全文获取类型
收费全文 | 8726篇 |
免费 | 277篇 |
国内免费 | 37篇 |
专业分类
化学 | 6253篇 |
晶体学 | 71篇 |
力学 | 204篇 |
综合类 | 3篇 |
数学 | 857篇 |
物理学 | 1652篇 |
出版年
2023年 | 78篇 |
2022年 | 248篇 |
2021年 | 257篇 |
2020年 | 206篇 |
2019年 | 222篇 |
2018年 | 183篇 |
2017年 | 155篇 |
2016年 | 324篇 |
2015年 | 267篇 |
2014年 | 326篇 |
2013年 | 536篇 |
2012年 | 541篇 |
2011年 | 611篇 |
2010年 | 425篇 |
2009年 | 389篇 |
2008年 | 533篇 |
2007年 | 454篇 |
2006年 | 408篇 |
2005年 | 357篇 |
2004年 | 300篇 |
2003年 | 252篇 |
2002年 | 226篇 |
2001年 | 160篇 |
2000年 | 140篇 |
1999年 | 96篇 |
1998年 | 89篇 |
1997年 | 89篇 |
1996年 | 71篇 |
1995年 | 69篇 |
1994年 | 78篇 |
1993年 | 74篇 |
1992年 | 71篇 |
1991年 | 58篇 |
1990年 | 43篇 |
1989年 | 38篇 |
1988年 | 45篇 |
1987年 | 32篇 |
1986年 | 34篇 |
1985年 | 38篇 |
1984年 | 28篇 |
1983年 | 33篇 |
1982年 | 33篇 |
1981年 | 38篇 |
1980年 | 29篇 |
1979年 | 27篇 |
1978年 | 32篇 |
1977年 | 27篇 |
1976年 | 30篇 |
1975年 | 25篇 |
1974年 | 25篇 |
排序方式: 共有9040条查询结果,搜索用时 15 毫秒
961.
Geninatti-Crich S Alberti D Szabo I Deagostino A Toppino A Barge A Ballarini F Bortolussi S Bruschi P Protti N Stella S Altieri S Venturello P Aime S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(30):8479-8486
The upregulation of low-density lipoprotein (LDL) transporters in tumour cells has been exploited to deliver a sufficient amount of gadolinium/boron/ligand (Gd/B/L) probes for neutron capture therapy, a binary chemio-radiotherapy for cancer treatment. The Gd/B/L probe consists of a carborane unit (ten B atoms) bearing an aliphatic chain on one side (to bind LDL particles), and a Gd(III)/1,4,7,10-tetraazacyclododecane monoamide complex on the other (for detection by magnetic resonance imaging (MRI)). Up to 190 Gd/B/L probes were loaded per LDL particle. The uptake from tumour cells was initially assessed on cell cultures of human hepatoma (HepG2), murine melanoma (B16), and human glioblastoma (U87). The MRI assessment of the amount of Gd/B/L taken up by tumour cells was validated by inductively coupled plasma-mass-spectrometric measurements of the Gd and B content. Measurements were undertaken in vivo on mice bearing tumours in which B16 tumour cells were inoculated at the base of the neck. From the acquisition of magnetic resonance images, it was established that after 4-6 hours from the administration of the Gd/B/L-LDL particles (0.1 and 1 mmol kg(-1) of Gd and (10)B, respectively) the amount of boron taken up in the tumour region is above the threshold required for successful NCT treatment. After neutron irradiation, tumour growth was followed for 20 days by MRI. The group of treated mice showed markedly lower tumour growth with respect to the control group. 相似文献
962.
Todeschini V Sangoi Mda S Volpato NM 《European journal of mass spectrometry (Chichester, England)》2011,17(3):287-296
A simple, specific, fast and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the simultaneous analysis of delapril (DEL) and manidipine (MAN) from their combination formulation was developed and validated using fesoterodine as the internal standard (IS). The LC-MS/MS method was carried out on a Luna C8 column (50 × 3.0 mm i.d., 3 μm) with a mobile phase consisting of methanol and 10 mmol L(-1) ammonium acetate (90 : 0, v/v), run at a flow rate of 0.25 mL min(-1). The mass spectrometry method was performed employing positive electrospray ionization operating in multiple reaction monitoring mode, monitoring the transitions of m/z 453.1 → 234.1 for DEL, m/z 611.1 → 167.0 for MAN and m/z 412.2 → 223.0 for IS. The total analysis time was 3 min and the method was linear in the concentration range of 6-1080 ng mL(-1) and 2-360 ng mL(-1) for DEL and MAN, respectively. Parameters investigated for the method validation, such as the specificity, linearity, precision, accuracy and robustness, gave results within the acceptable range. Moreover, the proposed method was successfully applied for the simultaneous determination of DEL and MAN and the results were compared to validated liquid chromatography and capillary electrophoresis methods showing non-significant differences (P = 0.9). 相似文献
963.
