How to make water run uphill

A surface having a spatial gradient in its surface free energy was capable of causing drops of water placed on it to move uphill. This motion was the result of an imbalance in the forces due to surface tension acting on the liquid-solid contact line on the two opposite sides ("uphill" or "downhill") of the drop. The required gradient in surface free energy was generated on the surface of a polished silicon wafer by exposing it to the diffusing front of a vapor of decyltrichlorosilane, Cl(3)Si(CH(2))(9)CH(3). The resulting surface displayed a gradient of hydrophobicity (with the contact angle of water changing from 97 degrees to 25 degrees ) over a distance of 1 centimeter. When the wafer was tilted from the horizontal plane by 15 degrees , with the hydrophobic end lower than the hydrophilic, and a drop of water (1 to 2 microliters) was placed at the hydrophobic end, the drop moved toward the hydrophilic end with an average velocity of approximately 1 to 2 millimeters per second. In order for the drop to move, the hysteresis in contact angle on the surface had to be low (相似文献   

Free energy and temperature dependence of electron transfer at the metal-electrolyte interface

The rate constant of the electron-transfer reaction between a gold electrode and an electroactive ferrocene group has been measured at a structurally well-defined metal-electrolyte interface at temperatures from 1 degrees to 47 degrees C and reaction free energies from -1.0 to +0.8 electron volts (eV). The ferrocene group was positioned a fixed distance from the gold surface by the self-assembly of a mixed thiol monolayer of (eta(5)C(5)H(5))Fe(eta(5)C(5)H(4))CO(2)(CH(2))(16)SH and CH(3)(CH(2))(15)SH. Rate constants from 1 per second (s(-1)) to 2 x 10(4) s(-1) in 1 molar HClO(4) are reasonably fit with a reorganization energy of 0.85 eV and a prefactor for electron tunneling of 7 x 10(4) s(-1) eV(-1). Such self-assembled monolayers can be used to systematically probe the dependence of electron-transfer rates on distance, medium, and spacer structure, and to provide an empirical basis for the construction of interfacial devices such as sensors and transducers that utilize macroscopically directional electron-transfer reactions.     

Self-Assembly of n-Alkyl Thiols as Disulfides on Au(111)

A grazing incidence x-ray diffraction study of CH(3)(CH(2))(9)SH self-assembled on the (111) surface of gold revealed a disulfide head group structure, which provides a context in which to understand the structure and self-assembly process of this widely studied system. The structure consists of a nearly hexagonal two-dimensional arrangement of the hydrocarbon chains with a dimerization of the sulfur head groups (accommodated through a gauche bond), resulting in a S-S spacing of 2.2 angstroms. These results demonstrate the importance of internal molecular degrees of freedom in the templating of "soft" organic materials on inorganic substrates.     

Molecular-Level Control over Surface Order in Self-Assembled Monolayer Films of Thiols on Gold

Long-chain omegahydroxyalkanethiols [HS(CH(2))nOH] coordinate to gold surfaces through the sulfur atom and produce ordered, hydrophilic monolayers in which the hydroxyl groups are exposed at the outer surface. Coadsorption of two omega-hydroxyalkanethiols of different chain lengths n resulted in the formation of a monolayer having a disordered surface region that was markedly less hydrophilic than the homogeneous, hydroxylic surface formed from either pure compound. By controlling the composition of the monolayer, it was also possible to control simultaneously the degree of order in the surface and its hydrophilicity. In the monolayers containing a mixture of alkanethiol components, these components apparently did not phase-segregate into macroscopic islands, but were dispersed on a molecular scale. assistance and many useful discussions.     

