全文获取类型
收费全文 | 7421篇 |
免费 | 1369篇 |
国内免费 | 1191篇 |
专业分类
化学 | 6066篇 |
晶体学 | 81篇 |
力学 | 391篇 |
综合类 | 83篇 |
数学 | 786篇 |
物理学 | 2574篇 |
出版年
2024年 | 30篇 |
2023年 | 149篇 |
2022年 | 324篇 |
2021年 | 321篇 |
2020年 | 359篇 |
2019年 | 411篇 |
2018年 | 306篇 |
2017年 | 286篇 |
2016年 | 403篇 |
2015年 | 416篇 |
2014年 | 459篇 |
2013年 | 586篇 |
2012年 | 708篇 |
2011年 | 665篇 |
2010年 | 414篇 |
2009年 | 425篇 |
2008年 | 459篇 |
2007年 | 368篇 |
2006年 | 358篇 |
2005年 | 320篇 |
2004年 | 276篇 |
2003年 | 242篇 |
2002年 | 325篇 |
2001年 | 267篇 |
2000年 | 167篇 |
1999年 | 150篇 |
1998年 | 128篇 |
1997年 | 74篇 |
1996年 | 83篇 |
1995年 | 63篇 |
1994年 | 64篇 |
1993年 | 51篇 |
1992年 | 77篇 |
1991年 | 49篇 |
1990年 | 50篇 |
1989年 | 30篇 |
1988年 | 22篇 |
1987年 | 24篇 |
1986年 | 24篇 |
1985年 | 13篇 |
1984年 | 8篇 |
1983年 | 11篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1971年 | 1篇 |
1959年 | 2篇 |
1957年 | 2篇 |
1936年 | 3篇 |
排序方式: 共有9981条查询结果,搜索用时 0 毫秒
61.
62.
Using renewable green hydrogen and carbon dioxide (CO2) to produce methanol is one of the fundamental ways to reduce CO2 emissions in the future, and research and development related to catalysts for efficient and stable methanol synthesis is one of the key factors in determining the entire synthesis process. Metal nanoparticles stabilized on a support are frequently employed to catalyze the methanol synthesis reaction. Metal-support interactions (MSIs) in these supported catalysts can play a significant role in catalysis. Tuning the MSI is an effective strategy to modulate the activity, selectivity, and stability of heterogeneous catalysts. Numerous studies have been conducted on this topic; however, a systematic understanding of the role of various strengths of MSI is lacking. Herein, three Cu/ZnO-SiO2 catalysts with different strengths of MSI, namely, normal precipitation Cu/ZnO-SiO2 (Nor-CZS), co-precipitation Cu/ZnO-SiO2 (Co-CZS), and reverse precipitation Cu/ZnO-SiO2 (Re-CZS), were successfully prepared to determine the role of such interactions in the hydrogenation of CO2 to methanol. The results of temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) characterization illustrated that the MSI of the catalysts was considerably affected by the precipitation sequence. Fourier transform infrared reflection spectroscopy (FT-IR) results indicated that the Cu species existed as CuO in all cases and that copper phyllosilicate was absent (except for strong Cu-SiO2 interaction). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and N2O chemical titration results revealed that strong interactions between the Cu and Zn species would promote the dispersion of Cu species, thereby leading to a higher CO2 conversion rate and improved catalytic stability. As expected, the Re-CZS catalyst exhibited the highest activity with 12.4% CO2 conversion, followed by the Co-CZS catalyst (12.1%), and the Nor-CZS catalyst (9.8%). After the same reaction time, the normalized CO2 conversion of the three catalysts decreased in the following order: Re-CZS (75%) > Co-CZS (70%) > Nor-CZS (65%). Notably, the methanol selectivity of the Re-CZS catalyst was found to level off after a prolonged period, in contrast to that of Co-CZS and Nor-CZS. Investigation of the structural evolution of the catalyst with time on stream revealed that the high methanol selectivity of the catalyst was caused by the reconstruction of the catalyst, which was induced by the strong MSI between the Cu and Zn species, and the migration of ZnO onto Cu species, which caused an enlargement of the Cu/ZnO interface. This work offers an alternative strategy for the rational and optimized design of efficient catalysts. 相似文献
63.
64.
Peng Chen Xiaojun Luo Guanqi Dai Yuchuan Jiang Yue Luo Shuang Peng Hao Wang Penghui Xie Chen Qu Wenyu Lin Jian Hong Xue Ning Aimin Li 《Experimental & molecular medicine》2020,52(7):1062
Dexmedetomidine (DEX) is an anesthetic that is widely used in the clinic, and it has been reported to exhibit paradoxical effects in the progression of multiple solid tumors. In this study, we sought to explore the mechanism by which DEX regulates hepatocellular carcinoma (HCC) progression underlying liver fibrosis. We determined the effects of DEX on tumor progression in an orthotopic HCC mouse model of fibrotic liver. A coculture system and a subcutaneous xenograft model involving coimplantation of mouse hepatoma cells (H22) and primary activated hepatic stellate cells (aHSCs) were used to study the effects of DEX on HCC progression. We found that in the preclinical mouse model of liver fibrosis, DEX treatment significantly shortened median survival time and promoted tumor growth, intrahepatic metastasis and pulmonary metastasis. The DEX receptor (ADRA2A) was mainly expressed in aHSCs but was barely detected in HCC cells. DEX dramatically reinforced HCC malignant behaviors in the presence of aHSCs in both the coculture system and the coimplantation mouse model, but DEX alone exerted no significant effects on the malignancy of HCC. Mechanistically, DEX induced IL-6 secretion from aHSCs and promoted HCC progression via STAT3 activation. Our findings provide evidence that the clinical application of DEX may cause undesirable side effects in HCC patients with liver fibrosis.Subject terms: Cancer microenvironment, Cell growth 相似文献
65.
