Research Papers

ABSTRACT: Fuel is the single most import supply during war. Consider that the US Military is employing over 25,000 vehicles in Iraq and Afghanistan. Most fuel is obtained locally, and must be characterized to ensure proper operation of these vehicles. Fuel properties are currently determined using a deployed chemical laboratory. Unfortunately, each sample requires in excess of 6 hours to characterize. To overcome this limitation, we have developed a portable fuel analyzer capable of determine 7 fuel properties that allow determining fuel usage. The analyzer uses Raman spectroscopy to measure the fuel samples without preparation in 2 minutes. The challenge, however, is that as distilled fractions of crude oil, all fuels are composed of hundreds of hydrocarbon components that boil at similar temperatures, and performance properties can not be simply correlated to a single component, and certainly not to specific Raman peaks. To meet this challenge, we measured over 800 diesel and jet fuels from around the world and used chemometrics to correlate the Raman spectra to fuel properties. Critical to the success of this approach is laser excitation at 1064 nm to avoid fluorescence interference (many fuels fluoresce) and a rugged interferometer that provides 0.1 cm −1   wavenumber (x‐axis) accuracy to guarantee accurate correlations. Here we describe the portable fuel analyzer, the chemometric models, and the successful determination of these 7 fuel properties for over 100 unknown samples provided by the US Marine Corps, US Navy, and US Army.
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ABSTRACT: During the past decade, the use of portable Raman analyzers for field measurements has grown dramatically. However, most analyzers use 785 nm excitation lasers that can cause permanent eye damage. To overcome this safety concern, we have built a portable Fourier transform (FT) Raman analyzer using a 1550 nm retina-safe excitation laser and have compared its performance to our 1064 nm FT-Raman analyzer, which uses the same optical design. Raman theory predicts approximately five times lower peak intensities at 1550 nm. Although we found that intensities were as much as 20 times less intense, the analyzer is still capable of measuring spectra of sufficient quality to identify and differentiate chemicals.
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ABSTRACT: Portable Raman analyzers have great potential for identifying explosive materials associated with improvised explosive devices. However, most commercial analyzers employ 785-nm lasers that can generate fluorescence interference, limiting identification capabilities, and possibly cause permanent eye damage because of the use of high powers and open laser beams. Here we compare the Raman spectra obtained for TNT and RDX using 785-, 976-, 1064-, and 1550-nm lasers. The latter is of special interest, as it falls within the retina-safe spectral range.
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ABSTRACT:  The ability of Raman spectroscopy to detect anthrax-causing spores as they pass through a mail sorting system was investigated. A pump was connected to an existing vacuum manifold on a commercial sorter, and a filter designed to capture 0.5–3 µm particles was placed in-line. A standard business letter containing 0.23 g of Bacillus cereus spores, a Bacillus anthracis surrogate, was placed in a stack of 20 letters and passed through the system. Raman spectra of the filter positively identified the captured material as bacterial spores by the dominant calcium dipicolinate Raman spectral bands associated with the spore core. A limit of detection, using 400 mW of 785 nm laser excitation for a 1-s acquisition, is estimated at 4.5 mg. The ability of a Raman spectroscopy based system to detect and prevent the distribution of a letter containing gram levels of anthrax spores is discussed
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ABSTRACT: The bioterrorism of October 2001 caused by the distribution of anthrax through the U.S. postal system was compounded by the significant delay associated with positive identification of the Bacillus anthracis spores and the unknown extent of their distribution along the eastern seaboard. In the ensuing two years, literally thousands of hoaxes, letters containing harmless powders, have been mailed creating additional anxiety. Thus, there is a need for instruments and/or methods that can not only identify anthrax-causing spores to save lives, but also identify hoax materials to eliminate costly shutdowns. Here we present Raman spectra of Bacillus cereus spores, an anthrax surrogate, as well as of 30 common substances that might be used as hoax materials. We also examine the choice of laser excitation, 785 nm or 1064 nm, and its impact on the ability to measure visible particles in 5 minutes or less, and to provide a complete answer to the question of suspicious material identity.
