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1.
Anal Chem ; 96(11): 4343-4358, 2024 03 19.
Artigo em Inglês | MEDLINE | ID: mdl-38452774

RESUMO

Microplastics are increasingly reported, not only in the environment but also in a wide range of food commodities. While studies on microplastics in food abound, the current state of science is limited in its application to regulatory risk assessment by a continued lack of standardized definitions, reference materials, sample collection and preparation procedures, fit-for purpose analytical methods for real-world and environmentally relevant plastic mixtures, and appropriate quality controls. This is particularly the case for nanoplastics. These methodological challenges hinder robust, quantitative exposure assessments of microplastic and nanoplastic mixtures from food consumption. Furthermore, limited toxicological studies on whether microplastics and nanoplastics adversely impact human health are also impeded by methodology challenges. Food safety regulatory agencies must consider both the exposure and the risk of contaminants of emerging concern to ascertain potential harm. Foundational to this effort is access to and application of analytical methods with the capability to quantify and characterize micro- and nanoscale sized polymers in complex food matrices. However, the early stages of method development and application of early stage methods to study the distribution and potential health effects of microplastics and nanoplastics in food have largely been done without consideration of the stringent requirements of methods to inform regulatory activities. We provide regulatory science perspectives on the state of knowledge regarding the occurrence of microplastics and nanoplastics in food and present our general approach for developing, validating, and implementing analytical methods for regulatory purposes.


Assuntos
Microplásticos , Poluentes Químicos da Água , Humanos , Plásticos/análise , Poluentes Químicos da Água/análise , Inocuidade dos Alimentos
2.
Environ Sci Technol ; 52(16): 9468-9477, 2018 08 21.
Artigo em Inglês | MEDLINE | ID: mdl-30004222

RESUMO

We fabricated polymer nanocomposites (PNCs) from low-density polyethylene and CdSe quantum dots (QDs) and used these materials to explore potential exposure after long-term storage in different acidic media that could be encountered in food contact applications. While the low-level release of QD-associated mass into all the food simulants was observed, exposure to dilute acetic acid resulted in more than double the mass transfer compared to that which occurred during exposure to dilute hydrochloric acid at the same pH. Conversely, exposure to citric acid resulted in a suppression of QD release. Permeation experiments and confocal microscopy were used to reveal mechanistic details underlying these mass-transfer phenomena. From this work, we conclude that the permeation of undissociated acid molecules into the polymer, limited by partitioning of the acids into the hydrophobic polymer, plays a larger role than pH in determining exposure to nanoparticles embedded in plastics. Although caution must be exercised when extrapolating these results to PNCs incorporating other nanofillers, these findings are significant because they undermine current thinking about the influence of pH on nanofiller release phenomena. From a regulatory standpoint, these results also support current guidance that 3% acetic acid is an acceptable acidic food simulant for PNCs fabricated from hydrophobic polymers because the other acids investigated resulted in significantly less exposure.


Assuntos
Compostos de Cádmio , Nanocompostos , Pontos Quânticos , Compostos de Selênio , Polímeros
3.
Compr Rev Food Sci Food Saf ; 13(4): 669-678, 2014 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-33412712

RESUMO

This article is one of a series of 4 that report on a task of the NanoRelease Food Additive (NRFA) project of the International. Life Science Institute Center for Risk Science Innovation and Application. The project aims are to identify, evaluate, and develop methods that are needed to confidently detect, characterize, and quantify intentionally produced engineered nanomaterials (ENMs) released from food along the alimentary tract. This particular article offers an overview of the NRFA project, describing the project scope and goals, as well as the strategy by which the task group sought to achieve these goals. A condensed description of the general challenge of detecting ENMs in foods and a brief review of available and emerging methods for ENM detection is provided here, paying particular attention to the kind of information that might be desired from an analysis and the strengths and weaknesses of the various approaches that might be used to attain this information. The article concludes with an executive summary of the task group's broad findings related to the 3 topic areas, which are covered in more detail in 3 subsequent articles in this series. The end result is a thorough evaluation of the state of ENM measurement science specifically as it applies to oral uptake of ENMs from human dietary sources.

