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1.
Double-ended aryl dithiols [alpha,alpha'-xylyldithiol (XYL) and 4,4'-biphenyldithiol] formed self-assembled monolayers (SAMs) on gold(111) substrates and were used to tether nanometer-sized gold clusters deposited from a cluster beam. An ultrahigh-vacuum scanning tunneling microscope was used to image these nanostructures and to measure their current-voltage characteristics as a function of the separation between the probe tip and the metal cluster. At room temperature, when the tip was positioned over a cluster bonded to the XYL SAM, the current-voltage data showed "Coulomb staircase" behavior. These data are in good agreement with semiclassical predictions for correlated single-electron tunneling and permit estimation of the electrical resistance of a single XYL molecule (approximately18 ± 12 megohms).  相似文献   

2.
Lehn JM 《Science (New York, N.Y.)》1985,227(4689):849-856
Supramolecular chemistry is the study of the structures and functions of the supermolecules that result from binding substrates to molecular receptors. Macropolycyclic receptors and coreceptors have been designed that form cryptate inclusion complexes and display molecular recognition towards spherical, tetrahedral, and linear substrates of various kinds (metal cations, inorganic anions, and organic or biological cations or anions). Anion binding has led to the development of anion coordination chemistry. Metalloreceptors simultaneously bind organic molecules and metal ions; speleands combine polar and nonpolar binding subunits. Receptors bearing reactive functional groups may act as molecular reagents or catalysts, performing a chemical transformation on the bound substrates (by such reactions as hydrogen transfer, ester cleavage, and protoadenosinetriphosphatase and protokinase activities). Receptors fitted with lipophilic groups can operate as molecular carriers, translocating bound species through a membrane; this transport can be coupled to chemical potentials (proton and redox gradients).  相似文献   

3.
[目的]红外光谱可提供黏土矿物及微生物表面吸附重金属前后官能团的变化情况,从而为重金属吸附机理的判断提供较为丰富的信息。[方法]采用红外光谱技术探讨了耐重金属细菌NTG-01对褐土胶体、红壤胶体吸附Cu^2+、Cd^2+的影响。[结果]细菌促进了褐土胶体表面的Si-O-H-Si基团与Cu^2+、Cd^2+的反应;加菌前后吸附Cu^2+、Cd^2+的红壤胶体表面功能团红外光谱特征频率无明显差异。[结论]微生物在土壤吸附重金属元素的过程中起着重要作用。  相似文献   

4.
The relative importance of x-rays alone and of x-ray-generated primary and secondary electrons in damaging organic materials was explored by use of self-assembled monolayers (SAMs) on multilayer thin-film supports. The substrates were prepared by the deposit of thin films of silicon (0, 50, 100, and 200 angstroms) on thick layers of gold (2000 angstroms). These systems were supported on chromium-primed silicon wafers. Trifluoroacetoxy-terminated SAMs were assembled on these substrates, and the samples were irradiated with common fluxes of monochromatic aluminum K(alpha) x-rays. The fluxes and energy distributions of the electrons generated by interactions of the x-rays with the various substrates, however, differed. The substrates that emitted a lower flux of electrons exhibited a slower loss of fluorine from the SAMs. This observation indicated that the electrons-and not the x-rays themselves-were largely responsible for the damage to the organic monolayer.  相似文献   

5.
【目的】探讨耐镉细菌对红壤、赤红壤和棕色石灰土3类型土壤胶体镉吸附性能的影响及细菌—土壤胶体复合体上所吸附镉形态的变化,为重金属污染土壤的生物修复提供理论依据。【方法】从矿区镉污染土壤中筛选分离出一株耐镉细菌,同时提取红壤、赤红壤和棕色石灰土3种土壤胶体,研究接种耐镉细菌后3种土壤胶体吸附镉的变化及细菌—土壤胶体复合体上所吸附镉形态的变化。【结果】接种耐镉细菌能提高3种土壤胶体对镉的吸附,以红壤有机—无机复合胶体的提高幅度最大;接种耐镉细菌使3种类型土壤胶体上弱酸可溶态和残渣态的镉含量降低,而可还原态和可氧化态含量则提高。接菌后,红壤胶体和赤红壤(自然土)无机胶体上不同形态镉含量为残渣态〉可还原态〉弱酸可溶态〉可氧化态,而赤红壤(耕作土)胶体和棕色石灰土胶体则为可还原态〉残渣态〉弱酸可溶态〉可氧化态。【结论】接种耐镉细菌能促进土壤胶体上镉形态由无效态向有效态转化,提高镉的有效性。  相似文献   

