An electrochemical study of 4-aminothiophenol/pt nanoparticle multilayers on gold electrodes

Quartz crystal microbalance (QCM) measurements of the formation of a 4-aminothiophenol (4-ATP)self-assembled monolayer (SAM) at a gold electrode showed that a surface coverage of 118 ng cm(-2) was obtained after a 3 h exposure period, indicating that good surface coverage was achieved. Cyclic voltammetry of the ferricyanide redox couple across this SAM modified surface produced similar results to those of a bare electrode; however, the electroreduction of oxygen was found to be impaired. The 4-ATP SAM layer was not stable to repeated electrochemical oxidation and reduction; it is believed that the 4-ATP SAM layer was first converted to a 4'-mercapto-N-phenylquinone diimine (NPQD) layer followed by subsequent formation of a 4'-mercapto-N-phenylquinone monoimine (NPQM) layer. We also report a quartz crystal microbalance study of the attachment of platinum nanoparticles to such SAM modified electrodes. We show that five times the amount of platinum nanoparticles can be attached to a 4-ATP modified electrode surface (observed frequency change - 187 Hz) compared with an NPQD modified electrode surface (observed frequency change -35 Hz). The presence of the platinum particles was confirmed electrochemically by their surface electrochemical properties, which were different from those of the underlying gold electrode. It is believed that this is the first time that such direct evidence of electrochemical communication between platinum nanoparticles and a SAM modified electrode surface has been obtained. It was also shown to be possible to build up multilayer SAM/nanoparticle modified surfaces while maintaining efficient electrochemical communication. Up to three SAM/nanoparticle sandwich layers were constructed.

The local adsorption geometry and electronic structure of alanine on Cu{110}

The adsorption of alanine on Cu {110} was studied by a combination of near edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). Large chemical shifts in the C 1s, N 1s, and O 1s XP spectra were found between the alanine multilayer and the chemisorbed and pseudo-(3 x 2) alaninate layers. From C, N, and O K-shell NEXAFS spectra the tilt angles of the carboxylate group (approximate to 26 degrees in plane with respect to [1 (1) over bar0] and approximate to 45 degrees out of plane) and the C-N bond angle with respect to [1 (1) over bar0] could be determined for the pseudo-(3 x 2) overlayer. Using this information three adsorption geometries could be eliminated from five p(3 x 2) structures which lead to almost identical heats of adsorption in the DFT calculations between 1.40 and 1.47 eV/molecule. Due to the small energy difference between the remaining two structures it is not unlikely that these coexist on the surface at room temperature. (c) 2006 Elsevier B.V. All rights reserved.

A method of synthesis of silicious inorganic ordered materials (MCM-41-SBA-1) employing polyacrylic acid-C(n)TAB-TEOS nanoassemblies

In this work we describe the synthesis of a variety of MCM-41 type hexagonal and SBA-1 type cubic mesostructures and mesoporous silicious materials employing a novel synthesis concept based on polyacrylic acid (Pac)-C(n)TAB complexes as backbones of the developing structures. The ordered porosity of the solids was established by XRD and TEM techniques. The synthesis concept makes use of Pac-C(n)TAB nanoassemblies as a preformed scaffold, formed by the gradual increase of pH. On this starting matrix the inorganic precursor species SiO2 precipitate via hydrolysis of TEOS under the influence of increasing pH. The molecular weight (MW) of Pac, as well as the length of carbon chain in C,TAB, determine the physical and structural characteristics of the obtained materials. Longer chain surfactants (C(16)TAB) lead to the formation of hexagonal phase, while shorter chain surfactants (C(14)TAB, C(12)TAB) favor the SBA-1 phase. Lower MW of Pac (approximate to2000) leads to better-organized structures compared to higher MW ( 450,000), which leads to worm-like mesostructures. Cell parameters and pore size increase with increasing polyelectrolyte and/or surfactant chain, while at the same time SEM photography reveals that the particle size decreases. Conductivity experiments provide some insight into the proposed self-assembling pathway. (C) 2003 Elsevier Inc. All rights reserved.

