Efficient adsorption of bulky reactive dyes from water using sustainably-derived mesoporous carbons.

Hazardous reactive dyes can cause serious environmental problems, as they are difficult to remove from water using conventional adsorbents due to their large molecular sizes and bulky structures. Sustainable mesoporous carbons derived from alginic acid demonstrated promising adsorbent capacity for several representative industrial bulky reactive dye molecules that account for almost 30% of the global textile dye market: Procion Yellow H-XEL (PY), Remazol Black (RB), Procion Crimson H-XEL (PC) and Procion Navy H-XEL (PN). These new adsorbents showed high mesoporosity (>90%) and large pore diameters (>20 nm) facilitating more straightforward and efficient adsorption and desorption processes when compared with predominately microporous activated carbon (AC), Norit, of similar surface chemistry, or with Silica gel (Sgel) that shows good mesoporosity but is hydrophilic. Their adsorption capacity was also significantly higher than that of both AC and Sgel, verifying suitability for bulky dye elimination from wastewater. Adsorption kinetic studies showed a best fit with the Elovich model, indicating a heterogeneous surface adsorption process. The adsorption isotherm data was best represented via the Toth model for almost all adsorbent/dye systems (R2 ≥ 0.98), validating the results of the Elovich model whereby the adsorbent is structurally heterogenous with multilayer dye coverage. From thermodynamic analysis, the derived parameters of ΔG (-11.6 âˆ¼ -6.2 kJ/mol), ΔH and ΔS demonstrate a spontaneous, enthalpy controlled adsorption process that was exothermic for RB (-10.0 kJ/mol) and PC (-23.9 kJ/mol) and endothermic for PY (3.9 kJ/mol) and PN (13.2 kJ/mol). Overall these alginic acid based mesoporous carbons are cost-effective, sustainable and efficient alternatives to current predominantly microporous adsorbent systems.

On-Surface Driven Formal Michael Addition Produces m-Polyaniline Oligomers on Pt(111).

On-surface synthesis is emerging as a highly rational bottom-up methodology for the synthesis of molecular structures that are unattainable or complex to obtain by wet chemistry. Here, oligomers of meta-polyaniline, a known ferromagnetic polymer, were synthesized from para-aminophenol building-blocks via an unexpected and highly specific on-surface formal 1,4 Michael-type addition at the meta position, driven by the reduction of the aminophenol molecule. We rationalize this dehydrogenation and coupling reaction mechanism with a combination of in situ scanning tunneling and non-contact atomic force microscopies, high-resolution synchrotron-based X-ray photoemission spectroscopy and first-principles calculations. This study demonstrates the capability of surfaces to selectively modify local molecular conditions to redirect well-established synthetic routes, such as Michael coupling, towards the rational synthesis of new covalent nanostructures.

Biochemical profiling of rat embryonic stem cells grown on electrospun polyester fibers using synchrotron infrared microspectroscopy.

Therapeutic options for spinal cord injuries are severely limited; current treatments only offer symptomatic relief and rehabilitation focused on educating the individual on how to adapt to their new situation to make best possible use of their remaining function. Thus, new approaches are needed, and interest in the development of effective strategies to promote the repair of neural tracts in the central nervous system inspired us to prepare functional and highly anisotropic polymer scaffolds. In this work, an initial assessment of the behavior of rat neural progenitor cells (NPCs) seeded on poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fiber scaffolds using synchrotron-based infrared microspectroscopy (SIRMS) is described. Combined with a modified touch imprint cytology sample preparation method, this application of SIRMS enabled the biochemical profiles of NPCs on the coated polymer fibers to be determined. The results showed that changes in the lipid and amide I-II spectral regions are modulated by the type and coating of the substrate used and the culture time. SIRMS studies can provide valuable insight into the early-stage response of NPCs to the morphology and surface chemistry of a biomaterial, and could therefore be a useful tool in the preparation and optimization of cellular scaffolds. Graphical abstract Synchrotron IR microspectroscopy can provide insight into the response of neural progenitor cells to synthetic scaffolds.

Chemistry below graphene: decoupling epitaxial graphene from metals by potential-controlled electrochemical oxidation.

