effects of solvents on chemical phenomena (rate and equilibrium constants, spectroscopic transitions, etc.) are conveniently described by solvation free‐energy relationships that take into account solvent acidity, basicity and dipolarity/polarizability. The latter can be separated into its components by manipulating the UV–vis spectra of two solvatochromic probes, 2‐(N,N‐dimethylamino)‐7‐nitrofluorene (DMANF) and a di‐(tert‐butyl)‐tetramethyl docosanonaen probe (ttbP9) whose synthesis is laborious and expensive. Recently, we have shown that the natural dye β‐carotene can be conveniently employed instead of ttbP9 for the determination of solvent polarizability (SP) of 76 molecular solvents and four ionic liquids. In the present work, we report the polarizabilities of further 24 solvents. Based on the solvatochromism of β‐carotene and DMANF, we have calculated solvent dipolarity (SD) for 103 protic and aprotic molecular solvents, and ionic liquids. The dependence of SD and SP on the number of carbon atoms in the acyl‐ or alkyl group of several homologous series (alcohols; 2‐alkoxyethanols; carboxylic acid‐ anhydrides, and esters, ionic liquids) is calculated and briefly discussed. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
79.
The study of thermodynamic properties of solutions provides important information on existing molecular interactions between the components present in a solution. These studies are critical for testing, validation and development of theories and mathematical models. The refractometric study of a solution is a simple assessment that can contribute to the understanding of these interactions. In this context, the behaviour of the binary water and glucose mixture was studied as well as ternary mixtures of water, glucose and acetonitrile at five different temperatures in the range 293–333 K by the determination of the refractive index of the solution. Due to the weakening of the molecular interactions with the increasing of the temperature, a decreasing dependence of refractive index with temperature was observed. The addition of acetonitrile provides an increase in the refractive index indicating the formation of clusters in the solution. 相似文献
80.
《Journal of separation science》2017,40(18):3612-3620
The linear solvent strength model was used to predict coverage in online comprehensive two‐dimensional reversed‐phase liquid chromatography. The prediction model uses a parallelogram to describe the separation space covered with peaks in a system with limited orthogonality. The corners of the parallelogram are assumed to behave like chromatographic peaks and the position of these pseudo‐compounds was predicted. A mix of 25 polycyclic aromatic compounds were used as a test. The precision of the prediction, span 0–25, was tested by varying input parameters, and was found to be acceptable with root mean square errors of 3. The accuracy of the prediction was assessed by comparing with the experimental coverages. Less than half of experimental coverages were outside prediction ± 1 × root mean square error and none outside prediction ± 2 × root mean square error. Accuracy was lower when retention factors were low, or when gradient conditions affected parameters not included in the model, e.g. second dimension gradient time affects the second dimension equilibration time. The concept shows promise as a tool for gradient optimization in online comprehensive two‐dimensional liquid chromatography, as it mitigates the tedious registration and modeling of all sample constituents, a circumstance that is particularly appealing when dealing with complex samples. 相似文献