Claudiu T. Lungu

pH-responsive hydrogel cubes for release of doxorubicin in cancer cells

We report on a novel type of shaped hydrogel microparticles which undergo large, rapid, and reversible volume changes in response to solution pH. The cubic hydrogels are produced as interconnected poly(methacrylic acid) (PMAA) network replicas of mesoporous manganese oxide templates by sequential infiltration of (PMAA) and poly(N-vinylpyrrolidone) (PVPON), followed by cross-linking of PMAA and template dissolution. The integrated advantages of the porous cubic sacrificial templates and responsive PMAA matrix enable synthesis of monodisperse and pH-sensitive hydrogel cubes in a rapid, facile, and reproducible manner. These hydrogel cubes display a reversible 2-fold change in size while maintaining their shape in response to pH variations. The swelling behavior of cubic and spherical hydrogel particles is controlled by the network structure which is regulated by the PMAA molecular weight. These networks maintain their three-dimensional shapes in the dry state. No cytotoxicity is found for cubic and spherical hydrogels upon their interactions with human cancer cells for various time intervals. Finally, pH-triggered loading and release of doxorubicin to and from the cubic hydrogels is shown and their anticancer effect is demonstrated. The viability of A549 and HeLa cancer cells was significantly decreased upon interaction with doxorubicin-loaded cubic hydrogels. The approach presented here provides a new platform of multi-functional particles with highly-controlled geometry, size, composition, and responsive properties to be potentially used in targeted drug delivery for cancer therapy.

Influence of temperature on styrene emission from a vinyl ester resin thermoset composite material.

Composite materials made with vinyl ester resins are lighter, stronger and corrosion resistant compared to most metals, and are increasingly being used as building materials and in public transportation. Styrene monomer is used as both a diluent and strengthener in the production of vinyl ester resin (VER) composites. Some researchers contend that free styrene in VER composites is available to diffuse out of the material into air, perhaps leading to adverse health effects via inhalation exposures in humans, yet there is no known data on styrene emissions from these materials in the literature. In this study, a typical VER composite made with resin containing 38% by weight styrene, reinforced with E-glass fiber and formed using a vacuum assisted resin transfer method was characterized for styrene emissions by environmental test chamber (ETC) methodology. Styrene concentrations in the ETC were measured over a temperature range of 10 to 50 °C. Initial evaporative styrene emissions increase with increasing temperature. There is a nearly linear relationship in the total mass of styrene emitted and emission factor as emissions increase with increasing temperature. Styrene emission factors appear to vary for different materials, which could indicate more complex processes or the influence of material physical properties on emission rates. These results can be used to validate and improve mass transfer emission models for the prediction of volatile organic compound concentrations in indoor environments.

Comprehension of hazard communication: Effects of pictograms on safety data sheets and labels

INTRODUCTION The United Nations has proposed the Globally Harmonized System (GHS) of Classification and Labelling of Chemicals to make hazard communication more uniform and to improve comprehension. METHOD Two experiments were conducted to test whether the addition of hazard and precautionary pictograms to safety data sheets and product labels would improve the transfer of information to users compared to safety data sheets and product labels containing text only. Additionally, naïve users, workers, and experts were tested to determine any potential differences among users. RESULTS The effect of adding pictograms to safety data sheets and labels was statistically significant for some conditions, but was not significant across all conditions. One benefit of the addition of pictograms was that the time to respond to the survey questions decreased when the pictograms were present for both the SDS and the labels. GHS format SDS and labels do provide benefits to users, but the system will need further enhancements and modifications to continue to improve the effectiveness of hazard communication. IMPACT ON INDUSTRY The final rule to modify the HCS to include the Globally Harmonized System (GHS) for the Classification and Labelling of Chemicals announced by OSHA (2012b) will change the information content of every chemical SDS and label used in commerce. This study suggests that the inclusion of GHS hazard pictograms and precautionary pictograms to SDS and labels may benefit the user.

Bayesian modeling of exposure and airflow using two-zone models.

