全文获取类型
收费全文 | 12760篇 |
免费 | 1923篇 |
国内免费 | 840篇 |
专业分类
化学 | 4045篇 |
晶体学 | 319篇 |
力学 | 1780篇 |
综合类 | 230篇 |
数学 | 4912篇 |
物理学 | 4237篇 |
出版年
2023年 | 159篇 |
2022年 | 201篇 |
2021年 | 315篇 |
2020年 | 304篇 |
2019年 | 276篇 |
2018年 | 300篇 |
2017年 | 525篇 |
2016年 | 616篇 |
2015年 | 561篇 |
2014年 | 668篇 |
2013年 | 1074篇 |
2012年 | 698篇 |
2011年 | 727篇 |
2010年 | 686篇 |
2009年 | 764篇 |
2008年 | 818篇 |
2007年 | 878篇 |
2006年 | 702篇 |
2005年 | 560篇 |
2004年 | 597篇 |
2003年 | 586篇 |
2002年 | 476篇 |
2001年 | 335篇 |
2000年 | 318篇 |
1999年 | 296篇 |
1998年 | 262篇 |
1997年 | 191篇 |
1996年 | 215篇 |
1995年 | 196篇 |
1994年 | 160篇 |
1993年 | 135篇 |
1992年 | 108篇 |
1991年 | 86篇 |
1990年 | 73篇 |
1989年 | 59篇 |
1988年 | 64篇 |
1987年 | 52篇 |
1986年 | 44篇 |
1985年 | 67篇 |
1984年 | 39篇 |
1983年 | 27篇 |
1982年 | 37篇 |
1981年 | 29篇 |
1980年 | 46篇 |
1979年 | 44篇 |
1978年 | 26篇 |
1977年 | 35篇 |
1976年 | 36篇 |
1974年 | 13篇 |
1957年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
《印度化学会志》2023,100(9):101074
In this paper, we report a facile and one-pot hydrothermal synthesis of FeVO4-rGO nanorod composite and its application as a heterogeneous catalyst in the oxidative esterification reaction of aldehydes using hydrogen peroxide oxidant. The nanomaterial is thoroughly characterized by different techniques, namely, XPS, FESEM, elemental mapping, XRD, Raman, HRTEM, etc. The as-prepared nanocatalyst shows good activity for the controlled base-free oxidative esterification of various aromatic aldehydes in alcohol solvents under refluxing conditions, achieving good yields of the desired esters. Furthermore, the substrate scope was explored over a wide array of substituted aromatic aldehydes with diverse electron-withdrawing and electron-donating groups in the phenyl ring. The presence of heterogeneous interfaces-induced properties in the nanorod composite results in synergistic effects to provide good catalytic performance. Thus, binary transition metal oxide-reduced graphene oxide-based nanocomposite as a nanocatalyst can open doors for efficient and sustainable esterification of aromatic aldehydes and aliphatic alcohols under oxidative conditions. 相似文献
72.
Shahzeb Ahmad Shazia Bashir Mahreen Akram Rizwan Amir Muhammad Shahid Rafique Wolfgang Husinsky Mubashir Javed 《Surface and interface analysis : SIA》2023,55(2):113-126
The present paper reports the investigation of surface morphology, elemental composition, phase changes and field emission properties of Si ion irradiated nickel (Ni) and titanium (Ti). The Ni and Ti targets have been irradiated with 500 keV Si ions generated by Pelletron accelerator at various fluences ranging from 6.9 × 1013 to 77.1 × 1013 ions/cm2. Stopping range of ions in matter analysis revealed higher values of electronic stopping and sputtering yield for Ni as compared with Ti. For both irradiated metals, electronic energy loss dominant over the nuclear stopping. The growth of induced surface structures have been analysed by using field emission scanning electron microscopy (FESEM) analysis. In case of Ni, as the ion fluence increases from 6.9 × 1013 to 65.8 × 1013 ions/cm2, the formation of spherical particulates, agglomers and sputtering is observed. Although in the case of Ti, with the increase of Si ion fluence from 11.6 × 1013 to 77.1 × 1013 ions/cm2, the formation of irregular-shaped particulates along with crater and sputtered channels is observed. X-ray diffraction (XRD) analysis shows that no new phase is identified. However, a significant increase in peak intensity is observed with increasing ion fluence. The variation in crystallite size and dislocation line density is also observed as a function of Si ion fluence. Fourier transform infrared spectroscopy analysis shows that no bands are formed after the Si ion irradiation. Field emission properties of ion-structured Ni and Ti are well correlated with the growth of surface structures observed by SEM and dislocation line density evaluated by XRD analysis. 相似文献
73.
