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Background and objectives: Capillary hemangiomas are rare, benign vascular tumors that mainly affect the skin and soft tissue, with scarce appearance within the nasal cavities and paranasal sinuses. Materials and methods: We present a case report of capillary hemangioma of the sphenoid sinus and a review of the literature in the last ten years. Results: Clinical and endoscopic examination of the nose, radiologic assessment and particular histologic features contribute to the correct diagnosis of capillary hemangioma of the nose and paranasal sinuses. Conclusions: Transnasal endoscopic resection of capillary hemangioma located in the nose and paranasal sinuses is a valuable treatment method with good outcomes.

The properties of newly synthesized Cu

International audience; Two mononuclear complexes [(Et3NH)[M(hfac)2L] (M = Ni, 1; Zn, 2) have been synthesized using a nitronyl-nitroxide radical substituted nitrophenol, that is 2-(2-hydroxy-3-methoxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl, HL, as a proligand. The crystal structures of 1 and 2 have been solved and indicate an octahedral coordination geometry of the metal ions. The magnetic behavior for 1 is characterized by a strong antiferromagnetic metal–radical interaction (J = −351 ± 1 cm−1; H = −JSNiSRad). This exchange interaction was rationalized by DFT calculations. The EPR spectra recorded in both solution and solid state at 120 K confirm the S = ½ ground state for 1.

Alginate gels have been explored in different fields for applications in daily life such as pharmaceuticals and environmental remediation. The structural features of alginate allow its functionalization, which can modify its gel properties to a certain extent. Herein, we explored the properties of ionotropic gels resulting from the complexation of alginate chains functionalized with cyclodextrin (as host) or adamantane (as guest) units by calcium ions. Several commonly used physico-chemical methods together with electron paramagnetic resonance (EPR) spectroscopy were employed as characterisation tools in this study. The SEM images of alginate xerogels revealed morphological changes in gel networks, which were induced by the functionalization of polysaccharide chains and subsequent interactions between the appended host and guest units. The rheological properties of alginate hydrogels were also influenced by derivatization and host–guest interactions. Higher storage and elastic moduli values were recorded for gels obtained from a mixture of adamantane-functionalized and cyclodextrin-functionalized alginates. Furthermore, spin labelling of the alginate chain made it possible to use EPR spectroscopy to characterise these gel systems. The EPR method allowed us to evidence the local host–guest interactions and to correlate the information with data provided by techniques offering comprehensive gel properties. Overall, these investigations demonstrated that although host–guest interactions are not the driving force for the generation of alginate gels, their presence influences and can modulate the properties of gels.

International audience; A new nitronyl-nitroxide ligand (H2L) featuring alcoholic and phenolic groups has been synthesised starting from 2-hydroxy-3-(hydroxymethyl)-5-methylbenzaldehyde (A). Using this ligand, three 2p–4 f binuclear complexes have been obtained and crystallographically characterized: [Ln2(HL)2(hfac)4], (Ln=Gd 1, Tb 2, Dy 3). Apart from the desired compounds, two by-products have been isolated as a molecular alloy containing an intermediate bearing hydroxylamino and N-oxide groups, i. e. (1-hydroxy-2-(2-hydroxy-3-(hydroxymethyl)-5-methylphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 3-oxide, B, and the imino-nitroxide derivative, C. This system was characterized by single crystal X-ray diffraction, UV-VIS and EPR spectroscopy. During the synthesis of compounds 1–3, two other complexes have been obtained and characterized: [Ln(C)(hfac)3] (4, Ln=Tb) and [Ln2(A−H)2(hfac)4] (5, Ln=Tb), where (A−H) results from the deprotonation of the phenolic group in A. The synthetic procedure was optimized in order to obtain pure 1–3 complexes. The cryomagnetic properties of compounds 1–3 have been investigated. Continuous-wave (CW) electron paramagnetic resonance (EPR) measurements were carried out at X- and Q-band for compound 1. Time-dependent experiments were performed at three magnetic fields. Phase memory times, Tm, were found to be about 1000 ns at 6 K.