自身阳离子型松香施胶剂及其施胶性能

以两条路线分别合成了自身阳离子型的N-(3-松香酰氧-2-羟)丙基-N,N,N-三甲基氯化铵和N-(3-松香酰氧-2-羟)丙基-N,N,N-三乙基氯化铵,并对其性能进行了简单分析和评价。结果表明,虽然这两种松香季铵盐具有较高的Zeta电位,能够不依赖于矾土的“架桥”作用而吸附于纸张的纤维表面,但是由于在合成中向松香分子上引入了较强的亲水基团,使其疏水性能下降,成纸施胶度较低,且耐老化性能略有下降,加上合成过程使成本增加,松香季铵盐不适于作施胶剂产品主要成分。     

X-ray diffraction and computation yield the structure of alkanethiols on gold(111)

The structure of self-assembled monolayers (SAMs) of long-chain alkyl sulfides on gold(111) has been resolved by density functional theory-based molecular dynamics simulations and grazing incidence x-ray diffraction for hexanethiol and methylthiol. The analysis of molecular dynamics trajectories and the relative energies of possible SAM structures suggest a competition between SAM ordering, driven by the lateral van der Waals interaction between alkyl chains, and disordering of interfacial Au atoms, driven by the sulfur-gold interaction. We found that the sulfur atoms of the molecules bind at two distinct surface sites, and that the first gold surface layer contains gold atom vacancies (which are partially redistributed over different sites) as well as gold adatoms that are laterally bound to two sulfur atoms.     

Dianion Stabilization by (M(C5(CH3)5)2)+: Theoretical Evidence for a Localized Ring in (DDQ)2-

Organic dianions have been stabilized by (M(C(5)(CH(3))(5))(2))(+), where M is iron or cobalt. This has allowed the structural and spectroscopic characterization of these dianions. The structure of (M(C(5)(CH(3))(5))(2))(2)(+) (DDQ)(2-), where DDQ is 2,3-dichloro-5,6-dicyanobenzoquinone, has been determined by x-ray crystallography. The structure of (DDQ)(2-)is consistent with ab initio molecular orbital calculations that suggest a localizd as opposed to a delocalized (aromatic) ring structure.     

Deep UV photochemistry of chemisorbed monolayers: patterned coplanar molecular assemblies

Deep ultraviolet (UV) irradiation is shown to modify organosilane self-assembled monolayer (SAM) films by a photocleavage mechanism, which renders the surface amenable to further SAM modification. Patterned UV exposure creates alternating regions of intact SAM film and hydrophilic, reactive sites. The exposed regions can undergo a second chemisorption reaction to produce an assembly of SAMs in the same molecular plane with similar substrate attachment chemistry. The UV-patterned films are used as a template for selective buildup of fluorophores, metals, and biological cells.     

Lanthanide complexes as nuclear magnetic resonance structural probes: paramagnetic anisotropy of shift reagent adducts

Magnetic anisotropy measurements on single crystals of a series of paramagnetic 8-coordinate lanthanide shift reagent adducts of the type Ln[(CH(3))(3)CCOCHCOC(CH(3))(3)(4-CH(3)C(5)H(1)N)(2) have been made for the following lanthanides: praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, and ytterbium. The susceptibility tensors are highly anisotropic and nonaxial. Dipolar nuclear magnetic resonance shifts evaluated from the solid-state date are in satisfactory agreement with the solution results.     

Chemical modification of the photoluminescence quenching of porous silicon

The photoluminescence of porous silicon can be quenched by adsorbates, and the degree of quenching can be tuned by chemical derivatization of the porous silicon surface. Thus, as-prepared porous silicon has a hydrophobic, hydrogen-terminated surface, and the photoluminescence is strongly quenched by ethanol and weakly quenched by water. Mild chemical oxidation (iodine followed by hydrolysis) produces a hydrophilic porous silicon surface. Photoluminescence from this hydrophilic material is quenched to a lesser extent by ethanol and to a greater extent by water, relative to the original surface. This demonstrates that the visible luminescence from porous silicon is highly surface-sensitive, and the surface interactions can be tuned by specific chemical transformations.     

