全文获取类型
收费全文 | 53496篇 |
免费 | 2902篇 |
国内免费 | 9273篇 |
专业分类
化学 | 56939篇 |
晶体学 | 856篇 |
力学 | 231篇 |
综合类 | 402篇 |
数学 | 1085篇 |
物理学 | 6158篇 |
出版年
2024年 | 60篇 |
2023年 | 449篇 |
2022年 | 1303篇 |
2021年 | 1261篇 |
2020年 | 1337篇 |
2019年 | 2310篇 |
2018年 | 1344篇 |
2017年 | 2342篇 |
2016年 | 1913篇 |
2015年 | 1749篇 |
2014年 | 2157篇 |
2013年 | 4738篇 |
2012年 | 3456篇 |
2011年 | 3189篇 |
2010年 | 2524篇 |
2009年 | 3003篇 |
2008年 | 3273篇 |
2007年 | 3545篇 |
2006年 | 3314篇 |
2005年 | 3070篇 |
2004年 | 2914篇 |
2003年 | 2359篇 |
2002年 | 2007篇 |
2001年 | 1584篇 |
2000年 | 1566篇 |
1999年 | 1249篇 |
1998年 | 1062篇 |
1997年 | 1003篇 |
1996年 | 876篇 |
1995年 | 825篇 |
1994年 | 664篇 |
1993年 | 585篇 |
1992年 | 551篇 |
1991年 | 404篇 |
1990年 | 281篇 |
1989年 | 274篇 |
1988年 | 204篇 |
1987年 | 137篇 |
1986年 | 111篇 |
1985年 | 100篇 |
1984年 | 102篇 |
1983年 | 51篇 |
1982年 | 90篇 |
1981年 | 72篇 |
1980年 | 53篇 |
1979年 | 65篇 |
1978年 | 43篇 |
1977年 | 25篇 |
1976年 | 19篇 |
1973年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
21.
The discharge of diverse pollutants has led to a complex water environment and posed a huge health threat to humans and animals. Self-propelled micromotors have recently attracted considerable attention for efficient water remediation due to their strong localized mass transfer effect. However, a single functionalized component is difficult to tackle with multiple contaminants and requires to combine different decontamination effects together. Here, we introduced a multifunctional micromotor to implement the adsorption and degradation roles simultaneously by integrating the poly(aspartic acid) (PASP) adsorbent with a MnO2-based catalyst. The as-prepared micromotors are well propelled in contaminated waters by MnO2 catalyzing hydrogen peroxide. In addition, the catalytic ramsdellite MnO2(R-MnO2) inner layer is decorated with Fe2O3 nanoparticles to improve their catalytic performance, contributing to an excellent degradation ability with 90% tetracycline (TC) removal in 50 minutes by enhanced Fenton-like reactions. Combining the attractive adsorption capability of poly (aspartic acid) (PASP), the composite micromotors offer an efficient removal of heavy metal ions in short time. Moreover, the designed micromotors are able to simultaneously remove antibiotic and heavy metals in mixed contaminants circumstance just in single treatment. This multifunctional micromotor with distinctive decontamination ability exhibits a promising prospective in treating multiple pollutants in the future. 相似文献
22.
Ieva
Dauickait Amos S. Lawless Jennifer A. Scott Peter Jan van Leeuwen 《Numerical Linear Algebra with Applications》2020,27(5)
We consider the large sparse symmetric linear systems of equations that arise in the solution of weak constraint four‐dimensional variational data assimilation, a method of high interest for numerical weather prediction. These systems can be written as saddle point systems with a 3 × 3 block structure but block eliminations can be performed to reduce them to saddle point systems with a 2 × 2 block structure, or further to symmetric positive definite systems. In this article, we analyse how sensitive the spectra of these matrices are to the number of observations of the underlying dynamical system. We also obtain bounds on the eigenvalues of the matrices. Numerical experiments are used to confirm the theoretical analysis and bounds. 相似文献
23.
