全文获取类型
收费全文 | 34225篇 |
免费 | 2392篇 |
国内免费 | 2608篇 |
专业分类
化学 | 32139篇 |
晶体学 | 154篇 |
力学 | 715篇 |
综合类 | 212篇 |
数学 | 1026篇 |
物理学 | 4979篇 |
出版年
2024年 | 19篇 |
2023年 | 401篇 |
2022年 | 597篇 |
2021年 | 684篇 |
2020年 | 934篇 |
2019年 | 877篇 |
2018年 | 835篇 |
2017年 | 1185篇 |
2016年 | 1367篇 |
2015年 | 1229篇 |
2014年 | 1296篇 |
2013年 | 2153篇 |
2012年 | 2075篇 |
2011年 | 2080篇 |
2010年 | 1692篇 |
2009年 | 1981篇 |
2008年 | 1514篇 |
2007年 | 1847篇 |
2006年 | 1664篇 |
2005年 | 1528篇 |
2004年 | 1391篇 |
2003年 | 1122篇 |
2002年 | 961篇 |
2001年 | 723篇 |
2000年 | 789篇 |
1999年 | 727篇 |
1998年 | 683篇 |
1997年 | 667篇 |
1996年 | 543篇 |
1995年 | 617篇 |
1994年 | 547篇 |
1993年 | 426篇 |
1992年 | 316篇 |
1991年 | 398篇 |
1990年 | 344篇 |
1989年 | 332篇 |
1988年 | 423篇 |
1987年 | 395篇 |
1986年 | 302篇 |
1985年 | 274篇 |
1984年 | 296篇 |
1983年 | 150篇 |
1982年 | 254篇 |
1981年 | 197篇 |
1980年 | 162篇 |
1979年 | 154篇 |
1978年 | 31篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 125 毫秒
11.
ABSTRACTThis study was to investigate the piezotolerance and diversity indices of microflora of Indian white prawn (Fenneropenaeus indicus) after high pressure (HP)-treatment. Indian white prawns subjected to HP-treatments and its effect was studied up to species level and compared with unpressurized samples. The bacterium was identified by using bacterial identification schemes, biochemical tests and API kits (bioMérieux, Marcyl’Etoile, France). Diversity analysis was performed using PRIMER (Plymouth Routines in Multivariate Research) software v 5.2.2. The significant elimination of microflora was found to be proportional with the pressure level. In the case of spore formers, mere destruction was noticed after HP-treatment. Arthrobacter spp., Listeria grayi and Corynebacterium spp. were the most piezotolerant bacteria in HP-treated samples. Diversity indices revealed a significant reduction of microflora of Indian white prawn. The apparent reduction of microflora with pressure level was clearly evident from the diversity indices; moreover a diminished piezotolerance of Gram negative spoilage bacteria was also observed. 相似文献
12.
A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air‐assisted liquid–liquid microextraction from human urine and plasma samples followed by gas chromatography–nitrogen phosphorous detection 下载免费PDF全文
Mir Ali Farajzadeh Mohammad Reza Afshar Mogaddam Ali Akbar Alizadeh Nabil 《Biomedical chromatography : BMC》2015,29(12):1921-1931
In present study, a simultaneous derivatization and air‐assisted liquid–liquid microextraction method combined with gas chromatography–nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1‐flouro‐2,4‐dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05–0.34 ng mL?1 are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
13.
The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes 下载免费PDF全文
Prof. Biao Wu Dr. Shaoguang Li Prof. Yibo Lei Prof. Huaiming Hu Dr. Nader de Sousa Amadeu Prof. Dr. Christoph Janiak Dr. Jennifer S. Mathieson Dr. De‐Liang Long Prof. Leroy Cronin Prof. Xiao‐Juan Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2588-2593
By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A2L3 complexes (A represents anion, here orthophosphate PO43?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes. 相似文献
14.
《Arabian Journal of Chemistry》2021,14(11):103421
Processing of Carapa guianensis seeds to obtain oil on an industrial scale generates a significant amount of by-product, approximately 66% w/w, which is called cake and is a potential source of biomolecules, including simple phenolic structures. For this reason, studies were carried out on the chemical profiles of hydrolyzed extract from this agro-industrial by-product through High Performance Thin-Layer Chromatography (HPTLC) and Gas Chromatography coupled to Mass Spectrometry (GC–MS). These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product. The sample antioxidant capacity was determined by methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH)and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS+) radicals direct sequestration. The hydrolyzed fraction showed a total of 63.47% in the relative abundance of the total of compounds, standing out: p-hydroxybenzoic acid (39.19%) and protocatechuic acid (3,4-dihydroxybenzoic acid) (5.62%), both from hydroxybenzoic acids and 3-(3,4-dihydroxyphenyl)lactic acid, (7.76%) hydroxycinnamic acids derivatives. In these results, the fraction rich in simple phenolic acids was obtained, attributing the prominent behavior of this matrix antioxidant activity, expressed by (IC50: of 16.42 µg/mL and 6.52 µg/mL for DPPH and ABTS+ radicals, respectively). The research demonstrated an alternative to applicability that involves sustainability from agro-industrial. These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product, generating a process capable of converting biomass into a bioproduct, consisting of bioactive compounds, in addition to adding value to the industrial chain. 相似文献
15.
