Fluoropolymer Nanoparticles Prepared Using Trifluoropropene Telomer Based Fluorosurfactants.

A fluorosurfactant based on 3,3,3-trifluoropropene (TFP) telomer was synthesized as an environmentally friendly alternative to perfluorooctanoic acid (PFOA) using TFP and 2-iodoperfluoropropane ((CF3)2CF-I) as starting materials. TFP telomerization was initiated by addition of di-tert-butylperoxide in the presence of (CF3)2CF-I as a chain transfer agent. The surfactant was obtained by modification of the iodine end-group on the TFP telomer to form an allylic functionality followed by the addition of thioglycolic acid via a thiol-ene reaction. The resulting fluorosurfactant exhibited a lower critical micellar concentration (CMC = 0.87 g·L-1) than that of PFOA (CMC = 3.0 g·L-1). This surfactant was used to prepare fluoropolymer nanoparticles by solvent evaporation from a solution composed of the surfacant and poly[2-(perfluorobutyl)ethyl methacrylate]. The oil-in-water emulsion was initially formed due to the adsorption of the surfactant molecules at the oil/water interface and subsequently converted into a nanoparticle suspension after solvent evaporation. Because of the strong hydrophobic interactions between the fluorinated surfactant tail and fluoropolymer, the obtained nanoparticle suspension was quite stable against water dialysis.

A monolithic immersion metalens for imaging solid-state quantum emitters.

Quantum emitters such as the diamond nitrogen-vacancy (NV) center are the basis for a wide range of quantum technologies. However, refraction and reflections at material interfaces impede photon collection, and the emitters' atomic scale necessitates the use of free space optical measurement setups that prevent packaging of quantum devices. To overcome these limitations, we design and fabricate a metasurface composed of nanoscale diamond pillars that acts as an immersion lens to collect and collimate the emission of an individual NV center. The metalens exhibits a numerical aperture greater than 1.0, enabling efficient fiber-coupling of quantum emitters. This flexible design will lead to the miniaturization of quantum devices in a wide range of host materials and the development of metasurfaces that shape single-photon emission for coupling to optical cavities or route photons based on their quantum state.

Nanocardboard as a nanoscale analog of hollow sandwich plates.

Corrugated paper cardboard provides an everyday example of a lightweight, yet rigid, sandwich structure. Here we present nanocardboard, a monolithic plate mechanical metamaterial composed of nanometer-thickness (25-400 nm) face sheets that are connected by micrometer-height tubular webbing. We fabricate nanocardboard plates of up to 1 centimeter-square size, which exhibit an enhanced bending stiffness at ultralow mass of ~1 g m-2. The nanoscale thickness allows the plates to completely recover their shape after sharp bending even when the radius of curvature is comparable to the plate height. Optimally chosen geometry enhances the bending stiffness and spring constant by more than four orders of magnitude in comparison to solid plates with the same mass, far exceeding the enhancement factors previously demonstrated at both the macroscale and nanoscale. Nanocardboard may find applications as a structural component for wings of microflyers or interstellar lightsails, scanning probe cantilevers, and other microscopic and macroscopic systems.

Investigation of a novel fluorinated surfactant-based system for the design of spherical wormhole-like mesoporous silica.

In contrast to hydrogenated based systems that led to many studies, fluorinated surfactants have been little reported. Thanks to their high chemical and thermal stability, these compounds are considered as suitable candidates for the synthesis of porous materials with an enhanced hydrothermal stability. This study reports the synthesis of a new fluorinated surfactant, 2-trifluoromethyl-7,7,8,8,9,9,10,10,11,11,12,12,12-tridecafluoro-4-thia-1-dodecanoic acid (FSC) obtained from the thiol-ene radical addition of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanethiol onto 2-trifluoromethyl acrylic acid in 85% yield. In the aim of achieving micelles in water to design mesoporous materials according to the cooperative templating mechanism, FSC was modified with water-soluble telechelic diamine (Jeffamine) ED-600. The modified surfactant was deeply characterized by spectroscopic methods and the FSC-Jeffamine ED-600 micellar system was used as porogen to prepare mesoporous materials via the cooperative templating mechanism. Spherical wormhole-like mesostructured silica materials of high specific surface area (850m2/g) and homogeneous pore size distribution (ca. 3.4nm) were obtained by conveniently adjusting the porogen/silica molar ratio and the hydrothermal conditions.

