全文获取类型
收费全文 | 318篇 |
免费 | 15篇 |
专业分类
化学 | 302篇 |
晶体学 | 1篇 |
数学 | 11篇 |
物理学 | 19篇 |
出版年
2024年 | 1篇 |
2023年 | 3篇 |
2022年 | 9篇 |
2021年 | 5篇 |
2020年 | 11篇 |
2019年 | 6篇 |
2018年 | 1篇 |
2017年 | 1篇 |
2016年 | 5篇 |
2015年 | 8篇 |
2014年 | 8篇 |
2013年 | 14篇 |
2012年 | 19篇 |
2011年 | 24篇 |
2010年 | 15篇 |
2009年 | 14篇 |
2008年 | 26篇 |
2007年 | 17篇 |
2006年 | 21篇 |
2005年 | 19篇 |
2004年 | 11篇 |
2003年 | 13篇 |
2002年 | 17篇 |
2001年 | 11篇 |
2000年 | 7篇 |
1998年 | 1篇 |
1997年 | 5篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1972年 | 2篇 |
1962年 | 2篇 |
排序方式: 共有333条查询结果,搜索用时 20 毫秒
71.
Carsten Bolm Hiroaki Okamura Marinella Verrucci 《Journal of organometallic chemistry》2003,687(2):444-450
The palladium-catalyzed cyclization of N-(2-bromobenzyl)- and N-(2-bromobenzoyl)-sulfoximines affords six-membered heterocycles in moderate to good yield. In both cases, the α-arylations of the sulfoximine methyl groups are catalyzed by combination of Pd(OAc)2 and rac-BINAP in the presence of a base such as Cs2CO3 or K2CO3. 相似文献
72.
Fluorene derivatives, having substituted benzyl groups bonded to position 9, have been investigated by variable temperature NMR spectroscopy. Stereodynamic processes involving restricted rotation about the fluorenyl-CH2 and aryl-CH2 bonds have been observed, leading to conformers and enantiomeric forms, and the corresponding barriers were determined by line shape simulation. These dynamic processes are interpreted as being due to correlated rotation pathways, on the basis of DFT computations that satisfactorily reproduce the experimental barriers. The structures of two such compounds were also determined by single-crystal X-ray diffraction. 相似文献
73.
Andreiadis ES Imbert D Pécaut J Demadrille R Mazzanti M 《Dalton transactions (Cambridge, England : 2003)》2012,41(4):1268-1277
Two tridentate pyridine-tetrazolate ligands (H(2)pytz and H(2)pytzc), analogues of the well-known dipicolinate (H(2)dpa) ligand, have been synthesized in a straightforward manner and used for lanthanide(III) coordination. The structures of the resulting tris-ligand complexes were determined in solution ((1)H-NMR), where they remain undissociated, as well as in the solid state (X-ray diffraction). The solubility of these anionic complexes can be easily tuned by changing the countercation. The bis-tetrazolate-pyridine ligand H(2)pytz sensitizes very efficiently both the visible and near-IR emission of the lanthanides, with unusually high luminescence quantum yields in solid state (61% and 65% for Eu and Tb, respectively, and 0.21% for Nd) and in water (63% for Tb and 18% for Eu). Furthermore, the absorption window of the complexes is significantly extended towards the visible region up to 330 nm. The results show that the bis-tetrazolate-pyridine ligand provides a very attractive alternative to the classic dipicolinate ligand. 相似文献
74.