福建省长汀县河田盆地区近35年来地表裸土变化的遥感时空分析

福建省长汀县河田盆地区是中国南方最典型的红壤水土流失区之一,当地人民和各级政府一直为治理该区的水土流失进行着不懈的努力.利用遥感技术对该区1976年以来地表裸土分布的时空变化进行了分析,基于所提出的双重遥感指数法对该区的裸土信息进行提取,查明了该区地表裸土分布的时空变化情况.研究表明,该区近35年的治理已大大减轻了地表的裸露程度,地表裸土面积从1976年的159.17 km2锐减到2010年的51.98 km2.在3个不同的观察时间段里,裸土面积的变化呈现逐次减少、减速加快的趋势,客观地反映了该区水土流失治理的3个重要历史时期和政策所产生的效应.     

A Molecular Ferromagnet with a Curie Temperature of 6.2 Kelvin: [Mn(C5(CH3)5)2]+[TCNQ]-

The study of magnetic phase transitions in insulating molecular solids provides new insights into mechanisms of magnetic coupling in the solid state and into critical phenomena associated with these transitions. Only a few such materials are known to display cooperative magnetic properties. The use of high-spin molecular components would enhance intermolecular spin-spin interactions and thus a series of chargetransfer (CT) salts have been synthesized that utilize the spin S = 1 molecular cation, [Mn(C(5)(CH(3))(5))(2)](+) (decamethylmanganocenium). The structure and cooperative magnetic behavior of [Mn(C(5)(CH(3))(5))(2)](+)[TCNQ(-) (decamethylmanganocenium 7,7,8,8-tetracyano-p-quinodimethanide) are reported. This salt is a bulk molecular ferromagnet with the highest critical (Curie) temperature (T(c) = 6.2 K) and coercive field (3.6 x 10(3) gauss), yet reported for such a material.     

Efficient dehydrogenation of formic acid using an iron catalyst

Hydrogen is one of the essential reactants in the chemical industry, though its generation from renewable sources and storage in a safe and reversible manner remain challenging. Formic acid (HCO(2)H or FA) is a promising source and storage material in this respect. Here, we present a highly active iron catalyst system for the liberation of H(2) from FA. Applying 0.005 mole percent of Fe(BF(4))(2)·6H(2)O and tris[(2-diphenylphosphino)ethyl]phosphine [P(CH(2)CH(2)PPh(2))(3), PP(3)] to a solution of FA in environmentally benign propylene carbonate, with no further additives or base, affords turnover frequencies up to 9425 per hour and a turnover number of more than 92,000 at 80°C. We used in situ nuclear magnetic resonance spectroscopy, kinetic studies, and density functional theory calculations to explain possible reaction mechanisms.     

A Synchrotron X-ray Study of a Solid-Solid Phase Transition in a Two-Dimensional Crystal

A measurement and interpretation on a molecular level of a phase transition in an ordered Langmuir monolayer is reported. The diagram of surface pressure (pi) versus molecular area of a monolayer of chiral (S)-[CF(3)-(CF(2))(9)-(CH(2))(2)-OCO-CH(2)-CH (NH(3)(+))CO(2)(-)] over water shows a change in slope at about pi(s)= 25 millinewtons per meter. Grazing-incidence x-ray diffraction and specular reflectivity measurements indicate a solid-solid phase transition at pi(s). The diffraction pattren at low pressures reveals two diffraction peaks of equal intensities, with lattice spacings d of 5.11 and 5.00 angstroms; these coalesce for pi >/=pi(s). Structural models that fit the diffraction data show that at pi> pi(s) the molecules pack in a two-dimensional crystal with the molecules aligned vertically. At pi < pi(s) there is a molecular tilt of 16 degrees +/- 7 degrees . Independent x-ray reflectivity data yield a tilt of 26 degrees +/- 7 degrees . Concomitant with the tilt, the diffraction data indicate a transition from a hexagonal to a distorted-hexagonal lattice. The hexagonal arrangement is favored because the -(CF(2))(9)CF(3) moiety adopts a helical conformation. Compression to 70 millinewtons per meter yields a unit cell with increased crystallinity and a coherence length exceeding 1000 angstroms.     

