全文获取类型
收费全文 | 673篇 |
免费 | 16篇 |
国内免费 | 1篇 |
专业分类
化学 | 456篇 |
晶体学 | 6篇 |
力学 | 15篇 |
数学 | 70篇 |
物理学 | 143篇 |
出版年
2023年 | 4篇 |
2022年 | 16篇 |
2021年 | 16篇 |
2020年 | 11篇 |
2019年 | 16篇 |
2018年 | 12篇 |
2017年 | 21篇 |
2016年 | 24篇 |
2015年 | 20篇 |
2014年 | 21篇 |
2013年 | 45篇 |
2012年 | 29篇 |
2011年 | 51篇 |
2010年 | 37篇 |
2009年 | 23篇 |
2008年 | 39篇 |
2007年 | 33篇 |
2006年 | 26篇 |
2005年 | 40篇 |
2004年 | 30篇 |
2003年 | 25篇 |
2002年 | 14篇 |
2001年 | 13篇 |
2000年 | 7篇 |
1999年 | 10篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 10篇 |
1995年 | 5篇 |
1994年 | 3篇 |
1993年 | 8篇 |
1992年 | 3篇 |
1991年 | 5篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1976年 | 2篇 |
1972年 | 2篇 |
1968年 | 4篇 |
1967年 | 2篇 |
1928年 | 2篇 |
1927年 | 3篇 |
1920年 | 3篇 |
1893年 | 2篇 |
1883年 | 2篇 |
排序方式: 共有690条查询结果,搜索用时 15 毫秒
41.
Kirill Kulish Cosimo Boldrini Dr. Marta Castiñeira Reis Dr. Juana M. Pérez Prof. Dr. Syuzanna R. Harutyunyan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(68):15843-15846
Two-step dearomative functionalization of naphthols promoted by Lewis acids and copper(I) catalysis was developed. Initially, Lewis acid complexation inverted the electronic properties of the ring and established an equilibrium with the dearomatized counterpart. Subsequent trapping of the dearomatized intermediate with organometallics as well as organophosphines was demonstrated and provided the corresponding dearomatized products. 相似文献
42.
Alves GA Amato S Anjos JC Appel JA Astorga J Bracker SB Cremaldi LM Dagenhart WD Darling CL Dixon RL Errede D Fenker HC Gay C Green DR Jedicke R Karchin PE Kennedy C Kwan S Lueking LH de Mello Neto JR Metheny J Milburn RH de Miranda JM da Motta Filho H Napier A Passmore D Rafatian A dos Reis AC Ross WR Santoro AF Sheaff M Souza MH Spalding WJ Stoughton C Streetman ME Summers DJ Takach SF Wallace A Wu Z 《Physical review letters》1996,77(12):2388-2391
43.
XDS: a flexible beamline for X‐ray diffraction and spectroscopy at the Brazilian synchrotron 下载免费PDF全文
F. A. Lima M. E. Saleta R. J. S. Pagliuca M. A. Eleotério R. D. Reis J. Fonseca Júnior B. Meyer E. M. Bittar N. M. Souza-Neto E. Granado 《Journal of synchrotron radiation》2016,23(6):1538-1549
The majority of the beamlines at the Brazilian Synchrotron Light Source Laboratory (LNLS) use radiation produced in the storage‐ring bending magnets and are therefore currently limited in the flux that can be used in the harder part of the X‐ray spectrum (above ~10 keV). A 4 T superconducting multipolar wiggler (SCW) was recently installed at LNLS in order to improve the photon flux above 10 keV and fulfill the demands set by the materials science community. A new multi‐purpose beamline was then installed at the LNLS using the SCW as a photon source. The XDS is a flexible beamline operating in the energy range between 5 and 30 keV, designed to perform experiments using absorption, diffraction and scattering techniques. Most of the work performed at the XDS beamline concentrates on X‐ray absorption spectroscopy at energies above 18 keV and high‐resolution diffraction experiments. More recently, new setups and photon‐hungry experiments such as total X‐ray scattering, X‐ray diffraction under high pressures, resonant X‐ray emission spectroscopy, among others, have started to become routine at XDS. Here, the XDS beamline characteristics, performance and a few new experimental possibilities are described. 相似文献
44.
