Cavitand-functionalized SWCNTs for N-methylammonium detection

Single-walled carbon nanotubes (SWCNTs) have been functionalized with highly selective tetraphosphonate cavitand receptors. The binding of charged N-methylammonium species to the functionalized SWCNTs was analyzed by X-ray photoelectron spectroscopy and confirmed by (31)P MAS NMR spectroscopy. The cavitand-functionalized SWCNTs were shown to function as chemiresistive sensory materials for the detection of sarcosine and its ethyl ester hydrochloride in water with high selectivity at concentrations as low as 0.02 mM. Exposure to sarcosine and its derivative resulted in an increased conductance, in contrast to a decreased conductance response observed for potential interferents such as the structurally related glycine ethyl ester hydrochloride.     

Lithographically-defined 3D porous networks as active substrates for surface enhanced Raman scattering

Interferometric lithographically fabricated porous carbon acts as active substrates for Surface Enhanced Raman Scattering (SERS) applications with enhancement factors ranging from 7 to 9 orders of magnitude.     

Fine-tuning in size and surface morphology of rod-shaped polypyrrole using porous silicon as template

We investigated electropolymerization of polypyrrole into porous silicon template. We used three types of porous silicon templates, i.e., porous silicon with ordered macro pores, medium-sized pores and meso pores. Polypyrrole was electropolymerized from pore bottoms to pore tops in all the porous silicon templates. After removal of the templates we obtained rod-shaped polypyrrole arrays. Changing the porous silicon templates easily controlled the size of the rod-shaped polypyrrole. We also used dendritic medium-sized pores for template, and then polypyrrole rod having a roughened surface was obtained. Here we demonstrated that the size and the surface morphology of polypyrrole rod were easily tuned using porous silicon.     

TOF-SIMS and FT-IR investigations of surface modified silicon wafers — porous silicon

Surface modification of silicon wafers by anodic etching in hydrofluoric acid results in the formation of porous silicon layers consisting of nanocrystallites covered with SiH bonds. A combination of high resolution Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) and Fourier Transform Infrared Spectroscopy (FT-IR) was used to study the surface chemistry of this new material.     

Affinity mass spectrometry from a tailored porous silicon surface

The development of chemically stable porous silicon (pSi) materials for DIOS (Desorption/Ionization on Silicon) mass spectrometry, covalent linkers cleaved in the DIOS laser pulse, and efficient methods for bond formation to immobilized species, allows for on-chip affinity purification and mass detection.     

IR detection of NO2 using p+ porous silicon as a high sensitivity sensor

Mesoporous silicon doped with 3.0 x 10(19) B atoms cm-3 (p(+)-type) is an insulating material which dramatically increases its electrical conductivity when exposed to traces of gaseous NO2; nitrogen dioxide chemisorption at the surface generates carriers, the population of which is readily evaluated through the intensity of IR absorption.     

Functionalized porous silicon surfaces as MALDI-MS substrates for protein identification studies

Alkyl monolayer modified porous silicon functional surfaces are employed for selective binding of proteins from complex mixtures (through washing of the deposited mixture spot using appropriate buffer) and MALDI-MS is used to detect the components retained on the surface.     

Study of porous silicon nanostructures as hydrogen reservoirs

The amount of hydrogen present in porous silicon (PS) nanostructures is analyzed in detail. Concentration of atomic hydrogen chemically bound to the specific surface of PS is quantitatively evaluated by means of attenuated total reflection infrared (ATR-IR) spectroscopy and temperature-programmed desorption (TPD) spectroscopy. The concentration values are correlated to the PS nanoscale morphology. In particular, the influence of porosity, silicon nanocrystallite dimension, and shape on hydrogen concentration values is described. Hydrogen concentrations in fresh, aged, as well as in chemically and thermally treated PS layers are measured. Maximal hydrogen concentration of 66 mmol/g is detected in nanoporous layers with high (>95%) porosity consisting of nanocrystallites with dimensions of about 2 nm. Mass energy density that can be potentially obtained from this amount of hydrogen through a low-temperature fuel cell is estimated to be about 2176 W-h/kg and is found to be comparable with other substances containing hydrogen, such as hydride materials and methanol, which are usually used as hydrogen reservoirs.     