4.
Compr Rev Food Sci Food Saf ; 13(4): 705-729, 2014 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-33412716

RESUMO

This article is one of a series of 4 that report on a task of the NanoRelease Food Additive project of the International Life Science Institute Center for Risk Science Innovation and Application to identify, evaluate, and develop methods that are needed to confidently detect, characterize, and quantify intentionally produced engineered nanomaterials (ENMs) released from food along the alimentary tract. This particular article focuses on the problem of detecting and characterizing ENMs in the various compartments of the alimentary tract after they have been ingested from dietary sources. An in depth analysis of the literature related to oral toxicity of ENMs is presented, paying particular attention to analytical methodology and sample preparation. The review includes a discussion of model systems that can be used to study oral uptake of ENMs in the absence of human toxicological data or other live-animal studies. The strengths and weaknesses of various analytical and sample preparation techniques are discussed. The article concludes with a summary of findings and a discussion of potential knowledge gaps and targets for method development in this area.

5.
Compr Rev Food Sci Food Saf ; 13(4): 679-692, 2014 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-33412706

RESUMO

This article is one of a series of 4 that report on a task of the NanoRelease Food Additive project of the Intl. Life Science Inst. Center for Risk Science Innovation and Application to identify, evaluate, and develop methods that are needed to confidently detect, characterize, and quantify intentionally produced engineered nanomaterials (ENMs) released from food along the alimentary tract. This particular article focuses on the problem of detecting ENMs that become released into food indirectly from food contact materials. In this review, an in-depth analysis of the release literature is presented and relevant release mechanisms are discussed. The literature review includes discussion of articles related to the release phenomenon in general, as experimental methods to detect ENMs migrating from plastic materials into other (nonfood) complex matrices were determined to be relevant to the focus problem of food safety. From the survey of the literature, several "control points" were identified where characterization data on ENMs and materials may be most valuable. The article concludes with a summary of findings and a discussion of potential knowledge gaps and targets for method development in this area.

6.
Compr Rev Food Sci Food Saf ; 13(4): 693-704, 2014 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-33412711

RESUMO

This article is one of a series of 4 that reports on a task of the NanoRelease Food Additive project of the International Life Science Institute Center for Risk Science Innovation and Application to identify, evaluate, and develop methods that are needed to confidently detect, characterize, and quantify intentionally produced engineered nanomaterials (ENMs) released from food along the alimentary tract. This particular article focuses on the problem of detecting ENMs in food, paying special attention to matrix interferences and how to deal with them. In this review, an in-depth analysis of the literature related to detection of ENMs in complex matrices is presented. The literature review includes discussions of sampling methods, such as centrifugation and ENM extraction. Available analytical methods, as well as emerging methods, are also presented. The article concludes with a summary of findings and an overview of potential knowledge gaps and targets for method development in this area.

7.
J Hazard Mater ; 439: 129687, 2022 10 05.
Artigo em Inglês | MEDLINE | ID: mdl-36104913

RESUMO

Polymers incorporating quantum dots (QDs) have attracted interest as components of next-generation consumer products, but there is uncertainty about how these potentially hazardous materials may impact human health and the environment. We investigated how the transport (migration) of QDs out of polymers and into the environment is linked to their size and surface characteristics. Cadmium selenide (CdSe) QDs with diameters ranging from 2.15 to 4.63 nm were incorporated into low-density polyethylene (LDPE). Photoluminescence was used as an indicator of QD surface defect density. Normalized migration of QDs into 3% acetic acid over 15 days ranged from 13.1 ± 0.6-452.5 ± 31.9 ng per cm2 of polymer surface area. Migrated QD mass was negatively correlated to QD diameter and was also higher when QDs had photoluminescence consistent with larger surface defect densities. The results imply that migration is driven by oxidative degradation of QDs originating at surface defect sites and transport of oxidation products along concentration gradients. A semi-empirical framework was developed to model the migration data. The model supports this mechanism and suggests that QD surface reactivity also drives the relationship between QD size and migration, with specific surface area playing a less important role.


