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1.
The observed basal spacings of the alkyl derivatives of boehmite, AlO(OH)1−x(OR)x, obtained by the reaction of aluminum metal or aluminum alkoxides with alcohols at 250–300 °C was only slightly affected by the population (x) of the alkyl groups (x=0.39−0.21) (Chem. Mater. 12 (2000) 55). In order to clarify the origin of this independency, the molecular mechanics (MM) calculation was carried out, and the effect of the alkyl population upon the basal spacing of the butyl derivative of boehmite, AlO(OH)1−x(OCH2CH2 CH2CH3)x, was examined in a range of x=0.00–0.30. The calculated results clearly suggested that in the range of x from 0.3 to 0.2, the boehmite derivative has the bilayer arrangement of the alkyl groups with essentially all-trans conformation. In this range, the basal spacing was only slightly affected by the population of the alkyl groups because it is determined by the most crowded part of the assembly of the alkyl chains. Since the alkyl chains are fixed to the host layers through the covalent bonding, decrease in the alkyl population does not affect essential feature of the alkyl derivatives of layered inorganics.  相似文献   

2.
We have studied self-assembled monolayers (SAMs) of asymmetric dialkyldisulfide derivatives of the form CH3-(CH2)11+m-S-S-(CH2)11-OH with m = −4, −3, 0, +2 and +4 on gold. Sub-nanoscale changes in the length of the CH3-terminated alkylchain have been used to selectively protrude one particular end group in the resulting film. The alteration of the chain length in only two methylene units already results in changes of surface properties, which have been detected with local (chemical force microscopy) and macroscopic (contact angle) techniques. In particular, advancing contact angles can be adjusted between 40° and 80°. The adhesion between a hydrophobic tip and these SAMs in water is determined by the chemical nature of the protruding end group. Chemical force microscopy, X-ray photoelectron spectroscopy and infrared reflection absorption spectroscopy have shown that these SAMs are composed of mixed, well-packed CH3- and OH-alkylthiolate branches. The surface composition ratio is close to 1:1 for all investigated SAMs.  相似文献   

3.
The vibrational analysis of allyl mercaptan has vener been published. There are two internal rotors, the SH group and the CH2SH group, in the allyl mercaptan molecule. As in the case of propylene (1), the molecule has only one plane of symmetry (Cs point group) in its most symmetrical configuration (when the thiol group lies in the plane of the vinyl group). However, microwave studies have shown that it exhibits C1 symmetry (2). The infrared and Raman spectra of allyl mercaptan have been investigated in this study. The assignment of its fundamental modes has been made based on C1 symmetry of the molecule.  相似文献   

4.
Interfacial adhesion between metals and organic polymers plays a crucial role in the mechanical properties and reliability performance of multiplayer thin film structures. To improve their interfacial bonding strength and so the reliability, the self-assembled monolayer (SAM) method is considered as an effective means. The present study is devoted to studying the effects of SAM coating on the interfacial bonding strength of the Au-epoxy and the Au-Au bonding structures through molecular dynamics (MD) simulation. Three different types of functionalized alkanethiol SAMs (SH(CH2)nX, X = CH3, OH, NH2) chemisorbed onto two different Au crystal planes, i.e., (1 0 0) and (1 1 1), are considered. The study starts from the characterization of the interfacial bonding strength of both the SAM-coated Au-epoxy and Au-Au systems, followed by the investigation of the dependence of the interfacial bonding strength on the chain lengths and tail groups of the n-alkanethiolates. A comparative study of the effects of the crystal orientation of Au substrate on the bonding strength is reported, and the elastic moduli of these SAMs through uniaxial tensile simulation are also examined. The calculated results are compared with the published experimental data, and also with each other to identify the optimal SAM candidate.Results show that the interfacial bonding strength of the SAM-coated Au-epoxy and Au-Au systems exhibits a strong dependency on the crystal orientation of Au substrate and also on the chain length of the monolayer where it tends to increase with an increasing SAM chain length. In specific, the interfacial bonding strength of the SH(CH2)nCH3 SAM-coated Au-Au joint would reach a maximal value at the chain length n = 8 while that of the SAM/epoxy interface in the SH(CH2)nCH3 SAM-coated Au-epoxy system attains a minimal value at n = 4 and becomes the maximum at n = 10, regardless of the crystal orientation of the Au substrates. Besides, the Au substrate with (1 1 1) crystal orientation would outperform the Au(1 0 0) substrate in the SAM/epoxy interfacial bonding strength of the SAM-coated Au-epoxy system while there is a totally opposite result for that of the SAM-coated Au-Au joint.  相似文献   