Synthesis of cationic water-soluble copolymers and hydrogels based on [2-(methacryloyloxy)ethyl]trimethylammonium cloride and 2-hydroxyethylacrylate and their complex formation with poly(acrylic acid)

Water-soluble cationic copolymers and hydrogels were synthesized by radical copolymerization of [2-(methacryloyloxy)ethyl]trimetilylammonium chloride (MADQUAT) and 2-hydroxyethylacrylate (HEA). The kinetics of copolymerization has been studied and the reactivity ratios were determined. It was found that MADQUAT exhibits higher reactivity in copolymerization. The complexation between linear MADQUAT-HEA and linear poly(acrylic acid) (PAA) has been studied in aqueous solutions at different pH. It results in the formation of insoluble polyelectrolyte complexes, whose composition and stability to aggregate depends on MADQUAT content in copolymers and pH. The hydrogels were synthesized by three-dimensional radical copolymerization of MADQUAT and HEA in the presence of a crosslinker. The effects of the feed mixture composition on yield and swelling properties of the hydrogels were studied. The interactions of these hydrogels with linear PAA result in formation of gel-polyelectrolyte complexes and contraction of the samples. It was found that the contraction depends on copolymer composition, PAA molecular weight, and solution pH. (c) 2006 Wiley Periodicals, Inc.

Adsorption of frog foam nest proteins at the air-water interface

The surfactant properties of aqueous protein mixtures ( ranaspumins) from the foam nests of the tropical frog Physalaemus pustulosus have been investigated by surface tension, two-photon excitation. uorescence microscopy, specular neutron reflection, and related biophysical techniques. Ranaspumins lower the surface tension of water more rapidly and more effectively than standard globular proteins under similar conditions. Two- photon excitation. uorescence microscopy of nest foams treated with fluorescent marker ( anilinonaphthalene sulfonic acid) shows partitioning of hydrophobic proteins into the air-water interface and allows imaging of the foam structure. The surface excess of the adsorbed protein layers, determined from measurements of neutron reflection from the surface of water utilizing H2O/D2O mixtures, shows a persistent increase of surface excess and layer thickness with bulk concentration. At the highest concentration studied ( 0.5 mg ml(-1)), the adsorbed layer is characterized by three distinct regions: a protruding top layer of similar to20 Angstrom, a middle layer of similar to30 Angstrom, and a more diffuse submerged layer projecting some 25 Angstrom into bulk solution. This suggests a model involving self-assembly of protein aggregates at the air-water interface in which initial foam formation is facilitated by specific surfactant proteins in the mixture, further stabilized by subsequent aggregation and cross-linking into a multilayer surface complex.

Interference filters and coatings for mid-infrared astronomy (8-30µm)

The VISIR instrument for the European Southern Observatory (ESO) Very Large Telescope (VLT) is a thermal-infrared imager and spectrometer currently being developed by the French Service d'Astrophysique of CEA Saclay, and Dutch NFRA ASTRON Dwingeloo consortium. This cryogenic instrument will employ precision infrared bandpass filters in the N-( =7.5-14µm) and Q-( =16-28µm) band mid-IR atmospheric windows to study interstellar and circumstellar environments crucial for star and planetary formation theories. As the filters in these mid-IR wavelength ranges are of interest to many astronomical cryogenic instruments, a worldwide astronomical filter consortium was set up with participation from 12 differing institutes, each requiring instrument specific filter operating environments and optical metrology. This paper describes the design and fabrication methods used to manufacture these astronomical consortium filters, including the rationale for the selection of multilayer coating designs, temperature-dependant optical properties of the filter materials and FTIR spectral measurements showing the changes in passband and blocking performance on cooling to <50K. We also describe the development of a 7-14µm broadband antireflection coating deposited on Ge lenses and KRS-5 grisms for cryogenic operation at 40K

Investigation of cadmium alternatives in thin-film coatings - art. no. 62860C

The health risks associated with the inhalation or ingestion of cadmium are well documented([1,2]). During the past 18 years, EU legislation has steadily been introduced to restrict its use, leaving a requirement for the development of replacement materials. This paper looks at possible alternatives to various cadmium II-VI dielectric compounds used in the deposition of optical thin-films for various opto-electronic devices. Application areas of particular interest are for infrared multilayer interference filter fabrication and solar cell industries, where cadmium-based coatings currently find widespread use. The results of single and multilayer designs comprising CdTe, CdS, CdSe and PbTe deposited onto group IV and II-VI materials as interference filters for the mid-IR region are presented. Thin films of SnN, SnO2, SnS and SnSe are fabricated by plasma assisted CVD, reactive RF sputtering and thermal evaporation. Examination of these films using FTIR spectroscopy, SEM, EDX analysis and optical characterisation methods provide details of material dispersion, absorption, composition, refractive index, energy band gap and layer thicknesses. The optimisation of deposition parameters in order to synthesise coatings with similar optical and semiconductor properties as those containing cadmium has been investigated. Results of environmental, durability and stability trials are also presented.

High-performance infrared narrow-bandpass filters for the Indian National Satellite System meteorological instrument (INSAT-3D)

This paper describes the design and manufacture of a set of precision cooled (210K) narrow-bandpass filters for the infrared imager and sounder on the Indian Space Research Organisation (ISRO) INSAT-3D meteorological satellite. We discuss the basis for the choice of multilayer coating designs and materials for 21 differing filter channels, together with their temperature-dependence, thin film deposition technologies, substrate metrology, and environmental durability performance. (C) 2008 Optical Society of America.