Assuntos
Compostos de Cádmio , Pontos Quânticos , Compostos de Selênio , Humanos , Tamanho da Partícula , Plásticos , Polímeros
8.
NanoImpact ; 28: 100426, 2022 10.
Artigo em Inglês | MEDLINE | ID: mdl-36096361

RESUMO

We show that inorganic sulfides strongly influence transfer (migration) of nanoparticle mass out of polymer nanocomposites (PNCs) and into aqueous environments. We first manufactured two families of PNCs: one incorporating silver nanoparticles (AgNPs) and one incorporating CdSe quantum dots (QDs). Then, we assessed migration out of these PNCs and into aqueous media containing Na2S at concentrations ranging from 0 to 10-4 M. Results show that Na2S strongly suppressed migration of Ag from AgNP-based PNCs: the migration into water spiked with 10-6 M Na2S was 79% less than migration into water without Na2S, and no migration was detected (LOD ≈ 0.01 ng/cm2) in water spiked with Na2S at 10-5 M or 10-4 M. With CdSe QD-based PNCs, Na2S suppressed Cd migration but enhanced Se migration, resulting in only a small net effect on the total QD migration but a large shift of the leachate composition (from favoring Cd by an average of 5.8 to 1 in pure water to favoring Se 9.4 to 1 when Na2S was present at 10-4 M). These results show that common inorganic substances like sulfides may play a strong role in determining the environmental fate of polymer-dispersed nanoparticles and imply that migration tests conducted in purified water may not always accurately reflect migration into real environments.


Assuntos
Nanopartículas Metálicas , Sulfetos , Plásticos , Cádmio , Prata , Água
9.
Nat Nanotechnol ; 16(3): 251-265, 2021 03.
Artigo em Inglês | MEDLINE | ID: mdl-33712739

RESUMO

Nanotechnology-adapted detection technologies could improve the safety and quality of foods, provide new methods to combat fraud and be useful tools in our arsenal against bioterrorism. Yet despite hundreds of published studies on nanosensors each year targeted to the food and agriculture space, there are few nanosensors on the market in this area and almost no nanotechnology-enabled methods employed by public health agencies for food analysis. This Review shows that the field is currently being held back by technical, regulatory, political, legal, economic, environmental health and safety, and ethical challenges. We explore these challenges in detail and provide suggestions about how they may be surmounted. Strategies that may have particular effectiveness include improving funding opportunities and publication venues for nanosensor validation, social science and patent landscape studies; prioritizing research and development of nanosensors that are specifically designed for rapid analysis in non-laboratory settings; and incorporating platform cost and adaptability into early design decisions.


Assuntos
Agricultura/tendências , Técnicas Biossensoriais/tendências , Nanotecnologia/tendências , Análise de Alimentos/métodos , Inocuidade dos Alimentos , Humanos
10.
ACS Appl Mater Interfaces ; 13(1): 1398-1412, 2021 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-33398990

RESUMO

Nanotechnology-based packaging may improve food quality and safety, but packages manufactured with polymer nanocomposites (PNCs) could be a source of human dietary exposure to engineered nanomaterials (ENMs). Previous studies showed that PNCs release ENMs to foods predominantly in a dissolved state, but most of this work used food simulants like dilute acetic acid and water, leaving questions about how substances in real foods may influence exposure. Here, we demonstrate that food and beverage ingredients with reducing properties, like sweeteners, may alter exposure by inducing nanoparticle formation in foods contacting silver nanotechnology-enabled packaging. We incorporated 12.8 ± 1.4 nm silver nanoparticles (AgNPs) into polyethylene and stored media containing reducing ingredients in packages manufactured from this material under accelerated room-temperature and refrigerated conditions. Analysis of the leachates revealed that reducing ingredients increased the total silver transferred to foods contacting PNC packaging (by as much as 7-fold) and also induced the (re)formation of AgNPs from this dissolved silver during storage. AgNP formation was also observed when Ag+ was introduced to solutions of natural and artificial sweeteners (glucose, sucrose, aspartame), commercial beverages (soft drinks, juices, milk), and liquid foods (yogurt, starch slurry), and the amount and morphology of reformed AgNPs depended on the ingredient formulation, silver concentration, storage conditions, and light exposure. These results imply that food and beverage ingredients may influence dietary exposure to nanoparticles when PNCs are used in packaging applications, and the practice of using food simulants may in certain cases underpredict the amount of ENMs likely to be found in foods stored in these materials.