Molecular structure of an unusual organoactinide hydride complex determined solely by neutron diffraction

The structure of an unusual organometallic complex, {Th[(CH(3))(5)C(5)](2) H(micro-H)}(2) . C(6)H(5)CH(3), has been determined from neutron diffraction data, using only the direct-methods program MULTAN. Besides providing accurate metrical information on the first organometallic actinide hydride complex, these results have general and far-reaching implications concerning the complexity and size of crystal structures that can be elucidated solely on the basis of neutron diffraction data.     

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]{middle dot}4H2O

Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH(3))(2)NH(2)]K(4)[V(10)O(10)(H(2)O)(2)(OH)(4)(PO(4))(7)].4H(2)O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P(5+). These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH(3))(2)NH(2)(+) and K(+) cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P4(3) with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.     

Synthesis and structure of a terminal uranium nitride complex

The terminal uranium nitride linkage is a fundamental target in the study of f-orbital participation in metal-ligand multiple bonding but has previously eluded characterization in an isolable molecule. Here, we report the preparation of the terminal uranium(V) nitride complex [UN(Tren(TIPS))][Na(12-crown-4)(2)] {in which Tren(TIPS) = [N(CH(2)CH(2)NSiPr(i)(3))(3)](3-) and Pr(i) = CH(CH(3))(2)} by reaction of the uranium(III) complex [U(Tren(TIPS))] with sodium azide followed by abstraction and encapsulation of the sodium cation by the polydentate crown ether 12-crown-4. Single-crystal x-ray diffraction reveals a uranium-terminal nitride bond length of 1.825(15) angstroms (where 15 is the standard uncertainty). The structural assignment is supported by means of (15)N-isotopic labeling, electronic absorption spectroscopy, magnetometry, electronic structure calculations, elemental analyses, and liberation of ammonia after treatment with water.     

Patterned condensation figures as optical diffraction gratings

Heterogeneous, patterned surfaces comprising well-defined hydrophobic and hydrophilic regions and having micrometer-scale periodicities were prepared by patterning the adsorption of omega-functionalized alkanethiolates in self-assembled monolayers (SAMs) on gold. Condensation of water on such surfaces resulted in drops that followed the patterns in the SAMs. These patterned condensation figures (CFs) acted as optical diffraction gratings for reflected (or transmitted) light from a helium-neon laser (wavelength of 632.8 nanometers). Under an atmosphere of constant relative humidity, the development of the condensation figure was monitored quantitatively, as the temperature of the surface was lowered, by following the change in intensity of a first-order diffraction spot. This experimental technique may be useful in the development of new types of optical sensors that respond to their environment by changing the reflectivity of patterned regions and for studying phenomena such as drop nucleation, contact angle hysteresis, and spontaneous dewetting and break-up of thin liquid films.     

Structural aspects of reversible molecular oxygen uptake

The system IrX(CO)[P(C(6)H(5))(3)](2) in benzene solution adds mo lecular oxygen reversibly if X is chlorine and irreversibly if X is iodine. The crystal structure of the complex IrIO(2)(CO)[P(C(6)H(5))(3)](2) * CH(2)Cl(2) is reported here and compared with a previous study of the structure of IrClO(2)(CO)[P(C(6)H(5))(3)](2). The O-O bond length is 1.47 +/- 0.02 angstroms in the irreversibly oxygenated iodo-compound and 1.30 +/- 0.03 angstroms in the reversibly oxygenated chloro compound.     

雾滴体积和测量时间与雾滴接触角的关系

农药喷雾质量直接关系到药效的发挥,喷雾液滴与靶标的接触角可以用来表征喷雾质量的好坏,并可说明喷洒液的表面张力与靶标的表面张力是否匹配。针对喷雾液滴在靶标上接触角测量的重现性不佳等问题,以玻璃和石蜡模拟靶标表面,研究了去离子水在亲水和疏水靶标表面上液滴体积(重力)和测量时间对接触角测量的影响,结果表明:液滴体积越大接触角越小,这种趋势在亲水表面比疏水表面上更突出,测量时体积可分别选择在0.5~1μl和1~5μl;液滴滴下30~50 s后与固体表面基本达到平衡,对接触角测量的准确度影响较小。