全文获取类型
收费全文 | 184篇 |
免费 | 4篇 |
专业分类
化学 | 115篇 |
晶体学 | 1篇 |
力学 | 6篇 |
数学 | 7篇 |
物理学 | 59篇 |
出版年
2022年 | 4篇 |
2021年 | 8篇 |
2020年 | 2篇 |
2019年 | 7篇 |
2018年 | 1篇 |
2017年 | 1篇 |
2016年 | 6篇 |
2015年 | 8篇 |
2014年 | 8篇 |
2013年 | 12篇 |
2012年 | 11篇 |
2011年 | 16篇 |
2010年 | 8篇 |
2009年 | 20篇 |
2008年 | 8篇 |
2007年 | 7篇 |
2006年 | 9篇 |
2005年 | 6篇 |
2004年 | 4篇 |
2003年 | 1篇 |
2002年 | 1篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1999年 | 5篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 5篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1988年 | 3篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 2篇 |
排序方式: 共有188条查询结果,搜索用时 46 毫秒
21.
Fernando Dures Patrícia M. A. Silva Pedro Novais Isabel Amorim Luís Gales Ctia I. C. Esteves Samuel Guieu Hassan Bousbaa Madalena Pinto Emília Sousa 《Molecules (Basel, Switzerland)》2021,26(11)
Thioxanthones are bioisosteres of the naturally occurring xanthones. They have been described for multiple activities, including antitumor. As such, the synthesis of a library of thioxanthones was pursued, but unexpectedly, four tetracyclic thioxanthenes with a quinazoline–chromene scaffold were obtained. These compounds were studied for their human tumor cell growth inhibition activity, in the cell lines A375-C5, MCF-7 and NCI-H460. Photophysical studies were also performed. Two of the compounds displayed GI50 values below 10 µM for the three tested cell lines, and structure–activity relationship studies were established. Three compounds presented similar wavelengths of absorption and emission, characteristic of dyes with a push-pull character. The structures of two compounds were elucidated by X-ray crystallography. Two tetracyclic thioxanthenes emerged as hit compounds. One of the two compounds accumulated intracellularly as a bright fluorescent dye in the green channel, as analyzed by both fluorescence microscopy and flow cytometry, making it a promising theranostic cancer drug candidate. 相似文献
22.
Subbiah Meenakshisundaram RM. Sockalingam 《Journal of molecular catalysis. A, Chemical》2000,160(2):269-275
Catalytic activity of Os(VIII) in the oxidation of some twenty organic sulfides with sodium salt of N-chlorobenzenesulfonamide (CAB) has been investigated in alkaline (pH8.7) t-butanol–water (1:1 v/v) medium. Significant retarding influence of [OH−] on the reactivity is exhibited. The catalysed reaction is strongly accelerated in the presence of Hg(II). Imperfections are observed in the linear Hammett relationship in the case of –NO2 substituents. 相似文献
23.
Alexandra Mara De Amorim Ana Cristina Franzoi Paula Nunes Oliveira Alfredo Tibúrcio Nunes Pires Almir Spinelli José Roberto Bertolino 《Journal of Polymer Science.Polymer Physics》2009,47(22):2206-2214
The influence of molecular weight and the amount of the poly(vinylpyrrolidone) (PVP) on the growth of poly(vinylpyrrolidone)–based films on copper surfaces was studied by electrochemical, infrared and electronic spectroscopy, and thermogravimetric methods. Complex polymer/metal ions were deposited onto a copper surface, as the result of the electrochemically generated reaction of copper cations with PVP and SCN?, in sulfuric acid media. Spontaneous film growth on copper surfaces was generated and characterized as a Cu(II)/PVP/SCN? complex. Infrared spectra and thermal gravimetric curves of the films generated at + 0.7 V were compared with the chemically synthesized complex, and show the same patterns. The oxidation process can be described as: Cu(0)→Cu(I) and Cu(I)→Cu(II), and the copper complex formed at more positive potentials was characterized as Cu(II)/PVP/SCN?, with copper bonded to the oxygen atom of PVP and thiocyanate ligand N‐linked. This study focuses on the complex formation on a copper surface in acid media and its characterization through electrochemical and spontaneously generated reactions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2206–2214, 2009 相似文献
24.