Ricardo G. Alvim Petrina Georgala Lucas Nogueira Alexander J. Somma Karan Nagar Jasmine Thomas Laura Alvim Amelia Riegel Christopher Hughes Jie Chen Augusto B. Reis Souhil Lebdai Avigdor Scherz Steven Zanganeh Rui Gardner Kwanghee Kim Jonathan A. Coleman 《Molecules (Basel, Switzerland)》2021,26(12)
Purpose: Vascular targeted photodynamic therapy (VTP) is a nonsurgical tumor ablation approach used to treat early-stage prostate cancer and may also be effective for upper tract urothelial cancer (UTUC) based on preclinical data. Toward increasing response rates to VTP, we evaluated its efficacy in combination with concurrent PD-1 inhibitor/OX40 agonist immunotherapy in a urothelial tumor-bearing model. Experimental design: In mice allografted with MB-49 UTUC cells, we compared the effects of combined VTP with PD-1 inhibitor/OX40 agonist with those of the component treatments on tumor growth, survival, lung metastasis, and antitumor immune responses. Results: The combination of VTP with both PD-1 inhibitor and OX40 agonist inhibited tumor growth and prolonged survival to a greater degree than VTP with either immunotherapeutic individually. These effects result from increased tumor infiltration and intratumoral proliferation of cytotoxic and helper T cells, depletion of Treg cells, and suppression of myeloid-derived suppressor cells. Conclusions: Our findings suggest that VTP synergizes with PD-1 blockade and OX40 agonist to promote strong antitumor immune responses, yielding therapeutic efficacy in an animal model of urothelial cancer. 相似文献
45.
This work reports the transport of carbon dioxide, oxygen, and nitrogen in amorphous membranes of vulcanized natural rubber reinforced with regenerated cellulose. The values of the permeability coefficient of carbon dioxide, oxygen, and nitrogen in the composites with 25% of cellulose, measured at 25 °C and 15 cmHg of pressure, are roughly one‐third of those measured in the same conditions for these gases in natural rubber. The isotherms representing the variation of both the permeability and diffusion coefficients of the gases with pressure present a relatively sharp increase in the region of low pressures, attributed to changes in the free volume. The analysis of the permeability characteristics of the membranes in terms of the free‐volume theory suggests that gas transport is severely hindered in both the cellulose phase and the cellulose–rubber interphase of the composites. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 393–402, 2000 相似文献
46.
Cella R Cunha RL Reis AE Pimenta DC Klitzke CF Stefani HA 《The Journal of organic chemistry》2006,71(1):244-250
[reaction: see text] Palladium(0)-catalyzed cross-coupling between potassium aryltrifluoroborate salts and aryl tellurides proceeds readily to afford the desired biaryls in good to excellent yield. The reaction seems to be unaffected by the presence of electron-withdrawing or electron-donating substituents in both the potassium aryltrifluoroborate salts and aryl tellurides partners. Biaryls containing a variety of functional groups can be prepared. A chemoselectivity study was also carried out using aryl tellurides bearing halogen atoms in the same compound. In addition, this new version of the Suzuki-Miyaura cross-coupling reaction was monitored by electrospray ionization mass spectrometry where some reaction intermediates were detected and analyzed. 相似文献
47.
Reis A Domingues MR Amado FM Ferrer-Correia AJ Domingues P 《Biomedical chromatography : BMC》2006,20(1):109-118
Linoleic acid radical products formed by radical reaction (Fenton conditions) were trapped using 5,5-dimethyl-1-pyrrolidine-N-oxide (DMPO) and analysed by reversed-phase liquid chromatography coupled to electrospray mass spectrometry (LC-MS). The linoleic acid radical species detected as DMPO spin adducts comprised oxidized linoleic acid and short-chain radical species that resulted from the breakdown of carbon and oxygen centred radicals. Based on the m/z values, the short-chain products were identified as alkyl and carboxylic acid DMPO radical adducts that exhibited different elution times. The ions identified as DMPO radical adducts were studied by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The LC-MS/MS spectra of linoleic acid DMPO radical adducts exhibited the fragment ion at m/z 114 and/or the loss of neutral molecule of 113 Da (DMPO) or 131 Da (DMPO + H2O), indicated to be DMPO adducts. The short-chain products identified allowed inference of the radical oxidation along the linoleic acid chain by abstraction of hydrogen atoms in carbon atoms ranging from C-8 to C-14. Other ions containing the fragment ion at m/z 114 in the LC-MS/MS spectra were attributed to DMPO adducts of unsaturated aldehydes, hydroxy-aldehydes and oxocarboxylic acids. The identification of aldehydic products formed by radical oxidation of linoleic acid peroxidation products, as short-chain product DMPO adducts, is a means of identifying lipid peroxidation products. 相似文献
48.