5.
S.J. Park  R.E. Palmer 《Surface science》2008,602(7):1492-1496
We have investigated the vibrational frequencies and excitation cross-section of self-assembled monolayers (SAMs) of 4-ethylbenzenethiol (CH3CH2(C6H4)SH) on Au(1 1 1) by high resolution electron energy loss spectroscopy (HREELS). Negative ion resonances were observed in the energy loss intensities as a function of the incident electron energy. Analysis of the C–H stretching modes indicates resonances of different energies are localised in both the ethyl and phenyl functional groups of the SAM molecules, which regulate the observed vibrational lineshape.  相似文献   

6.
Self-assembled monolayers (SAMs) of 4-trifluoromethyl-azobenzene-4′-methyleneoxy-alkanethiols (CF3– C6H4–N=N–C6H4–O–(CH2) n –SH on (111)-oriented poly-crystalline gold films on mica were examined by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The spectra are analyzed with the help of density-functional-theory calculations of the isolated molecule. Only one doublet is detected in the sulphur 2p spectra of the investigated SAMs, consistent with a thiolate bond of the molecule to the gold surface. The C 1s XP spectra and the corresponding XAS π * resonance exhibit a rich structure which is assigned to the carbon atoms in the different chemical surroundings. Comparing XPS binding energies of the azobenzene moiety and calculated initial-state shifts reveals comparable screening of all C 1s core holes. While the carbon 1s XPS binding energy lies below the π *-resonance excitation-energy, the reversed order is found comparing core ionization and neutral core excitation of the nitrogen 1s core-hole of the azo group. This surprising difference in core-hole binding energies is interpreted as site-dependent polarization screening and charge transfer among the densely packed aromatic moieties. We propose that a quenching of the optical excitation within the molecular layer is thus one major reason for the low trans to cis photo-isomerization rate of azobenzene in aromatic-aliphatic SAMs.  相似文献   

7.
A self-assembled monolayers (SAMs) of (3-mercaptopropy) trimethoxysilane (3-MPT) chemisorbed on silver surface was chemically modified by 1-octadecanethiol (C18H37SH) (to form self-assembled mixed-monolayer (SAMM)) and the co-polymer of N-vinylcarbazole and methyl methacrylate ester to form complex self-assemblied film (CSAF). The combinative state of interface between SAMs (or SAMM) and co-polymer were characterized by dynamic mechanical thermal analysis (DMTA). The thickness of film on Ag was characterized by X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) measurements in 10% NaOH aqueous solution with the silver surface and covered with film indicated that 3-MPT SAMs modified with C18H37SH and then with co-polymer have higher capability against oxidation.  相似文献   

8.
Photoelectron spectra of some thiocyanates (RSCN, R = CH3, C2H5, n-C4H9), isocyanates (RNCO, R = C2H5, n-C4H9) and isothiocyanates (RNCS, R = C2H5, n-C4H9) have been measured, to study interactions between nonbonding and π orbitals, mainly localized on the SCN, NCO or NCS fragments. The spectral interpretation of CH3SCN is based on semiempirical CNDO/S calculations, sum-rule considerations, and intensity differences between He(I) and HE(II) spectra. For the larger molecules, comparison of the spectra is used as an aid in the interpretation. In a number of aromatic isocyanates (o?, m?, p-tolylisocyanate and m?, p-chlorophenylisocyanate), interactions between the isocyanate group and the highest occupied π and σ orbitals of the phenyl ring are studied. Spectra are assigned on the basis of semiempirical INDO/S calculations.  相似文献   

9.
A simple method was developed for the preparation of cyano- and carboxyl-terminated alkylsiloxane monolayers on the hydroxylated surface of the SiO2/Si substrate through using adsorption and hydrolysis reaction of a short-chain 2-cyanoethyl triethoxysilane [(CH3CH2O)3SiCH2CH2CN]. The contact angle and the X-ray photoelectron spectroscopy (XPS) measurements have proved that the cyano terminal group indeed formed on the substrate and was transformed into the carboxylic terminal group after hydrolysis. The ellipsometry shows the presence of an intact monolayer with thickness of around 0.7 nm before and during the hydrolysis reaction. The surface morphology was observed with atomic force microscopy (AFM) imaging. Those all indicate that uniform and ordered self-assembled monolayers (SAMs) were formed on the substrate.  相似文献   