While high-quality defect-free epitaxial graphene can be efficiently grown on metal substrates, strong interaction with the supporting metal quenches its outstanding properties. Thus, protocols to transfer graphene to insulating substrates are obligatory, and these often severely impair graphene properties by the introduction of structural or chemical defects. Here we describe a simple and easily scalable general methodology to structurally and electronically decouple epitaxial graphene from Pt(111) and Ir(111) metal surfaces. A multi-technique characterization combined with ab-initio calculations was employed to fully explain the different steps involved in the process. It was shown that, after a controlled electrochemical oxidation process, a single-atom thick metal-hydroxide layer intercalates below graphene, decoupling it from the metal substrate. This decoupling process occurs without disrupting the morphology and electronic properties of graphene. The results suggest that suitably optimized electrochemical treatments may provide effective alternatives to current transfer protocols for graphene and other 2D materials on diverse metal surfaces.

On-Surface Bottom-Up Synthesis of Azine Derivatives Displaying Strong Acceptor Behavior.

On-surface synthesis is an emerging approach to obtain, in a single step, precisely defined chemical species that cannot be obtained by other synthetic routes. The control of the electronic structure of organic/metal interfaces is crucial for defining the performance of many optoelectronic devices. A facile on-surface chemistry route has now been used to synthesize the strong electron-acceptor organic molecule quinoneazine directly on a Cu(110) surface, via thermally activated covalent coupling of para-aminophenol precursors. The mechanism is described using a combination of in situ surface characterization techniques and theoretical methods. Owing to a strong surface-molecule interaction, the quinoneazine molecule accommodates 1.2 electrons at its carbonyl ends, inducing an intramolecular charge redistribution and leading to partial conjugation of the rings, conferring azo-character at the nitrogen sites.

Hydrogen-Induced Reduction Improves the Photoelectrocatalytic Performance of Titania.

One of the main challenges to expand the use of titanium dioxide (titania) as a photocatalyst is related to its large band gap energy and the lack of an atomic scale description of the reduction mechanisms that may tailor the photocatalytic properties. We show that rutile TiO2 single crystals annealed in the presence of atomic hydrogen experience a strong reduction and structural rearrangement, yielding a material that exhibits enhanced light absorption, which extends from the ultraviolet to the near-infrared (NIR) spectral range, and improved photoelectrocatalytic performance. We demonstrate that both magnitudes behave oppositely: heavy/mild plasma reduction treatments lead to large/negligible spectral absorption changes and poor/enhanced (×10) photoelectrocatalytic performance, as judged from the higher photocurrent. To correlate the photoelectrochemical performance with the atomic and chemical structures of the hydrogen-reduced materials, we have modeled the process with in situ scanning tunneling microscopy measurements, which allow us to determine the initial stages of oxygen desorption and the desorption/diffusion of Ti atoms from the surface. This multiscale study opens a door toward improved materials for diverse applications such as more efficient rutile TiO2-based photoelectrocatalysts, green photothermal absorbers for solar energy applications, or NIR-sensing materials.

A Web-based approach to blood donor preparation.

BACKGROUND: Written and video approaches to donor education have been shown to enhance donation attitudes and intentions to give blood, particularly when the information provides specific coping suggestions for donation-related concerns. This study extends this work by comparing Web-based approaches to donor preparation among donors and nondonors. STUDY DESIGN AND METHODS: Young adults (62% female; mean [±SD] age, 19.3 [±1.5] years; mean [range] number of prior blood donations, 1.1 [0-26]; 60% nondonors) were randomly assigned to view 1) a study Web site designed to address common blood donor concerns and suggest specific coping strategies (n = 238), 2) a standard blood center Web site (n = 233), or 3) a control Web site where participants viewed videos of their choice (n = 202). Measures of donation attitude, anxiety, confidence, intention, anticipated regret, and moral norm were completed before and after the intervention. RESULTS: Among nondonors, the study Web site produced greater changes in donation attitude, confidence, intention, and anticipated regret relative to both the standard and the control Web sites, but only differed significantly from the control Web site for moral norm and anxiety. Among donors, the study Web site produced greater changes in donation confidence and anticipated regret relative to both the standard and the control Web sites, but only differed significantly from the control Web site for donation attitude, anxiety, intention, and moral norm. CONCLUSION: Web-based donor preparation materials may provide a cost-effective way to enhance donation intentions and encourage donation behavior.

Comparative study of the covalent diazotization of graphene and carbon nanotubes using thermogravimetric and spectroscopic techniques.