Laís Peres Silva Ivanilson Pimenta Santos Dahara Keyse Carvalho Silva Bruna Padilha Zurita Claro dos Reis Cssio Santana Meira Marcos Venícius Batista de Souza Castro Jos Maurício dos Santos Filho Joo Honorato de Araujo-Neto Javier Alcides Ellena Rafael Gomes da Silveira Milena Botelho Pereira Soares 《Molecules (Basel, Switzerland)》2022,27(23)
Immunomodulatory agents are widely used for the treatment of immune-mediated diseases, but the range of side effects of the available drugs makes necessary the search for new immunomodulatory drugs. Here, we investigated the immunomodulatory activity of new ferrocenyl-N-acyl hydrazones derivatives (SintMed(141–156). The evaluated N-acyl hydrazones did not show cytotoxicity at the tested concentrations, presenting CC50 values greater than 50 µM. In addition, all ferrocenyl-N-acyl hydrazones modulated nitrite production in immortalized macrophages, showing inhibition values between 14.4% and 74.2%. By presenting a better activity profile, the ferrocenyl-N-acyl hydrazones SintMed149 and SintMed150 also had their cytotoxicity and anti-inflammatory effect evaluated in cultures of peritoneal macrophages. The molecules were not cytotoxic at any of the concentrations tested in peritoneal macrophages and were able to significantly reduce (p < 0.05) the production of nitrite, TNF-α, and IL-1β. Interestingly, both molecules significantly reduced the production of IL-2 and IFN-γ in cultured splenocytes activated with concanavalin A. Moreover, SintMed150 did not show signs of acute toxicity in animals treated with 50 or 100 mg/kg. Finally, we observed that ferrocenyl-N-acyl hydrazone SintMed150 at 100 mg/kg reduced the migration of neutrophils (44.6%) in an acute peritonitis model and increased animal survival by 20% in an LPS-induced endotoxic shock model. These findings suggest that such compounds have therapeutic potential to be used to treat diseases of inflammatory origin. 相似文献
49.
Novel adsorbent based on silkworm chrysalides for removal of heavy metals from wastewaters 总被引:1,自引:0,他引:1
Paulino AT Minasse FA Guilherme MR Reis AV Muniz EC Nozaki J 《Journal of colloid and interface science》2006,301(2):479-487
In this contribution, maximum capacity for adsorption of Pb(2+), Ni(2+), and Cu(2+) by silkworm chrysalides (SC) was determined. The raw silkworm chrysalides (SC(r)) and chrysalides after acidic washing (SC(w)) were used. Chitin (CT), extracted from SC, and chitosan (CS), with 85% deacetylation, were employed as reference samples. Adsorption tests showed that all the studied adsorbents exhibited excellent performance in removal of metals. The choice of a more appropriate adsorbent is related to its efficiency for removal of a specific metal. The studied materials presented different intensities for metal adsorption as follows: (i) Ni(2+)>Cu(2+)>Pb(2+) for SC(r); (ii) Pb(2+)>Cu(2+)>Ni(2+) for SC(w); (iii) Ni(2+)>Cu(2+)>Pb(2+) for CT; and (iv) Cu(2+)>Pb(2+)>Ni(2+) for CS. Metal adsorption onto SC(r) and CS was analyzed by Freundlich and Langmuir isotherm equations. Adsorption values for CS-Pb and SC(r)-Ni were provided by the Freundlich model, while the adsorption values for CS-Cu, CS-Ni, SC(r)-Pb, and SC(r)-Cu were provided by the Langmuir model. The studied adsorbents are suitable for use in treatment of wastewater. From the economic point of view, the use of SC(r) as an adsorbent of heavy metals (mainly Ni(2+)) on the large industrial scale would be more appropriate. 相似文献
50.
An automatic system that performs two analytical procedures, allowing the evaluation of the relative antioxidant capacity of wine samples, was developed. Automation was carried out using a sequential injection analysis (SIA) system that allowed, thanks to its versatility, the development of two methodologies. One is based on the decolorization assay of the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical, using a spectrophotometric detector. A second methodology allowed the evaluation of the hydrogen peroxide scavenging activity by measuring the oxidation of homovanylic acid (HVA) to its fluorescent dimer, using a fluorescent detector.The developed automatic methodologies were evaluated using trolox as standard and subsequently using other antioxidant substances as gallic acid, caffeic acid, ascorbic acid, catechin and taxifolin which are abundant in wine and whose antioxidant activities were compared to that shown by trolox. The spectrophotometric and fluorimetric assays showed linearity intervals between 0.001 and 0.01 mM, and 0.001 and 0.008 mM of trolox, respectively.The evaluation of the antioxidant power of 20 white and red wine samples, from different Portuguese wine producing regions, was carried out sequentially, in the automatic system. The results were expressed in trolox equivalent antioxidant capacity (TEAC) and presented, for the ABTS and hydrogen peroxide scavenging activity methodologies, detection limits of 8.4 × 10−7 and 1.4 × 10−4 mM and relative standard deviation (R.S.D. (%)) in the range 0.6-2.4 and 1-1.8, respectively. 相似文献