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ABSTRACT: The superior strength-to-weight ratio of fiberreinforced polymer matrix composites make them suitable for applications ranging from sporting goods to aircraft components. However, consistent fabrication of components with desired mechanical properties has proven difficult and has led to high production costs. This is largely due to the inability to monitor and control polymer cure, which chemically is the process of polymer chain extension and cross-linking. Optimized process control with minimum waste will require a sensor to gather real-time process data, a cure model based on reaction mechanisms and physical changes, correlations between molecular structure and macroscopic properties, and an expert system to control the fabrication device. This paper presents simultaneous rheology and Raman measurements during the cure of diglycidyl ether of bisphenol A by triethyl tetramine (an epoxy resin). Correlations between molecular reaction kinetics and physical property changes are developed, forming the basis of a cure model.
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ABSTRACT: Fiber reinforced epoxy resins manufactured in autoclaves are expected to continue to dominate the composites market through 2010. However, the ability to obtain consistent mechanical properties from product-to-product remains difficult.  This is largely due to the inability to monitor and control epoxy cure, loosely defined as the process of chain extension and cross-linking. Current autoclave process control employs a heat schedule based on a time-temperaturetransformation (TTT) phase diagram that is determined by dynamic mechanical rheology. The phase diagram defines epoxy cure in terms of gelation and vitrification. We have been using an FT-Raman spectrometer to develop correlations between molecular (chain extension and cross-linking) and macroscopic (gelation and vitrification) data. The basis of a TTT phase diagram using Raman kinetic data for process control is presented for several reactions.
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ABSTRACT: The superior engineering properties of fiber reinforced polymer matrix composites, primarily the high strength-to-weight ratio, make them suitable to applications ranging from sporting goods to aircraft components (e.g. helicopter blades). Unfortunately, consistent fabrication of components with desired mechanical properties has proven difficult, and has led to high production costs. This is largely due to the inability to monitor and control polymer cure, loosely defined as the process of polymer chain extension and cross-linking. Even with stringent process control, slight variations in the pre-polymer formulations (e.g. prepreg) can influence reaction rates, reaction mechanisms, and ultimately, product properties. In an effort to optimize the performance of thermoset composites, we have integrated fiber optic probes between the plies of laminates and monitored cure by Raman spectroscopy, with the eventual goal of process control. Here we present real-time measurements of two high performance aerospace composites cured within an industrial autoclave.
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ABSTRACT: Increases in illicit drug use and the number of emergency-room visits attributable to drug misuse or abuse highlight the need for an efficient, reliable method to detect drugs in patients in order to provide rapid and appropriate care. A surface-enhanced Raman spectroscopy (SERS)-based method was successfully developed to rapidly measure cocaine in saliva at clinical concentrations, as low as 25 ng/mL. Pretreatment steps comprising chemical separation, physical separation, and solid-phase extraction were investigated to recover the analyte drug from the saliva matrix. Samples were analyzed using Fourier-transform (FT) and dispersive Raman systems, and statistical analysis of the results shows that the method is both reliable and accurate, and could be used to quantify unknown samples. The procedure requires minimal space and equipment and can be completed in less than 16 minutes. Finally, due to the inclusion of a buffer solution and the use of multiple robust pretreatment steps, with minimal further development this method could also be applied to other drugs of interest. Read full article.

ABSTRACT: The need for portable technologies that can rapidly identify biological warfare agents (BWAs) in the field remains an international priority as expressed at the 2011 Biological Weapons Convention. In recent years, the ability of surface-enhanced Raman spectroscopy (SERS) to rapidly detect various BWAs at very low concentrations has been demonstrated. However, in the specific case of Bacillus anthracis, differentiation at the species level is required since other bacilli are common in the environment, representing potential false-positive responses. To overcome this limitation, we describe the use of a peptide attached to the SERS-active metal that selectively binds Bacillus anthracis-Sterne as the target analyte. Using this approach, 10⁹  B. anthracis-Sterne spores/mL produced an intense dipicolinic acid spectrum upon the addition of acetic acid, while the same concentration and treatment of B. cereus and B. subtilis did not. Read full article.

