全文获取类型
收费全文 | 1547篇 |
免费 | 53篇 |
国内免费 | 1篇 |
专业分类
化学 | 1238篇 |
晶体学 | 6篇 |
力学 | 35篇 |
数学 | 170篇 |
物理学 | 152篇 |
出版年
2023年 | 20篇 |
2022年 | 60篇 |
2021年 | 70篇 |
2020年 | 36篇 |
2019年 | 41篇 |
2018年 | 38篇 |
2017年 | 35篇 |
2016年 | 45篇 |
2015年 | 55篇 |
2014年 | 46篇 |
2013年 | 100篇 |
2012年 | 113篇 |
2011年 | 122篇 |
2010年 | 81篇 |
2009年 | 77篇 |
2008年 | 98篇 |
2007年 | 109篇 |
2006年 | 77篇 |
2005年 | 74篇 |
2004年 | 58篇 |
2003年 | 45篇 |
2002年 | 45篇 |
2001年 | 11篇 |
2000年 | 12篇 |
1999年 | 13篇 |
1998年 | 9篇 |
1997年 | 3篇 |
1996年 | 7篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 6篇 |
1989年 | 4篇 |
1987年 | 3篇 |
1985年 | 3篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1978年 | 4篇 |
1976年 | 3篇 |
1973年 | 3篇 |
1964年 | 3篇 |
1960年 | 3篇 |
1959年 | 2篇 |
1958年 | 3篇 |
1955年 | 2篇 |
1932年 | 2篇 |
1929年 | 2篇 |
1925年 | 2篇 |
1911年 | 2篇 |
排序方式: 共有1601条查询结果,搜索用时 12 毫秒
101.
Nearly all the available information on the transient flow behaviour of liquid crystalline polymers has been obtained on model systems, especially on solutions of polybenzylglutamate (PBG) and hydroxypropylcellulose (HPC). The assessment of rheological models has been based almost entirely on these model systems. It is not clear how much of the available theoretical and experimental knowledge can be applied to systems of industrial relevance, which have quite different molecular structures. Here, an industrial lyotropic system, poly(p-phenylenetherephthalamide) (PpPTA) in sulphuric acid (TWARON from AKZO), is investigated. Various techniques to study transient behaviour are used, these include measurements of transient shear and normal stresses after sudden changes in shear rate, dynamic moduli and stress relaxation after cessation of flow and elastic recoil. At all shear rates studied the PpPTA solution is shear thinning, and the first normal stress difference remains positive. For the stress transients a strain scaling applies reasonably well as it did in model systems. The moduli increase with time upon cessation of flow, indicating that the molecules become less oriented in the previous flow direction. This particular behaviour is similar to that of HPC. Transients also resemble more closely those of HPC rather than those of PBG. This latter difference might be attributed to the higher flexibility of HPC and PpPTA chains as compared with PBG molecules. 相似文献
102.
CdTe quantum dots (QDs), capped with mercaptopropionic acid (MPA), were synthesized and the variation of their fluorescence properties (steady state and lifetime) with pH was assessed in solution and when immobilized in a sol-gel host. Three different sizes of CdTe QDs with excited state lifetimes ranging from 42 to 48 ns and with emission maximum at 540 nm (QD540), 580 nm (QD580) and 625 nm (QD625) were selected. The solution pH affects the maximum emission wavelength (shifts to higher wavelengths of 23, 24 and 27 nm for QD540, QD580 and QD625, respectively), the excited state lifetime and the fluorescence intensity in a reversible way. Linearization of the maximum emission wavelength variation with the pH allows the estimation of an apparent ionization constant (pKa) for each QD: 6.5 ± 0.1 (QD540), 6.1 ± 0.5 (QD580) and 5.4 ± 0.3 (QD625). The variation of the QDs fluorescence properties was further explored using confocal laser scanning microscopy allowing the implementation of a new calibration method for pH imaging in solution. QDs were successfully immobilized on the tip of an optical fiber by dip-coating using sol-gel procedure. The immobilized QDs showed a similar pH behaviour to the one observed in solution and an apparent lifetime of 80, 68 and 99 ns, respectively. The proposed QDs based methodology can be successfully used to monitor pH using wavelength encoded data in imaging and fiber optic sensing applications. 相似文献
103.