6.
【目的】探讨耐镉细菌对红壤、赤红壤和棕色石灰土3类型土壤胶体镉吸附性能的影响及细菌—土壤胶体复合体上所吸附镉形态的变化,为重金属污染土壤的生物修复提供理论依据。【方法】从矿区镉污染土壤中筛选分离出一株耐镉细菌,同时提取红壤、赤红壤和棕色石灰土3种土壤胶体,研究接种耐镉细菌后3种土壤胶体吸附镉的变化及细菌—土壤胶体复合体上所吸附镉形态的变化。【结果】接种耐镉细菌能提高3种土壤胶体对镉的吸附,以红壤有机—无机复合胶体的提高幅度最大;接种耐镉细菌使3种类型土壤胶体上弱酸可溶态和残渣态的镉含量降低,而可还原态和可氧化态含量则提高。接菌后,红壤胶体和赤红壤(自然土)无机胶体上不同形态镉含量为残渣态>可还原态>弱酸可溶态>可氧化态,而赤红壤(耕作土)胶体和棕色石灰土胶体则为可还原态>残渣态>弱酸可溶态>可氧化态。【结论】接种耐镉细菌能促进土壤胶体上镉形态由无效态向有效态转化,提高镉的有效性。  相似文献   

7.
8.
We present a low-temperature scanning tunneling microscopy (STM) study of K(x)C60 monolayers on Au(111) for 3 < or = x < or = 4. The STM spectrum evolves from one that is characteristic of a metal at x = 3 to one that is characteristic of an insulator at x = 4. This electronic transition is accompanied by a dramatic structural rearrangement of the C60 molecules. The Jahn-Teller effect, a charge-induced mechanical deformation of molecular structure, is directly visualized in the K4C60 monolayer at the single-molecule level. These results, along with theoretical analyses, provide strong evidence that the transition from metal to insulator in K(x)C60 monolayers is caused by the Jahn-Teller effect.  相似文献   

9.
Model studies in molecular recognition   总被引:5,自引:0,他引:5  
J Rebek 《Science (New York, N.Y.)》1987,235(4795):1478-1484
Recognition at the molecular level is a fundamental characteristic of biochemical systems. Recent models developed in bioorganic chemistry have revealed the importance of complementarity in size, shape, and functional groups in molecular recognition. Structures that feature a cleft are particularly effective in regard to complementarity since functional groups attached to the interior of the cleft converge on substrates held inside. The molecular clefts offer the advantage of efficient construction; their surfaces can be tailored for specific applications. This article describes their use for recognition of acids, bases, amino acids, metal ions, and neutral substrates. Their ability to provide microenvironments complementary to asymmetric molecules and their future promise are discussed.  相似文献   

10.
夏季,液化气储罐外表面需采用喷淋水降温,该方法不仅消耗大量的工业水和电能,而且使罐体表面防腐层和金属本体腐蚀严重。为了解决这一难题,在10座100m^3卧式液化气储罐上试用了上海大通研究所生产的DT-22型凉凉隔热胶,该产品可直接涂覆于储罐的外表面,从而达到隔热降温的效果。凉凉隔热胶与红丹防锈漆相比,其抗化学性能好、防锈性能极佳、耐磨性好、附着力强,涂覆在液化气储罐上,取消了夏季的喷淋水降温,省去  相似文献   

11.
腐殖酸?高岭土?铜在多孔介质中的迁移及相互作用   总被引:1,自引:0,他引:1  
[目的]控制重金属在地下水深处污染。[方法]采用静态吸附试验和动态模拟试验比较了腐殖酸和高岭土对铜的吸附及其在多孔介质中的迁移。[结果]铜的存在抑制了高岭土在多孔介质中的迁移,高岭土胶体在多孔介质中沉积量增大,导致高岭土对铜的迁移促进作用不明显,腐殖酸降低了胶体沉积的同时促进了铜的迁移,在动态迁移过程中腐殖酸和高岭土对铜产生了竞争吸附,同时高岭土占据了腐殖酸在石英砂上的吸附点位,促进了腐殖酸的迁移。[结论]减少地下水中腐殖酸含量可以降低重金属在地下水深处的富集。  相似文献   

12.
The optical and electronic properties of thin films of the solution-processible polymer poly-(CH(3))(3)Si-cyclooctatetraene are presented. This conjugated polymer is based on a polyacetylene backbone with (CH(3))(3)Si side groups. Thin transparent films have been cast onto n-doped silicon (n-Si) substrates and doped with iodine to form surfacebarrier solar cells. The devices produce photovoltages that are at the theoretical limit and that are much greater than can be obtained from n-Si contacts with conventional metals. Two methods for forming layered polymeric materials, one involving the spincoating of preformed polymers and the other comprising the sequential polymerization of different monomers, are also described. An organic polymer analog of a metal/insulator/metal capacitor has been constructed with the latter method.  相似文献   

13.
Nanoparticles can be used as the building blocks for materials such as supracrystals or ionic liquids. However, they lack the ability to bond along specific directions as atoms and molecules do. We report a simple method to place target molecules specifically at two diametrically opposed positions in the molecular coating of metal nanoparticles. The approach is based on the functionalization of the polar singularities that must form when a curved surface is coated with ordered monolayers, such as a phase-separated mixture of ligands. The molecules placed at these polar defects have been used as chemical handles to form nanoparticle chains that in turn can generate self-standing films.  相似文献   