Assis AC Couto N Duarte MF Rodrigues P Barros MT Costa ML Cabral BJ Fernandez MT 《Journal of mass spectrometry : JMS》2011,46(7):696-704
The relevance of metal interactions with azides has led us to the study of the complexation of some transition metals, nickel and cobalt, by azidoacetone by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of NiCl(2) and CoCl(2) , in methanol/water. Nickel was electrosprayed with other counter ion, bromide (Br), as well as other solvent (ethanol/water). For nickel and cobalt, the complexes detected were single positively charged, with various stoichiometries, some resulted from the fragmentation of the ligand, the loss of N(2) being quite common. The most abundant species were [Ni(II)Az(2)X](+) where X = Cl, Br and Az = azidoacetone. Some of the complexes showed solvation with the solvent components. Metal reduction was observed in complexes where a radical was lost, resulting from the homolytic cleavage of a metal coordination bond. Collision-induced dissociation (CID) experiments followed by tandem mass spectrometry (MS-MS) analysis were not absolutely conclusive about the coordination site. However, terminal ions of the fragmentation routes were explained by a gas-phase mechanism proposed where a C-C bond was activated and the metal inserted subsequently. Density functional theory calculations provided structures for some complexes. In [Ni(II)Az(2)X](+) species, one azidoacetone ligand is monodentate and the dominant binding location is the alkylated nitrogen and not the carbonyl group. The other azidoacetone ligand is bidentate showing coordination through alkylated nitrogen and the carbonyl group. These are also the preferential binding sites for the most stable isomer of [Ni(II)AzX](+) species. 相似文献
964.
Pereira AM Soares AR Hausmann A Neves MG Tomé AC Silva AM Cavaleiro JA Guldi DM Torres T 《Physical chemistry chemical physics : PCCP》2011,13(25):11858-11863
In the current work, we report on the synthesis and photophysical features of supramolecular hybrid systems that are based on newly fused porphyrin-phthalocyanine (P-Pc) conjugates and a pyridylfullerene. The ZnP-ZnPc conjugate was synthesized in three steps starting with a Diels-Alder reaction between β-vinylporphyrin and fumaronitrile. The resulting mixture of isomeric adducts was then dehydrogenated to yield the corresponding benzo[b]porphyrin-2(1),2(2)-dicarbonitrile. In the final step, cyclotetramerization with 4-tert-butylphthalonitrile, in the presence of zinc acetate, afforded the bis-metalated conjugate. Selective demetallation of ZnP led to the H(2)P-ZnPc conjugate. For both conjugates steric hindrance is the inception to a bent configuration, which does, however, not preclude enlargement of the π-conjugated system, that is, the porphyrins and the phthalocyanines. The two conjugates coordinate N-(4-pyridyl)fullero[c]pyrrolidine giving rise to the corresponding supramolecular porphyrin-phthalocyanine-fullerene systems. Photophysical measurements corroborate a sequential deactivation in the excited state, namely an initial intramolecular energy transfer from ZnP or H(2)P to ZnPc followed by an intramolecular charge transfer to yield ZnP-(ZnPc)˙(+)-(C(60))˙(-) and H(2)P-(ZnPc)˙(+)-(C(60))˙(-), respectively. 相似文献
965.
Ferreira BS de Almeida CG Faza LP de Almeida A Diniz CG da Silva VL Grazul RM Le Hyaric M 《Molecules (Basel, Switzerland)》2011,16(7):5875-5885
Pequi (Caryocar brasiliense Camb.), baba?u (Orbignya phalerata Mart.), buriti (Mauritia flexuosa), and passion fruit (Passiflora edulis) oils were studied to determine their antibacterial, antioxidant and cytotoxic activities, as well as their total phenol and carotenoid contents. The fatty acid contents were determined by GC-MS. The three types of passion fruit oils studied were refined, cold pressed or extracted from seeds in a Soxhlet apparatus. The oils thus obtained showed differences in antioxidant activity and carotenoid content, but were similar in regard to total phenols. Buriti and pequi had the highest carotenoid contents, while refined and cold pressed passion fruit oil displayed the highest antioxidant activity. Pequi oil was the only oil to display antibacterial and cytotoxic activity. 相似文献
966.