Background: Despite the fact that keratoconus has been tipically defined as a noninflammatory condition, recent research has promoted the role of inflammatory factors and protein changes of tear film in disease progression. Aims: to determine the level of serum albumin, lactoferrin and lyzozyme in tears of keratoconic patients and their correlations with corneal biomechanical properties. Subjects and methods: 16 eyes of keratoconus patients and 14 eyes of control cases were enrolled in an observational prospective study. We performed a complete ophthalmological examination on all participants. In order to determine the concentration of tear film proteins, a minimum of 20 microlitres of tears from the lower conjunctival fornix were collected from each subject and measured by enzyme-linked immunosorbent assay (ELISA) analysis. Results: The level of lactoferrin measured in the tear film was significantly decreased in the keratoconus group compared to the normal subjects in all cases (p Conclusions: We can state that the protein composition of tears is modified in keratoconus by increased levels of protein with inflammatory properties such as albumin or by decreased levels of protein with anti-inflammatory properties such as lactoferrin.

The aim of this study was firstly to determine and quantify the dry eye symptomatology of patients with keratoconus, in comparison with those without this condition and secondly to evaluate the suitability of the spin probe method of electron paramagnetic resonance spectroscopy in analysis of tears secretion. As such were considered two groups of patients for evaluation: 36 cases with keratoconus (keratoconus group) and 36 cases without ocular disease (control group). Besides general ophthalmological examination we have conducted Schirmer test I, tears break-up time (BUT) and quantify the answers about dry eye symptomatology to establish ocular surface disease index (OSDI). We have included a prospective correlation of ophthalmologic parameters with parameters of the spin probes added in tear secretions collected from both groups of patients. The results show that the value of OSDI for patients with keratoconus was higher (41.07 � 23.68) than the corresponding value of the control group (14.63 � 9.27). Also, the patients with keratoconus present lower mean values for BUT and Schirmer tests comparatively with the cases from control group. The electron paramagnetic resonances spectra of the spin probe CAT16 in tear secretions obtained from patients revealed changes that can be related with ophthalmologic parameters.

Tear composition is a source of information on the health state of the eye. Dry eye syndrome represents nowadays a common disorder that can be associated with other eye diseases, in particular keratoconus. As such, we focussed on the correlation of selected protein levels with ophthalmic parameters and, as a novelty, we explored the possible correlation of these data, classically used in examination, with electron paramagnetic resonance (EPR) spectral parameters of spin probes. Three groups of patients with (i) dry eye syndrome, (ii) dry eye syndrome and keratoconus and (iii) healthy eyes were considered. Tears were collected from the subjects to determine the levels of total protein, lactoferrin, lysozyme and human serum albumin, and to record the EPR spectra of spin probes with fatty acid-like structures: 5-doxyl stearic acid (5-DSA) and 4-(N,N′-dimethyl-N-hexadecyl)ammonium-2,2′,6,6′-tetramethylpiperidine-1-oxyl iodide (CAT16). In tear secretion, the EPR spectra of spin probes showed two components, one with slow dynamics and another one revealing a quasi-isotropic, rapid motion. We analysed in depth the changes observed in the EPR spectra of 5-DSA for the reason that the differences in dynamics between the 5-DSA components are more evident. The challenge of this study was to provide an alternative to biochemical analysis in monitoring the evolution of the health state of patients diagnosed with dry eye syndrome or keratoconus using the information provided by EPR spectra of spin probes. The results indicate a decreased contribution of the EPR component with rapid motion following treatment, and a significant correlation with the Schirmer and/or BUT values.

A series of nine dual molecular probes containing dansyl and TEMPO groups with fluorescent and paramagnetic properties, respectively, linked by linear alkyl chains were synthesized and characterized. The series of probes bearing only the dansyl moiety was also obtained. The photophysical properties of the probes were investigated in aqueous solution and the results evidenced the quenching effect of the nitroxide group on the fluorescence quantum yield of the dansyl moiety. Host–guest interactions of these dual molecular probes with β-cyclodextrin were investigated simultaneously by electron paramagnetic resonance (EPR) and fluorescence spectroscopies. The analysis of both EPR and fluorescence data evidenced the formation of complexes with preferential inclusion of the dansyl group in the cyclodextrin cavity and 1 : 1 stoichiometry. The association constants for the inclusion complexes were of the 102 M−1 order of magnitude. Diffusion experiments of the probes in natural and functionalised alginate gels bearing adamantane and/or cyclodextrin units have shown the suitability of these compounds to describe interactions in complex and non-uniform systems in which host–guest interactions play an important role.

