BOBO dHHHHHH PH B  -ZHAZExHH@ Rc(hh @d'- 1l/k \ 4HH k5l  H4(}DSET(:2 x t p |. . x.^ ,.' $.0`.:^ z " < F   +,de' ( uv wE p q     j   M   ! i  9s Q%pT4} W1}@A{|~-."#lm  b  !5!!""^""#9##$$b$$%%]%%%&&&>&?&T&U&d&e&~&((((() )T))**E*Y**+7+}+,,T,,-2-3-N-O---.<..../@/d//010x00 00111&1'16171Q1R55555j556D6677a778@8\889:99::: :::X "E          '  u  vw     o  q      A {  | k  m    %  & &>  &? ( (  ( -2  -3 -N  -R 0  0  0  0 1  1 5 5  5 ::  :  :  '   "&i*].I25#7 Special Research Programs Code 6170 ---------------------------------------------------------------------------- The Surface Chemistry Branch is engaged in research programs that are significantly important to the Navy and involve Surface Science not directly associated with a given Section research program already discussed. To allow flexibility within the Branch and to more effectively address Navy issues, a group of researchers was established under the heading of "Special Research Programs". Their research programs include: Chemically sensitive coatings and their applications to chemical microsensors; the chemistry of stabilized ceramic coatings; the fabrication and chemistry of nanostructures; and environmental science and technology. Each of these programs is described below, along with the Key Personnel directing the research who may be contacted for more information. ---------------------------------------------------------------------------- Amplification of molecular recognition and sensor development Chemically sensitive coatings and chemical microsensors Environmental electrochemistry Environmental science and technology Fabrication and chemistry of nanostructures Solid-Liquid Interface Chemistry The chemistry of stabilized ceramic coatings ---------------------------------------------------------------------------- AMPLIFICATION OF MOLECULAR RECOGNITION AND SENSOR DEVELOPMENT Dr. David A. Kidwell (202) 767-3575 kidwell@ccf.nrl.navy.mil This program develops systems that translate the microscopic binding events of biological or chemical recognition into a microscopic signal useful to humans. The approach used in this program is highly interdisciplinary. It often requires development of a fundamental understanding of the basic mechanisms and processes associated with molecule-molecule or molecule-surface interactions. This understanding is then exploited in the development of new labels/sensors that change an observable property upon interaction with another molecule. Biological sensors exploiting novel labels are being explored that change their chemiluminescence, colorimetric, enzymetic, of fluorescent intensities when the labeled molecules recognize and bind to other species or surfaces. These changes are translated to microscopic signals by employing optical instrumentation, mass spectrometry, Atomic Force Microscopy, or Near Field Scanning Optical Microscopy. Such sensors are capable of detecting a wide variety of materials including drugs of abuse, viruses, bacteria, toxins, chemical pollutants, DNA/RNA, and gaseous species in various complex matrices. CURRENT AREAS OF RESEARCH: * Detection of drugs of abuse in human urine, saliva, sweat, and hair. Procedures and instrumentation for ultra-sensitive detection (1-10 pg/mL) of LSD and its metabolites in human urine are being developed. The metabolism of LSD in humans is being investigated to determine if one of its metabolites has a longer window of detection than the parent drug. The mechanisms of drugs of abuse binding to hair, the potential for passive incorporation of drugs of abuse from the external environment, and the differences in racial hair types in detecting drugs of abuse in hair are being investigated. These investigations will assist in determining if hair analysis can supplement/replace urinalysis in the Navy Drug Screening Program. Likewise, saliva and sweat are being explored as adjuncts to urine for drug screening/detection under certain field scenarios. All these matrices require new instrumentation and analysis techniques. * Novel labels based upon the change in fluorescent properties of pyrene when in proximity to another label are being explored for the detection of small molecules with antibodies and DNA/RNA binding to their complimentary strand. This process, termed PORSCHA (Pi Overlapping Ring Systems Contained in a Homogeneous Assay) is being applied to homogeneous detection of DNA amplified in the polymerase chain reaction. Sensors based upon immobilized strands of DNA/RNA will also be coupled to fiber optics and planer waveguides for continuous detection of specific nucleic acid sequences coded by biological agents. * Detection of viral/bacterial agents is complicated by the small number of entities that are necessary for a threat. Higher numbers of DNA/RNA copies are more readily detected. Many detection schemes incorporate replication of the initial viral/bacterial nucleic acids through the polymerase chain reaction (PCR). However, PCR