Mathematical modeling is being increasingly used as a means for assessing occupational exposures. However, predicting exposure in real settings is constrained by lack of quantitative knowledge of exposure determinants. Validation of models in occupational settings is, therefore, a challenge. Not only do the model parameters need to be known, the models also need to predict the output with some degree of accuracy. In this paper, a Bayesian statistical framework is used for estimating model parameters and exposure concentrations for a two-zone model. The model predicts concentrations in a zone near the source and far away from the source as functions of the toluene generation rate, air ventilation rate through the chamber, and the airflow between near and far fields. The framework combines prior or expert information on the physical model along with the observed data. The framework is applied to simulated data as well as data obtained from the experiments conducted in a chamber. Toluene vapors are generated from a source under different conditions of airflow direction, the presence of a mannequin, and simulated body heat of the mannequin. The Bayesian framework accounts for uncertainty in measurement as well as in the unknown rate of airflow between the near and far fields. The results show that estimates of the interzonal airflow are always close to the estimated equilibrium solutions, which implies that the method works efficiently. The predictions of near-field concentration for both the simulated and real data show nice concordance with the true values, indicating that the two-zone model assumptions agree with the reality to a large extent and the model is suitable for predicting the contaminant concentration. Comparison of the estimated model and its margin of error with the experimental data thus enables validation of the physical model assumptions. The approach illustrates how exposure models and information on model parameters together with the knowledge of uncertainty and variability in these quantities can be used to not only provide better estimates of model outputs but also model parameters.

Comparison of toluene adsorption among granular activated carbon and different types of activated carbon fibers (ACFs).

Activated carbon fiber (ACF) has been demonstrated to be a good adsorbent for the removal of organic vapors in air. Some ACF has a comparable or larger surface area and higher adsorption capacity when compared with granular activated carbon (GAC) commonly used in respiratory protection devices. ACF is an attractive alternative adsorbent to GAC because of its ease of handling, light weight, and decreasing cost. ACF may offer the potential for short-term respiratory protection for first responders and emergency personnel. This study compares the critical bed depths and adsorption capacities for toluene among GAC and ACF of different forms and surface areas. GAC and ACF in cloth (ACFC) and felt (ACFF) forms were challenged in stainless steel chambers with a constant concentration of 500 ppm toluene via conditioned air at 25°C, 50% RH, and constant airflow (7 L/min). Breakthrough data were obtained for each adsorbent using gas chromatography with flame ionization detector. Surface areas of each adsorbent were determined using a physisorption analyzer. Results showed that the critical bed depth of GAC is 275% higher than the average of ACFC but is 55% lower than the average of ACFF. Adsorption capacity of GAC (with a nominal surface area of 1800 m2/g) at 50% breakthrough is 25% higher than the average of ACF with surface area of 1000 m2/g, while the rest of ACF with surface area of 1500 m2/g and higher have 40% higher adsorption capacities than GAC. ACFC with higher surface area has the smallest critical bed depth and highest adsorption capacity, which makes it a good adsorbent for thinner and lighter respirators. We concluded that ACF has great potential for application in respiratory protection considering its higher adsorption capacity and lower critical bed depth in addition to its advantages over GAC, particularly for ACF with higher surface area.

Adsorption Characteristics of Activated Carbon Fibers (ACFs) for Toluene: Application in Respiratory Protection

Granular activated carbon (GAC) is currently the standard adsorbent in respirators against several gases and vapors because of its efficiency, low cost, and available technology. However, a drawback of GAC due to its granular form is its need for containment, adding weight and bulkiness to respirators. This makes respirators uncomfortable to wear, resulting in poor compliance in their use. Activated carbon fibers (ACF) are considered viable alternative adsorbent materials for developing thinner, light-weight, and efficient respirators because of their larger surface area, lighter weight, and fabric form. This study aims to determine the critical bed depth and adsorption capacity of different types of commercially available ACFs for toluene to understand how thin a respirator can be and the service life of the adsorbents, respectively. ACF in cloth (ACFC) and felt (ACFF) forms with three different surface areas per form were tested. Each ACF type was challenged with six concentrations of toluene (50, 100, 200, 300, 400, 500 ppm) at constant air temperature (23°C), relative humidity (50%), and airflow (16 LPM) at different adsorbent weights and bed depths. Breakthrough data were obtained for each adsorbent using gas chromatography with flame ionization detector. The ACFs’ surface areas were measured by an automatic physisorption analyzer. The results showed that ACFC has a lower critical bed depth and higher adsorption capacity compared to ACFF with similar surface area for each toluene concentration. Among the ACF types, ACFC2000 (cloth with the highest measured surface area of 1614 ± 5 m2/g) has one of the lowest critical bed depths (ranging from 0.11–0.22 cm) and has the highest adsorption capacity (ranging from 595–878 mg/g). Based on these studied adsorption characteristics, it is concluded that ACF has great potential for application in respiratory protection against toluene, particularly the ACFC2000, which is the best candidate for developing thinner and efficient respirators.