19 F DOSY diffusion-NMR spectroscopy of fluoropolymers.

A new pulse sequence for obtaining 19 F detected DOSY (diffusion ordered spectroscopy) spectra of fluorinated molecules is presented and used to study fluoropolymers based on vinylidene fluoride and chlorotrifluoroethylene. The performance of 19 F DOSY NMR experiments (and in general any type of NMR experiment) on fluoropolymers creates some unique complications that very often prevent detection of important signals. Factors that create these complications include: (1) the presence of many scalar couplings among 1 H, 19 F and 13 C; (2) the large magnitudes of many 19 F homonuclear couplings (especially 2 JFF ); (3) the large 19 F chemical shift range; and (4) the low solubility of these materials (which requires that experiments be performed at high temperatures). A systematic study of the various methods for collecting DOSY NMR data, and the adaptation of these methods to obtain 19 F detected DOSY data, has been performed using a mixture of low molecular weight, fluorinated model compounds. The best pulse sequences and optimal experimental conditions have been determined for obtaining 19 F DOSY spectra. The optimum pulse sequences for acquiring 19 F DOSY NMR data have been determined for various circumstances taking into account the spectral dispersion, number and magnitude of couplings present, and experimental temperature. Pulse sequences and experimental parameters for optimizing these experiments for the study of fluoropolymers have been studied. Copyright © 2016 John Wiley & Sons, Ltd.

A Versatile Strategy to Synthesize Perfluoropolyether-Based Thermoplastic Fluoropolymers by Alkyne-Azide Step-Growth Polymerization.

Perfluoropolyether (PFPE)-based thermoplastic fluoropolymers are synthesized by A2 + B2 step-growth polymerization between PFPE-diyne and fluorinated diazides. This versatile method allows synthesizing PFPE-based materials with tunable physicochemical properties depending on the exact nature of the fluorinated segment of the diazide precursor. Semicrystalline or amorphous materials endowed with high thermostability (≈300 °C under air) and low glass transition temperature (≈-100 °C) are obtained, as confirmed by differential scanning calorimetry, thermogravimetry, and rheometry. Step-growth polymerizations can be copper-catalyzed but also thermally activated in some cases, thus avoiding the presence of copper residues in the final materials. This strategy opens up new opportunities to easily access PFPE-based materials on an industrial scale. Furthermore, a plethora of developments can be envisioned (e.g., by adding a third trifunctional component to the formulations for the synthesis of PFPE-based elastomers).

The Nanolithography Toolbox.

This article introduces in archival form the Nanolithography Toolbox, a platform-independent software package for scripted lithography pattern layout generation. The Center for Nanoscale Science and Technology (CNST) at the National Institute of Standards and Technology (NIST) developed the Nanolithography Toolbox to help users of the CNST NanoFab design devices with complex curves and aggressive critical dimensions. Using parameterized shapes as building blocks, the Nanolithography Toolbox allows users to rapidly design and layout nanoscale devices of arbitrary complexity through scripting and programming. The Toolbox offers many parameterized shapes, including structure libraries for micro- and nanoelectromechanical systems (MEMS and NEMS) and nanophotonic devices. Furthermore, the Toolbox allows users to precisely define the number of vertices for each shape or create vectorized shapes using Bezier curves. Parameterized control allows users to design smooth curves with complex shapes. The Toolbox is applicable to a broad range of design tasks in the fabrication of microscale and nanoscale devices.

Synthesis of Chlorotrifluoroethylene-Based Block Copolymers by Iodine Transfer Polymerization.

Various fluorinated macro-chain transfer agents (CTAs) based on vinylidene fluoride (VDF), chlorotrifluoroethylene (CTFE), or CTFE and vinylidene chloride (VDC), were synthesized by iodine transfer polymerization (ITP). These macro-CTAs were involved in a further ITP reaction that led to the synthesis of original CTFE-based block copolymers exhibiting molecular weight ranging from 2500 to 40000 g/mol and endowed with high thermal stabilities (decomposition temperature at 10% weight loss of ca. 380 °C, under air). ITP of CTFE and VDC as well as ITP of VDF thermally initiated at 100 °C by a catalytic amount of dimanganese decacarbonyl (Mn2(CO)10) are reported for the first time.

The effect of economic, physical, and psychological abuse on mental health: a population-based study of women in the Philippines.

Background. The comparative effect of economic abuse and other forms of abuse in predicting depression and other mental health disorders has not been previously investigated despite its relevance for mental illness prevention. Objective. To determine the differential association of economic abuse on psychological distress and suicide attempts. Study Design. We used cross-sectional data from women aged 15-49 years in the 2008 Philippines Demographic and Health Surveys (PDHS) (N = 9,316). Results. Adjusting for sociodemographic confounders revealed positive associations between economic, physical, or psychological abuse and suicide attempts and psychological distress. Psychological and economic abuse were the strongest predictors of suicide attempts and psychological distress, respectively. Economic abuse was also negatively associated with psychological distress. Comorbidity with one mental health disorder greatly increased the odds of reporting the other mental health disorder. Conclusion. Overall, the results elucidate the differential effects of these forms of abuse on women's mental health.

