全文获取类型
收费全文 | 2750篇 |
免费 | 120篇 |
国内免费 | 22篇 |
专业分类
化学 | 2022篇 |
晶体学 | 35篇 |
力学 | 89篇 |
综合类 | 3篇 |
数学 | 185篇 |
物理学 | 558篇 |
出版年
2024年 | 17篇 |
2023年 | 36篇 |
2022年 | 115篇 |
2021年 | 151篇 |
2020年 | 73篇 |
2019年 | 101篇 |
2018年 | 82篇 |
2017年 | 74篇 |
2016年 | 143篇 |
2015年 | 98篇 |
2014年 | 115篇 |
2013年 | 196篇 |
2012年 | 216篇 |
2011年 | 220篇 |
2010年 | 119篇 |
2009年 | 107篇 |
2008年 | 126篇 |
2007年 | 117篇 |
2006年 | 117篇 |
2005年 | 114篇 |
2004年 | 81篇 |
2003年 | 74篇 |
2002年 | 49篇 |
2001年 | 23篇 |
2000年 | 19篇 |
1999年 | 17篇 |
1998年 | 12篇 |
1997年 | 14篇 |
1996年 | 12篇 |
1995年 | 8篇 |
1994年 | 13篇 |
1993年 | 14篇 |
1992年 | 14篇 |
1991年 | 11篇 |
1990年 | 11篇 |
1989年 | 11篇 |
1988年 | 10篇 |
1987年 | 11篇 |
1986年 | 12篇 |
1985年 | 14篇 |
1984年 | 15篇 |
1983年 | 10篇 |
1982年 | 16篇 |
1981年 | 19篇 |
1980年 | 11篇 |
1979年 | 9篇 |
1978年 | 6篇 |
1977年 | 10篇 |
1976年 | 7篇 |
1962年 | 3篇 |
排序方式: 共有2892条查询结果,搜索用时 62 毫秒
11.
Sankar Prasad Bhuniya Safikur Rahman Anshul J. Satyanand Mahendrasinh M. Gharia Ashok M. Dave 《Journal of polymer science. Part A, Polymer chemistry》2003,41(11):1650-1658
Maize starch was modified by allyl chloride adopting an interfacial reaction technique with cetyltrimethyl ammonium bromide as a phase‐transfer catalyst and pyridine as an acid acceptor. The degree of substitution was determined from an increasing carbon content of the modified starch. The percentage of carbon and hydrogen of the allyl‐modified starch was estimated by elemental analysis (C, H, and N), and the product characterization was done through 1H NMR and 13C NMR analyses. The allyl‐modified starch was then copolymerized with methacrylic acid and a combination of methacrylic acid and acrylamide at 50 and 70 °C with potassium persulfate as an initiator. The copolymer thus formed swelled in distilled water after neutralization with sodium carbonate. The percentage of absorption capacity of the hydrogels was determined with distilled water and 0.9% NaCl solution. The highest percentage of absorption, 6500%, was achieved for the developed hydrogel containing allyl starch and acrylic monomer in a 1.7:1 w/w ratio and acrylic monomer, namely, methacrylic acid and acrylamide in a 3.2:1 w/w ratio. The study on biodegradability of the developed hydrogel showed that the hydrogel is degradable in the presence of diastase (amylase). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1650–1658, 2003 相似文献
12.