Simultaneous quantitative determination of 20 active components in the traditional Chinese medicine formula Zhi‐Zi‐Da‐Huang decoction by liquid chromatography coupled with mass spectrometry: application to study the chemical composition variations in different combinations 下载免费PDF全文
Zheng Tang Ran Yin Kaishun Bi Heyun Zhu Fei Han Kelin Chen Fenrong Wang 《Biomedical chromatography : BMC》2015,29(9):1406-1414
16.
Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions 下载免费PDF全文
Luca Assumma Cristina Iojoiu Régis Mercier Sandrine Lyonnard Huu Dat Nguyen Emilie Planes 《Journal of polymer science. Part A, Polymer chemistry》2015,53(16):1941-1956
Partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions (ps‐PES‐FPES), with ionic exchange capacity (IEC) ranging between 0.9 and 1.5 meq H+/g, are synthesized by regioselective bromination of partially fluorinated poly(arylene ether sulfone) multiblock copolymers (PES‐FPES), followed by Ullman coupling reaction with lithium 1,1,2,2‐tetrafluoro‐2‐(1,1,2,2‐tetrafluoro‐2‐iodoethoxy)ethanesulfonate. The PES‐FPES are prepared by aromatic nucleophilic substitution reaction by an original approach, that is, “one pot two reactions synthesis.” The chemical structures of polymers are analyzed by 1H and 19F NMR spectroscopy. The resulted ionomers present two distinct glass transitions and α relaxations revealing phase separation between the hydrophilic and the hydrophobic domains. The phase separation is observed at much lower block lengths of ps‐PES‐FPES as compared with the literature. AFM and SANS observations supported the phase separation, the hydrophilic domains are well dispersed but the connectivity to each other depends on the ps‐PES block lengths. The thermomechanical behavior, the water up‐take, and the conductivity of the ps‐PES‐FPES membranes are compared with those of Nafion 117® and randomly functionalized polysulfone (ps‐PES). Conductivities close or higher to those of Nafion 117® are obtained. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1941–1956 相似文献
17.
Karen Beatriz Méndez-Rodríguez Nicté Figueroa-Vega César Arturo Ilizaliturri-Hernandez Mónica Cardona-Alvarado Jaime Antonio Borjas-García Carlos Kornhauser Juan Manuel Malacara Rogelio Flores-Ramírez Francisco Javier Pérez-Vázquez 《Biomedical chromatography : BMC》2020,34(12):e4956
Metabolomics is a potential tool for the discovery of new biomarkers in the early diagnosis of diseases. An ultra-fast gas chromatography system equipped to an electronic nose detector (FGC eNose) was used to identify the metabolomic profile of Volatile Organic Compounds (VOCs) in type 2 diabetes (T2D) urine from Mexican population. A cross-sectional, comparative, and clinical study with translational approach was performed. We recruited twenty T2D patients and twenty-one healthy subjects. Urine samples were taken and analyzed by FGC eNose. Eighty-eight compounds were identified through Kovats's indexes. A natural variation of 30% between the metabolites, expressed by study groups, was observed in Principal Component 1 and 2 with a significant difference (p < 0.001). The model, performed through a Canonical Analysis of Principal coordinated (CAP), allowed a correct classification of 84.6% between healthy and T2D patients, with a 15.4% error. The metabolites 2-propenal, 2-propanol, butane- 2,3-dione and 2-methylpropanal, were increased in patients with T2D, and they were strongly correlated with discrimination between clinically healthy people and T2D patients. This study identified metabolites in urine through FGC eNose that can be used as biomarkers in the identification of T2D patients. However, more studies are needed for its implementation in clinical practice. 相似文献
18.
Jigneshkumar P. Patel Zou Guo Xiang Shaw Ling Hsu Andrew B. Schoch Sena Ada Carleen Dean Matsumoto 《Journal of Polymer Science.Polymer Physics》2015,53(21):1519-1526
A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526 相似文献
19.
Inflation of balloons provides a straightforward way of achieving large biaxial deformations. Previous studies have shown that when a balloon bursts, crack propagation occurs at very high speed – much higher than would be expected from the low strain modulus and elastic wave velocity of the rubber. The present paper is concerned with studies of the deformation and fracture of cylindrical balloons. On inflation, the deformations of such a balloon pass through an unstable region but subsequently increase monotonically with pressure. In this relatively high pressure region, the ratio of the longitudinal and circumferential extension ratios is broadly in accord with expectations from high-strain elasticity theory when the ratio of the corresponding stresses is taken into account. On bursting, crack speeds up to around 300 m/s in this region. It is shown that these speeds are in accord with large increase in incremental moduli for the highly-strained rubber. Marked changes in crack tip profile observed at very high crack speeds are consistent with control of the rate of growth by inertia rather than by the viscoelastic properties of the rubber (as is believed to be the case at lower speeds). Consistent with this, various elastomers having different glass transition temperatures show similar crack growth behaviour in the very high speed region. 相似文献
20.
D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity 下载免费PDF全文
Yohei Ohkoda Akane Asaishi Tomoya Namiki Tomoaki Hashimoto Midori Yamada Koichiro Shirai Yuta Katagami Dr. Tomoaki Sugaya Prof. Makoto Tadokoro Prof. Akiharu Satake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11745-11756
The one‐step synthesis of D3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η3‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η3‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands. 相似文献