Physical aging in amorphous poly(ethylene furanoate): Enthalpic recovery,density, and oxygen transport considerations
下载免费PDF全文
![点击此处可从《Journal of Polymer Science.Polymer Physics》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Steven K. Burgess Christopher R. Mubarak Robert M. Kriegel William J. Koros 《Journal of Polymer Science.Polymer Physics》2015,53(6):389-399
The current work utilizes three separate techniques to study the physical aging process in amorphous poly(ethylene furanoate) (PEF), which is a recently introduced engineering thermoplastic with enhanced properties compared to petroleum‐sourced poly(ethylene terephthalate). Differential scanning calorimetry aging experiments were conducted at multiple aging temperatures and times, and the resultant enthalpic recovery values compared to the theoretical maximum enthalpy loss evaluated from calculations involving extrapolation of the equilibrium liquid line. Density measurements reveal densification of the matrix for the aged versus unaged samples, and provide an estimate for the reduction in free volume for the aged samples. Complementary oxygen permeation and pressure‐decay sorption experiments provide independent verification of the free volume reduction mechanism for physical aging in glassy polymers. The current work provides the first detailed aging study for PEF. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 389–399 相似文献
24.
《Journal of Saudi Chemical Society》2020,24(10):754-764
A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λmax = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k1 versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k1) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = sN (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. . 相似文献
25.
Rizwan Ahmad Niyaz Ahmad Fatimah AlOthman Haya Mohammad Fatimah AlZahrani 《Biomedical chromatography : BMC》2020,34(1):e4712
Coffee and tea are the most widely consumed beverages worldwide. However, the consumer may be unaware of the exact amount of methyl xanthine (MX, i.e. caffeine [C], theobromine [TB] and theophylline [TH]) consumed, as most of the products do not list the proper amounts. This may lead to serious risks including cardiovascular, kidney and stimulant effects. The aim of the study was to determine the MX amount in ready-to-use beverages (coffee and tea) collected from various outlets in the city of Al-Khobar, Saudi Arabia. Forty different samples of espresso, black coffee and red tea were collected. A fast, reliable and efficient UHPLC–DAD method was developed and validated for MX determination. Total lipids were extracted and fractionated in order to determine glycolipids, phospholipids and neutral lipids. The r2 value for the method was 0.980–0.988 in a linearity range of 0.5–200 ppm. The range for MX (C [0.02–2.39 mg/ml], TB [0.00–0.10 mg/ml] and TH [0.00–0.004 mg/ml]) and total lipids was 1–5 g. The amount of glycolipids (3.1 g) was higher among the lipid fractions followed by phospholipids (1.8 g) and neutral lipids (0.25 g). In general, espresso beverages (20–30 ml) contained high amounts of MX whereas black coffee beverages contained high amount of lipids. Most of the beverages expressed C, TB, TH, lipids or their fractions; however, the product with high amounts of MX and lipids at the same time was espresso (brands Chemistry and Wogard). Although the MX and lipid levels in these beverages well below the allowed limits, care must still be taken, especially when using the beverages with high serving volumes (200–250 ml) or coffee prepared via the filter method i.e. black coffee, using a high temperature for a longer time. 相似文献
26.
Elsye Agustina Jeungchoon Goak Suntae Lee Youngho Seo Jun-Young Park Naesung Lee 《ChemistryOpen》2015,4(5):613-619
Iron catalysts have been used widely for the mass production of carbon nanotubes (CNTs) with high yield. In this study, UV/visible spectroscopy was used to determine the Fe catalyst content in CNTs using a colorimetric technique. Fe ions in solution form red–orange complexes with 1,10-phenanthroline, producing an absorption peak at λ=510 nm, the intensity of which is proportional to the solution Fe concentration. A series of standard Fe solutions were formulated to establish the relationship between optical absorbance and Fe concentration. Many Fe catalysts were microscopically observed to be encased by graphitic layers, thus preventing their extraction. Fe catalyst dissolution from CNTs was investigated with various single and mixed acids, and Fe concentration was found to be highest with CNTs being held at reflux in HClO4/HNO3 and H2SO4/HNO3 mixtures. This novel colorimetric method to measure Fe concentrations by UV/Vis spectroscopy was validated by inductively coupled plasma optical emission spectroscopy, indicating its reliability and applicability to asses Fe content in CNTs. 相似文献
27.