Federica Rizzi Rachele Castaldo Tiziana Latronico Pierluigi Lasala Gennaro Gentile Marino Lavorgna Marinella Striccoli Angela Agostiano Roberto Comparelli Nicoletta Depalo Maria Lucia Curri Elisabetta Fanizza 《Molecules (Basel, Switzerland)》2021,26(14)
Mesoporous silica nanostructures (MSNs) attract high interest due to their unique and tunable physical chemical features, including high specific surface area and large pore volume, that hold a great potential in a variety of fields, i.e., adsorption, catalysis, and biomedicine. An essential feature for biomedical application of MSNs is limiting MSN size in the sub-micrometer regime to control uptake and cell viability. However, careful size tuning in such a regime remains still challenging. We aim to tackling this issue by developing two synthetic procedures for MSN size modulation, performed in homogenous aqueous/ethanol solution or two-phase aqueous/ethyl acetate system. Both approaches make use of tetraethyl orthosilicate as precursor, in the presence of cetyltrimethylammonium bromide, as structure-directing agent, and NaOH, as base-catalyst. NaOH catalyzed syntheses usually require high temperature (>80 °C) and large reaction medium volume to trigger MSN formation and limit aggregation. Here, a successful modulation of MSNs size from 40 up to 150 nm is demonstrated to be achieved by purposely balancing synthesis conditions, being able, in addition, to keep reaction temperature not higher than 50 °C (30 °C and 50 °C, respectively) and reaction mixture volume low. Through a comprehensive and in-depth systematic morphological and structural investigation, the mechanism and kinetics that sustain the control of MSNs size in such low dimensional regime are defined, highlighting that modulation of size and pores of the structures are mainly mediated by base concentration, reaction time and temperature and ageing, for the homogenous phase approach, and by temperature for the two-phase synthesis. Finally, an in vitro study is performed on bEnd.3 cells to investigate on the cytotoxicity of the MNSs. 相似文献
75.
76.
77.
Marta Llorca Marinella Farré Yolanda Picó Damià Barceló 《Journal of chromatography. A》2009,1216(43):7195-7204
This paper describes the development and validation of an analytical methodology to determine eight perfluorinated compounds (PFCs) in edible fish using pressurized liquid extraction (PLE) with water and solid-phase extraction (SPE) with an ion-exchanger as extraction and pre-concentration procedures, followed by liquid chromatography–quadrupole-linear ion trap mass spectrometry (LC–QqLIT–MS). The rapidity and effectiveness of the proposed extraction procedure were compared with those most commonly used to isolate PFCs from fish (ion-pairing and alkaline digestion). The average recoveries of the different fish samples, spiked with the eight PFCs at three levels (the LOQ, 10 and 100 μg kg−1 of each PFC), were always higher than 85% with relative standard deviation (RSD) lower than 17%. A good linearity was established for the eight PFCs in the range from 0.003–0.05 to 100 μg kg−1, with r > 0.9994. The limits of quantification (LOQs) were between 0.003 and 0.05 μg kg−1, which are well below those previously reported for this type of samples. Compared with previous methods, sample preparation time and/or LOQs are reduced. The method demonstrated its successful application for the analysis of different parts of several fish species. Most of the samples tested positive, mainly for perfluoropentanoic acid (PFPA), perfluorobutane sulfonate (PFBS) and perfluorooctanoic acid (PFOA) but other of the eight studied PFCs were also present. 相似文献
78.