Electron paramagnetic resonance (EPR) spectroscopy is the main tool for evidencing the formation of inclusion complexes of cyclodextrins with paramagnetic guests, based on changes in the EPR parameters. In-depth information on complexation can only be obtained by a combination of physico-chemical methods. Herein we report on the interaction of three TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) type radicals with cyclodextrins by collecting and analysing data provided experimentally by EPR and circular dichroism spectroscopies and theoretically by density functional theory and molecular docking. The study focused on the pH influence on the complexation of three paramagnetic probes with cyclodextrins. The EPR spectra revealed that the type and protonation state of the substituent linked to the TEMPO structure influences the affinity of the paramagnetic group for the cyclodextrin cavity. Neutral radical species favour stronger association with cyclodextrins and inclusion of the nitroxide group into the cavity, especially in the case of 4-carboxy-TEMPO. Induced circular dichroism signals of neutral species varied in sign and intensity as a function of substituent and cyclodextrin type. Density functional theory and molecular docking results supported the experimental data regarding the conformational preferences of TEMPO radicals in complexes with cyclodextrins.

Bis-dansyl fluorescent probes bearing aliphatic diamine linkers of increasing length (2DA1.n, n = 2, 4, 6, 8, 10, 12) were synthesized, and their emissive characteristics in solvents and in cyclodextrin solutions were discussed. Dual emission from locally excited (LE) and intramolecular charge transfer (CT) excited states was observed. The LE/CT relative magnitude is sensitive to solvent polarity and linker length. In water, the CT or LE state is favoured for short chain or long chain probes, respectively. The LE/CT relative magnitude also depends on the CD type: 2-hydroxypropyl-β-CD favours the CT state, while β- and γ-CD stabilise the LE state.

A series of novel derivatives of 3,5-dinitro-4-methoxyamino-benzoic acid were synthesized and fully characterized. Synthesis were performed by simple coupling reactions of the starting material with benzylamine, n-butylamine, 4-amino-antipyrine, benzocaine, 3,4-dimethyl-5-amino-isoxazole, 3,4-dimethoxyphenyl-2-ethylamine; besides, the corresponding methyl ester was also synthesized. The structural characterization of the new compounds was made by elemental analysis, IR, 1H and 13C NMR, UV–Vis, ESR, cyclic voltammetry, and single crystal X-ray diffraction (where appropriate). All compounds exhibits reversible acid-base behavior accompanied by colour change (yellow in acid media and blue at basic pH). Cyclic voltammetry showed an irreversible oxidation peak, however by chemical oxidation, these compounds generates persistent free radicals, evidenced also by ESR. Hydrophobicity and total antioxidant capacity of the compounds were also evaluated.

In order to modulate their biological activity in relation with microbial and mammalian cells, new compounds of type M(pmtp)(ClO4)2·nH2O (M: Co, Ni, Cu, Zn; pmtp: 5-phenyl-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine) were synthesised and characterised by chemical analysis, FAB-MS, IR, UV–Vis–NIR, EPR spectroscopy, cyclic voltammetry and magnetic data at room temperature. The thermal behaviour of these derivatives was also investigated by TG–DSC/MS measurements to evidence the changes induced by heating and also the thermodynamics effects that accompany them. Processes as water elimination, perchlorate decomposition, fragmentation and oxidative degradation of the triazolopyrimidine species were observed during the thermal studies. The in vitro screening of the antimicrobial activity was performed against Gram positive (S. aureus, B. subtilis) and Gram negative (E. coli, K. pneumoniae, P. aeruginosa), both reference and clinical multidrug-resistant bacterial strains and Candida albicans fungal strain. The copper(II) complex was the most active against planktonic microbial cells, exhibiting minimum inhibitory concentration values in the range of 31–125 μg mL−1. Remarkably, all complexes showed an inhibitory activity against biofilm development on the inert substratum, showing a promising potential for the design of new efficient anti-biofilm strategies.

The betainic title compound represents a structure with interesting physicochemical properties. These were studied by cyclic voltammetry (CV), electron paramagnetic resonance (EPR) spectroscopy, magnetic and spectral measurements. CV investigations show that the process in acetonitrile corresponds to chemically reversible one-electron reduction leading to the formation of a radical-anion. Chemical reduction of the betaine in dichloromethane with powdered sodium ascorbate in the presence of 15-crown-5 ether yielded a radical-anion (with an EPR spectrum similar to that of 2,2-diphenyl-1-picrylhydrazyl, DPPH). Linnett’s theory explains the similarity of EPR spectra for DPPH and the radical-anion. The title betaine is diamagnetic in solid state. In solution, it shows a weak hypsochromic effect.