10.
By means of coupled cluster theory and correlation consistent basis sets we investigated the thermochemistry of dimethyl sulphide (DMS), dimethyl disulphide (DMDS) and four closely related sulphur-containing molecules: CH3SS, CH3S, CH3SH and CH3CH2SH. For the four closed-shell molecules studied, their enthalpies of formation (EOFs) were derived using bomb calorimetry. We found that the deviation of the EOF with respect to experiment was 0.96, 0.65, 1.24 and 1.29 kcal/mol, for CH3SH, CH3CH2SH, DMS and DMDS, respectively, when ΔHf,0 = 65.6 kcal/mol was utilised (JANAF value). However, if the recently proposed ΔHf,0 = 66.2 kcal/mol was used to estimate EOF, the errors dropped to 0.36, 0.05, 0.64 and 0.09 kcal/mol, respectively. In contrast, for the CH3SS radical, a better agreement with experiment was obtained if the 65.6 kcal/mol value was used. To compare with experiment avoiding the problem of the ΔHf,0 (S), we determined the CH3–S and CH3–SS bond dissociation energies (BDEs) in CH3S and CH3SS. At the coupled cluster with singles doubles and perturbative triples correction level of theory, these values are 48.0 and 71.4 kcal/mol, respectively. The latter BDEs are 1.5 and 1.2 kcal/mol larger than the experimental values. The agreement can be considered to be acceptable if we take into consideration that these two radicals present important challenges when determining their EOFs. It is our hope that this work stimulates new studies which help elucidate the problem of the EOF of atomic sulphur.  相似文献   

11.
Fourier transform surface enhanced Raman spectrometer is used to characterize Ω-mercaptoalkanols (HO(CH2)nSH, n=2, 6) chemisorption on silver surface from their aqueous solution of different pH values.  相似文献   

12.
The propensity of n-C60 to aggregate and deposit will play a key role in determining its longevity in aquatic systems, and therefore the potential exposure and risk presented by these colloids. We consider the origin of n-C60 stability and compare the aggregation and deposition characteristics of n-C60 under conditions of variable ionic strength using an indifferent electrolyte. Relatively weak electrolyte solutions (0.001 M) were observed to destabilize suspensions of n-C60 resulting in the formation of settleable aggregates. This behavior supports the hypothesis that the stabilizing mechanism for n-C60 clusters is electrostatic in origin. Similarly, the deposition of n-C60 in porous media increased as ionic strength increased. These observations suggest that under some conditions present in natural aquatic systems, these materials may have limited mobility as they form large aggregates that may settle out of suspension or deposit on surfaces. These phenomena may, at least partially, offset any risk presented by n-C60 toxicity due to a reduced potential for exposure.  相似文献   

13.
The adsorption and desorption of butanethiol (CH3(CH2)3SH: C4), hexanethiol (CH3(CH2)5SH: C6) and octanethiol (CH3(CH2)7SH: C8) on Au (1 1 1) under vacuum condition have been studied by temperature programmed desorption (TPD). Desorptions of thiolate radical species were observed for C6 and C8. Connecting the desorption temperatures of parent thiols from the first layer and that of hydrogen, we were able to find a condition for thiolate radicals to be desorbed from the surface.  相似文献   

14.
Electron impact energy loss spectra at impact energies of 100 eV and 50 eV and a scattering angle of 2 degrees are presented for alkyl derivatives of H2O and related compounds. Spectra of H2O, CH3OH, CH3OCH3, ethylene oxide, CH3CH2OH, (CH3)2CHOH, (CH3)3C C2H5OC2H5 and tetrahydrofuran are tentatively assigned using derived term values and ionization potentials from photoelectron spectrosc Substituent effects on Rydberg orbital energies are discussed using Taft σ* values.  相似文献   

15.
Experimental data for the diamagnetic susceptibility of two series of monodisperse normal diamides [R′─HNOC─(CH2)n/2─(CH2)n/2─CONH─R′] and ketodiamides (R′─HNOC─(CH2)n/2─CO─(CH2)n/2─CONH─R′] with R′═CH3─(CH2)s─ranging between n=2 and 8 in the solid state are reported. For the normal diamides the molecular susceptibility χM increases linearly with n, though the χM values are lower than Pascal data derived from the additivity of atomic susceptibilities. For the ketodiamides, χM is longer a linear function of n. Thus, while even ketodiamides show χM values near to Pascal data the odd members present an abnormally high diamagnetism. The study of the melting points for the two series supports the trend of diamagnetic data, thus stressing the anomalous behavior of the odd ketodiamides which present very low melting temperatures. The x-ray long spacings of the two diamide series have been quantitatively correlated with various chain inclined crystal forms. However, while normal diamides show a zigzag extended chain conformation with formation of hydrogen bonded sheets (two hydrogen bonds per molecule), ketodiamides adopt a twisted conformation which seems to contribute to the enhancement of diamagnetism. In addition, the long periods of the odd ketodiamides reveal tilted twisted molecular structures which are associated with the observed anomalous elevation of χM and depression of melting points.  相似文献   

