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There is great interest in the use of microfluidic paper-based analytical devices (μPADs) for low-cost diagnostics. In this contribution, we illustrate the utility of Raman spectral imaging for both μPAD characterization and for quantification of the transport of applied reagents and analytes within these devices. We evaluated the transport of nanoscale particles within μPADs using a suite of differentially functionalized gold (AuNP) and silver (AgNP) nanoparticles with diameters of 8-64 nm. Nanoparticle transport within the cellulose matrix was characterized by collection of both Raman and surface-enhanced Raman spectroscopy (SERS) spectral maps that enabled differentiation of cellulose fibers and characterization of analyte deposition patterns. The transport of citrate (cit), BSA, PEG, PVP, and DNA functionalized AuNP and AgNP in wax-printed μPADs was primarily affected by nanoparticle surface chemistry rather than particle size or core composition. Sample pH (3-10) influenced the transport of 15 nm BSA-cit-AuNP, but not 15 nm cit-AuNP, because of the effects of solution pH on the charge and conformation of BSA. Derjaguin, Landau, Verwey, and Overbeek theory (DLVO) and extended DLVO (xDLVO) theory are used to explain the collected experimental results.

Objective: As the first part of a larger study on curing characteristics of a resin-based composite (RBC), the major objectives were to create an energy-hardness relationship (EHR) that relates Knoop hardness (KHN) with radiant exposure (H), and to do the same for degree of conversion (DC) in the form of an energy-conversion relationship (ECR). Both of these are meant to be universal relationships that satisfy reciprocity between irradiance and time for a given H value., Methods: RBC specimens were made by curing the material in 6mm diameter, stainless steel molds for 10-40s and allowing the material to cure for 24h. Cure depths were determined by a scrape-back method. KHN and DC values were determined along the central axis of the specimens, and these values were related to the internal H values using a measured transmission relationship, T(d), for the RBC., Results: Suitable EHR and ECR relationships were developed for the RBC material that can be used to describe the curing characteristics under various curing conditions. However, predictive accuracy is affected for incident radiant exposures below about 12J/cm(2) to some extent. A relationship between KHN and DC was established., Significance: For the RBC examined, KHN measurements can be used as an alternate method or in conjunction with DC for describing the curing characteristics., (Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

A universal energy-conversion relationship (ECRu) predictive of conversion of a resin-based composite (RBC) polymerized with any light source has been described. This relationship was derived from an energy conversion relationship for RBC polymerized with a tungsten-halogen lamp and the lamp's efficiency relative to a hypothetical standard lamp. The ECRu was then used to predict conversion throughout RBC polymerized with an LED lamp using the lamp's relative efficiency compared to the standard lamp. The universal energy scale has also been described as predictive of scrape-back lengths for this RBC family when polymerized with any light source. Despite a 31% greater relative efficiency, scrape-back lengths from RBC polymerized using the LED lamp were predicted to be only 6% greater than those polymerized with the tungsten-halogen lamp when RBC is polymerized on an equal energy basis. This result was experimentally verified.

Objective: This study examines the influence of filler loading and silane content on the conversion of photoactivated, resin-based composites as determined using Fourier transform infrared spectroscopy (FTIR)., Method: Zirconia/silica filler was processed with a silane coupling agent (gamma-methacryloxypropyltrimethoxysilane) to achieve a range of silane-to-filler compositions. Treated fillers were compounded with a photoactivated BisGMA/TEGDMA resin to yield a series of pastes all containing 72 wt% total solids. Diffuse reflectance FTIR was used to characterize methacrylate unsaturation of the silane on the filler particles while paste conversion was determined using transmission FTIR. A resin matrix conversion was determined by adjusting the paste conversion for silane unsaturation. Two additional series of pastes were compounded to achieve variable filler-to-resin ratios using non-treated filler and filler processed with 8 wt% silane. Paste conversion was determined using transmission FTIR., Results: Pastes compounded from fillers containing variable percent silane demonstrated linearly decreasing conversion (R(2)=0.986) with increasing silane content and ranged from 52.7 to 62.8%. Adjusting paste conversion for silane unsaturation yielded similar resin matrix conversion for all cured pastes (65.1+/-0.8%). Pastes compounded with increasing filler-to-resin ratios had progressively decreasing conversion. Correcting for silane unsaturation suggests this effect was independent of whether the filler was silane-treated or not., Significance: Composite resin matrix conversion as determined via FTIR can be underestimated by the presence of unreacted methacrylate from silane on the filler. A corrected resin matrix conversion can be estimated by adjusting for silane unsaturation. Additionally, increasing filler-to-resin ratio progressively decreases conversion independent of the presence of silane on the filler.

Predicting the polymerization throughout resin-based composite (RBC) has been reduced to a set of variables involving irradiance of the light source, exposure duration and RBC transmission properties, together with an energy-conversion relationship (ECR) derived from Fourier Transform Infrared Spectroscopic analysis (FTIR) of a single shade of photo-polymerized RBC. The ECR describes the localized energy density required to achieve a desired conversion independent of shade. Using this ECR, conversion was predicted and experimentally verified throughout different opacities of RBC based on knowledge of their transmission properties and the incident radiant energy density (irradiance times exposure time). Also, using RBC transmission properties, a critical scrape-back energy of approximately 32 mJcm(-2) was determined from cylindrical samples of photo-polymerized RBC in which the poorly polymerized material was removed. This value correlates to approximately 22% conversion. The critical scrape-back energy was then used to predict scrape-back lengths obtained from samples polymerized at various energy densities. These results confirm the logarithmic relationship between depth of cure and energy of exposure and the reciprocal relationship between irradiance and time of exposure.

Objective: This study explores the relationship between the extent of polymerization and the radiant energy (dose) applied during the photopolymerization of resin-based composites., Method: FTIR was used to measure the 5-min and 24-h conversion of four resin-based composites prepared in a thin film and polymerized under conditions of decreasing intensity and a constant exposure time (30s) using a tungsten halogen curing light. The measured conversion was obtained over a wide range of applied radiant energy. Additionally, samples for two of the materials were polymerized at various intensities and exposure times such that the dose remained constant. This process was performed at four dose levels representing approximately 75% of the conversion range., Results: The curing profiles (percent conversion versus applied radiant energy) depict a gradual decrease in conversion with decreasing energy followed by a rapid descent. Though there are differences in the maximum conversion attained between the materials, when conversion is represented as a fractional conversion relative to the maximum 24-h value, their 5-min and 24-h curing profiles appear quite similar. Additionally, very similar conversion was measured when the films were exposed using equivalent doses providing evidence for a reciprocal relationship between irradiance (power density) and exposure time. For the 24-h measurements, statistical equivalence (Fishers protected LSD at the 0.05 level) was noted for most of the combinations of exposure time and power density within a given dose. Generally, the exceptions occurred with the shortest exposure times., Significance: A reciprocal relationship between exposure time and power density adds significance to the study of conversion as a function of the total applied dose. This relationship establishes the curing profile as a universal correlation between exposure time and power density.