ABSTRACT: US Military forces are dependent on indigenous water supplies, which are considered prime targets to effect a chemical or biological attack. Consequently, there is a clear need for a portable analyzer capable of evaluating water supplies prior to use. To this end we have been investigating the use of a portable Raman analyzer with surface-enhanced Raman spectroscopy (SERS) sampling systems. The superior selectivity and exceptional sensitivity of SERS has been demonstrated by the detection of single molecules. However, the extreme sensitivity provided by SERS is attributed to “hot spot” structures, such as particle junctions that can provide as much as 10 orders of magnitude enhancement. Unfortunately, hotspots are not evenly distributed across substrates, which results in enhancements that cannot be quantitatively reproduced. Here we present analysis of uniformity for a newly developed substrate and commercial sample vials using benzenethiol and bispyridylethylene, two chemicals often used to characterize SERS substrates, and methyl phosphonic acid, a major hydrolysis product of the nerve agents. Read full article

ABSTRACT: Since the distribution of Bacillus anthracis causing spores through the US Postal System, there has been a persistent fear that biological warfare agents (BWAs) will be used by terrorists against our military abroad and our civilians at home. Despite the substantial effort to develop BWA analyzers, they remain either too slow, produce high falsealarm rates, lack sensitivity, or cannot be fielded. Consequently there remains a need for a portable analyzer that can overcome these limitations as expressed at the 2011 Biological Weapons Convention. To meet this need we have been developing a sample system that selectively binds BWAs and produce surface-enhanced Raman (SER) spectra using portable Raman spectrometers. Here we describe the use of a short peptide ligand functionalized on silver nanoparticles to selectively capture Bacillus cereus spores (a surrogate of B. anthracis) and their subsequent detection by SER spectroscopy. This technique was used to specifically detect B. cereus spores over closely related species like B. subtilis belonging to the same genus within 15 minutes. Sensitivity of the method was demonstrated by detecting 104 B. cereus spores/mL of water. The technology, once developed should prove invaluable for rapid monitoring of BWAs, which will immensely help first responders and emergency personnel in implementing appropriate counter measures.
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ABSTRACT: Foodborne diseases resulting from Campylobacter, Escherichia, Listeria, Salmonella, Shigella and Vibrio species affect as many as 76 million persons in the United States each year, resulting in 325,000 hospitalizations and 5,000 deaths. The challenge to preventing distribution and consumption of contaminated foods lies in the fact that just a few bacterial cells can rapidly multiply to millions, reaching infectious doses within a few days. Unfortunately, current methods used to detect these few cells rely on lengthy growth enrichment steps that take a similar amount of time (1 to 4 days). Consequently, there is a critical need for an analyzer that can rapidly extract and detect foodborne pathogens in 1-2 hours (not days), at 100 colony forming units per gram of food, and with a specificity that differentiates from indigenous microflora, so that false alarms are eliminated. In an effort to meet this need, we have been developing a sample system that extracts such pathogens from food, selectively binds these pathogens, and produces surface-enhanced Raman spectra (SERS). Here we present preliminary SERS measurements of Listeria and Salmonella.
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ABSTRACT: Many trace chemical analyses are being transitioned from the lab to the field, among which is surface-enhanced Raman spectroscopy. Although initial portable Raman analyzers primarily employ 785 nm laser excitation, recent studies suggest longer wavelengths, with an appropriate surface-enhanced Raman-active substrate, may provide equal sensitivity. Furthermore, 1550 nm excitation may provide added safety for the user, in that permanent retina damage does not occur. Here, we show that a reasonable enhancement factor can be obtained for melamine using 1550 nm laser excitation that is nearly equivalent to those obtained using 785 and 1064 nm laser excitation. We also demonstrate that a number of other chemicals of interest can be measured by 1550 nm surface-enhanced Raman scattering, albeit only modest sensitivity is achieved because of instrument limitations, not enhancement factors.
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ABSTRACT: Eighty drugs of abuse and metabolites were successfully measured by surface-enhanced Raman spectroscopy (SERS) using gold- and silver-doped sol-gels immobilized in glass capillaries. A method was developed that provided consistent detection of 50 ppb cocaine in saliva in a focused study. This general method was successfully applied to the detection of a number of additional drugs in saliva, such as amphetamine, diazepam, and methadone.
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DESCRIPTION: Bringing several disparate aspects of food science and analysis together in one place, Applications of Vibrational Spectroscopy to Food Science provides a comprehensive, state-of the-art text presenting the fundamentals of the methodology, as well as underlying current areas of research in food science analysis.  All of the major spectroscopic techniques are also covered – showing how each one can be used beneficially and in a complementary approach for certain applications.  Case studies illustrate the many applications in vibrational spectroscopy to the analysis of foodstuffs.