Comparison of a Novel Surface Laser Scanning Anthropometric Technique to Traditional Methods for Facial Parameter Measurements

This study was designed to determine if three-dimensional (3D) laser scanning techniques could be used to collect accurate anthropometric measurements, compared with traditional methods. The use of an alternative 3D method would allow for quick collection of data that could be used to change the parameters used for facepiece design, improving fit and protection for a wider variety of faces. In our study, 10 facial dimensions were collected using both the traditional calipers and tape method and a Konica-Minolta Vivid9i laser scanner. Scans were combined using RapidForm XOR software to create a single complete facial geometry of the subject as a triangulated surface with an associated texture image from which to obtain measurements. A paired t-test was performed on subject means in each measurement by method. Nine subjects were used in this study: five males (one African-American and four Caucasian females) and four females displaying a range of facial dimensions. Five measurements showed significant differences (p < 0.05), with most accounted for by subject movements or amended by scanning technique modifications. Laser scanning measurements showed high precision and accuracy when compared with traditional methods. Significant differences found can be very small changes in measurements and are unlikely to present a practical difference. The laser scanning technique demonstrated reliable and quick anthropometric data collection for use in future projects in redesigning respirators.

Morphologic and Surface Characterization of Different Types of Activated Carbon Fibres

This study provides a comparison of different types of commercially available activated carbon fibres (ACFs). Thus, ACFs in cloth (ACFC) and felt forms (ACFF) with three different surface areas were each analyzed for their pore volumes, pore sizes and pore-size distributions. The fibre morphology and organization was visualized using scanning electron microscopy (SEM). The microporosity of the ACF materials based on nitrogen isotherms, the percentage of micropores by area and volume, the average pore size and the pore-size distribution were also determined. An increase in the surface areas of the ACFC types led to an increase in the total pore volume, micropore volume, micropore area and pore width, but led to a decrease in the percentage of micropores by area and volume. The nitrogen isotherms demonstrated that the surface area dictated the amount of adsorption onto the ACF regardless of the form of the latter. The difference in the volume of smaller micropores between the ACFC and ACFF types may be attributed to the difference in the adsorbent density and the accessibility of the fibre surface to the activating gas during the activation process. An understanding of the pore structure of ACFs by form and surface area is crucial in determining the appropriate specific applications of such adsorbents.

Breakthrough Curves for Toluene Adsorption on Different Types of Activated Carbon Fibers: Application in Respiratory Protection

Activated carbon fibers (ACF) are considered viable alternative adsorbent materials in respirators because of their larger surface area, lighter weight, and fabric form. The purpose of this study was to characterize the breakthrough curves of toluene for different types of commercially available ACFs to understand their potential service lives in respirators. Two forms of ACF, cloth (AC) and felt (AF), with three surface areas each were tested. ACFs were challenged with six toluene concentrations (50-500 p.p.m.) at constant air temperature (23°C), relative humidity (50%), and air flow (16 l min-1) at different bed depths. Breakthrough data were obtained using continuous monitoring by gas chromatography using a gas sampling valve. The ACF specific surface areas were measured by an automatic physisorption analyzer. Results showed unique shapes of breakthrough curves for each ACF form: AC demonstrated a gradual increase in breakthrough concentration, whereas AF showed abrupt increase in concentration from the breakpoint, which was attributed to the difference in fiber density between the forms. AF has steeper breakthrough curves compared with AC with similar specific surface area. AC exhibits higher 10% breakthrough times for a given bed depth due to higher mass per bed depth compared with AF, indicating more adsorption per bed depth with AC. ACF in respirators may be appropriate for use as protection in environments with toluene concentration at the Occupational Safety and Health Administration Permissible Exposure Limit, or during emergency escape for higher toluene concentrations. ACF has shown great potential for application in respiratory protection against toluene and in the development of thinner, lighter, and more efficient respirators.

Preparation and characterization of flax, hemp and sisal fiber-derived mesoporous activated carbon adsorbents

The first aim of this study was to investigate mesoporous activated carbon adsorbents from sisal, hemp, and flax fibers by cost-effective methods. Fibers were impregnated with low concentration (20 wt.%) phosphoric acid. Carbonization temperatures were defined by thermal analysis. Bast fibers (hemp, flax) decompose at lower temperatures (419.36℃, 434.96℃) than leaf fibers (sisal, 512.92℃). The second aim was to compare bast and leaf fibers-derived activated carbon adsorbents by determining physical adsorption properties, chemical compositions, scanning electron microscope, and Fourier transform infrared spectroscopy. Results showed that natural fibers have good candidates to prepare mesoporous activated carbon adsorbents with high surface area (1186–1359 m2/g), high mesopore percentage (60–72%), and high C content (80–86%). Even though leaf-derived activated carbon developed more mesoporous structure (72%), bast-derived activated carbons provided higher surface areas (Shemp = 1359 m2/g; Sflax = 1257 m2/g) and C content. Fourier transform infrared spectra for bast fibers-derived activated carbon adsorbents were quite similar while leaf fiber-derived activated carbon adsorbent had a different spectrum.