《Journal of Saudi Chemical Society》2023,27(4):101684
Biochar (BC) and ferrihydrite (Fh) were used together in activation of H2O2 for removal of sulfamethazine (SMZ), a refractory antibiotic pollutant. The results show a complementary effect between biochar and ferrihydrite on activation of H2O2, namely biochar accelerated Fe(Ⅲ)/Fe(Ⅱ) cycle through electron donation/transfer, while ferrihydrite enhanced the yield of •OH through a sustainable release of dissolved Fe. Thus several times more •OH was produced in the co-activated system (BC + Fh/H2O2) than either in the ferrihydrite-catalyzed Fenton-like system (Fh/H2O2) or in the biochar-activated system (BC/H2O2). Consequently, a more efficient oxidation of SMZ was observed in BC + Fh/H2O2, in which the reaction rate constant (kobs) is 30.7 times in Fh/H2O2 and 6.08 times in BC/H2O2, respectively. This research provides a simple and sustainable strategy for enhancing the efficiency of Fenton-like oxidation of pollutants. 相似文献
74.
Simultaneous application of multiple sinusoidal waveforms perturbations superimposed onto DC staircase step significantly enriches current response. The measured current is characterized by a matrix of data rather than a conventional voltammetric output in a form of a vector. This increase of the dimensionality of the current response and therefore the wealth of analytical information is achieved without compromising the time of analysis. The natural approach for compression of such data and extraction of relevant information is by utilizing multi-way chemometric decomposition techniques. An electroplating solution presents a very challenging analyte for electroanalysis as its constituents interact synergistically with each other during both the plating process and its simulation during electroanalysis. For some components the mechanism is not entirely understood. Therefore, the only way to benefit from the analytical data is by employing soft modeling. The electrode processes involving additives rely heavily on adsorption and, indirectly, on electron transfer kinetics for which AC voltammetry is an analytical technique capable of delivering informative signals. This paper presents a rigorous universal method for calculating and validating an exemplary multi-way calibration of a leveler component in a copper electroplating bath used in the semiconductor industry. The method presented employs comparatively Parallel Factor Analysis coupled with Inverse Least Squares Regression and multi-linear Partial Least Squares. The calibration training set consists of multi-frequency AC voltammetric data subjected to pretreatments aiming to select informative independent variables and exclude outliers. 相似文献
75.
Here we describe the story behind the link between molecular chirality and macroscopic phenomena, the latter being a probe for the direct assignment of absolute configuration of chiral molecules. First, a brief tour of the history of molecular stereochemistry, starting with the classic experiment reported by Pasteur in 1848 on the separation of enantiomorphous crystals of a salt of tartaric acid, and his conclusion that the molecules of life are chiral of single-handedness. With time, this study raised, inter alia, two fundamental questions: the absolute configuration of chiral molecules and how a molecule of given configuration shapes the enantiomorphous morphology of its crystal. As for the first question, following the beginning of crystal structure determination by X-ray diffraction in 1912, it took almost 40 years before Bijvoet assigned molecular chirality through the esoteric method involving anomalous X-ray scattering. We have been able to address and link both questions through ‘everyday concepts of left and right’ (in the words of Jack Dunitz) by the use of ‘tailor-made’ auxiliaries. By such means, it proved possible to reveal, through morphology, etch patterns, epitaxy and symmetry reduction of both chiral and, paradoxically, centrosymmetric crystals, the basic chiral symmetry of the molecules of life, the α-amino acids and sugars. 相似文献
76.
Dr. Aline Varella Rodrigues Bruno Seiki Domingos Onishi Prof. Dr. Sidney José Lima Ribeiro 《Chemphyschem》2023,24(21):e202300134
This research endeavors to overcome the significant challenge of developing materials that simultaneously possess photostability and photosensitivity to UV-visible irradiation. Sulfurized nanorod (NR)-like ZnO/Zn(OH)2 and hierarchical flower-like γ-Zn(OH)2/ϵ-Zn(OH)2 were identified from XRD diffraction patterns and Raman vibrational modes. The sulfurized material, observed by FEG-SEM and TEM, showed diameters ranging from 10 and 40 nm and lengths exceeding 200 nm. The S2− ions intercalated Zn2+, modulating NRs to dumbbell-like microrods. SAED and HRTEM illustrated the atomic structure in (101) crystal plane. Its direct band gap of 3.0 eV was attributed to the oxygen vacancies, which also contribute to the deep-level emissions at 422 and 485 nm. BET indicated specific surface area of 4.4 m2 g−1 and pore size as mesoporosity, which are higher compared to the non-sulfurized analogue. These findings were consistent with the observed photocurrent, photostability and photoluminescence (PL), further supporting the suitability of sulfurized NR-like ZnO/Zn(OH)2 as a promising candidate for Luminescent solar concentrators (LSC)-photovoltaic (PV) system. 相似文献
77.
