Alkanethiols on platinum: multicomponent self-assembled monolayers

We have studied the formation of self-assembled monolayers (SAMs) of n-alkanethiols on platinum thin films using X-ray photoelectron spectroscopy (XPS), reflection-absorption infrared spectroscopy (RAIRS), spectroscopic ellipsometry (SE), and contact angle (CA) measurements. Specifically, SAMs of 1-hexanethiol, 1-dodecanethiol, and 1-octadecanethiol were grown on polycrystalline Pt films, and the effects of Pt surface preparation, deposition conditions, and solvent treatments on the initial quality and stability of the monolayer in air were investigated. The SAMs prepared under ambient conditions on piranha-cleaned and UV/ozone-cleaned substrates were compared to monolayers formed on template-stripped Pt in an inert atmosphere. We found that alkanethiols deposited from 1 mM ethanolic solutions on piranha-cleaned Pt formed densely packed monolayers in which alkyl chains were oriented close to the surface normal. Stored in the laboratory ambient, these monolayers were unchanged over about 1 week but were largely oxidized in about 1 month. No evidence was found of molecules being weakly bound within the monolayer or having undergone C-S bond scission; however, three distinct sulfur states were observed for all samples in the XPS of the S 2p region. The lowest- and highest-binding-energy components are assigned to alkylthiolate and partially oxidized alkylthiolate species, respectively. The remaining S 2p component (approximately one-third of the sulfur layer), intermediate in binding energy between the other two components, is attributed to a chemisorbed species with a S binding configuration distinct from the majority alkylthiolate: for example, S bound to Pt bound to O, S with a different Pt coordination number, or S in an adsorbed disulfide.     

Direct writing of a conducting polymer with molecular-level control of physical dimensions and orientation

Polymer nanostructures composed of poly(3-dodecylthiophene) (PDDT) have been directly written with control of polymer strand alignment and monolayer-by-monolayer thickness down to a single molecular monolayer (2.6 nm). The molecularly ordered nanostructures were written on silicon oxide surfaces using thermal dip-pen nanolithography, where an atomic force microscope cantilever with integrated tip heater was precoated with solid PDDT. The PDDT was precisely deposited onto the surface when the tip temperature was set close to PDDT's melting temperature.     

Base-dependent competitive adsorption of single-stranded DNA on gold

We characterize the room-temperature adsorption of single-stranded DNA homo-oligonucleotides from solution onto polycrystalline Au films, including competitive adsorption between all possible pairs of unmodified oligomers. Fourier transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopy analysis of the resulting films shows that oligonucleotides adsorb with a strongly base-dependent affinity, adenine (A) > cytosine (C) >/= guanine (G) > thymine (T). In competitive adsorption experiments on Au, oligo(dA) strongly dominates over the other oligonucleotides. The relative adsorption affinity of oligo(dA) is so great that it competes effectively against adsorption of thiolated oligomers and even causes hybridized oligo(dA).oligo(dT) duplexes to denature in the presence of Au.     

Synthesis,chiroptical properties and absolute configuration of α-phenylglycidic acid

The (+)- and (-) enantiomers of potassium α-phenylglycidate, an irreversible inhibitor of the enzyme mandelate racemase, were synthesized by resolution of the diastereomeric esters with R-(-)-2-octanol. Base-catalyzed ring-opening of the resolved α-phenylglycidate esters gave the enantiomers of 2,3-dihydroxy-2-phenylpropanoic acid, also obtained by resolution of the racemic dihydroxy acid using ephedrine. A comparison of the chiroptical properties of the esters of α-phenylglycidic and 2,3-dihydroxy-2-phenylpropanoic acids with those of the structurally similar atrolactic and mandelic acids and their 2-methoxy-derivatives showed that the (-)-methyl 2,3-dihydroxy-2-phenylpropanoate corresponding to the (+)-enantiomer of potassium α-phenylglycidate, as well as the esters of α-phenylglycidic acid derived from the same (+)-potassium salt, were all configurationally related to S-(+)-atrolactic and mandelic acids. The configurational assignments made on the basis of the chiroptical data were confirmed by lithium aluminum hydride reduction of the (-)-2-octyl S- and R-α-phenylglycidates, which led exclusively to the R-(-)- and S-(+)-2-phenyl-1, 2-propanediols, respectively, previously related configurationally to R-(-)- and S-(+)-atrolactic acids.     

The harmonic-map structure of the axially symmetric stationary Einstein equations

We systematically review the solutions of the vacuum Einstein equations for the axially symmetric stationary case which are harmonic maps. In particular, we show that the interesting part of the Kerr solution is a composition of a harmonic map intoH ₁ ² with a totally geodesic map fromH ₁ ² into SS(1,1). We also point out, relying on Sanchez' results, that there is an analogous structure for the Lorentz-domain cases involving cylindrical gravitational waves and colliding plane waves.     

Structure of III-Sb(001) growth surfaces: the role of heterodimers

We have determined the structure of AlSb and GaSb (001) surfaces prepared by molecular beam epitaxy under typical Sb-rich device growth conditions. Within the range of flux and temperature where the diffraction pattern is nominally (1x3), we find that there are actually three distinct, stable (4x3) surface reconstructions. The three structures differ from any previously proposed for these growth conditions, with two of the reconstructions incorporating mixed III-V dimers within the Sb surface layer. These heterodimers appear to play an important role in island nucleation and growth.     

Automation of a graphite-furnace atomic absorption spectrometry system with a Z80-based microcomputer

A microprocessor was used to control the operation of an atomic absorption spectrometer and a graphite-furnace atomizer. The system allows complete and flexible control of the graphite furnace heating program and active feedback with an optical temperature sensor, control of purge gas flows, and control of an autosampler. With micro-processor control, the graphite furnace can be heated from 0 to 2500°C in about 3 s with little or no overshoot. Reproducibility data for cadmium to oyster tissue gave relative standard deviations between 1.3 and 3.3% with microprocessor control and between 2.1 and 7.8% without control. Digitized data may be plotted and stored on disk.     

Redox inactivation of human 15-lipoxygenase by marine-derived meroditerpenes and synthetic chromanes: archetypes for a unique class of selective and recyclable inhibitors

The selective inhibition of human 15-lipoxygenase (15-hLO) could serve as a promising therapeutic target for the prevention of atherosclerosis. A screening of marine sponges revealed that crude extracts of Psammocinia sp. exhibited potent 15-hLO inhibitory activity. Bioassay-guided fractionation led to the isolation of chromarols A-E (8-12) as potent and selective inhibitors of 15-hLO. An additional 22 structurally related compounds, including meroditerpenes from the same Psammocinia sp. (3, 4, 13-16) and our pure compound repository (17, 18), commercially available tocopherols (19-24), and synthetic chromanes (25-32), were evaluated for their ability to inhibit human lipoxygenases. The 6-hydroxychromane moiety found in chromarols A-D was identified as essential for the selective redox inhibition of 15-hLO. Furthermore, the oxidized form of the 6-hydroxychromane could be reduced by ascorbate, suggesting a potential regeneration pathway for these inhibitors in the body. This pharmacophore represents a promising paradigm for the development of a unique class of recyclable 15-hLO redox inhibitors for the treatment of atherosclerosis.