A string of four new hetero binuclear Ru(III) complexes of ferrocenecarboxaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized by various spectral (infrared, ultraviolet–visible, Electron Paramagnetic Resonance (EPR) and High Resolution Mass Spectrometry (HR-MS) techniques. The binding abilities of the ligands/complexes with nucleic acid (calf thymus DNA, CT-DNA) and bovine serum albumin (BSA) were analyzed by absorption and emission titration methods. The complexes exhibited better DNA binding affinity than their parent ligands. The interaction with CT-DNA was found to be intercalative and with BSA static quenching mechanism was observed. All the synthesized Ru(III) complexes were subjected to study their in vitro cytotoxicity against MCF-7 (human breast cancer) and HT-29 (human colon cancer) cell lines. Among the four complexes, complex 3 [RuCp (FF-etsc)PPh3]Cl exhibited the highest cytotoxicity in MCF-7 cells and complex 4 [RuCp (FF-ptsc)PPh3]Cl was the most active on HT-29 cells. 相似文献
28.
In this study, stoichiometric protonation constants of L-tyrosine, L-cysteine, L-tryptophane, L-lysine, and L-histidine, and
their methyl and ethyl esters in water and ethanol–water mixtures of 30, 50, and 70% ethanol (v/v), were determined potentiometrically
using a combined pH electrode system calibrated as the concentration of hydrogen ion. Titrations were performed at 25∘C and the ionic strength of the medium was maintained at 0.10 mol⋅L−1 using sodium chloride. Protonation constants were calculated by using the BEST computer program. The effect of solvent composition
on the protonation constants is discussed. The log10 K2 values of esters generally decreased with increasing ethanol content. However, the log10 K1 values of the esters of L-tyrosine, L-cysteine, and L-tryptophane were found to increase with increasing ethanol content
in contrast those of L-lysine and L-histidine esters. 相似文献
29.
双掺(Tm3+,Tb3+)LiYF4激光器1.5 μm波长激光阈值分析 总被引:1,自引:0,他引:1
由速率方程推出了双掺(Tm^3 ,Tb^3 )离子准四能级系统的激光阈值解析式,讨论了Tm^3 和Tb^3 离子之间的相互作用。分析了1.5μm波长附近的激光阈值和Tm^3 、Tb^3 离子的掺杂原子数分数及晶体长度的关系。结果表明,对于对应Tm^3 离子^3H4→^3F4跃迁的约1.5μm波长的激光,激活离子Tm^3 的掺杂原子数分数过大时,交叉弛豫作用将使系统阈值迅速增加。Tb^3 离子的加入,一方面能抽空激光下能级,起到降低阈值的作用;另一方面亦减少了激光上能级的寿命,使阈值升高。故Tb^3 离子有最佳掺杂原子数分数。对于Tm原子数分数为y=0.01的Tm:LiYF4晶体,Tb^3 离子的最佳掺杂原子数分数为0.002左右,同时表明,激光阈值与晶体长度有关。最佳晶体长度与Tm^3 、Tb^3 离子的掺杂原子数分数以及晶体的衍射损耗和吸收损耗有关。 相似文献
30.
A. Negr n-Mendoza G. Albarran S. Ramos-Bernal 《Radiation Physics and Chemistry》1993,42(4-6):1003-1006
The effect of clay on the radiolysis of malonic acid solutions was studied. The results showed an enhanced of decarboxylation rather than condensation reactions. 相似文献