Ionic composition of seawaters and derived saline solutions determined by ion chromatography and its relation to other water quality parameters 总被引:2,自引:0,他引:2
Ion chromatography (IC) presents new possibilities for assessing information about environmental samples, namely waters of various compositions, ranging from high-purity water to highly saline ones. Constant proportion between major ions present in seawater, has been assumed in the past, from which the first practical equation relating chlorinity and salinity has been developed, being later substituted by a practical salinity scale, derived from conductivity measurements relative to a standard seawater, according to internationally accepted recommended procedures. Seawaters are characterized by salinity values around 35 while derived saline solutions may present considerable changes in ionic composition, conductivity, hence on salinity. Natural and anthropogenic phenomena may introduce new issues requiring clarification for which qualitative and quantitative information from additional sources is useful, e.g. ionic composition from IC. The different ranges of concentration of major and minor species present in seawater and derived saline solutions are a challenge for the optimization of a practical methodology for composition assessment in two single IC runs, one for anions and another one for cations, which has been attained in this work. Composition of saline solutions determined by IC was critically assessed in terms of anion-cation balance and further related to conductivity and salinity measurements aiming to evaluate the quality/completeness of ion chromatographic analyses performed at preselected conditions and to search for other meaningful relations for efficient recognition/distinction between saline solutions of different types. 相似文献
967.
968.
Catia S. RadatzRodrigo B. Silva Gelson PerinEder J. Lenardão Raquel G. Jacob Diego Alves 《Tetrahedron letters》2011,52(32):4132-4136
We described herein the use of glycerol as solvent in the catalyst-free synthesis of benzodiazepines and benzimidazoles. This simple and efficient method furnishes the corresponding 1-H-1,5-benzodiazepines and 1,2-disubstituted benzimidazoles in good yields by the condensation of o-phenylenediamine with several ketones and aldehydes, respectively. In addition, glycerol can be easily re-utilized for further condensation reactions up to four times without lost of activity. 相似文献
969.
Soares SF Galvão RK Araújo MC da Silva EC Pereira CF de Andrade SI Leite FC 《Analytica chimica acta》2011,(1):30-28
This work proposes a modification to the successive projections algorithm (SPA) aimed at selecting spectral variables for multiple linear regression (MLR) in the presence of unknown interferents not included in the calibration data set. The modified algorithm favours the selection of variables in which the effect of the interferent is less pronounced. The proposed procedure can be regarded as an adaptive modelling technique, because the spectral features of the samples to be analyzed are considered in the variable selection process. The advantages of this new approach are demonstrated in two analytical problems, namely (1) ultraviolet–visible spectrometric determination of tartrazine, allure red and sunset yellow in aqueous solutions under the interference of erythrosine, and (2) near-infrared spectrometric determination of ethanol in gasoline under the interference of toluene. In these case studies, the performance of conventional MLR-SPA models is substantially degraded by the presence of the interferent. This problem is circumvented by applying the proposed Adaptive MLR-SPA approach, which results in prediction errors smaller than those obtained by three other multivariate calibration techniques, namely stepwise regression, full-spectrum partial-least-squares (PLS) and PLS with variables selected by a genetic algorithm. An inspection of the variable selection results reveals that the Adaptive approach successfully avoids spectral regions in which the interference is more intense. 相似文献
970.
Ferreira da Silva F Almeida D Antunes R Martins G Nunes Y Eden S Garcia G Limão-Vieira P 《Physical chemistry chemical physics : PCCP》2011,13(48):21621-21629
Electron transfer to uracil (U), 5-chlorouracil (5-ClU) and 5-fluorouracil (5-FU) yielding anion formation has been investigated in 30-100 eV potassium-molecule collisions. The rich fragmentation patterns of all three molecules suggest that electron transfer in collisions with electronegative neutrals may cause efficient damage to RNA. The main ring fragment anion in all the mass spectra was NCO(-) while the production of X(-) (X = F, Cl) was a strong decomposition of the halouracil temporary negative ions. Cl(-) was the most intense fragment anion in the 5-chlorouracil measurements, whereas NCO(-) production dominated in the U and 5-FU data. Arguments based on energetics and vibrational dynamics have been proposed to explain these differences. Electronic coupling between dipole- and valence-bound states may play a particularly important role in the fragmentation pathways of the 5-ClU parent anion. The stabilizing influence of the potassium cation following electron transfer (ionic scattering) on the observed fragmentation patterns is discussed, notably in the context of comparisons with free electron attachment processes. 相似文献