Synthesis of fluorinated telechelic diols based on 3,3,3-trifluoropropene as precursors of well-defined fluoropolymers.

Original fluorinated α,ω-diols containing 3,3,3-trifluoropropene (TFP) units were synthesized. The first step dealt with the radical telomerization of TFP with 1,6-diiodoperfluorohexane. Isolated I(TFP)RF(TFP)I diadduct was subsequently reacted with ethylene, and then a two-step hydrolysis gave rise to α,ω-diols in 25% overall yield. The other strategies dealing with the radical addition of I(TFP)RF(TFP)I onto allyl alcohol or allyl acetate led to α,ω-diols in 13% overall yield. These diols display satisfactory thermal stabilities and low Tg (ca. -60 °C).

Access to and use of health services among undocumented Mexican immigrants in a US urban area.

OBJECTIVES: We assessed access to and use of health services among Mexican-born undocumented immigrants living in New York City in 2004. METHODS: We used venue-based sampling to recruit participants from locations where undocumented immigrants were likely to congregate. Participants were 18 years or older, born in Mexico, and current residents of New York City. The main outcome measures were health insurance coverage, access to a regular health care provider, and emergency department care. RESULTS: In multivariable models, living in a residence with fewer other adults, linguistic acculturation, higher levels of formal income, higher levels of social support, and poor health were associated with health insurance coverage. Female gender, fewer children, arrival before 1997, higher levels of formal income, health insurance coverage, greater social support, and not reporting discrimination were associated with access to a regular health care provider. Higher levels of education, higher levels of formal income, and poor health were associated with emergency department care. CONCLUSIONS: Absent large-scale political solutions to the challenges of undocumented immigrants, policies that address factors shown to limit access to care may improve health among this growing population.

Hunger and health among undocumented Mexican migrants in a US urban area.

OBJECTIVES: To measure the occurrence and correlates of hunger and to evaluate the association between hunger and three health indicators among undocumented Mexican immigrants. DESIGN: Non-probability cross-sectional sample. SETTING: Neighbourhoods within New York City. SUBJECTS: Four hundred and thirty-one undocumented Mexican immigrants living in the USA. RESULTS: Hunger was indicated by approximately 28% of respondents. In a multivariate model, working as a day labourer was associated with hunger (odds ratio (OR) 3.33, 95% confidence interval (CI) 1.83-6.06) while receiving public assistance protected against hunger (OR 0.23, 95% CI 0.06-0.88). In multivariate models, respondents who reported experiencing hunger also reported poorer overall health (OR 1.69, 95% CI 0.95-3.02) and more days of poor mental (P = 0.045) and physical health (P < 0.0001). Greater amount of time lived in the USA was also associated with worse overall health (P = 0.054) and more days of poor mental and physical health (P < 0.01). CONCLUSIONS: The present study shows that food insecurity and hunger may be problems among undocumented migrants living in the USA. Uncertain and unpredictable work schedules and limited access to public assistance may contribute to high levels of hunger, which in turn may also negatively affect mental and physical health. Increasing amount of time lived in the USA is also associated with poorer health indicators. Programmes that provide undocumented migrants with emergency access to resources may reduce food insecurity and lead to improved health outcomes among this vulnerable population.

Investigation of the specificity of an alpha-L-arabinofuranosidase using C-2 and C-5 modified alpha-L-arabinofuranosides.

The synthesis of three novel glycosyl donors presenting the same scaffold as alpha-L-arabinofuranose but modified at the C-2 or C-5 positions has been achieved. Furthermore, chemoenzymatic syntheses using the alpha-L-arabinofuranosidase AbfD3 and these unnatural furanosides were investigated. The use of the novel p-nitrophenyl furanoside donors revealed that AbfD3 can perform transglycosylation with the C-5 deoxygenated donor but not with the C-2 modified one. These results emphasize the vital role for OH-2 in AbfD3 substrate recognition.

Thioimidoyl furanosides as first inhibitors of the alpha-L-arabinofuranosidase AbfD3.

Two sets of five thioimidoyl alpha-L-arabino- and beta-D-galactofuranosides were designed, synthesized and subjected to docking studies to evaluate their ability to be recognized by the active site of the alpha-L-arabinofuranosidase AbfD3. Further in vitro assays showed that the targeted furanosides are the first potent inhibitors of this furanosyl hydrolase and that the most efficient one, the thiazolyl alpha-L-arabinofuranoside 1, is a competitive inhibitor having a KI of 1.4 microM.