全文获取类型
收费全文 | 49853篇 |
免费 | 4339篇 |
国内免费 | 6774篇 |
专业分类
化学 | 41935篇 |
晶体学 | 1429篇 |
力学 | 1736篇 |
综合类 | 377篇 |
数学 | 5650篇 |
物理学 | 9839篇 |
出版年
2023年 | 484篇 |
2022年 | 743篇 |
2021年 | 1384篇 |
2020年 | 1558篇 |
2019年 | 1504篇 |
2018年 | 1290篇 |
2017年 | 1628篇 |
2016年 | 1747篇 |
2015年 | 1624篇 |
2014年 | 2129篇 |
2013年 | 3779篇 |
2012年 | 2859篇 |
2011年 | 3179篇 |
2010年 | 2833篇 |
2009年 | 3379篇 |
2008年 | 3162篇 |
2007年 | 3221篇 |
2006年 | 3003篇 |
2005年 | 2705篇 |
2004年 | 2730篇 |
2003年 | 2174篇 |
2002年 | 2335篇 |
2001年 | 1452篇 |
2000年 | 1207篇 |
1999年 | 956篇 |
1998年 | 843篇 |
1997年 | 758篇 |
1996年 | 761篇 |
1995年 | 800篇 |
1994年 | 718篇 |
1993年 | 571篇 |
1992年 | 566篇 |
1991年 | 379篇 |
1990年 | 262篇 |
1989年 | 285篇 |
1988年 | 278篇 |
1987年 | 193篇 |
1986年 | 144篇 |
1985年 | 140篇 |
1984年 | 152篇 |
1983年 | 51篇 |
1982年 | 110篇 |
1981年 | 154篇 |
1980年 | 153篇 |
1979年 | 150篇 |
1978年 | 115篇 |
1977年 | 86篇 |
1976年 | 73篇 |
1973年 | 37篇 |
1972年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
For seeking high‐efficiency narrow‐band‐gap donor materials to enhance short‐circuit current density for organic solar cells, a series of oligo‐selenophene (OS) and oligo(3,4‐ethylenedioxyselenophene) (OEDOS) with various chain lengths were designed and characterized using density functional theory (DFT) and time‐dependent DFT calculations. Based on the results, it can be seen that with increasing chain length of the oligomers in both syn‐ and anti‐adding manners, the bond length alternation is decreased which indicates that the π‐electron delocalization is increased. Also, when the chain length is increased the electronic energy gap and the optical energy gap are decreased. It can be concluded that the syn‐(OS)n=10,14,15, anti‐(OS)n=14 and anti‐(OEDOS)n=7–12 oligomers can act as low‐band‐gap polymers. Therefore they can absorb more sunlight based on maximum wavelength (higher than 620 nm). Furthermore, a red shift in the simulated absorption spectra of (OS)n and (OEDOS)n donors is observed. It is found that (OS)n=14,15 with syn configuration of the extended oligomers is the most suitable donor for the design of high‐performance organic solar cells possessing a narrow electronic band gap, high exciton lifetime and broad and intense absorption spectra that cover the solar spectrum leading to complete light‐harvesting efficiency. 相似文献
72.
Osama Abdallah Moustafa El Agamy Ehab Abdelraheem Farag Malhat 《Biomedical chromatography : BMC》2019,33(6)
An analytical method for the determination of buprofezin residues in cabbage and cauliflower was developed and validated using gas chromatography with ion trap mass spectrometry. The analyte protectant d ‐sorbitol was used at a concentration level of 0.5 mg mL?1 in acetonitrile instead of in matrix for constructing the calibration curves of the buprofezin standard. The average recoveries ranged from 91.3 to 96.8%, with an RSD of ≤2.7%. The limits of detection and quantitation of the method in cabbage and cauliflower were 1.3, 1.7 and 4.3, 6.2 μg kg?1, respectively. The residual levels and dissipation kinetics of buprofezin 25% wettabe powder in cabbage and cauliflower cultivated under open field conditions was investigated at the single (T1) and double (T2) recommended rates of application. Half‐life periods were found to be 1.73 and 2.1 days in cabbage, whereas in cauliflower, these values were 1.85 and 2.36 days at T1 and T2, respectively. Based on the dissipation study, and the maximum residue limit value of 0.05 mg kg?1, the proposed pre‐harvest interval of buprofezin in cabbage was 3–6 days and that in cauliflower was 4–10 days. The results showed that buprofezin is safe for application at both recommended application rates. 相似文献
73.