The direct diazotization of the sp(2) carbon network of graphene and multi-walled carbon nanotubes (MWNTs) is one of the many methods employed to introduce functional groups into these nanostructures. Herein, a methodical study on solvent-free diazotization with ethynylaniline in the presence of isoamyl nitrite is reported. Thermogravimetric analysis and UV-visible, infrared and Raman spectroscopies are used to precisely determine the degree of modification, confirm the presence of physisorption and describe the mechanism of elimination of the modifying groups. The results suggest that the same synthetic protocol in both cases leads to a certain degree of covalent modification, whilst a proportion of the modifying groups remains adsorbed to the carbon nanostructure. A higher level of global modification was observed for MWNTs. It was found that the elimination mechanism of the covalently-linked modifiers is identical for both nanostructures and involves two steps; acetylenic-aromatic bond rupture in the modifier followed by modifier-carbon nanostructure cleavage.

PET/Graphene Nanocomposite Fibers Obtained by Dry-Jet Wet-Spinning for Conductive Textiles.

The combination of polyethylene terephthalate (PET), one of the most used polymers in the textile industry, with graphene, one of the most outstanding conductive materials in recent years, represents a promising strategy for the preparation of conductive textiles. This study focuses on the preparation of mechanically stable and conductive polymer textiles and describes the preparation of PET/graphene fibers by the dry-jet wet-spinning method from nanocomposite solutions in trifluoroacetic acid. Nanoindentation results show that the addition of a small amount of graphene (2 wt.%) to the glassy PET fibers produces a significant modulus and hardness enhancement (≈10%) that can be partly attributed to the intrinsic mechanical properties of graphene but also to the promotion of crystallinity. Higher graphene loadings up to 5 wt.% are found to produce additional mechanical improvements up to ≈20% that can be merely attributed to the superior properties of the filler. Moreover, the nanocomposite fibers display an electrical conductivity percolation threshold over 2 wt.% approaching ≈0.2 S/cm for the largest graphene loading. Finally, bending tests on the nanocomposite fibers show that the good electrical conductivity can be preserved under cyclic mechanical loading.

Graphene functionalisation with a conjugated poly(fluorene) by click coupling: striking electronic properties in solution.

Graphene flakes covalently modified with a conjugated polymer, poly[(9,9-dihexylfluorene)-co-alt-(9,9-bis-(6-azidohexyl)fluorene)] (PFA), were efficiently synthesised by a Cu-catalysed Huisgen 1,3-dipolar cycloaddition between alkyne-modified graphene and an azide-functionalised polymer. Two approaches for the modification of graphene with alkyne groups were investigated (coupling with a diazonium salt generated in situ or an amidation reaction) and the optimum conditions determined. The success of the click-coupling approach was confirmed by FTIR, (1)H NMR, Raman, and X-ray photoelectron spectroscopy (XPS). The absorption and emission spectra of the click product show a strong solvent dependency.

Assessment of donor fear enhances prediction of presyncopal symptoms among volunteer blood donors.

BACKGROUND: Fear is an important contributor to the risk of presyncopal reactions to blood donation. However, concern that asking donors about their fears may increase the risk of reactions is a potential impediment to incorporating fear assessment into donor screening. STUDY DESIGN AND METHODS: Before donation, participants responded to a series of questions that either did (n = 488) or did not (n = 494) include questions related to fear of seeing blood drawn. Immediately after donation all participants provided ratings of presyncopal reactions. RESULTS: Among those asked predonation fear questions, fear was most strongly related to presyncopal symptoms when compared against other donor characteristics (e.g., age, number of prior donations, body mass index, estimated blood volume, blood pressure, and pulse). However, Mann-Whitney U tests revealed that being asked about fear before donation was not associated with higher reports of presyncopal reactions for the sample as a whole, nor among novice donors. Further, regression analyses indicated that fear remained a significant predictor of presyncopal reactions in final models that included age and number of prior donations as significant predictors. CONCLUSION: Predonation assessment of fear of blood draws may help to identify donors who are most likely to benefit from brief interventions designed to enhance donor coping, reduce risk of presyncopal reactions, and increase donor retention.

Designing New Sustainable Polyurethane Adhesives: Influence of the Nature and Content of Diels-Alder Adducts on Their Thermoreversible Behavior.