Literature data are abundant in oxidations catalyzed by nitroxides free radicals, while hydrazyls free radicals are very seldom encountered. In this work we made a comparison between some nitroxides and hydrazyl free radicals towards the ability to selectively oxidize activated alcohols to the corresponding carbonyl derivatives. As nitroxides we used 2,2,6,6-tetramethylpirrolidin-N-oxide (TEMPO) and phtalimide-N-oxyl (PINO) free radicals, while as hydrazyls were used 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2-p-nitrophenyl-1-picrylhydrazyl (DN-DPPH). The differences in the physico-chemical properties between nitroxides and hydrazyls were evaluated by UV–vis, EPR and cyclic voltammetry. For DN-DPPH the X-ray crystal structure was resolved. It has been shown that a nitroxide radical is a far better catalyst in such aerobic oxidations comparatively with a hydrazyl one. The explanation of these results consists firstly in a different mechanism involved in the oxidation procedures and secondly in the variation of the oxidation potentials of nitroxides comparatively with hydrazyls.

Hierarchical flowers-like zinc oxide structures have been successfully obtained by a simple and fast ultrasound-assisted method performed in a ordinary ultrasonic bath using an ammonia solution and zinc acetate, in the absence of any surfactant or template. The composition, structure, crystallinity, morphology and optical properties of the materials obtained at different ultrasound irradiation times were characterized by infrared, UV-Vis and photoluminescence spectroscopy, X-ray diffraction, scanning and transmission electron microscopy investigations. It was proved that the ultrasound irradiation time manipulates both the defect content (implicit the photoluminescent properties) and morphology of the ZnO materials: shorter irradiation times leads to the synthesis of high-defected ZnO structures of flower morphology with triangular-shaped petals, while higher irradiation times favours the formation of low-defected ZnO structures with tipped rod-like petals. A plausible growth mechanism of the architectures that implies aggregation via oriented attachment followed by an Ostwald ripening is advanced based on these results. The ZnO flower-like structures present high photocatalytic activities, a total phenol mineralization being registered in the case of visible light experiments. Electron-spin resonance measurements demonstrate the generation of reactive oxygen species, namely hydroxyl radicals but also C centred radicals adducts derived most probable from the residual acetate adsorbed on ZnO surface.

Nitroxide-based radicals, having the advantage of firm chemical stability, are usable as probes in the detection of nanoscale details in the chemical environment of various multi-component systems, based on subtle variations in their electron paramagnetic resonance spectra. We propose a systematic walk through the vast area of problems and inquires that are implied by the rationalization of solvent effects on the spectral parameters, by first-principle methods of structural chemistry. Our approach consists of using state-of-the-art procedures, like Density Functional Theory (DFT), on properly designed systems, kept at the border of idealization and chemical realism. Thus, we investigate the case of real solvent molecules intervening in different configurations between two radical molecules, in comparison with radicals taken in vacuum or having the solvent that is treated by surrogate models, such as polarization continuum approximation. In this work, we selected the dichloromethane as solvent and the prototype radicals abbreviated TEMPO ((2,2,6,6-Tetramethylpiperidin-1-yl) oxyl). In another branch of the work, we check the interaction of radicals with large toroidal molecules, &beta, cyclodextrin, and cucurbit[6]uril, modeling the interaction energy profile at encapsulation. The drawn synoptic view offers valuable rationales for understanding spectroscopy and energetics of nitroxide radicals in various environments, which are specific to soft chemistry.

The formation and growth of gold nanoparticles (AuNPs) were investigated in pH 7 buffer solution of bovine serum albumin (BSA) at room temperature. The processes were monitored by UV-Vis, circular dichroism, Raman and electron paramagnetic resonance (EPR) spectroscopies. TEM microscopy and dynamic light scattering (DLS) measurements were used to evidence changes in particle size during nanoparticle formation and growth. The formation of AuNPs at pH 7 in the absence of BSA was not observed, which proves that the albumin is involved in the first step of Au(III) reduction. Changes in the EPR spectral features of two spin probes, CAT16 and DIS3, with affinity for BSA and AuNPs, respectively, allowed us to monitor the particle growth and to demonstrate the protective role of BSA for AuNPs. The size of AuNPs formed in BSA solution increases slowly with time, resulting in nanoparticles of different morphologies, as revealed by TEM. Raman spectra of BSA indicate the interaction of albumin with AuNPs through sulfur-containing amino acid residues. This study shows that albumins act as both reducing agents and protective corona of AuNPs.