Assuntos
Bebidas , Embalagem de Alimentos , Nanopartículas Metálicas/química , Prata/química , Animais , Aspartame/química , Temperatura Baixa , Contaminação de Alimentos/análise , Glucose/química , Nanopartículas Metálicas/análise , Oxirredução , Polietileno/química , Prata/análise , Amido/química , Sacarose/química , Edulcorantes/química , Iogurte
11.
ACS Sens ; 5(7): 2118-2127, 2020 07 24.
Artigo em Inglês | MEDLINE | ID: mdl-32527082

RESUMO

Botulinum neurotoxins (BoNTs) are potent toxins produced by Clostridium bacteria that are responsible for the illness botulism and are listed as bioterrorism agents. BoNT serotype E (BoNT/E) is one of four BoNT serotypes that cause human botulism and is the second most frequent cause of foodborne botulism. Rapid detection and discrimination of BoNT serotypes implicated in human disease are critical for ensuring timely treatment of patients and identifying sources of toxins, but there have been few reported detection methods for BoNT/E and even fewer methods usable for BoNT serotyping. We report a nanobiosensor based on Förster resonance energy transfer (FRET) between semiconductor nanocrystals (quantum dots, QDs) and dark quencher-labeled peptide probes to detect biologically active BoNT/E in aqueous media. The peptide probes contain a specific cleavage site for active BoNT/E. QD photoluminescence, which changes intensity due to FRET when the peptide probe is cleaved, was used to indicate toxin presence and quantity. The detection of a BoNT/E light chain (LcE) and holotoxin was observed within 3 h. The limits of detection were 0.02 and 2 ng/mL for LcE and holotoxin, respectively. The nanobiosensor shows good specificity toward the target in tests with nontarget BoNT serotypes. The high sensitivity, simple operation, short detection time, and ability to be used in parallel with probes developed for other BoNT serotypes indicate that the nanobiosensor will be useful for rapid BoNT/E detection and serotype discrimination in food analysis.


Assuntos
Toxinas Botulínicas , Botulismo , Pontos Quânticos , Transferência Ressonante de Energia de Fluorescência , Humanos , Sorogrupo
12.
Toxicol Sci ; 178(1): 201-211, 2020 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-33111940

RESUMO

Toxicological risk assessment approaches are increasingly being used in lieu of animal testing to address toxicological concerns associated with release of chemical constituents from polymeric medical device components. These approaches currently rely on in vitro extraction testing in aggressive environments to estimate patient exposure to these constituents, but the clinical relevance of the test results is often ambiguous. Physics-based mass transport models can provide a framework to interpret extraction test results to provide more clinically relevant exposure estimates. However, the models require system-specific material properties, such as diffusion (D) and partition coefficients (K), to be established a priori for the extraction conditions. Using systems comprised high-density polyethylene and 4 different additives, we demonstrate that these properties can be quantified through standard extraction testing in hexane and isopropyl alcohol. The values of D and K derived in this manner were consistent with theoretical predictions for these quantities. Based on these results, we discuss both the challenges and benefits to leveraging extraction data to parameterize physics-based exposure models. Our observations suggest that clinically relevant, yet still conservative, exposure dose estimates provided by applying this approach to a single extraction measurement can be more than 100 times lower than would be measured under typical aggressive extraction conditions. However, to apply the framework on a routine basis, limiting values of D and K must be established for device-relevant systems either through the aggregation and analysis of more extensive extraction test data and/or advancements in theoretical and computational modeling efforts to predict these quantities.


Assuntos
Equipamentos e Provisões/efeitos adversos , Polímeros , Animais , Humanos , Modelos Teóricos , Polietileno , Polímeros/efeitos adversos , Medição de Risco
13.
J Phys Chem B ; 113(40): 13216-21, 2009 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-19791819

RESUMO

We report a new method to generate families of organic fluorophores with any desirable emission wavelengths based upon the controlled oxidation of the light-emitting conjugated polymer, poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV), with meta-chloroperbenzoic acid (m-CPBA). In this method, m-CPBA reacts with ethylene moieties along the MEH-PPV backbone to create conjugation breaks, which gives rise to a gradual and controllable change in the emission wavelength. By simply adjusting the reaction time, light-emitting polymers possessing emission wavelengths spanning a 470-555 nm wavelength range can be easily prepared. Significantly, fluorescence quantum yields (QYs) of the oxidized polymers were comparable to or greater than that of the pristine polymer, contrary to the products typically resulting from oxidation of MEH-PPV by dioxygen. This new method should provide a simple way to generate color-tunable organic fluorophores with high QYs in a time- and cost-effective manner.