Eduardo Lutterbach Bandeira Marcelo Amorim Savi Paulo Cesar da Camara Monteiro Jr. Theodoro Antoun Netto 《Archive of Applied Mechanics (Ingenieur Archiv)》2006,76(3-4):133-144
This contribution deals with the nonlinear analysis of shape memory alloy (SMA) adaptive trusses employing the finite element method. Geometrical nonlinearities are incorporated into the formulation together with a constitutive model that describes different thermomechanical behaviors of SMA. It has four macroscopic phases (three variants of martensite and an austenitic phase), and considers different material properties for austenitic and martensitic phases together with thermal expansion. An iterative numerical procedure based on the operator split technique is proposed in order to deal with the nonlinearities in the constitutive formulation. This procedure is introduced into ABAQUS as a user material routine. Numerical simulations are carried out illustrating the ability of the developed model to capture the general behavior of shape memory bars. After that, it is analyzed the behavior of some adaptive trusses built with SMA actuators subjected to different thermomechanical loadings. 相似文献
25.
Gomes de Melo J de Sousa Araújo TA Thijan Nobre de Almeida e Castro V Lyra de Vasconcelos Cabral D do Desterro Rodrigues M Carneiro do Nascimento S Cavalcanti de Amorim EL de Albuquerque UP 《Molecules (Basel, Switzerland)》2010,15(12):8534-8542
The objective of this study was to evaluate antiproliferative activity, antioxidant capacity and tannin content in plants from semi-arid northeastern Brazil (Caatinga). For this study, we selected 14 species and we assayed the methanol extracts for antiproliferative activity against the HEp-2 (laryngeal cancer) and NCI-H292 (lung cancer) cell lines using the (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazole) (MTT) method. In addition, the antioxidant activity was evaluated with the DPPH (2,2-diphenyl-2-picrylhydrazyl) assay, and the tannin content was determined by the radial diffusion method. Plants with better antioxidant activity (expressed in a dose able to decrease the initial DPPH concentration by 50%, or IC50) and with higher levels of tannins were: Poincianella pyramidalis (42.95±1.77 μg/mL IC50 and 8.17±0.64 tannin content), Jatropha mollissima (54.09±4.36μg/mL IC50 and 2.35±0.08 tannin content) and Anadenanthera colubrina (73.24±1.47 μg/mL IC50 and 4.41±0.47 tannin content). Plants with enhanced antiproliferative activity (% living cells) were Annona muricata (24.94±0.74 in NCI-H292), Lantana camara (25.8±0.19 in NCI-H292), Handroanthus impetiginosus (41.8±0.47 in NCI-H292) and Mentzelia aspera (45.61±1.94 in HEp-2). For species with better antioxidant and antiproliferative activities, we suggest future in vitro and in vivo comparative studies with other pharmacological models, and to start a process of purification and identification of the possible molecule(s) responsible for the observed pharmacological activity. We believe that the flora of Brazilian semi-arid areas can be a valuable source of plants rich in tannins, cytotoxic compounds and antioxidant agents. 相似文献
26.
Angel Bustamante Enrico Mattievich Helio S. de Amorim Ivo Vencato Máximo M. Silveira 《Hyperfine Interactions》2005,166(1-4):599-603
The crystal structure of synthetic ferrous hureaulite, Fe5 2+ (H2O)4(PO4H)2(PO4)2, was refined from single-crystal X-ray data. It is monoclinic, space group C2/c, with a=17.487(4), b=9.017(2), c=9.338(2) Å, β=96.27(3)°, V=1463.6(6) Å3, Z=4 and D calc=3.327 g/cm3. This end member of the hureaulite series was crystallized under distinctly acidic conditions, by a method that gives perfect crystals, large enough for X-ray single crystal studies. The main feature of the hureaulite structure is that it has an equal number of normal (PO4)3+ and acid (PO4H)2+ tetradentate groups. These are centered on Fe2+ atoms and share corners with edge-linked octahedra, forming pentamer units. The five Fe2+ atoms are distributed on three distinct sites in these units. This can be directly observed in the Mössbauer spectrum at 295 K, which contains three doublets whose relative intensities correspond to the 1:2:2 distributions of crystallographic sites. 相似文献
27.
Study of a Novel Bisnaphthalimidopropyl Polyamine as Electroactive Material for Perchlorate‐selective Potentiometric Sensors
下载免费PDF全文
![点击此处可从《Electroanalysis》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Renato Gil Célia G. Amorim Laura Crombie Paul Kong Thoo Lin Alberto Araújo Maria da Conceição Montenegro 《Electroanalysis》2015,27(12):2809-2819
In this work, the new polyamine bisnaphthalimidopropyl‐4,4’‐diaminodiphenylmethane is proposed as a new ionophore for perchlorate potentiometric sensors. The optimal formulation for the membrane comprised of 12 mmol kg?1 of the ionophore, and 68 % (w/w) of 2‐nitrophenyl phenyl ether as plasticizer and 31 % (w/w) of high molecular weight PVC. The sensors were soaked in water for a week to allow leakage of anionic impurities and for one day in a perchlorate solution (10?4 mol L?1) to improve reproducibility due to its first usage. The stability constant for the ionophore‐perchlorate association in the membrane, log βIL1=3.18±0.04, ensured a performance characterized by the slope of 54.1 (±0.7) mV dec?1 to perchlorate solutions with concentrations between 1.24×10?7 and 1.00×10?3 mol L?1. The sensors are insensitive to pH between 3.5 to 11.0, they have a practical detection limit of 7.66 (±0.42) ×10?8 mol L?1 and a response time below 60 s for solutions with perchlorate concentrations above 5×10?6 mol L?1. The accuracy of the results was confirmed by the analysis of the contaminant in a certified reference water sample. 相似文献
28.