M.Iqbal Choudhary SyedGhulam Musharraf Amtul Sami Atta‐ur‐Rahman 《Helvetica chimica acta》2004,87(10):2685-2694
The microbial transformation of (?)‐Ambrox® ( 1 ), a perfumery sesquiterpene, by a number of fungi, by means of standard two‐stage‐fermentation technique, afforded ambrox‐1α‐ol ( 2 ), ambrox‐1α,11α‐diol ( 3 ), ambrox‐1α,6α‐diol ( 4 ), ambrox‐1α,6α,11α‐triol ( 5 ), ambrox‐3‐one ( 6 ), ambrox‐3β‐ol ( 7 ), ambrox‐3β,6β‐diol ( 8 ), 13,14,15,16‐tetranorlabdane‐3,8,12‐triol ( 9 ), and sclareolide ( 10 ) (Schemes 1 and 2). Further incubation of compound 10 with Cunninghamella elegans afforded 3‐oxosclareolide ( 11 ), 3β‐hydroxysclareolide ( 12 ), 2α‐hydroxysclareolide ( 13 ), 2α,3β‐dihydroxysclareolide ( 14 ), 1α,3β‐dihydroxysclareolide ( 15 ), and 3β‐hydroxy‐8‐episclareolide ( 16 ) (Scheme 3). Metabolites 2 – 5, 12, 13 , and 16 were found to be new compounds. The major transformations include a reaction path involving hydroxylation, ether‐bond cleavage and inversion of configuration. Metabolites 11 – 16 of sclareolide showed significant phytotoxicity (Table 1). The structures of the metabolites were characterized on the basis of spectroscopic techniques. 相似文献
13.
Himansu Sekhar Sahoo S. Mahalakshmi Md. Hedayetullah Mir R. Raghunathan 《Tetrahedron letters》2007,48(5):761-765
A remarkable upfield shift of the pyα protons of complexed 2,2′-bipyridine in [cis-Pd(bpy)(NO3)2] is observed which is considered to originate from the anisotropic influence of suitably positioned coordinated nitrate anions around the Pd(II) centre of the molecule. A typical complexation-induced downfield shift is observed for the NH2 protons in [cis-Pd(en)(NO3)2] where ‘en’ stands for ethylenediamine. 相似文献
14.
The new compound, Na[(Mo2
VO4)(pte)(OMe)(MeOH)2] (pte = anion of 6-acetonylisoxanthopterin), has been prepared using the redox non-innocent title ligand in MeOH–H2O, and characterized by elemental analysis and physico-chemical methods including e.s.m.s., i.r., u.v.–vis. and 1H-n.m.r. spectra. Rate constants data (1.4 × 10–3 s–1 at 300 K) for its oxygen atom transfer with dimethyl sulphoxide tally with those of synthetic analogue systems reported earlier by different authors. The negative activation entropy (–206.3 J mol–1 deg–1) is consistent with an associative mechanism for this reaction. 相似文献
15.
16.
Md Sharif Ullah Vladimir V. Zhivonitko Anatoliy Samoylenko Artem Zhyvolozhnyi Sirja Viitala Santeri Kankaanp Sanna Komulainen Leif Schrder Seppo J. Vainio Ville-Veikko Telkki 《Chemical science》2021,12(24):8311
Exosomes are a subset of secreted lipid envelope-encapsulated extracellular vesicles (EVs) of 50–150 nm diameter that can transfer cargo from donor to acceptor cells. In the current purification protocols of exosomes, many smaller and larger nanoparticles such as lipoproteins, exomers and microvesicles are typically co-isolated as well. Particle size distribution is one important characteristics of EV samples, as it reflects the cellular origin of EVs and the purity of the isolation. However, most of the physicochemical analytical methods today cannot illustrate the smallest exosomes and other small particles like the exomers. Here, we demonstrate that diffusion ordered spectroscopy (DOSY) nuclear magnetic resonance (NMR) method enables the determination of a very broad distribution of extracellular nanoparticles, ranging from 1 to 500 nm. The range covers sizes of all particles included in EV samples after isolation. The method is non-invasive, as it does not require any labelling or other chemical modification. We investigated EVs secreted from milk as well as embryonic kidney and renal carcinoma cells. Western blot analysis and immuno-electron microscopy confirmed expression of exosomal markers such as ALIX, TSG101, CD81, CD9, and CD63 in the EV samples. In addition to the larger particles observed by nanoparticle tracking analysis (NTA) in the range of 70–500 nm, the DOSY distributions include a significant number of smaller particles in the range of 10–70 nm, which are visible also in transmission electron microscopy images but invisible in NTA. Furthermore, we demonstrate that hyperpolarized chemical exchange saturation transfer (Hyper-CEST) with 129Xe NMR indicates also the existence of smaller and larger nanoparticles in the EV samples, providing also additional support for DOSY results. The method implies also that the Xe exchange is significantly faster in the EV pool than in the lipoprotein/exomer pool.Diffusion and xenon NMR based methods to determine a very broad range of sizes and sub-sets of extracellular vesicles. 相似文献
17.