14.
Cooloid concentrates were obtained by employing a cross-flow filtration system to ultrafiltrate seawater(which was pre-filtrated by 0.45 μm acetate cellulose membrane)sucessively with three membranes.The retentions(colloid concentrates)and control sample(in which colloid was removed)were then inoculated with a microalga and cultivated in vitro.After continuously monitoring cell content during cultivation,it was found that colloid had an obvious beneficial effect on the growth of microalga.Although colloids with different sizes influenced microalga‘s growth in different extent and ways,a brief conclusion could be draw from experiments that colloid might be a potential nutrition source for microalga‘s growth.  相似文献   

15.
原油改性机理研究中的几个问题   总被引:17,自引:5,他引:12  
简述了高分子聚合物对石蜡、沥青质的改性作用,并对现有原油改性机理、胶体流变学、胶体化学、非电解质理论进行综合研究,提出了改变原油均相分布,使原油形成非均相胶体,形成轻馏分油包蜡晶、胶质聚集体的新构想。在保留化学剂与石蜡进行物理作用的基础上,将化学反应、配位化学引用到原油改性中,不仅改变胶质的形态,形成胶质聚集体,而且可能改变胶质对蜡晶改性剂影响。  相似文献   

16.
Highly uniform and conformal coatings can be made by the alternating exposures of a surface to vapors of two reactants, in a process commonly called atomic layer deposition (ALD). The application of ALD has, however, been limited because of slow deposition rates, with a theoretical maximum of one monolayer per cycle. We show that alternating exposure of a surface to vapors of trimethylaluminum and tris(tert-butoxy)silanol deposits highly conformal layers of amorphous silicon dioxide and aluminum oxide nanolaminates at rates of 12 nanometers (more than 32 monolayers) per cycle. This process allows for the uniform lining or filling of long, narrow holes. We propose that these ALD layers grow by a previously unknown catalytic mechanism that also operates during the rapid ALD of many other metal silicates. This process should allow improved production of many devices, such as trench insulation between transistors in microelectronics, planar waveguides, microelectromechanical structures, multilayer optical filters, and protective layers against diffusion, oxidation, or corrosion.  相似文献   

17.
Sequence-specific peptide cleavage catalyzed by an antibody   总被引:6,自引:0,他引:6  
Monoclonal antibodies have been induced that are capable of catalyzing specific hydrolysis of the Gly-Phe bond of peptide substrates at neutral pH with a metal complex cofactor. The antibodies were produced by immunizing with a Co(III) triethylenetetramine (trien)-peptide hapten. These antibodies as a group are capable of binding trien complexes of not only Co(III) but also of numerous other metals. Six peptides were examined as possible substrates with the antibodies and various metal complexes. Two of these peptides were cleaved by several of the antibodies. One antibody was studied in detail, and cleavage was observed for the substrates with the trien complexes of Zn(II), Ga(III), Fe(III), In(III), Cu(II), Ni(II), Lu(III), Mg(II), or Mn(II) as cofactors. A turnover number of 6 x 10(-4) per second was observed for these substrates. These results demonstrate the feasibility of the use of cofactor-assisted catalysis in an antibody binding site to accomplish difficult chemical transformations.  相似文献   

18.
Mussel-inspired surface chemistry for multifunctional coatings   总被引:2,自引:0,他引:2  
We report a method to form multifunctional polymer coatings through simple dip-coating of objects in an aqueous solution of dopamine. Inspired by the composition of adhesive proteins in mussels, we used dopamine self-polymerization to form thin, surface-adherent polydopamine films onto a wide range of inorganic and organic materials, including noble metals, oxides, polymers, semiconductors, and ceramics. Secondary reactions can be used to create a variety of ad-layers, including self-assembled monolayers through deposition of long-chain molecular building blocks, metal films by electroless metallization, and bioinert and bioactive surfaces via grafting of macromolecules.  相似文献   

19.
Pham TC  Kim HS  Yoon KB 《Science (New York, N.Y.)》2011,334(6062):1533-1538
Applications of zeolite films benefit from alignment of the integrated channels, but methods for film growth have nearly always introduced orientational randomization in the direction normal to the substrate. We now report facile methods to grow silicalite-1 films and pure silica beta zeolite films on substrates with straight or sinusoidal channels positioned uniformly upright at a thickness of up to 8 micrometers. Precise gel compositions and processing temperatures are critical to promote secondary growth on pre-formed oriented crystal monolayers while suppressing self-crystallization in the bulk medium. Preliminary results highlight the potential of these uniformly oriented films in the nonlinear optical response and separation of xylene isomers.  相似文献   

20.
Carbon-fluorine bonds are the strongest known single bonds to carbon and as a consequence can prove very hard to cleave. Alhough vinyl and aryl C-F bonds can undergo oxidative addition to transition metal complexes, this reaction has appeared inoperable with aliphatic substrates. We report the addition of C(sp(3))-F bonds (including alkyl-F) to an iridium center via the initial, reversible cleavage of a C-H bond. These results suggest a distinct strategy for the development of catalysts and promoters to make and break C-F bonds, which are of strong interest in the context of both pharmaceutical and environmental chemistry.  相似文献   

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