疏水缔合型增稠剂聚(丙烯酰胺-丙烯酸高级酯)的合成及增稠性能研究 总被引:5,自引:0,他引:5
采用沉淀聚合法合成了聚(丙烯酰胺-丙烯酸十四酯),聚(丙烯酰胺-丙烯酸十六酯)和聚(丙烯酰胺-丙烯酸十八酯),重点讨论了共聚物中疏水基团数量及疏水基团链长对增稠性能的影响。采用凯达尔定氮法和动态热分析(DMTA)测定了共聚物的组成及玻璃化温度。 相似文献
66.
trans-RhCl(CO)(TPPTS)2 (TPPTS=tris(m-sulfonatophenyl)phosphine) has been intercalated into Zn-Al layered double hydroxides (LDHs) by the method of ion exchange. The structure, composition and thermal stability of the composite material have been characterized by powder X-ray diffraction, Fourier transform infrared and 31P solid-state magic-angle spinning nuclear magnetic resonance spectroscopy, elemental analysis, thermogravimetry, and differential thermal analysis. The geometry of trans-RhCl(CO)(TPPTS)2 was fully optimized using the PM3 semiempirical molecular orbital method, and a schematic model for the intercalated species has been proposed. The thermal stability of trans-RhCl(CO)(TPPTS)2 is significantly enhanced by intercalation, which suggests that such materials may have prospective application as the basis of a supported catalyst system for the hydroformylation of higher olefins. 相似文献
67.
68.
Maximum spectrum of continuous wavelet transform and its application in resolving an overlapped signal 总被引:2,自引:0,他引:2
Xiaoquan L Hongde L Zhonghua X Qiang Z 《Journal of chemical information and computer sciences》2004,44(4):1228-1237
To estimate the number of peaks and to find the individual peak positions in an overlapped signal, a new method called maximum spectrum of continuous wavelet transform (MSCWT) was developed by extracting the maximum coefficients of continuous wavelet transform (CWT). The peak position in MSCWT was the same as that in its original signal. In this process, CWT was performed not on a single dilation but on an appreciation dilation range. To obtain such a range, a new criterion was introduced to choose a center dilation, which was used to form the dilation range. If Cdilation denoted the center dilation, the proper dilation range was [Cdilation -6 +/- 2, Cdilation +1 +/- 1]. The Mexican Hat function was an analytical wavelet. Utilizing the information of the peak number and the position detected by MSCWT, a fitting route was performed to recover the original signal. One simulated and four true overlapped signals, including high performance liquid chromatography (HPLC), ultraviolet-visible (UV) spectrum, and differential pulse voltammetric (DPV), were processed, and the results indicated that MSCWT could detect an overlapped peak number and position, and the curve fitting based on information of MSCWT had a higher accuracy. The proposed method was an efficient one in resolving different types of overlapped signals. 相似文献
69.
Wen Xu Guoqun Liu Gang Xue Wentao Yu 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(8):m436-m438
The crystal structure of the title compound, (C16H36N)[Ni(C3S5)2], is isomorphous with that of the corresponding Pt complex but different from the structures reported for compounds of the same chemical composition, and so provides a new crystalline phase of this complex. The nickel complex anion has good planarity and lies on a crystallographic inversion centre. There is disorder in the two terminal C atoms of two of the butyl chains of the tetra‐n‐butylammonium cation, the N atom of which is located on a twofold axis. 相似文献
70.
Swelling and network parameters of crosslinked thermoreversible hydrogels of poly(N-ethylacrylamide)
Samples of Poly(N-ethylacrylamide) (PEA) have been synthesized by free radical polymerization in water using N,N′-methylene bis-acrylamide (BIS) as crosslinker. Hydrogels obtained by swelling them in water, 15 wt% KCl and 1 wt% sodium dodecyl sulphate (SDS) were examined by gravimetric, dimensional and compression-strain measurements to afford values of swelling ratio, polymer-solvent interaction parameters, elastic moduli and effective crosslinking density νe. Crosslinking inefficiency is evidenced by the low value (0.23) of νe relative to the theoretical crosslinking density νt based on the content of BIS in the synthesis. A small but finite extrapolated value of νe at νt = 0 is indicative of hydrophobic physical interactions. In water at 298 K increasing the content of BIS leads to a decrease in swelling and increases in values of elastic moduli and polymer-water interaction parameter. At a fixed content of BIS the values of νe and the elastic moduli exhibit an unusual increase with temperature, the crosslinking thus being thermally reversible. It is proposed that this results from a balance between hydrophobic interaction and breakage of hydrophilic hydrogen bonding. Although KCl in the medium decreases the swelling compared with that in water, the opposite effect occurs on incorporation of SDS, which is assumed to confer some polyelectrolyte character to the PEA chains. The finding, that these two swelling media reduce the values of νe and elastic moduli cf the value in water, has not been resolved satisfactorily. 相似文献