Covalently derivatized NTA microarrays on porous silicon for multi-mode detection of His-tagged proteins

Porous silicon(PSi)was applied as a supporting substrate for stepwise covalent derivatization of undecylenic acid, N-hydroxysuccinimidyl ester(NHS-ester)and nitrilotriacetic acid(NTA).By taking the advantages of porous silicon as a supporting matrix such as high surface area to volume ratio,infrared transparency,porous semiconductors for laser desorption/ionization mass spectroscopy,and low fluorescence background,a multi-mode detection biochip prototype can be realized. We prepared such a protein microarra...     

Copper supported on phenanthroline-functionalized porous polymer as an active catalyst for the oxidative carbonylation of methanol

Porous organic polymer has recently attracted tremendous interest because of its potential to combine the best features of homogeneous and heterogeneous catalysts. In this study, copper supported on phenanthroline-functionalized porous polymer (Cu@PCP-Phen) was prepared by a co-polymerization method and used as a heterogeneous catalyst for dimethyl carbonate synthesis via the oxidative carbonylation of methanol. The catalyst was characterized by N₂ adsorption, scanning electron microscopy, transmission electron microscopy, ¹³C solid-state nuclear magnetic resonance, and X-ray photoelectron spectroscopy, which suggested that it possessed a big surface area, hierarchical porous structure, and strong electron-donating effect toward copper species. The Cu@PCP-Phen catalyst showed high catalytic activity, which was significantly higher than those achieved with Cu-based catalysts under similar reaction conditions. In addition, the catalyst can be easily separated and reused at least six times with only a slight decrease in activity. The salient features of this protocol are the simplicity in handling of the catalyst, high catalytic activity, excellent selectivity, low copper leaching, and good catalyst recyclability.     

Lantibiotics as surface active agents for biomedical applications

The unique physical structure of lantibiotics, (e.g. double bonds, thioethers rings, and unusual amino acid residues), makes these antimicrobial peptides highly reactive, and thus different in mode-of-action from clinical antibiotics. Members of the lantibiotic group have been successfully tested against pathogenic organisms for decades. Some lantibiotics have been studied for use in treating skin infections, and several have been characterized for their anti-viral activity. In addition to their antimicrobial capabilities, lantibiotics possess amphiphilic characteristics, making them potentially valuable as emulsifiers in drug formulations. The small size and surface activity of these peptides also may allow them to enhance the transport of therapeutic compounds across cell membranes. Over 30 lantibiotics are presently known, and more are being discovered each year. With the rising incidence of resistant bacteria, lantibiotics offer considerable potential as safe, antimicrobial barriers for use on synthetic material surfaces, as emulsifiers in formulation of hydrophobic drugs, and as absorption promoters for selected compounds across mucosal membranes. The major hindrance to research in this area is that lantibiotics are difficult to obtain. But with improved methods for production and purification of these unusual antimicrobial agents, the promise of cost-effective application of lantibiotics may eventually be realized.     

Atomic and electronic structure of the surface of porous silicon layers

Atomic and electronic structure of the surface layers of porous silicon was studied by the methods of the near fine structure spectroscopy at the edge of X-ray absorption and ultrasoft X-ray emission spectroscopy. The thickness of the oxide layer and the degree of distortion of silicon-oxygen tetrahedra in this layer were estimated. The thickness of the surface oxide layer on the amorphous layer covering the nanocrystals of porous silicon that was kept during one year is several times greater than the thickness of the natural oxide in the single crystal silicon wafers. Distortion of the silicon-oxygen tetrahedron, the basic structural units of the silicon oxide, is accompanied by elongation of Si-O bonds and an increase in the Si-O-Si bond angles.     

High surface area of porous silicon drives desorption of intact molecules

The surface structure of porous silicon used in desorption/ionization on porous silicon (DIOS) mass analysis is known to play a primary role in the desorption/ionization (D/I) process. In this study, mass spectrometry and scanning electron microscopy (SEM) are used to examine the correlation between intact ion generation with surface ablation and surface morphology. The DIOS process is found to be highly laser energy dependent and correlates directly with the appearance of surface ions (Si(n)(+) and OSiH(+)). A threshold laser energy for DIOS is observed (10 mJ/cm(2)), which supports that DIOS is driven by surface restructuring and is not a strictly thermal process. In addition, three DIOS regimes are observed that correspond to surface restructuring and melting. These results suggest that higher surface area silicon substrates may enhance DIOS performance. A recent example that fits into this mechanism is the surface of silicon nanowires, which has a high surface energy and concomitantly requires lower laser energy for analyte desorption.     