Nano titanium dioxide (nTiO2), generally considered to be toxicologically inert, is manufactured in large quantities and extensively applied in consumer products. The small size and large surface area endow them with an active group or intrinsic toxicity. Advances in instrumentation are making Raman spectroscopy the tool of choice for an increasing number of (bio) chemical applications. One of the great advantages of this technique is its ability to provide information on the concentration, structure and interaction of biochemical molecules in their microenvironments within intact cells and tissues, non-destructively. Zebrafish (Danio rerio), one of the most important vertebrate model organisms used in developmental biology, are increasingly used in biomedical research, particularly as a model of human disease. In the present work, an attempt is made to study the effect of titanium dioxide, both nano and bulk, on the microenvironment of the liver tissues of Zebrafish using FT-Raman spectroscopy. The results of the present study suggest that TiO2 exposure demonstrate a marked influence on the microenvironments of the liver tissues of Zebrafish. A shift to a higher wavenumber and an increase in the intensity of the band at ∼1087 cm−1 in the TiO2 exposed tissues suggest that some of the conformational changes resulting from the alkali recovery process takes place due to TiO2 exposure. The decreased intensity ratio (I3220/I3400) observed in the titanium-exposed tissues suggests a decreased water domain size, which could be interpreted in terms of weaker hydrogen-bonded molecular species of water in the TiO2 exposed tissues. The observed shift of COO− bands to higher frequencies shows the disruption of salt bridges as a result of a change in the oppositely charged partners and due to the enhanced random coil conformation. The variation in the intensity ratio of the tyrosyl doublet (I858/I825) indicates variation in the hydrogen bonding of the phenolic hydroxyl group due to TiO2 exposure. The results further suggest that the microenvironments are greatly altered due to titanium nano exposure when compared to titanium bulk. In conclusion, the results indicate that FT-Raman spectroscopy might be a useful tool for rapid assessment of nano particle biological interactions. 相似文献
29.
Madeira PJ Faddoul M Afonso MB Vaz PD Fernandez MT Leal JP 《Journal of mass spectrometry : JMS》2011,46(7):640-648
Some antioxidant mechanisms displayed by several phenolic compounds relate with OH bond dissociation energy. One way for its determination, in the gas-phase, relies on acidity measurements. Gas-phase acidities were determined experimentally, applying the kinetic method, for chromanol and four dimethoxyphenols, and theoretically through quantum chemical DFT calculations for chromanol, six dimethoxyphenols and 3,4,5-trimethoxyphenol. The experimental acidity order, 2,3-dimethoxyphenol > 3,5-dimethoxyphenol > 2,6-dimethoxyphenol > 3,4-dimethoxyphenol ≈ phenol > chromanol shows good agreement with the theoretical acidity order, 2,5-dimethoxyphenol > 2,3-dimethoxyphenol > 3,4,5-trimethoxyphenol > 3,5-dimethoxyphenol ≈ 2,4-dimethoxyphenol > 2,6-dimethoxyphenol > 3,4-dimethoxyphenol > phenol > chromanol. These acidity trends were rationalized in terms of the substituent effects on the thermodynamic stabilities both of the parent phenols and the corresponding phenoxide ions. DFT calculations also evidenced the occurrence of intramolecular C-H···O hydrogen bonds whenever there are vicinal substituents (either OH, O(-) or OCH(3)) which induce further stabilization of the geometries. 相似文献
30.
Ana Paula Amorim Jacobo de Uña-ÁlvarezLuís Meira-Machado 《Statistics & probability letters》2011,81(7):797-806
One major goal in clinical applications of multi-state models is the estimation of transition probabilities. In a recent paper, Meira-Machado et al. (2006) introduce a substitute for the Aalen-Johansen estimator in the case of a non-Markov illness-death model. The idea behind their estimator is to weight the data by the Kaplan-Meier weights pertaining to the distribution of the total survival time of the process. In this paper we propose a modification of Meira-Machado et al. (2006) estimator based on presmoothing. Consistency is established. We investigate the finite sample performance of the new estimator through simulations. Data from a study on colon cancer are used for illustration purposes. 相似文献