Novel Approaches to Prepare and Utilize SERS Substrates: Multiplex Microfluidics and Nanotransfer Printing

Over the past few decades, surface enhanced Raman spectroscopy (SERS) has garnered respect as an analytical technique with significant chemical and biological applications. SERS is important for the life sciences because it can provide trace level detection and a high level of molecular structure information. The development of quantitative, highly sensitive substrates requires control over size, shape, and position of metal nanoparticles which function as the SERS active medium. Thus, creating and successfully implementing a sensitive, reproducible, and robust SERS active substrate continues to be a challenging ask. Its future development depends critically on techniques for lithography and nanofabrication. Herein, we report a novel method for SERS that is based upon using colloidal silver nanoparticles in a multiplexed microfluidics (MMFs) platform. The MMF is created in polydimethylsiloxane (PDMS) polymer material and used to perform parallel, high throughput, and sensitive detection/identification of single or various analytes under easily manipulated conditions. A facile passive pumping method is used to deliver samples into the channels under flowing conditions that are highly conducive for SERS measurments. Also an unconventional nanofabrication approach is modified to produce efficient SERS substrates. Metallic nanopatterns of silver discs are transferred from a stamp onto PDMS to create nanocomposite substrates with regular periodic morphologies. The stamp with periodic arrays of square, triangular, and elliptical pillars is created via Electron Beam Lithography of ma-N 2403 resist. A modified cyclodextrin is thermally evaporated on the stamp to overcome the adhesive nature of the ebeam resist and to function as a releasing layer. Subsequently, the stamp is over coated with Ag by physical vapor deposition at a controlled rate and thickness and used directly for nanotransfer printing (nTP). Stamps, substrates, and the efficiency of the nTP process were explored by SEM. Ag nano-disc-PDMS substrates are studied by SERS using Rhodamine 6G as the probe analyte. The SERS response of metallic nano-discs of various shapes/sizes on the original stamp is compared to the corresponding nTP substrates. We demonstrate that physical manipulation of the PDMS post nTP can be used to alter morphology. Additionally, stamps are shown to be reusable after the nTP process

Agriculture, Forestry and Other Land Uses (Chapter 7)

The Agriculture, Forestry and Other Land Use (AFOLU) sector encompasses managed ecosystems and offers significant mitigation opportunities while delivering food, wood and other renewable resources as well as biodiversity conservation, provided the sector adapts to climate change. Land-based mitigation measures represent some of the most important options currently available. They can both deliver carbon dioxide removal (CDR) and substitute for fossil fuels, thereby enabling emissions reductions in other sectors. The rapid deployment of AFOLU measures is essential in all pathways staying within the limits of the remaining budget for a 1.5°C target (high confidence). Where carefully and appropriately implemented, AFOLU mitigation measures are uniquely positioned to deliver substantial co-benefits and help address many of the wider challenges associated with land management. If AFOLU measures are deployed badly then, when taken together with the increasing need to produce sufficient food, feed, fuel and wood, they may exacerbate trade-offs with the conservation of habitats, adaptation, biodiversity and other services. At the same time the capacity of the land to support these functions may be threatened by climate change itself (high confidence)

A Hybrid Least Squares and Principal Component Analysis Algorithm for Raman Spectroscopy

Raman spectroscopy is a powerful technique for detecting and quantifying analytes in chemical mixtures. A critical part of Raman spectroscopy is the use of a computer algorithm to analyze the measured Raman spectra. The most commonly used algorithm is the classical least squares method, which is popular due to its speed and ease of implementation. However, it is sensitive to inaccuracies or variations in the reference spectra of the analytes (compounds of interest) and the background. Many algorithms, primarily multivariate calibration methods, have been proposed that increase robustness to such variations. In this study, we propose a novel method that improves robustness even further by explicitly modeling variations in both the background and analyte signals. More specifically, it extends the classical least squares model by allowing the declared reference spectra to vary in accordance with the principal components obtained from training sets of spectra measured in prior characterization experiments. The amount of variation allowed is constrained by the eigenvalues of this principal component analysis. We compare the novel algorithm to the least squares method with a low-order polynomial residual model, as well as a state-of-the-art hybrid linear analysis method. The latter is a multivariate calibration method designed specifically to improve robustness to background variability in cases where training spectra of the background, as well as the mean spectrum of the analyte, are available. We demonstrate the novel algorithm’s superior performance by comparing quantitative error metrics generated by each method. The experiments consider both simulated data and experimental data acquired from in vitro solutions of Raman-enhanced gold-silica nanoparticles

Large-Area, Highly Sensitive SERS Substrates with Silver Nanowire Thin Films Coated by Microliter-Scale Solution Process

A microliter-scale solution process was used to fabricate large-area, uniform films of silver nanowires (AgNWs). These thin films with cross-AgNWs were deposited onto Au substrates by dragging the meniscus of a microliter drop of a coating solution trapped between two plates. The hot spot density was tuned by controlling simple experimental parameters, which changed the optical properties of the resulting films. The cross-AgNW films on the Au surface served as excellent substrates for surface-enhanced Raman spectroscopy, with substantial electromagnetic field enhancement and good reproducibility