As a representative class of sustainable polymer materials, biodegradable polymers have attracted increasing interest in recent years. Despite significant advance of related polymerization techniques, realizing high sequence-control and easy-handling in ring-opening (co)polymerizations still remains a central challenge. To this end, a promising solution is the development of valence-variable metal-based catalysts for redox-induced switchable polymerization of cyclic esters, cyclic ethers, epoxides, and CO2. Through a valence-determined electron effect, the switch between different catalytically active states as well as dormant state contributes to convenient formation of polymer products with desired microstructures and various practical performances. This redox-controlled switchable strategy for controlled synthesis of polymers is overviewed in this Review with a focus on potential applications and challenges for further studies. 相似文献
78.
Nina Wei Dandan Song Chang Lu Yong Jiang Qin Liu Lunyuan Liu Liu Xu Linwei Chen Zhipeng Chen 《Journal of separation science》2023,46(17):2300235
Aconitum carmichaelii is widely used to treat chronic and intractable diseases due to its remarkable curative effect, but it is also a highly toxic herb with severe cardiac and neurotoxicity. It has been combined with honey for thousands of years to reduce toxicity and enhance efficacy, but there has been no study on the chemical constituent changes in the honey-processing so far. In this study, the chemical constituents of A. carmichaelii before and after honey-processing were characterized by ultra-high-performance liquid chromatography-quadrupole time-of-flight tandem mass spectrometry. The results showed that a total of 118 compounds were identified, of which six compounds disappeared and five compounds were newly produced after honey-processing, and the cleavage pathway of main components was elucidated. At the same time, 25 compounds were found to have significant effects on different products, among which four compounds with the biggest difference were selected for quantitative analysis by ultra-high-performance liquid chromatography-tandem mass spectrometry. This study not only explained the chemical differences between the different products, but also helped to control the quality of the honey-processed products more effectively, and laid a foundation for further elucidating the mechanism of chemical constituent change during the honey-processing of A. carmichaelii. 相似文献
79.
Dr. Manuel Moliner Dr. Cristina Martínez Prof. Avelino Corma 《Angewandte Chemie (International ed. in English)》2015,54(12):3560-3579
In the last few years, important efforts have been made to synthesize so‐called “multipore” zeolites, which contain channels of different dimensions within the same crystalline structure. This is a very attractive subject, since the presence of pores of different sizes would favor the preferential diffusion of reactants and products through those different channel systems, allowing unique catalytic activities for specific chemical processes. In this Review we describe the most attractive achievements in the rational synthesis of multipore zeolites, containing small to extra‐large pores, and the improvements reported for relevant chemical processes when these multipore zeolites have been used as catalysts. 相似文献
80.
Effect of polyethylene glycol on the crystallization and impact properties of polylactide‐based blends 下载免费PDF全文
Polylactide (PLA) was plasticized by polyethylene glycols (PEGs) with five different molecular weights (Mw = 200–20,000 g/mol). The effects of content and molecular weight of PEG on the crystallization and impact properties of PLA were studied by wide‐angle X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, transmission electron microscopy, and V‐notched impact tests, respectively. The results revealed that PEG‐10,000 could significantly improve the crystallization capacity and impact toughness of PLA. When the PEG‐10,000 content ranged from 0 to 20 wt%, the increases in both V‐notched Izod and Charpy impact strengths of PLA/PEG‐10,000 blends were 206.10% and 137.25%, respectively. Meanwhile, the crystallinity of PLA/PEG‐10,000 blends increased from 3.95% to 43.42%. For 10 wt% PEG content, the crystallization and impact properties of PLA/PEG blends mainly depended upon PEG molecular weight. With increasing the Mw of PEG, the crystallinity and impact strength of PLA/PEG blends first decreased and then increased. The introduction of PEG reduced the intermolecular force and enhanced the mobility of PLA chains, thus improving the crystallization capacity and flexibility of PLA. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献