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By Atanu Sengupta, Hermes Huang, Chetan Shende, David Drapcho, Igor Zlatkin, Stuart Farquharson, Frank Inscore
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Jun 02, 2005; By Wayne Smith, Stuart Farquharson, Carl Brouillette, Frank Inscore
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ABSTRACT: Detection of chemical agents as poisons in water supplies not only requires μg/L sensitivity, but also requires the ability to distinguish their hydrolysis products. We have been investigating the ability of surface-enhanced Raman spectroscopy (SERS) to detect chemical agents at these concentrations. Here we expand these studies and present the SERS spectra of the nerve agent VX (ethyl S-2-diisopropylamino ethyl methylphosphonothioate) and its hydrolysis products, ethyl S-2-diisopropylamino methylphosphonothioate, 2(diisopropylamino) ethanethiol, ethyl methylphosphonic acid, and methylphosphonic acid. Vibrational mode assignments for the observed SERS peaks are also provided. Overall, each of these chemicals produces a series of peaks between 450 and 900 cm−1 that are sufficiently unique to allow identification. SERS measurements were performed in silver-doped sol-gel-filled capillaries that are being developed as part of an extractive point sensor.
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ABSTRACT: The ability of surface-enhanced Raman spectroscopy (SERS) to measure the chemotherapy drug 5-fluorouracil in saliva is presented. A silver-doped sol–gel provided SERS and also some chemical selectivity. 5-Fluorouracil and physiological thiocyanate produced SERS, whereas large biochemicals, such as enzymes and proteins, did not, supporting the expectation that the larger molecules do not diffuse through the sol–gel to any appreciable extent. In addition, 5-fluorouracil samples of 2 µg ml−1 were easily measured, and an estimated limit of detection of 150 ng ml−1 in 5 min should provide sufficient sensitivity to perform pharmacokinetic studies and to monitor and regulate patient dosage. This would fill a critical need for this highly used drug, since genetic-based variations in its metabolism can range by as much as five-fold from one patient to another
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ABSTRACT: The United States and its allies have been increasingly challenged by terrorism, and since the September 11, 2001 attacks and the war in Afghanistan and Iraq, homeland security has become a national priority. The simplicity in manufacturing chemical warfare agents, the relatively low cost, and previous deployment raises public concern that they may also be used by terrorists or rogue nations. We have been investigating the ability of surface-enhanced Raman spectroscopy (SERS) to detect extremely low concentrations (e.g. part-per-billion) of chemical agents, as might be found in poisoned
water. Since trace quantities of nerve agents can be hydrolyzed in the presence of water, we have expanded our studies to include such degradation products. Our SERS-active medium consists of silver nanoparticles incorporated into a solgel matrix, which is immobilized in a glass capillary. The choice of sol-gel precursor allows controlling hydrophobicity, while the porous silica network offers a unique environment for stabilizing the SERS-active silver particles. Here we present the use of these silver-doped sol-gels to selectively enhance the Raman signal of the hydrolyzed products of the G-series nerve agents.
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ABSTRACT: Protecting the nation’s drinking water from terrorism, requires microg/L detection of chemical agents and their hydrolysis products in less than 10 minutes. In an effort to aid military personnel and the public at large, we have been investigating the ability of surface-enhanced Raman spectroscopy (SERS) to detect microgram per liter (part-per-billion) concentrations of chemical agents in water. It is equally important to detect and distinguish the hydrolysis products of these agents to eliminate false-positive responses and evaluate the extent of an attack. Previously, we reported the SER spectra of GA, GB, VX and most of their hydrolysis products. Here we extend these studies to include the chemical agent sulfur-mustard, also known as HD, and its principle hydrolysis product thiodiglycol. We also report initial continuous measurements of thiodiglycol flowing through a SERS-active capillary.
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ABSTRACT: Raman spectroscopy has been employed to detect Bacillus cereus spores, an anthrax surrogate, collected from a letter as it passed through a mail sorting system. Raman spectroscopy also has the capability to identify many common substances used as hoaxes. A three-step method also is decribed for the detection of dipicolinic acid extracted from surface spores by SERS.
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