With a view to the development of new sustainable and functional adhesives, two Diels-Alder (DA) adducts are incorporated as a third component into the curing process of solvent-based and solvent-free polyurethanes in this study. The influence of the nature and content of the DA molecules on the retro-DA (rDA) reaction and its reversibility and cyclability is investigated. It is demonstrated that the bonding/debonding properties of the adhesives are mainly controlled by the concentration of the DA adducts, with a minimum thermoreversible bond (TB) content required that depends on the system and the total ratio between all the diols in the formulation. For the solvent-based system, rDA/DA reversibility can be repeated up to ~20 times without deterioration, in contrast to the solvent-free system where a gradual loss in the DA network reconstruction efficiency is observed. Despite this limitation, the solvent-free system presents clear advantages from an environmental point of view. The changes observed in the physical properties of these new thermoreversible adhesives are of great relevance for recycling strategies and, in particular, their potential for separating multilayered film packaging materials in order to recycle the individual polymer films involved.

Preventive medication adherence in African American and Caucasian headache patients.

STUDY OBJECTIVES: To examine race-related differences in adherence to preventive medication agents in headache patients and identify factors predictive of medication adherence in Caucasian and African American headache patients. METHODS: Using a longitudinal naturalistic study design, data from 77 Caucasian and 32 African American headache patients were collected through (1) 30-day daily diaries that assessed medication adherence, headache frequency, and headache episode severity; (2) self-administered surveys that assessed headache management self-efficacy; and (3) telephone-administered psychiatric interviews that yielded psychiatric diagnoses. Using daily diary adherence data, patients' adherence to preventive agents was dichotomized as "Inconsistent" (ie, adhered fewer than 80% of days) or "Consistent" (ie, adhered ≥ 80% of days during the past month). RESULTS: The proportion of adherent African American patients (69%) did not differ significantly from the proportion of adherent Caucasian patients (82%). Exploratory univariate logistic regression analyses found that preventive medication adherence levels of 80% or less were associated with being diagnosed with major depressive disorder and lower levels of headache management self-efficacy. CONCLUSIONS: Future research should test if interventions that reduce depressive symptoms and increase patients' levels of headache management self-efficacy can produce concomitant increases in adherence to preventive headache agents.

Laser microperforated biodegradable microbial polyhydroxyalkanoate substrates for tissue repair strategies: an infrared microspectroscopy study.

Flexible and biodegradable film substrates prepared by solvent casting from poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) solutions in chloroform were microperforated by ultraviolet laser ablation and subsequently characterized using infrared (IR) microspectroscopy and imaging techniques and scanning electron microscopy (SEM). Both transmission synchrotron IR microspectroscopy and attenuated total reflectance microspectroscopy measurements demonstrate variations in the polymer at the ablated pore rims, including evidence for changes in chemical structure and crystallinity. SEM results on microperforated PHBHV substrates after cell culture demonstrated that the physical and chemical changes observed in the biomaterial did not hinder cell migration through the pores.

Recent advances in the covalent modification of graphene with polymers.

Covalent binding of polymers to graphene represents an interesting alternative for the development of novel composite materials with a compendium of interfacial interactions. Through covalent linking, the concept of interface changes from a traditional view of interactions between components, such as van der Waals, hydrogen bonding, and so on, that is to say, at a polymer-filler interface, to a single compound concept where graphene forms an integral part of the polymeric chains. This feature article provides an overview of the strategies currently employed to functionalize graphene with polymers. We focus on the grafting-from and grafting-to methods used to bind polymers to graphene. The advantages and drawbacks, as well as the influence of each method on the final properties, are highlighted.

Chloroaluminate Gel Electrolytes Prepared with Copolymers Based on Imidazolium Ionic Liquids and Deep Eutectic Solvent AlCl3:Urea.

Polymer gel electrolytes (PGEs) have been prepared with copolymers based on imidazolium ionic liquids and the deep eutectic mixture of AlCl3:urea (uralumina) as liquid electrolyte. The copolymers were synthesized by photopolymerization of vinylpirrolidone or methylmethacrylate with imidazolium bis (trifluoromethane sulfonyl) imide (TFSI) ionic liquid monomer and mixed in an increasing range of wt.% with uralumina. The rheology and electrochemical activity of PGEs were highly dependent on the molar ratio of charged groups and copolymer content. Structure of the PGEs was studied by FTIR and Raman spectroscopy and a correlation between interactions polymer/uralumina and changes in speciation of uralumina was established. Despite the low molecular weight of the copolymers, the resulting polymer electrolytes develop elastomeric character associated with the binding ionic species. Although there is room to improve the electrochemical activity, in this study these new gels provide sufficient electroactivity to make them feasible alternatives as electrolytes in secondary aluminum batteries.