Finding new, biocompatible matrices that allow us to model the generation of free radicals is of utmost importance for balancing the harmful and beneficial effects of the latter. In this respect, we report here the simultaneous encapsulation of the radical source and the antioxidant agent in a polyethylene glycol/β-cyclodextrin (PEG/β-CD) covalent gel network. We used electron paramagnetic resonance spectroscopy to evaluate the scavenging action of plant extracts (purple loosestrife, comfrey, milfoil, horsetail, thyme, carob, green coffee) embedded in PEG/β-CD gels. Free radicals were generated in situ by UV irradiation of riboflavin co-embedded in the gels. Prior to this, the extracts were characterized in what concerns their antioxidant activity, and their major polyphenolic constituents were quantified by liquid chromatography-electrospray ionization-tandem mass spectrometry. Purple loosestrife showed the highest antioxidant capacity, followed by comfrey and milfoil. Using the 5,5-dimethyl-1-pyrroline N-oxide spin trap, we have demonstrated that the gel-embedded extracts effectively scavenge the reactive carbon-centered free radicals generated in gel. The PEG/β-CD gels have been shown to be a valuable alternative matrix for the encapsulation of plant active principles having antioxidant activity. Moreover, co-encapsulation of the radical source transforms these gels into a controlled environment in which free radical processes can be tailored.

This manuscript reviews the development and implementation process of the Client Reported Outcome Monitoring Information System in the VA Canada Operational Stress Injury National Network, and reports on outcomes of an evaluation to assess usage, barriers, and facilitators to implementation. The majority of clinicians reported regular use of routine outcomes monitoring, although objective data suggested somewhat lower actual use. In general, clinicians endorsed all barriers and most facilitators as influencing their use of routine outcomes monitoring in a minor way. However, users and non-users differed in their endorsement of facilitators and barriers. Implications for research and implementation efforts are discussed.

The interaction of human serum albumin (HSA) with amphiphilic block copolymer Pluronic F127 has been investigated by several physical methods. Interest in studying this system stems from a broad range of bioactivities involving both macromolecules. Serum albumins constitute a significant class of proteins in the circulatory system, acting as carriers for a wide spectrum of compounds or assemblies. Pluronic block copolymers have revealed their capacity to ferry a variety of biologically active compounds. Circular dichroism, rheological measurements, and differential scanning microcalorimetry (μDSC) were employed to get insight into the interaction betweeen the two macromolecules. The results reveal that Pluronic F127 induces conformational changes to albumin if it is organized in a micellar form, while albumin influences the self-assembly of Pluronic F127 into micelles or gels. F127 micelles, however, induce smaller conformational changes compared to ionic surfactants. The μDSC thermograms obtained for HSA and/or F127 show that HSA shifts the critical micellar temperature (cmt) to lower values, while concurrently the HSA denaturation behavior is influenced by F127, depending on its concentration. Rheological measurements on solutions of F127 17% have shown that a sol-to-gel transition occurs at higher temperatures in the presence of HSA and the resulting gel is weaker. The global profile on HSA/F127 systems was complemented by local information provided by EPR measurements. A series of X-band EPR experiments was performed with spin probes 4-(N,N'-dimethyl-N-hexadecyl)ammonium-2,2',6,6'-tetramethylpiperidine-1-oxyl iodide (CAT16) and 5-doxyl stearic acid (5-DSA). These spin probes bind to albumin sites and are sensitive to phase transformations in Pluronic block copolymer solutions. For a given F127 concentration, the spin probe binds only to HSA below cmt and migrates to the F127 micelles above cmt. The collective data suggest soft interactions between the macromolecules, with the emerging results projecting potential applications linked to reaching optimal conditions for certain drug formulations.