Assuntos
Cor , Corantes Fluorescentes/química , Luz , Fotoquímica/métodos , Polímeros/química , Clorobenzoatos/química , Estrutura Molecular , Oxidantes/química , Oxirredução , Compostos de Vinila/química
14.
ACS Omega ; 4(8): 13349-13359, 2019 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-31460463

RESUMO

Clay/polymer nanocomposites (CPNs) are polymers incorporating refined clay particles that are frequently functionalized with quaternary ammonium cations (QACs) as dispersion aids. There is interest in commercializing CPNs for food contact applications because they have improved strength and barrier properties, but there are few studies on the potential for QACs in CPNs to transfer to foods under conditions of intended use. In this study, we manufactured low-density poly(ethylene) (LDPE)-based CPNs and assessed whether QACs can migrate into several food simulants under accelerated storage conditions. QACs were found to migrate to a fatty food simulant (ethanol) at levels of ∼1.1 µg mg-1 CPN mass after 10 days at 40 °C, constituting about 4% total migration (proportion of the initial QAC content in the CPN that migrated to the simulant). QAC migration into ethanol was ∼16× higher from LDPE containing approximately the same concentration of QACs but no clay, suggesting that most QACs in the CPN are tightly bound to clay particles and are immobile. Negligible QACs were found to migrate into aqueous, alcoholic, or acidic simulants from CPNs, and the amount of migrated QACs was also found to scale with the temperature and the initial clay concentration. The migration data were compared to a theoretical diffusion model, and it was found that the diffusion constant for QACs in the CPN was several orders of magnitude slower than predicted, which we attributed to the potential for QACs to migrate as dimers or other aggregates rather than as individual ions. Nevertheless, the use of the migration model resulted in a conservative estimate of the mass transfer of QAC from the CPN test specimens.

15.
J Am Chem Soc ; 130(30): 9773-84, 2008 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-18611010

RESUMO

Formed through cooperative self-assembly of amphiphilic diblock copolymers and electronically conjugated porphyrinic near-infrared (NIR) fluorophores (NIRFs), NIR-emissive polymersomes (50 nm to 50 microm diameter polymer vesicles) define a family of organic-based, soft-matter structures that are ideally suited for deep-tissue optical imaging and sensitive diagnostic applications. Here, we describe magic angle and polarized pump-probe spectroscopic experiments that: (i) probe polymersome structure and NIRF organization and (ii) connect emitter structural properties and NIRF loading with vesicle emissive output at the nanoscale. Within polymersome membrane environments, long polymer chains constrain ethyne-bridged oligo(porphinato)zinc(II) based supermolecular fluorophore (PZn n ) conformeric populations and disperse these PZn n species within the hydrophobic bilayer. Ultrafast excited-state transient absorption and anisotropy dynamical studies of NIR-emissive polymersomes, in which the PZn n fluorophore loading per nanoscale vesicle is varied between 0.1-10 mol %, enable the exploration of concentration-dependent mechanisms for nonradiative excited-state decay. These experiments correlate fluorophore structure with its gross spatial arrangement within specific nanodomains of these nanoparticles and reveal how compartmentalization of fluorophores within reduced effective dispersion volumes impacts bulk photophysical properties. As these factors play key roles in determining the energy transfer dynamics between dispersed fluorophores, this work underscores that strategies that modulate fluorophore and polymer structure to optimize dispersion volume in bilayered nanoscale vesicular environments will further enhance the emissive properties of these sensitive nanoscale probes.