16.
Self-assembled monolayers (SAMs) of n-dodecanethiol (C12H25SH) and n-dodecaneselenol (C12H25SeH) on polycrystalline copper have been elaborated with the purpose of achieving densely packed and crystalline-like assemblies. By combining the surface sensitivity of polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) and sum-frequency generation spectroscopy (SFG), the effect of the self-assembly time (15 min, 30 min, 1 h, 2 h and 24 h) on the formation of n-dodecanethiol and n-dodecaneselenol monolayers on untreated and electrochemically reduced polycrystalline copper has been investigated. On electrochemically reduced copper, PM-IRRAS spectroscopy shows that both molecules are able to form well organized layers. SFG spectroscopy indicates that the C12H25SeH SAMs are slightly better ordered than those achieved with C12H25SH. On untreated copper, the two molecules lead to different film organizations. Both PM-IRRAS and SFG indicate that C12H25SH SAMs are of the same film quality as those obtained on electrochemically reduced copper. On the contrary, C12H25SeH monolayers are invariably poorly organized at the molecular level.  相似文献   

17.
Permeation and sorption of methane and n-butane gases in polydimethylsiloxane (PDMS) and diphenylsiloxane-dimethylsiloxane (DPh-DM) block copolymer membranes were studied at room temperature and different upstream pressures. The membranes were prepared via room temperature vulcanization of vinyl terminated siloxanes through platinum catalyzed hydrosilylation reactions by mixing stoichiometric amounts of polymer, crosslinker, and catalyst, and casting of the mixture solutions with hexane. Composite membranes of polysiloxanes on a polyacrylonitrile microporous support were synthesized for permeation experiments and single layer dense films were used in sorption experiments. The effect of upstream pressure on permeability, solubility, and diffusivity of these membranes was evaluated. It was found that selectivity of the DPh-DM copolymer membrane for n-C4H10 relative to CH4 was up to 19% higher than that in PDMS membrane. Both solubility and diffusivity selectivities had positive contributions in permselectivity improvement. The improvement in selectivity was attained with less than a 6% decrease in permeability of n-C4H10. Up to 11% improvement in selectivity was also obtained in mixed gas experiment.  相似文献   

18.
Properties of as prepared or nanoengineered III-V semiconductor surfaces provide attractive means for photonic detection of different adsorbants from surrounding gaseous or liquid environments. To be practical, this approach requires that the surface is made selectively sensitive (functionalized) to targeted species. In addition, such surface has also to stay stable over extended period of time to make it available for rapid testing. Numerous reports demonstrate attractive properties of GaAs for sensing applications. One of the most fundamental issues relevant to these applications concerns the ability to functionalize chemically, or biologically, the surface of GaAs. The most studied method of GaAs surface functionalization is based on formation of self-assembled monolayers (SAMs) of various n-alkanethiols, HS-(CH2)n-T (T = CH3, COOH, NH2, etc.). In spite of multi-year research concerning this issue, it has only been recently that a comprehensive picture of SAMs formation on GaAs and an understanding of the natural limitation of the SAM-GaAs interface in some bio-chemical sensing architectures has begun to emerge.  相似文献   

19.
Temperature-dependent Mössbauer experiments have been carried out to examine the lattice-dynamic properties of tin atoms in complexes of the type (n-C n H2n+1NH3)2SnCl6 (6 n 12). The temperature dependence of the area intensity of Mössbauer lines for the studied complexes are correlated to the motion of long alkyl chains. Solid-solid phase transitions were clearly found in all the complexes above room temperature, accompanied by an increase in the interlayer spacing (6n 18). The transition temperature and transition entropy increase linearly with the number of carbon atoms in alkyl chains.  相似文献   

20.
Conformational energy calculations were employed to determine the effect of hydrogen-fluorine defects on the conformation of the polytrifluoroethylene chain. It was determined that the 31 helix was energetically favored for all but the highly syndiotactic polymers, which favored the all-trans conformation. The incorporation of head-to-head linkages into the polymer chain increased the Conformational energy of the 31 helix while the Conformational energy of the all-trans form decreased. The energies of these two conformations did not equalize until the head-to-head concentration reached 20 to 30%, depending on the tacticity of the polymer. The trans, gauche, trans, gauche' conformation was also determined to be energetically favorable for the syndiotactic polymer, but both tacticity defects and head-to-head linkages caused a rapid increase in the Conformational energy. This was, therefore, concluded to be unlikely structure when chemical defects are incorporated into the polymer chain.  相似文献   

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