requires an expensive thermal cycler for implementation, only doubles the target DNA/RNA in each cycle, and takes 1-2 hours for completion. A alternative amplification system has been conceived that replicates target nucleic acids analogously to PCR but in an isothermal system and in a super exponential manner (10-100 times/cycle). Once developed, billion-fold amplification of DNA/RNA should be readily accomplished in a few minutes. Coupled with a homogeneous nucleic acid detection system such as PORSCHA should provided a rapid, small, and powerful detection scheme for any viral or bacterial agent. ---------------------------------------------------------------------------- CHEMOSELECTIVE SORBENT COATINGS AND CHEMICAL MICROSENSORS Dr. R. Andrew McGill (202) 767-0063 amcgill@ccf.nrl.navy.mil This program seeks to understand and apply fundamental principles leading to the development of novel chemoselective and sorbent coatings for use with chemical sensor devices. Present research is focussed around a number of chemical sensor transducers including microfabricated Surface Acoustic Wave (SAW), Bulk Acoustic Wave (BAW) devices, Interdigitated MicroElectrode (IME), and Optical Waveguide (OW) devices. Sensor applications are being explored for analyte detection in gaseous or liquid media. The "active area" of the transducer is coated with the sorbent materials, and when exposed to ,analyte molecules, the coating acts to selectively sorb or partition molecules of interest. The coated SAW or BAW transducers respond to analyte molecules by a shift in oscillatory frequency, the coated IME responds to analyte by a change in electrical conductivity, and the OW responds by a change in refractive index or other spectral properties of the coating. Chemoselective materials in which the chemical selectivity is tailored towards a particular analyte molecule of interest were designed, synthesised and evaluated for their selectivity and sensitivity. The ultimate goal is to design materials that exhibit bio-like specificity in a chemical sensing format with both molecular shape and solubility properties being utilized to selectively sorb an analyte into the coating material. Fundamental solubility properties of the sorbent coatings are determined by inverse chromatographic and dye probe solvatochromic methods. The relationships between the activity of a new coating and its structural composition are used to develop methods to predict the coating needs for a given analyte challenge. The quantitative and qualititative sorbent properties of new materials are applied as a predictive tool to calculate analyte sorption/partitioning from gas or liquid media into the sorbent coating. Sensor arrays are utilized with different coatings to develop arrayed responses for different analytes which are evaluated by signal processing and chemometric methods including neural net and linear discriminant pattern recognition techniques. The chemical sensors, systems, and chemoselective materials developed in this program have potential application to diverse DoD and civilian problems, including toxic chemical detection, identification, and monitoring of open and enclosed atmospheres for chemical contamination of a wide range of organic and inorganic analytes. CURRENT AREAS OF RESEARCH: * Design, synthesis and characterize of new polymeric organic and inorganic materials for selective and sensitive sorption of analyte compounds. New sorbent materials are coated on a SAW, BAW, IME, or OW and analyte responses are measured as changes in oscillatory frequency, electrical conductivity, or spectral characteristics. * Theoretical and experimental studies are carried out to elucidate the mechanism of interaction between the chemical species being detected and the chemoselective coating of the sensor. In turn this aids in the design of new materials. Linear solvation energy relationships (LSER) are developed using specific analyte solubility properties such as dipolarity, hydrogen-bonding and dispersion forces. From multiple linear regression analysis of analyte sorption properties in a sorbent coating the complementary solubility properties of the coating are deduced. LSER equations for different equations greatly enhance our understanding of sorption processes and can predict analyte sorption or partitioning into chemoselective materials from gas or liquid media. * Development of arrays of sensors and chemometric methods to improve selectivity. Both neural net and linear dicriminant pattern recognition techniques are being utilized * Design/Enhance new microfabricated physical probe devices or transducers for chemical or bio-sensor sapplications. These devices include surface acoustic wave, bulk acoustic wave, planar microelectrode arrays, and optical waveguides. ---------------------------------------------------------------------------- ENVIRONMENTAL ELECTROCHEMISTRY Dr. Debra R. Rolison (202) 767-3617 rolison@ccf.nrl.navy.mil