Dual silane surface functionalization for the selective attachment of human neuronal cells to porous silicon

Porous silicon (pSi) surfaces were chemically micropatterned through a combination of photolithography and surface silanization reactions. This patterning technique produces discretely defined regions on a pSi surface functionalized with a specific chemical functionality, and the surrounding surface displays a completely different functionality. The generated chemical patterns were characterized by a combination of IR microscopy and the conjugation of two different fluorescent organic dyes. Finally, the chemically patterned pSi surface was used to direct the attachment of neuronal cells to the surface. This patterning strategy will be useful for the development of high-throughput platforms for investigating cell behavior.     

金属离子在多孔硅表面和吸附与电镀过程中金属在多孔硅表面的淀积

刚制备的多孔硅与金属盐溶液接触会产生金属离子在多孔硅表面和吸附现象。实验显示这一现象只发生在新鲜的多孔硅表面, 而存放一月以后的样品不具备此性质。文中把这一现象归因于新鲜的多孔硅表面电子的富集, 溶液中金属离子从多孔硅表面获得电子而附着。多孔硅表面电镀金属过程中, 一定电压下电镀电流密度在起始阶段逐渐下降, 可以用一个指数关系式较好地描述, 在本文中有一个唯象模型予以解释。     

金属离子在多孔硅表面和吸附与电镀过程中金属在多孔硅表面的淀积

刚制备的多孔硅与金属盐溶液接触会产生金属离子在多孔硅表面和吸附现象。实验显示这一现象只发生在新鲜的多孔硅表面, 而存放一月以后的样品不具备此性质。文中把这一现象归因于新鲜的多孔硅表面电子的富集, 溶液中金属离子从多孔硅表面获得电子而附着。多孔硅表面电镀金属过程中, 一定电压下电镀电流密度在起始阶段逐渐下降, 可以用一个指数关系式较好地描述, 在本文中有一个唯象模型予以解释。     

Chemical modification of a porous silicon surface induced by nitrogen dioxide adsorption

The effect of gaseous and liquid nitrogen dioxide on the composition and electronic properties of porous silicon (PS) is investigated by means of optical spectroscopy and electron paramagnetic resonance. It is detected that the interaction process is weak and strong forms of chemisorption on the PS surface, and the process may be regarded as an actual chemical reaction between PS and NO(2). It is found that NO(2) adsorption consists in forming different surface nitrogen-containing molecular groups and dangling bonds of Si atoms (P(b)-centers) as well as in oxidizing and hydrating the PS surface. Also observed are the formation of ionic complexes of P(b)-centers with NO(2) molecules and the generation of free charge carriers (holes) in the volume of silicon nanocrystals forming PS.     

Chiral symmetric phosphoric acid esters as sources of optically active organophosphorus compounds

Chiral symmetric di- and trialkylphosphites, derivatives of (−)-borneol, (−)-menthol and (−)-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose, were studied as starting reagents for the preparation of chiral organophosphorus compounds. The reaction occurs by asymmetric induction at the α-carbon atom of substituted α-alkylphosphonates. The stereoselectivity of the reaction depends on the structure of the starting compounds and the reaction conditions. The configuration of the alkylphosphonates was established by NMR spectroscopy, by transformation into α-hydroxyalkylphosphonic acids and by X-ray crystal structure analysis.     

A stable fused bicyclic disilene as a model for silicon surface

We synthesized the first fused bicyclic disilene 1 representing topologically a partial structure of the Si(001) surface up to the third layer. In the solid state, the five-membered rings adopt the envelope conformation, and the Si=Si double bond in 1 exists in the slightly cis-bent form (bent angle theta is 3.6 degrees ) compared to that of the highly cis-bent dimer on the Si(001) surface. Highly symmetric 1H NMR spectral pattern of 1 remains even at -80 degrees C, indicating the facile ring flipping of the bicyclic skeleton in solution. While syn-adduct was obtained in the reaction of 1 with water, anti-addition of chlorine atoms across the Si=Si double bond in 1 was observed in the reaction with carbon tetrachloride. The structural characteristics of the 9,10-phenanthrenequinone adduct 7 are in good accord with those of the proposed structure of the 9,10-phenanthrenequinone molecule adsorbed on the Si(001) surface.