A series of complexes of type M(pmtp)(CH3COO)2·nH2O ((1) M: Co, n = 4.5; (2) M: Ni, n = 3.5; (3) M: Cu, n = 0.5; (4) M: Zn, n = 0; pmtp: 5-phenyl-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine) were synthesised by one-pot condensation. The complexes were characterized by elemental analysis, ESI–MS, IR, UV–Vis-NIR, EPR spectra, magnetic susceptibility at room temperature as well as thermogravimetric analysis. The modifications in the IR spectra of complexes are in accordance with the condensation process and indicate the triazolopyrimidine coordination as unidentate. The electronic and EPR spectra together with magnetic moments indicate an octahedral stereochemistry for paramagnetic ions, except for Cu(II) with a square pyramidal geometry. Processes such as water elimination, acetate into carbonate transformation, as well as oxidative degradation of the triazolopyrimidine derivative were evidenced during thermal decomposition. The complexes exhibited an improved antimicrobial activity in comparison with the ligand, on both planktonic and biofilm-embedded microbial cells. The best antimicrobial activity in both susceptible and resistant strains was obtained for complex (3) followed by complex (1), which can be related to both oxidation state and stereochemical versatility. At high concentrations, the Cu(II) complex exhibits both cytotoxicity on HT 29 tumour cell line and anti-inflammatory activity.

Although integrating progress monitoring (PM) measures into psychotherapy practice can provide numerous benefits, including improved client outcomes, relatively few clinicians use these measures (e.g., Ionita & Fitzpatrick, 2014). To better understand the reasons for clinicians' reluctance, consensual qualitative research methodology was used to examine the challenges faced by clinicians currently using PM measures. Open-ended, semistructured interviews, with 25 clinicians who chose to use PM measures, revealed that clinicians tended to face challenges involving technical concerns, negative responses from others, and personal barriers such as anxiety. The majority of participants discussed ways to overcome the challenges they experienced, including ensuring the fit of the PM measure, explaining measures to others to help engender a positive response, adapting their own perspective, and increasing their own and others' knowledge of the measures. Implications for practicing psychologists and for knowledge translation efforts are discussed.

A number of ten stable free mono-, di- and tri-radicals of the TEMPO nitroxide type were synthesized and characterized via physico-chemical methods (elemental analysis, MS, UV-Vis, IR, ESR, and X-ray, where appropriate). The design of the compounds was chosen such that supramolecular interaction could be gained via hydrogen-bonding or π–π interactions; therefore the compounds should contain amino- or urea-moieties, (nitro)aromatic rings, or a crown ether residue. The formation of inclusion complexes between these (poly)radicals and cucurbit[6]uril was studied via Electron Spin Resonance (ESR) spectroscopy. The binding constants were evaluated from the analysis of the rotational correlation time dependence on the concentration of cucurbit[6]uril. These constants are an order of magnitude lower than the values reported before for complexes of TEMPO derivatives with β-cyclodextrin. The complexation behaviour of cucurbit[6]uril was revealed in the ESR spectra of the nitroxides in the presence and in the absence of the host molecules, recorded at low temperatures. The experiments revealed that the mobilities of the nitroxides investigated are higher in the absence of the host molecule, a different behaviour compared with complexes with cyclodextrins. This behavior can be understood by taking into account the role played by the presence of salts necessary to ensure the solubility of cucurbit[6]uril in water.

The use of Progress Monitoring (PM) measures has been shown to improve outcomes in therapy for clients who do not follow the normal trajectory of improvement. In addition to improved outcomes, there are several other documented benefits of PM that may motivate clinicians to use PM. Research has examined the broader field of selecting mental health care quality assessment tools and a review of the literature has pointed to the importance of considering motivation for assessment when selecting a measure. However, how motivation influences the selection or maintained usage of PM measures has not been studied. This study examined initial motivation as well as measure selection and continuing use of PM. Consensual Qualitative Research methodology was applied to characterize how clinicians (n = 25) started, selected, and maintained use of PM measures and how initial motivation related to measure selection and continued use. Regardless of initial motivation, convenience and effectiveness emerged as important when selecting and continuing to use a measure. Results are compared to current frameworks for selecting mental health- care quality indicators. Our results suggest that PM measures need to strike a balance, emphasizing convenience as well as efficacy in order to improve clinical uptake and adherence.