This program studies--in the broadest sense--the influence of electrochemistry on environmental problems and the influence of atypical environs on electron and chargetransfer reactions on electron-phenon and transport properties. The former is exemplified by the characterization of electrified microheterogeneous catalysis (EMC) for the decomposition of polychlorinated organic molecules to watersoluble fragments; the latter by the study of electrochemical reactions in nanoscale domains, such as zeolites, aerogels, and fuel-cell electrocatalysts. FACILITIES: * Solartron 1260 potentiostat and frequency analyzer for impedance spectroscopy. * Waters Quanta 4000E capillary electrophoresis instrumentation for cation and anion analyses at and below ppm levels * Varian 3400 GCFID/TCD for quantitation of aqueous and organicphase solutes and for online gasphase analyses * Varian 3400 GCFinnegan iontrap mass spectrometer for molecular identification * Potentiostats; wave function generators; rotating ringdisc electrode apparatus with hydrodynamic modulation capability, electrode polishing equipment; power supplies (>100 V @ 1.5 A); parallelplate flow and toroidal dispersion reactors; Barnstead NanoPure water purifier; Lindberg tube furnace; three standalone IBMcompatible computers * Analytical facilities (within the branch, the division, and the laboratory) available to this effort with operator status include: Xray Photoelectron (XPS), Scanning Electron (SEM), Xray Diffraction (XRD), and Inductively Coupled Plasma Atomic Absorption (ICP) spectrometers; thermal analyzers; and IR diffusereflection and FTIR spectrometers CURRENT AREAS OF RESEARCH: * Electrochemical decomposition of environmentally deleterious chemicals via EMC * Preparation and characterization of semiconducting and conducting aerogel monoliths and powders for catalysis and electrochemical devices * Surface analyses and electroanalyses Pt-based electrocatalysts of importance in fuels cells * Electrocatalysis and electrosynthesis with redoxmodified zeolite dispersions * Electrochemical cluster chemistry of small metal and metalorganic clusters supported on zeolites * Physicochemical characterization of nonaqueous cationexchange reactions between aluminosilicate zeolites and aprotic electrolytes * Electrodesulfurization of organosulfur from carbon slurries * Selective partial oxidation of propene to propylene oxide through liquidphase catalysis via EMC ---------------------------------------------------------------------------- ENVIRONMENTAL SCIENCE AND TECHNOLOGY Mr. Bruce D. Sartwell (202) 767-3550 sartwell@ccf.nrl.navy.mil National and international environmental laws and regulations will significantly impact the Navy's ability to conduct its mission. In the area of shipboard waste disposal, Congress directed in the Defense Authorization Act of 1994 that the Navy fully comply with Annex V of the MARPOL international maritime treaty which dictates that no discharge of solid waste will be made into designated special areas which include most strategically vital bodies of water. It is anticipated that restrictions on offboard discharge of aqueous waste will also be implemented. At Naval aviation depots and shipyards, chromium electroplating is extensively used to rebuild or impart wear resistance to components. However, restrictions on waste disposal have significantly increased the cost, and proposed decreased exposure limits for workers could actually shut down electroplating operations at some facilities, with a major impact on mission readiness. CURRENT AREAS OF RESEARCH: * A plasma arc research facility, containing a 150 kW DC plasma torch, is being utilized to support a three-year, Navy Advanced Technology Demonstration project to develop a prototype shipboard plasma arc system to demonstrate the high-temperature pyrolysis of shipboard solid and liquid waste. The NRL facility includes both solid and liquid feeder systems capable of introducing material in a controlled manner and a wide array of diagnostic techniques and equipment including optical emission spectrometry, on-line gas analysis using mass spectrometry, off-line gas chromatography, thermocouples, and CCD video cameras with optical filters. Studies are performed to examine the plasma chemistry and gaseous effluents in order to establish optimum processing parameters. * NRL is managing and supporting a major tri-service effort under the DoD-sponsored Environmental Security Technology Certification Program (ESTCP) to develop high-velocity oxygen-fuel (HVOF) thermal spraying and physical vapor deposition (PVD) as alternatives to chromium electroplating. Qualification testing, including corrosion, wear, and fatigue measurements, are being conducted on various HVOF and PVD coatings. In addition, quality con> ----------------------------------------------------------------------- Transfer interrupted! 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