Assuntos
Corantes Fluorescentes/química , Metaloporfirinas/química , Nanopartículas/química , Polímeros/química , Espectroscopia de Luz Próxima ao Infravermelho/métodos , Zinco/química , Materiais Biocompatíveis/química , Butadienos/química , Elastômeros/química , Interações Hidrofóbicas e Hidrofílicas , Cinética , Modelos Moleculares , Polietilenoglicóis/química , Termodinâmica
16.
J AOAC Int ; 101(6): 1873-1880, 2018 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-29852893

RESUMO

Background: A flow-injection MS (FI/MS) method was evaluated for the quantitation of quaternary ammonium cations (QACs) in simple food simulants. Methods: The calibration standard was dimethyldioctadecyl ammonium ion (C18-C18), and the internal standard was benzyldimethylhexadecyl (BDMHD) ammonium ion. Calibration standards based on the C18-C18 ion were prepared in ethanol with a range of 5 to 500 ppb and contained 100 ppb BDMHD. The mobile phase was 90 + 10 (v/v) acetonitrile-5 mM aqueous ammonium acetate and flowed directly into an electrospray source of the mass spectrometer. Detection was accomplished by single ion recording (SIR) in positive mode. Results: Calibration curves were linear with coefficients of determination above 0.995, and the LOQ was 5 ppb. Recoveries of four QACs derived from Arquad 2HT-75, a commercially available surfactant, were measured in common food simulants: ethanol, water, 10% (v/v) ethanol in water, and 3% (v/v) aqueous acetic acid. A solvent exchange procedure was employed for the three aqueous solvents, which included complete evaporation of the sample followed by reconstitution in ethanol prior to injection. The solvent exchange method minimized losses because of QAC adsorption on glass surfaces. Recoveries ranged from 74.4 ± 4.0 to 106.7 ± 6.6% for the two most abundant Arquad 2HT-75 component cations, dimethyldioctadecyl ammonium and dimethyloctadecyl-hexadecyl ammonium. Conclusions: This method is suitable to quantify trace levels of QACs in food simulants as part of exposure evaluations related to their use in emerging food contact materials.


Assuntos
Espectrometria de Massas/métodos , Compostos de Amônio Quaternário/análise , Ácido Acético/química , Calibragem , Etanol/química , Água/química
17.
J Biomed Mater Res B Appl Biomater ; 106(1): 310-319, 2018 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-28140510

RESUMO

Many polymeric medical device materials contain color additives which could lead to adverse health effects. The potential health risk of color additives may be assessed by comparing the amount of color additive released over time to levels deemed to be safe based on available toxicity data. We propose a conservative model for exposure that requires only the diffusion coefficient of the additive in the polymer matrix, D, to be specified. The model is applied here using a model polymer (poly(ether-block-amide), PEBAX 2533) and color additive (quinizarin blue) system. Sorption experiments performed in an aqueous dispersion of quinizarin blue (QB) into neat PEBAX yielded a diffusivity D = 4.8 × 10-10 cm2  s-1 , and solubility S = 0.32 wt %. On the basis of these measurements, we validated the model by comparing predictions to the leaching profile of QB from a PEBAX matrix into physiologically representative media. Toxicity data are not available to estimate a safe level of exposure to QB, as a result, we used a Threshold of Toxicological Concern (TTC) value for QB of 90 µg/adult/day. Because only 30% of the QB is released in the first day of leaching for our film thickness and calculated D, we demonstrate that a device may contain significantly more color additive than the TTC value without giving rise to a toxicological concern. The findings suggest that an initial screening-level risk assessment of color additives and other potentially toxic compounds found in device polymers can be improved. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 310-319, 2018.


Assuntos
Antraquinonas , Corantes , Modelos Químicos , Nylons/química , Antraquinonas/química , Antraquinonas/farmacocinética , Corantes/química , Corantes/farmacocinética , Medição de Risco
18.
Ann Biomed Eng ; 46(1): 14-24, 2018 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-28948381

RESUMO

A novel approach for rapid risk assessment of targeted leachables in medical device polymers is proposed and validated. Risk evaluation involves understanding the potential of these additives to migrate out of the polymer, and comparing their exposure to a toxicological threshold value. In this study, we propose that a simple diffusive transport model can be used to provide conservative exposure estimates for phase separated color additives in device polymers. This model has been illustrated using a representative phthalocyanine color additive (manganese phthalocyanine, MnPC) and polymer (PEBAX 2533) system. Sorption experiments of MnPC into PEBAX were conducted in order to experimentally determine the diffusion coefficient, D = (1.6 ± 0.5) × 10-11 cm2/s, and matrix solubility limit, C s = 0.089 wt.%, and model predicted exposure values were validated by extraction experiments. Exposure values for the color additive were compared to a toxicological threshold for a sample risk assessment. Results from this study indicate that a diffusion model-based approach to predict exposure has considerable potential for use as a rapid, screening-level tool to assess the risk of color additives and other small molecule additives in medical device polymers.