《大分子反应工程》2018,12(1)
A model is used to simulate batch copolymerization of caprolactam with hexamethylene diamine (HMD) and adipic acid (ADA) to produce nylon 6/6,6. Four different recipes are considered: a recipe containing caprolactam and an aqueous solution of HMD and ADA, a recipe containing caprolactam and dry HMD/ADA salt, and two recipes with a portion of the caprolactam replaced by nylon 6 cyclic dimer (CD). Consuming CD would be advantageous because CD is an undesirable side product from nylon 6 production. Simulation results lead to three important findings: (i) operation using dry salt rather than aqueous salt solution leads to higher degree of polymerization, (ii) substantial quantities of CD can be consumed to produce nylon 6/6,6 copolymer, and (iii) including water in the recipe is beneficial for achieving improved consumption of CD. The results of this study will be helpful in designing experiments aimed at improving industrial nylon 6/6,6 copolymerization processes. 相似文献
74.
A novel metal-doped metal–organic framework (MOF) was developed by incorporating salen–Mg into NH2–MIL-101(Cr) structure under ambient conditions. The Schiff base complex was successfully prepared by condensing salicylaldehyde with a free amino group and then coordinating metal ions. Such a structure can endow the sample with higher CO2 adsorption performance. At 0°C and 1 bar, the salen–Mg-modified sample achieves the maximum adsorption capacity of 2.18 mmol g−1 for CO2, which was 5.8% higher than the pristine salen–MOF under the same conditions. Notably, the Freundlich model indicates that the CO2 adsorption process of all samples conforms to reversible adsorption. However, the correlation coefficients (R2) of the Mg-doped sample are lower than that of the pristine sample. Besides, the CO2/N2 adsorption selectivity and isosteric heat also show a similar trend. These results indicate that the salen–Mg can enhance the interaction between the material and CO2 molecules. 相似文献
75.
In this research, the main emphasis has been focused on the preparation of a novel Fe3O4-supported propane-1-sulfonic acid-grafted graphene oxide quantum dots (Fe3O4@GOQD-O-(propane-1-sulfonic acid)) that it was readily synthesized via a five-step procedure as a hitherto unreported magnetic nanocatalyst. This newly prepared Fe3O4@GOQD-O-(propane-1-sulfonic acid) nanocomposite was structurally well-established by different analytical techniques including Fourier transform infrared (FT-IR), X-ray diffraction (XRD), energy-dispersive X-ray (EDX), thermal gravimetric analysis (TGA), field emission gun-scanning electron microscope (FESEM), high-resolution transmission electron microscopy (HRTEM) and vibrating sample magnetometer (VSM) analyses. The high catalytic performance of this nanocomposite was exhibited in one-pot synthesis of dihydropyrano[2,3-c]pyrazole and 4H-chromene derivatives under mild conditions. Low reaction times, excellent yields of the products, benignity of the catalyst, easy reaction work-up and magnetic recyclability of the catalyst are the main advantages of the present protocol. Also, our research indicated that the Fe3O4@GOQD-O-(propane-1-sulfonic acid) could be reused up to five times without considerable loss of catalytic activity. 相似文献
76.
Chin-Soon Phan Takashi Kamada Kazushi Kobayashi Toshiyuki Hamada 《Natural product research》2018,32(2):202-207
A new xenicane diterpenoid, 15-deoxy-isoxeniolide-A (1) along with four known compounds 9-deoxy-isoxeniolide-A (2), isoxeniolide-A (3), xeniolide-A (4) and coraxeniolide-B (5) were isolated from the Bornean soft coral Xenia sp. The structures of these metabolites were elucidated on the basis of spectral analysis, NMR and HRESIMS. Compound 5 showed cytotoxic activity against ATL cell line, S1T. 相似文献
77.