Ana M.G. Silva Andreia Leite Paula Gameiro Vítor Felix Maria Rangel 《Tetrahedron》2010,66(44):8544-8550
Two novel 3-hydroxy-4-pyridinone/naphthalene conjugates (L1 and L2) with different distances between the chelating and the fluorescent moieties were synthesized using conventional heating and microwave irradiation achieving a shorter reaction time. The structure of both compounds was confirmed by X-ray crystallography, revealing that these compounds were isolated as hydrochloride salts in dihydroxypyridinium forms. In solution and in the presence of a base, the tautomeric keto forms may be obtained as it was elucidated by NMR analysis. The dihydroxypyridinium form of L1 exhibits fluorescence at 450 nm, both in ACN and DMSO, whereas the corresponding keto form exhibits fluorescence at 365 nm. In contrast, the dihydroxypyridinium form of L2 only fluoresces in DMSO, exhibiting a band at 340 nm, while the keto form is non-fluorescent. These distinct fluorescent behaviors reveal that the tautomeric form in which the ligands are isolated and the distance between the chelating and fluorescent functions strongly influences their fluorescence properties. Ligand L1 exhibits better fluorescence properties and its fluorescence intensity is quenched in the presence of variable concentration of Cu2+, Zn2+, and Fe3+, thus making it suitable to be used as ion sensor. 相似文献
104.
Several 2,5-disubstituted oxazole-4-carboxylates were prepared in high yields from the methyl esters of N-acyl-β-halodehydroaminobutyric acid derivatives by treatment with a 2% solution of DBU in acetonitrile. The scope of this reaction was investigated and it was found that dehydrodipeptides having a β-bromodehydroaminobutyric acid residue gave the corresponding oxazoles in good yields. The photophysical properties of some of the oxazoles prepared were studied in four solvents of different polarity. All compounds have reasonable high fluorescence quantum yields and a moderate solvent sensitivity, which makes them good candidates to be used as fluorescent probes. One of the fluorescent oxazoles prepared was inserted after cleavage of the methyl ester into two model peptides using a conventional solution phase strategy. The photophysical properties of the labelled peptides were studied in ethanol and water and compared with those of the oxazole. The results obtained showed that the oxazole maintains a good fluorescence level and the same solvent sensitivity when linked to a peptide chain. 相似文献
105.
Douglas S. Werner Hanqing Dong Mridula Kadalbajoo Radoslaw S. Laufer Paula A. Tavares-Greco Brian R. Volk Mark J. Mulvihill Andrew P. Crew 《Tetrahedron letters》2010,51(30):3899-515
The preparation of 5,7-disubstituted imidazo[5,1-f][1,2,4]triazin-4-amines, exemplified by 5-[3-(benzyloxy)phenyl]-7-cyclobutylimidazo[5,1-f][1,2,4]triazin-4-amine, was developed through a linear and three convergent synthetic strategies, with the latter providing the greatest flexibility for diversification at the 5-position at the last step of the synthesis. 相似文献
106.
Sub-micron sized airborne particulate matter (PM) is not collected well on regular quartz or glass fiber filter papers. We used a micro-orifice uniform deposit impactor (MOUDI) to fractionate PM into six size fractions and deposit it on specially designed high purity thin aluminum disks. The MOUDI separated PM into fractions 56-100 nm, 100-180 nm, 180-320 nm, 320-560 nm, 560-1000 nm, and 1000-1800 nm. Since the MOUDI has a low flow rate (30 L/min), it takes several days to collect sufficient carbon on 47 mm foil disks. The small carbon mass (20-200 microgram C) and large aluminum substrate (~25 mg Al) present several challenges to production of graphite targets for accelerator mass spectrometry (AMS) analysis. The Al foil consumes large amounts of oxygen as it is heated and tends to melt into quartz combustion tubes, causing gas leaks. We describe sample processing techniques to reliably produce graphitic targets for (14)C-AMS analysis of PM deposited on Al impact foils. 相似文献
107.
Filgueira Dde M Guterres LP Votto AP Vargas MA Boyle RT Trindade GS Nery LE 《Photochemistry and photobiology》2010,86(6):1278-1284
The purpose of this study was to verify the occurrence of pigment dispersion in retinal pigment cells exposed to UVA and UVB radiation, and to investigate the possible participation of a nitric oxide (NO) pathway. Retinal pigment cells from Neohelice granulata were obtained by cellular dissociation. Cells were analyzed for 30 min in the dark (control) and then exposed to 1.1 and 3.3 J cm−2 UVA, 0.07 and 0.9 J cm−2 UVB, 20 n m β-PDH (pigment dispersing hormone) or 10 μ m SIN-1 (NO donor). Histological analyses were performed to verify the UV effect in vivo . Cultured cells were exposed to 250 μ m L-NAME (NO synthase blocker) and afterwards were treated with UVA, UVB or β-PDH. The retinal cells in culture displayed significant pigment dispersion in response to UVA, UVB and β-PDH. The same responses to UVA and UVB were observed in vivo . SIN-1 did not induce pigment dispersion in the cell cultures. l-NAME significantly decreased the pigment dispersion induced by UVA and UVB but not by β-PDH. All retinal cells showed an immunopositive reaction against neuronal nitric oxide synthases. Therefore, UVA and UVB radiation are capable of inducing pigment dispersion in retinal pigment cells of Neohelice granulata and this dispersion may be nitric oxide synthase dependent. 相似文献
108.