Assuntos
Corantes/química , Modelos Teóricos , Polímeros/química , Qualidade de Produtos para o Consumidor , Difusão , Equipamentos e Provisões , Indóis/química , Isoindóis , Medição de Risco
19.
J Phys Chem B ; 111(24): 6829-38, 2007 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-17489628

RESUMO

The electron transfer (ET) dynamics of an unusually rigid pi-stacked (porphinato)zinc(II)-spacer-quinone (PZn-Q) system, [5-[8'-(4' '-[8' ''-(2' '' ',5' '' '-benzoquinonyl)-1' ''-naphthyl]-1' '-phenyl)-1'-naphthyl]-10,20-diphenylporphinato]zinc(II) (2a-Zn), in which sub-van der Waals interplanar distances separate juxtaposed porphyryl, aromatic bridge, and quinonyl components of this assembly, have been measured by ultrafast pump-probe transient absorption spectroscopy over a 80-320 K temperature range in 2-methyl tetrahydrofuran (2-MTHF) solvent. Analyses of the photoinduced charge-separation (CS) rate data are presented within the context of several different theoretical frameworks. Experiments show that at higher temperatures the initially prepared 2a-Zn vibronically excited S1 state relaxes on an ultrafast time scale, and ET is observed exclusively from the equilibrated lowest-energy S1 state (CS1). As the temperature decreases, production of the photoinduced charge-separated state directly from the vibrationally unrelaxed S1 state (CS2) becomes competitive with the vibrational relaxation time scale. At the lowest experimentally interrogated temperature ( approximately 80 K), CS2 defines the dominant ET pathway. ET from the vibrationally unrelaxed S1 state is temperature-independent and manifests a subpicosecond time constant; in contrast, the CS1 rate constant is temperature-dependent, exhibiting time constants ranging from 4x10(10) s(-1) to 4x10(11) s(-1) and is correlated strongly with the temperature-dependent solvent dielectric relaxation time scale over a significant temperature domain. Respective electronic coupling matrix elements for each of these photoinduced CS1 and CS2 pathways were determined to be approximately 50 and approximately 100 cm-1. This work not only documents a rare, if not unique, example of a system where temperature-dependent photoinduced charge-separation (CS) dynamics from vibrationally relaxed and unrelaxed S1 states can be differentiated, but also demonstrates a temperature-dependent mechanistic transition of photoinduced CS from the nonadiabatic to the solvent-controlled adiabatic regime, followed by a second temperature-dependent mechanistic evolution where CS becomes decoupled from solvent dynamics and is determined by the extent to which the vibrationally unrelaxed S1 state is populated.

20.
Curr Opin Biotechnol ; 44: 74-86, 2017 04.
Artigo em Inglês | MEDLINE | ID: mdl-27940406

RESUMO

As far as chemical analysis is concerned, foods are among the most difficult matrices to work with because they are complex, heterogeneous substances with a high degree of variety. Assaying foods for trace levels of chemical and microbiological substances is a challenge that often requires the application of time-consuming, expensive analytical instrumentation in dedicated facilities populated by highly trained personnel. Therefore there is a continued demand for new analytical technologies that can detect small concentrations of chemicals or microbes in a more cost- and time-effective manner, preferably in the field, on the production line, and/or non-destructively, with little to no sample pre-treatment, and possibly by individuals with scant scientific training. In the last decade, nanotechnology - a branch of science that takes advantage of the unique chemical and physical properties of matter on the nanoscale - has created new opportunities for both qualitative and quantitative detection of vapors/gasses, small molecules, biopolymers, and even living microbes in a fraction of the time and expense of traditional analytical techniques. This article offers a focused review of recent progress in nanotechnology-enabled biosensing as applied to foods and related matrices, paying particular attention to trends in the field, recent breakthroughs, and current areas of need. Special focus is paid to two primary categories of nanobiosensors - optical and electrochemical - and the discussion includes a comparison of their various strengths and weaknesses as they pertain ensuring the safety of the food supply.


Assuntos
Técnicas Biossensoriais/métodos , Inocuidade dos Alimentos/métodos , Nanotecnologia/métodos , Humanos
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