A proposed tangential flow ultrafiltration method was compared to the widely used ultracentrifugation method for efficiency and efficacy in concentrating, size selecting, and minimizing the aggregation state of a silver nanoparticle (AgNP) colloid while probing the AgNPs' SERS-based sensing capabilities. The ultrafiltration method proved to be more efficient and more effective and was found to tremendously boost the SERS-based sensing capabilities of these AgNPs through the increased number of homogeneous SERS hot spots available for a biotarget molecule within a minimal focal volume. Future research studies and applications addressing the physiochemical properties or biological impact of AgNPs would greatly benefit from ultrafiltration for its ability to generate monodisperse colloidal nanoparticles, to eliminate excess toxic chemicals from nanoparticle synthesis, and to obtain minimum levels of aggregation during nanoparticle concentration.

R ecently, the National Science Foundation projected that the current 10-billion dollar nanotechnology sector will employ 2 million workers, including as many as 1 million workers in the United States. 1 It is expected that over 80% of the jobs created in this sector will require trained individuals in nanoscience. However, little training at the undergraduate level has been initiated to provide highly specialized scientists to this rapidly developing field. The proposed laboratory experiment, which was implemented for both undergraduate and graduate student laboratories in physical chemistry and nanotechnology, addresses the future projected demand.In 1998, G. C. Weaver and K. Norrod proposed an undergraduate laboratory to introduce the surface-enhanced Raman scattering (SERS) effect and to extend the scope of the Raman theory normally covered in physical chemistry courses. 2 A Raman-active molecule, pyridine, was adsorbed on colloidal silver nanoparticles (AgNPs) to demonstrate the large increase in Raman signal. Although successful, the SERS experiment did not estimate the analytical enhancement factor (AEF) and surface enhancement factor (SEF), the most important values for characterizing the SERS effect. 3,4 The Raman signal enhancement of 100À300 times was simply determined by calculating the ratio of integrated areas for specific vibrational modes of pyridine adsorbed on AgNPs and in solution. However, the pyridine concentrations (1.0 Â 10 À1 M for normal Raman and 6.25 Â 10 À3 M for SERS measurements) were extremely large when compared with the trace amounts of analyte that are now detected via SERS. In the following years, theoretical and experimental studies have demonstrated that single-molecule SERS-based detection and identification can be achieved under favorable circumstances. 5,6 Because of the enormous enhancement, SERS found numerous cutting-edge applications in medical, biological, chemical, military defense, homeland security, pharmacological, and environmental settings. 7À9 Most SERSbased detection and identification applications require an accurate determination of the magnitude of the signal enhancement.In this experiment, Raman and fluorescence spectrophotometers were employed to estimate the analytical and surface enhancement factors for rhodamine 6G adsorbed on a Creighton colloid. 10 Among the many kinds of SERS-active substrates, silver colloids are known to lead to huge enhancement factors and to enable single-molecule SERS experiments. 5À7,11 The Creighton method has been widely used for its simplicity, relative low cost, accessibility, and time efficiency. These parameters were critical in designing a feasible experiment for a laboratory. Not surprisingly, in 2007, Solomon et al. implemented the Creighton procedure for the synthesis of colloidal AgNPs as a new laboratory experiment for a general chemistry class. 12

In recent years, nanoscience and nanotechnology have been drawing enormous attention due to the numerous applications of nanomaterials. In an attempt to nurture interest towards these areas in young minds and to develop the next generation of environmentally conscious scientists and engineers, this new laboratory module focuses on the green and nongreen aspects of noble metal nanoparticles (NPs) synthesis. The element of novelty is represented by the guided, inquiry-based exploration of alternative, green fabrication methods using environmentally friendly reducing agents (e.g., tea extracts, coffee, honey, coconut oil, and banana peel). The inquiry-based learning was developed according to the five essential features laid by the National Research Council (NRC), and was successfully implemented after science and engineering students gained theoretical knowledge and hands-on experience with conventional, nongreen fabrication methods of colloidal silver and gold NPs (i.e., the Lee-Meisel and Turkevich methods). The student assignments and evaluations demonstrated that this inquiry-based laboratory increased students' interest in green nanochemistry, provided them with new laboratory skills, and stimulated their critical thinking.

Understanding the fate and transport of silver nanoparticles (AgNPs) is of importance due to their widespread use and potential harmful effects on humans and the environment. The present study investigates the fate and transport of widely used Creighton AgNPs in saturated porous media. Previous investigations of AgNP transport in the presence of natural organic matter (NOM) report contradictory results regarding how the presence of NOM affected the stability and mobility of AgNPs. In this work, a nonreactive tracer, AgNPs and a mixture of AgNPs and NOM were injected into a background solution (0.01 mM of NaNO 3 ) flowing through laboratory columns packed with water-saturated glass beads to obtain concentration versus time breakthrough curves. Transport of AgNPs in the presence of NOM was simulated with a model that accounted for both reversible and irreversible attachment. Based upon an analysis of the AgNP breakthrough curves, it was found that addition of NOM at concentrations ranging from 1 to 40 mg L -1 resulted in significant decreases in both the zeroth and first moments of the breakthrough curves. These observations may be attributed to NOM promoting AgNP aggregation and irreversible attachment. Raman and surface-enhanced Raman scattering analysis of NOM-AgNP mixtures revealed that a possible interaction of NOM with AgNP occurred through the carboxylic moieties (-COO -) located in the immediate vicinity of the metallic surface. At higher concentrations of NOM, both the zeroth and first moments of the breakthrough curves increased. Based on modeling and the literature, we hypothesize that as the NOM concentration increases, it begins to coat both the AgNPs and the glass beads, leading to a situation where AgNP transport may be described in the same way that transport of a sorbing hydrophobic compound partitioning to an immobile organic phase is typically described, assuming reversible, rate-limited sorption.

Laser-induced fluorescence (LIF) and polarization spectroscopy (PS) is used for OH-thermometry utilizing the off-diagonal A-X(1,0) band. Both techniques are used simultaneously in order to allow a comparison of the results. For deriving temperature information from the spectra, three methods are employed: (1) a contour fit method comparing experimental and calculated spectra, (2) spectral fitting of a single highly resolved spectral line and (3) a two-line intensity ratio approach. In general, both spectroscopic techniques gave similar results. The high-resolution approach (2) did not deliver reasonable results in our experiments. The most accurate but also most time consuming method was the contour fit (1). For future two-dimensional temperature measurements, the 2-line-method (3) was identified to be the method of choice. The present study contains, to the best of our knowledge, the first polarization spectroscopic study in the A-X (1,0) band of OH.