Wong SY Moskowitz JS Veselinovic J Rosario RA Timachova K Blaisse MR Fuller RC Klibanov AM Hammond PT 《Journal of the American Chemical Society》2010,132(50):17840-17848
Here we present a new bifunctional layer-by-layer (LbL) construct made by combining a permanent microbicidal polyelectrolyte multilayered (PEM) base film with a hydrolytically degradable PEM top film that offers controlled and localized delivery of therapeutics. Two degradable film architectures are presented: (1) bolus release of an antibiotic (gentamicin) to eradicate initial infection at the implant site, or (2) sustained delivery of an anti-inflammatory drug (diclofenac) to cope with inflammation at the site of implantation due to tissue injury. Each degradable film was built on top of a permanent base film that imparts the implantable device surface with microbicidal functionality that prevents the formation of biofilms. Controlled-delivery of gentamicin was demonstrated over hours and that of diclofenac over days. Both drugs retained their efficacy upon release. The permanent microbicidal base film was biocompatible with A549 epithelial cancer cells and MC3T3-E1 osteoprogenitor cells, while also preventing bacteria attachment from turbid media for the entire duration of the two weeks studied. The microbicidal base film retains its functionality after the biodegradable films have completely degraded. The versatility of these PEM films and their ability to prevent biofilm formation make them attractive as coatings for implantable devices. 相似文献
109.
Paula Santos Nunes Marília Santos Bezerra L. P. Costa Juliana Cordeiro Cardoso R. L. C. AlbuquerqueJr. M. O. Rodrigues Gabriela Borin Barin Francilene Amaral da Silva A. A. S. Araújo 《Journal of Thermal Analysis and Calorimetry》2010,99(3):1011-1014
The purpose of this study was to evaluate the physical–chemical properties of collagen (CL) and usnic acid/collagen-based
(UAC) films, using differential thermal analysis (DTA), thermogravimetry (TG/DTG), infrared spectroscopy (FTIR), and scanning
electron microscopy (SEM). Both films were prepared by casting process using polyethylene glycol 1500 (PEG 1500) as plasticizer.
In the spectrum of UAC, similar bands of the usnic acid are observed, indicating that the polymerization (film formation)
did not affect the stability of the drug. Distinctly, DTA curve of UAC did not show an endothermic peak at 201 °C, indicative
that the drug was incorporated into the polymeric system. These results were corroborated by the scanning electron microscopy
(SEM). The TG/DTG curves of UAC presented a different thermal decomposition profile compared to the individual compounds and
CL. These findings suggest the occurrence of molecular dispersion or solubilization of the drug in the collagen film. 相似文献
110.
Marli Roehsig Daniela Mendes Louzada de Paula Sidnei Moura Edna Maria de Albuquerque Diniz Mauricio Yonamine 《Journal of separation science》2010,33(14):2115-2122
A number of fatty acid ethyl esters (FAEEs) have recently been detected in meconium samples. Several of these FAEEs have been evaluated as possible biomarkers for in utero ethanol exposure. In the present study, a method was optimized and validated for the simultaneous determination of eight FAEEs (ethyl laurate, ethyl myristate, ethyl palmitate, ethyl palmitoleate, ethyl stearate, ethyl oleate, ethyl linoleate and ethyl arachidonate) in meconium samples. FAEEs were extracted by headspace solid‐phase microextraction. Analyte detection and quantification were carried out using GC‐MS operated in chemical ionization mode. The corresponding D5‐ethyl esters were synthesized and used as internal standards. The LOQ and LOD for each analyte were <150 and <100 ng/g, respectively. The method showed good linearity (r2>0.98) in the concentration range studied (LOQ – 2000 ng/g). The intra‐ and interday imprecision, given by the RSD of the method, was lower than 15% for all FAEEs studied. The validated method was applied to 63 authentic specimens. FAEEs could be detected in alcohol‐exposed newborns (>600 ng/g cumulative concentration). Interestingly, FAEEs could also be detected in some non‐exposed newborns, although the concentrations were much lower than those measured in exposed cases. 相似文献