A series of dansyl-based fluorescent probes bearing linear alkyl-1,n-diamine chains of different length (DA1.n, n = 2–8, 10, 12) was characterized in terms of the absorptive and emissive features in solvents of different polarity and hydrogen bond donor/hydrogen bond acceptor character. The probes show solvent-dependent absorption, a feature that is uncommon among dansyl derivatives. The dual emission of DA1.n probes is strong in non-aqueous solvents and is influenced by the chain length and interactions with the solvent. Solvent effects on the spectral parameters were rationalized on the basis of the Kamlet-Taft and Catalan solvatochromic models, in order to quantify the degree of polarity-driven and hydrogen bonding interactions. A comparative discussion of the results predicted by the two models was made. In ground state, the DA1.n probes act as hydrogen bond acceptors. In excited state, hydrogen bonding is less favoured, the solute-solvent interactions being governed by the increasing polarity of the solvent that results in a large bathochromic shift of the emission. A comparison was made with the spectral features previously reported for the corresponding series of bis-dansyl fluorescent probes (2DA1.n).

Given the climate change, the high levels of pollution nowadays and the depletion of lithographic resources, low carbon technologies for road reinforcement with low energy consumption are essential for a sustainable future. These technologies, including incorporation of nonconventional materials, such as oil sands or bituminous sands, in pavement construction and recycling techniques of the existing deteriorated pavements, represent significant methods which can be performed for a better conservation of resources, and therefore the environment. In terms of environmental indicators assessment, the results of recent research undertaken for road pavement reinforcement strategies are presented. The Global Warming Potential expressed as quantities of CO2e emissions for a road pavement incorporating various alternative materials, such as oil sand and reclaimed asphalt have been evaluated using a life cycle assessment (LCA) study performed with asPECT software. The results obtained from these studies are presented within this paper and specific recommendations with regards to various technologies usage are given. These are required for minimizing the environmental impact of transport infrastructure and thus advancing towards low carbon mobility. The paper aims to highlight the need for effective measures concerning road pavements maintenance and intervention works. These measures are intended to extend the pavements lifecycle and therefore to reduce the overall ecological impact associated with the reconstruction of the road pavement because this action is correlated with significant quantities of polluting emissions released into the atmosphere, enormous granular materials and energy consumption and thus, an exponential increase of the greenhouse effect. DOI: http://dx.doi.org/10.5755/j01.sace.21.4.18486

Keratoconus is a progressive corneal ectasia that may lead to severe visual impairment due to the irregular astigmatism caused by corneal thinning. In addition to its association with atopy, eye rubbing, or genetic component, late reports suggest the involvement of inflammation in the pathogenesis of the disease. Our aim was to determine the concentration of IL-4, IL-6, IL-10, RANTES, IFN gamma, and TNF alpha in the tear film of patients with keratoconus and their first degree family members. We analyzed forty-eight participants in an observational cross-sectional study. The diagnosis of keratoconus had to be confirmed in addition to a minimum of 47 D corneal refractive power by corneal topography readings provided by a Placido-based topography system and analysis of the pattern: irregular astigmatism with an asymmetric “bow-tie.” As for the other groups, the most important diagnosis criteria were a normal topographic pattern with a regular astigmatism. 17 keratoconus patients, 16 relatives, and 15 controls were recruited after clinical assessment as part of the research. The cytokine’s mean values were similar in the keratoconus group and the relatives’ samples but significantly higher compared to the controls. Important differences were found in IL-4 levels between keratoconus patients and relatives and between relatives and controls (mean difference of 302.42, p<0.0016 and 219.16, p<0.033, Tukey’s HSD procedure). In the keratoconus group, using the CORR procedure, we found statistically strong correlations of IL-6 lacrimal concentrations with the disease stage (r=0.56, p<0.01), keratometry (r=0.55, p<0.02), pachymetry (r=−0.64, p<0.048), and corneal hysteresis (r=−0.53, p<0.02). Cytokine overexpression may be relevant for the inflammatory etiology of keratoconus. In conclusion, in the case of some first degree family members, the elevated tear biomarkers may represent a supplementary risk factor.

Low-molecular-weight organic gelators generate physical gels by the formation of three-dimensional fibrous network structures as a response to various physicochemical stimuli such as heat, light, ultrasound and chemical environments. Dibenzylidene sorbitol (DBS) represents a typical compound able to generate gels because of some prerequisite structural features: the presence of functional groups to form intermolecular hydrogen bonds and of aromatic groups to be involved in π–π interactions, or chirality. Herein, we present the synthesis of three derivatives of DBS-bearing carboxy groups attached to phenyl rings and the corresponding spin-labelled compounds. We studied the formation of physical gels resulting from self-assembly of DBS derivatives with the aim of highlighting the influence of the position of the carboxy group on the gel properties. These types of compounds can form gels in polar solvents (such as water, DMSO) by either temperature treatment or variation of the pH. In this study, the systems were investigated by rheological measurements, SEM analysis and EPR measurements. The results showed that the introduction of carboxy groups into the structure of DBS generates weaker gels compared with the parent gelator, DBS. The spin probes used in this study (spin-labelled DBS derivatives and 5-doxyl stearic acid) demonstrated that assembly of gelator molecules is a highly selective process. The two-component feature of EPR spectra of spin probes in gels is proof that EPR spectroscopy is sensitive to the non-homogeneity of these systems.