Metal-catalyst-free gas-phase synthesis of long-chain hydrocarbons.

Development of sustainable processes for hydrocarbons synthesis is a fundamental challenge in chemistry since these are of unquestionable importance for the production of many essential synthetic chemicals, materials and carbon-based fuels. Current industrial processes rely on non-abundant metal catalysts, temperatures of hundreds of Celsius and pressures of tens of bars. We propose an alternative gas phase process under mild reaction conditions using only atomic carbon, molecular hydrogen and an inert carrier gas. We demonstrate that the presence of CH2 and H radicals leads to efficient C-C chain growth, producing micron-length fibres of unbranched alkanes with an average length distribution between C23-C33. Ab-initio calculations uncover a thermodynamically favourable methylene coupling process on the surface of carbonaceous nanoparticles, which is kinematically facilitated by a trap-and-release mechanism of the reactants and nanoparticles that is confirmed by a steady incompressible flow simulation. This work could lead to future alternative sustainable synthetic routes to critical alkane-based chemicals or fuels.

Primary mucin-producing tumours of the salivary glands: a clinicopathological and morphometric study.

AIMS: To determine clinicopathological and morphometric features that discriminate between mucin-producing primary salivary gland carcinomas. MATERIALS AND RESULTS: Fifteen mucin-producing tumours were stratified into five colloid carcinomas (CCs), four mucinous cystadenocarcinomas (MCAs), three mucin-rich salivary duct carcinomas (SDCs) and three mucin-rich mucoepidermoid carcinomas (MECs). The mean patient age was 70, 58, 43 and 63 years for CC, MCA, SDC and MEC, respectively. Eleven of 15 patients were female. The majority of CC cases originated from major salivary glands; MCA showed a predilection for the minor salivary glands. No disease-related mortality was observed in the CC group; one patient died in the MCA group, and one in the SDC group. Receiver-operating characteristic curve analysis revealed an optimal cut-off point of 17% of the tumour cells in contact with stroma that best distinguished between the CC and MCA. Histomorphometric measurements revealed that CC was best differentiated from MCA by smaller nuclear size and more regular chromatin. CONCLUSIONS: Strict morphological criteria of CC coupled with assessment of the tumour cell/stroma relationship and the nuclear features facilitate discrimination between mucinous tumours of salivary gland.

Graphene and Polyethylene: A Strong Combination Towards Multifunctional Nanocomposites.

The key to the preparation of polymer nanocomposites with new or improved properties resides in the homogeneous dispersion of the filler and in the efficient load transfer between components through strong filler/polymer interfacial interactions. This paper reports on the preparation of a series of nanocomposites of graphene and a polyolefin using different experimental approaches, with the final goal of obtaining multifunctional materials. A high-density polyethylene (HDPE) is employed as the matrix, while unmodified and chemically modified graphene fillers are used. By selecting the correct combination as well as the adequate preparation process, the nanocomposites display optimized thermal and mechanical properties, while also conferring good gas barrier properties and significant levels of electrical conductivity.

INFRA-ICE: An ultra-high vacuum experimental station for laboratory astrochemistry.

Laboratory astrochemistry aims at simulating, in the laboratory, some of the chemical and physical processes that operate in different regions of the universe. Amongst the diverse astrochemical problems that can be addressed in the laboratory, the evolution of cosmic dust grains in different regions of the interstellar medium (ISM) and its role in the formation of new chemical species through catalytic processes present significant interest. In particular, the dark clouds of the ISM dust grains are coated by icy mantles and it is thought that the ice-dust interaction plays a crucial role in the development of the chemical complexity observed in space. Here, we present a new ultra-high vacuum experimental station devoted to simulating the complex conditions of the coldest regions of the ISM. The INFRA-ICE machine can be operated as a standing alone setup or incorporated in a larger experimental station called Stardust, which is dedicated to simulate the formation of cosmic dust in evolved stars. As such, INFRA-ICE expands the capabilities of Stardust allowing the simulation of the complete journey of cosmic dust in space, from its formation in asymptotic giant branch stars to its processing and interaction with icy mantles in molecular clouds. To demonstrate some of the capabilities of INFRA-ICE, we present selected results on the ultraviolet photochemistry of undecane (C11H24) at 14 K. Aliphatics are part of the carbonaceous cosmic dust, and recently, aliphatics and short n-alkanes have been detected in situ in the comet 67P/Churyumov-Gerasimenko.