Lanthanide(II) Complexes Supported by N,O‐Donor Tripodal Ligands: Synthesis,Structure, and Ligand‐Dependent Redox Behavior 下载免费PDF全文
Julie Andrez Dr. Gülay Bozoklu Dr. Grégory Nocton Dr. Jacques Pécaut Dr. Rosario Scopelliti Dr. Lionel Dubois Dr. Marinella Mazzanti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15188-15200
The preparation and characterization of a series of complexes of the Yb and Eu cations in the oxidation state II and III with the tetradentate N,O‐donor tripodal ligands (tris(2‐pyridylmethyl)amine (TPA), BPA? (HBPA=bis(2‐pyridylmethyl)(2‐hydroxybenzyl)amine), BPPA? (HBPPA=bis(2‐pyridylmethyl)(3.5‐di‐tert‐butyl‐2‐hydroxybenzyl)amine), and MPA2? (H2MPA=(2‐pyridylmethyl)bis(3.5‐di‐tert‐butyl‐2‐hydroxybenzyl)amine) is reported. The X‐ray crystal structures of the heteroleptic Ln2+ complexes [Ln(TPA)I2] (Ln=Eu, Yb) and [Yb(BPA)I(CH3CN)]2, of the Ln2+ homoleptic [Ln(TPA)2]I2 (Ln=Sm, Eu, Yb) and [Eu(BPA)2] complexes, and of the Ln3+ [Eu(BPPA)2]OTf and [Yb(MPA)2K(dme)2] (dme=dimethoxyethane) complexes have been determined. Cyclic voltammetry studies carried out on the bis‐ligand complexes of Eu3+ and Yb3+ show that the metal center reduction occurs at significantly lower potentials for the BPA? ligand as compared with the TPA ligand. This suggests that the more electron‐rich character of the BPA? ligand results in a higher reducing character of the lanthanide complexes of BPA? compared with those of TPA. The important differences in the stability and reactivity of the investigated complexes are probably due to the observed difference in redox potential. Preliminary reactivity studies show that whereas the bis‐TPA complexes of Eu2+ and Yb2+ do not show any reactivity with heteroallenes, the [Eu(BPA)2] complex reduces CS2 to afford the first example of a lanthanide trithiocarbonate complex. 相似文献
79.
The electronic structure of various complexes of pentavalent uranyl species, namely UO2+, is described, using DFT methods, with the aim of understanding how the structure of the ligands may influence the localisation of the unpaired 5f electron of uranium (V) and, finally, the stability of such complexes towards oxidation. Six complexes have been inspected: [UO2py5]+ (1), [(UO2py5)KI2] (2), [UO2(salan-tBu2)(py)K] (3), [UO2(salophen-tBu2)(thf)K] (4), [UO2(salen-tBu2)(py)K] (5), [and UO2-cyclo[6]pyrrole]1? (6), chosen to explore various ligands. In the five first complexes, the UO2+ species is well identified with the unpaired electron localized on the 5f uranium orbital. Additionally, for the salan, salen and salophen ligands, some covalent interactions have been observed, resulting from the presence of both donor and acceptor binding sites. In contrast, the last complex is best described by a UO22+ uranyl (VI) coordinated by the anionic radical cyclopyrrole, the highly delocalized π orbitals set stabilizing the radical behaviour of this ligand. 相似文献
80.
Farré M Gajda-Schrantz K Kantiani L Barceló D 《Analytical and bioanalytical chemistry》2009,393(1):81-95
Nanotechnology is a major innovative scientific and economic growth area. However nanomaterial residues may have a detrimental
effect on human health and the environment. To date there is a lack of quantitative ecotoxicity data, and recently there has
been great scientific concern about the possible adverse effects that may be associated with manufactured nanomaterials. Nanomaterials
are in the 1- to 100-nm size range and can be composed of many different base materials (carbon, silicon and metals, such
as gold, cadmium and selenium) and they have different shapes. Particles in the nanometer size range do occur both in nature
and as a result of existing industrial processes. Nevertheless, new engineered nanomaterials and nanostructures are different
because they are being fabricated from the “bottom up”. Nanomaterial properties differ compared with those of the parent compounds
because about 40–50% of the atoms in nanoparticles (NPs) are on the surface, resulting in greater reactivity than bulk materials.
Therefore, it is expected that NPs will have different biological effects than parent compounds. In addition, release of manufactured
NPs into the aquatic environment is largely an unknown. The surface properties and the very small size of NPs and nanotubes
provide surfaces that may bind and transport toxic chemical pollutants, as well as possibly being toxic in their own right
by generating reactive radicals. This review addresses hazards associated and ecotoxicological data on nanomaterials in the
aquatic environment. Main weaknesses in ecotoxicological approaches, controversies and future needs are discussed. A brief
discussion on the scarce number of analytical methods available to determinate nanomaterials in environmental samples is included. 相似文献