Infrared filters and coatings for the High Resolution Dynamics Limb Sounder (6-18µm)

This paper describes the spectral design and manufacture of the narrow bandpass filters and 6-18µm broadband antireflection coatings for the 21-channel NASA EOS-AURA High Resolution Dynamics Limb Sounder (HIRDLS). A method of combining the measured spectral characteristics of each filter and antireflection coating, together with the spectral response of the other optical elements in the instrument to obtain a predicted system throughput response is presented. The design methods used to define the filter and coating spectral requirements, choice of filter materials, multilayer designs and deposition techniques are discussed.

An ultra-wide passband (5-30µm) filter for FTIR studies of Photosystem II

This paper reports on the design and manufacture of an ultra-wide (5-30µm) infrared edge filter for use in FTIR studies of the low frequency vibrational modes of metallo-proteins. We present details of the spectral design and manufacture of such a filter which meets the demanding bandwidth and transparency requirements of the application, and spectra that present the new data possible with such a filter. A design model of the filter and the materials used in its construction has been developed capable of accurately predicting spectral performance at both 300K and at the reduced operating temperature at 200K. This design model is based on the optical and semiconductor properties of a multilayer filter containing PbTe (IV-VI) layer material in combination with the dielectric dispersion of ZnSe (II-VI) deposited on a CdTe (II-VI) substrate together with the use of BaF2 (II-VII) as an antireflection layer. Comparisons between the computed spectral performance of the model and spectral measurements from manufactured coatings over a wavelength range of 4-30µm and temperature range 300-200K are presented. Finally we present the results of the FTIR measurements of Photosystem II showing the improvement in signal to noise ratio of the measurement due to using the filter, together with a light induced FTIR difference spectrum of Photosystem II.

The manufacture and spectral assessment of the filters and antireflection coatings for use in the HIRDLS instrument

This paper describes the design and manufacture of the filters and antireflection coatings used in the HIRDLS instrument. The multilayer design of the filters and coatings, choice of layer materials, and the deposition techniques adopted to ensure adequate layer thickness control is discussed. The spectral assessment of the filters and coatings is carried out using a FTIR spectrometer; some measurement results are presented together with discussion of measurement accuracy and the identification and avoidance of measurement artifacts. The post-deposition processing of the filters by sawing to size, writing of an identification code onto the coatings and the environmental testing of the finished filters are also described.

Improvements relating to the manufacture of coated substrates

This invention relates to the manufacture of coated substrates, and particularly, but not exclusively, to the deposition of multi-layer coatings in the manufacture of interference filters consisting of multiple thin films. An object of the invention is to allow accurate control of the deposition of a succession of layers having good uniformity, for example during the manufacture by vacuum evaporation of multilayer interference filters for use with infrared radiation of particularly long wavelength, using a method which is self calibrating and which avoids the repetitive use of individual control layers.

Space exposure of infrared filters and materials on the NASA Long Duration Exposure Facility (LDEF)

Infrared optical-multilayer filters and materials were exposed to the space environment of low Earth for a period of nearly six years on the NASA Long Duration Exposure Facility (LDEF) mission. This report describes the effects of that environment on the physical and optical properties of filters and materials used in an experiment designed by the University of reading Infrared multilayer Laboratory. Results of the experiment comprise IR processed spectra both before (1983), and after (1990) exposure, in conjunction with unexposed control samples.

Investigation of ultra wideband multi-channel dichroic beamsplitters from 0.3 to 52µm

The development of a set of multi-channel dichroics which includes a 6 channel dichroic operating over the wavelength region from 0.3 to 52µm is described. In order to achieve the optimum performance, the optical constants of PbTe, Ge and CdTe coatings in the strongly absorptive region have been determined by use of a new iterative method using normal incidence reflectance measurement of the multilayer together with initial values of energy gap Eg and infinite refractive index n for the semiconductor model. The design and manufacture of the dichroics is discussed and the final results are presented.

Spectral characterisation of cooled filters for remote sensing

The improvements obtained on cooling atmospheric remote-sensing instruments for space flight applications has promoted research in characterization of the necessary optical filters. By modelling the effects of temperature on the dispersive spectrum of some constituent thin film materials, the cooled performance can be simulated and compared. multilayer filter designs with the measured spectra from actual filters. Two actual filters are discussed, for the 7µm region, one a composite cut-on/cut-off design of 13% HBW and the other an integral narrowband design of 4% HBW.