Norimah Yusof A.H. Ainul Hafiza Rozaini M. Zohdi Md Zuki A. Bakar 《Radiation Physics and Chemistry》2007,76(11-12):1767-1770
Radiation at 25 and 50 kGy showed no effect on the acidic pH of the local honey, Gelam, and its antimicrobial property against Staphylococcus aureus but significantly reduced the viscosity. Honey stored up to 2 years at room temperature retained all the properties studied. Radiation sterilized Gelam honey significantly stimulated the rate of burn wound healing in Sprague-Dawley rats as demonstrated by the increased rate of wound contraction and gross appearance. Gelam honey attenuates wound inflammation; and re-epithelialization was well advanced compared to the treatment using silver sulphadiazine (SSD) cream. To enhance further the use of honey in wound treatment and for easy handling, Gelam honey was incorporated into our hydrogel dressing formulation, which was then cross-linked and sterilized using electron beam at 25 kGy. Hydrogel with 6% of honey was selected based on the physical appearance. 相似文献
18.
Md. Sadequl Islam 《Tetrahedron》2007,63(5):1074-1079
(−)-Mellein, (+)-ramulosin, (−)-O-methylmellein, (−)-6-hydroxymellein, (−)-6-methoxymellein, and (+)-6-hydroxyramulosin were synthesized as optically active forms using one-pot esterification-Michael addition-aldol reaction of δ-hydroxy-α,β-unsaturated aldehyde and diketene as a key step. 相似文献
19.
Coronado E Galán-Mascarós JR Martí-Gastaldo C Palomares E Durrant JR Vilar R Gratzel M Nazeeruddin MK 《Journal of the American Chemical Society》2005,127(35):12351-12356
The selectivity and sensitivity of two colorimetric sensors based on the ruthenium complexes N719 [bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) bis(tetrabutylammonium) bis(thiocyanate)] and N749 [(2,2':6',2' '-terpyridine-4,4',4' '-tricarboxylate)ruthenium(II) tris(tetrabutylammonium) tris(isothiocyanate)] are described. It was found that mercury ions coordinate reversibly to the sulfur atom of the dyes' NCS groups. This interaction induces a color change in the dyes at submicromolar concentrations of mercury. Furthermore, the color change of these dyes is selective for mercury(II) when compared with other ions such as lead(II), cadmium(II), zinc(II), or iron(II). The detection limit for mercury(II) ions--using UV-vis spectroscopy--in homogeneous aqueous solutions is estimated to be approximately 20 ppb for N719 and approximately 150 ppb for N749. Moreover, the sensor molecules can be adsorbed onto high-surface-area mesoporous metal oxide films, allowing reversible heterogeneous sensing of mercury ions in aqueous solution. The results shown herein have important implications in the development of new reversible colorimetric sensors for the fast, easy, and selective detection and monitoring of mercuric ions in aqueous solutions. 相似文献
20.
Pradeep Mathur Bala Manimaran Md. Munkir Hossain Arnold L. Rheingold Louise M. Liable-Sands Glenn P.A. Yap 《Journal of organometallic chemistry》1997,540(1-2):165-168
The tris-methylene bridged compound (NO)4Fe2Se(μ-CH2)3 has been isolated. It has been characterised by IR and 1H, 13C, and 77Se NMR spectroscopy. Its structure has been determined by single-crystal X-ray diffraction methods. The structure consists of a heavy atom triangle consisting of one Se and two Fe atoms. The Fe-Fe and the two Fe-Se edges are bridged by methylene groups. 相似文献