利用低温水热法在p-GaN薄膜上生长了铟(In)和镓(Ga)共掺杂的ZnO纳米棒。X射线衍射(XRD)、X射线光电子能谱(XPS)和X射线能量色谱仪(EDS)结果表明,In和Ga已固溶到ZnO晶格中。扫描电子显微镜(SEM)结果表明, ZnO纳米棒具有良好的c轴取向性,随着In和Ga共掺杂浓度的增加,纳米棒的直径减小,密度增加。XRD结果表明,In和Ga共掺杂引起ZnO晶格常数增大,导致(002)衍射峰向低角度方向偏移。同时,ZnO的光学性质受到In和Ga共掺杂的影响。与纯ZnO相比, 共掺杂ZnO纳米棒的紫外发射峰都出现轻微红移,这是表面共振和带隙重整效应综合作用的结果。I-V特性曲线表明,随着In和Ga共掺杂浓度的增加,n-ZnO纳米棒/p-GaN异质结具有更好的导电性。 相似文献
78.
Ai-hua Zhang Zhi-ming Ma Ling Kong Hong-lei Gao Hui Sun Xiang-qian Wang Jing-bo Yu Ying Han Guang-li Yan Xi-jun Wang 《Biomedical chromatography : BMC》2020,34(2):e4724
Lipid metabolism has a significant function in the central nervous system and Alzheimer's disease (AD) is an age-related senile disease characterized by central nerve degeneration. The pathological development of AD is closely related to lipid metabolism disorders. To reveal the influence of Kai-Xin-San (KXS) on lipid metabolism in APP/PSI transgenic mice and potential therapeutic targets for treating AD, brain tissue samples were collected and analyzed by high-throughput lipidomics based on UPLC–Q/TOF-MS. The collected raw data were processed by multivariate data analysis to discover the potential biomarkers and lipid metabolic profiles. Compared with the control wild-type mouse group, nine potential lipid biomarkers were found in the AD model group, of which seven were up-regulated and two were down-regulated. Orally administrated KXS can reverse the changes in these potential biomarkers. Compared with the model group, a total of six differential metabolites showed a recovery trend and may be potential targets for KXS to treat AD. This study showed that high-throughput lipidomics can be used to discover the perturbed pathways and lipid biomarkers as potential targets to reveal the therapeutic effects of KXS. 相似文献
79.
《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
80.
Recent research has focused on increasing the evidentiary value of latent fingerprints through chemical analysis. Although researchers have optimized the use of organic and metal matrices for matrix‐assisted laser desorption/ionization‐mass spectrometry imaging (MALDI‐MSI) of latent fingerprints, the use of development powders as matrices has not been fully investigated. Carbon forensic powder (CFP), a common nonporous development technique, was shown to be an efficient one‐step matrix; however, a high‐resolution mass spectrometer was required in the low mass range due to carbon clusters. Titanium oxide (TiO2) is another commonly used development powder, especially for dark nonporous surfaces. Here, forensic TiO2 powder is utilized as a single‐step development and matrix technique for chemical imaging of latent fingerprints without the requirement of a high‐resolution mass spectrometer. All studied compounds were successfully detected when TiO2 was used as the matrix in positive mode, although, generally, the overall ion signals were lower than the previously studied CFP. TiO2 provided quality mass spectrometry (MS) images of endogenous and exogenous latent fingerprint compounds. The subsequent addition of traditional matrices on top of the TiO2 powder was ineffective for universal detection of latent fingerprint compounds. Forensic TiO2 development powder works as an efficient single‐step development and matrix technique for MALDI‐MSI analysis of latent fingerprints in positive mode and does not require a high‐resolution mass spectrometer for analysis. 相似文献