Intramolecular spin exchange in four flexible PEG-based bis-nitroxides was studied by X-band electron paramagnetic resonance (EPR) spectroscopy as a function of temperature and solvent viscosity. A series of biradicals with different lengths of the ethylene glycol bridge connecting the two nitroxide groups was investigated in aqueous and mixed 1:1 i-propanol:water solutions. Conformational transitions in liquid solutions of the biradicals were analyzed, and thermodynamic parameters of the conformational reorganization were calculated from the EPR spectra. Intramolecular distances r between paramagnetic >N–O• fragments in biradicals in frozen solutions were calculated and compared with dynamic properties of the biradicals.

The formation of alginate gel from low molecular weight alginate and very low molecular weight alginate in the presence of divalent cations was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. The transition from sol to gel in the presence of divalent cations was monitored by the changes in the dynamics of spin labelled alginate. The immobilisation of the spin labelled alginate in the gel reflects the strength of interaction between the cation and alginate chain. Diffusion experiments showed that both the cation and alginate polyanion in the gel fibres can exchange with molecules in solution. In particular, we showed that dissolved alginate polyanions can replace alginates in the gel fibres, which can hence diffuse through the bulk of the gel. This illustrates the surprisingly highly dynamic nature of these gels and opens up the possibility of preparing multicomponent alginate gels via polyanion exchange process.

The focus of the present work was to investigate the interaction of the anticancer drug mitoxantrone with two bile salts, sodium taurodeoxycholate (NaTDC) and sodium taurocholate (NaTC). Ultraviolet-visible (UV-Vis) absorption and electron paramagnetic resonance (EPR) spectroscopy were used to quantify the interaction and to obtain information on the location of mitoxantrone in bile salt micelles. The presence of submicellar concentrations of both bile salts induces mitoxantrone aggregation and the extent of drug aggregation in NaTDC is higher than in NaTC. For micellar bile salts concentrations, mitoxantrone monomers are entrapped in the micellar core. Binding constants, micelle/water partition coefficients and the corresponding thermodynamic parameters for binding and partitioning processes were estimated using the changes in monomer absorbance in the presence of bile salts. Binding interaction of mitoxantrone is stronger for NaTDC than NaTC micelles, whereas partitioning efficiency is higher for NaTC micelles for all investigated temperatures. Thermodynamic parameters indicate that both binding and partitioning processes are spontaneous and entropy controlled. The spectral behavior and thermodynamic parameters indicate distinct types of mitoxantrone interaction with NaTDC and NaTC micelles supported by the differences in nature and structure of bile salts micelles.

In this work, we present evidence on the suitability of spin probes to report on the thermal treatment of bovine serum albumin (BSA), in the temperature range 293-343 K, and indirectly monitor the release of sodium dodecyl sulfate (SDS) from its complex with BSA using a covalent gel with β-cyclodextrin (β-CD) in the network. The spin probes used, 5- and 7-doxyl-stearic acids (5-DSA, 7-DSA) or 4-(N,N'-dimethyl-N-hexadecyl)ammonium-2,2',6,6'-tetramethylpiperidine-1-oxyl iodide (CAT16), present similar, fatty acid-like structural features. Their continuous wave electron paramagnetic resonance (CW-EPR) spectra, however, reflect different dynamics when complexed with BSA: a restricted motion for 5-DSA, almost nonsensitive to the heating/cooling cycle, and a faster temperature-dependent dynamic motion for CAT16. Molecular docking allows us to rationalize these results by revealing the different binding modes of 5-DSA and CAT16. The EPR data on the temperature effect on BSA are supported by circular dichroism results projecting recovery, upon cooling, of the initial binding ability of BSA for samples heated to 323 K. The interactions occurring in BSA/SDS/β-CD systems are investigated by CW-EPR and FT-ESEEM spectroscopies. It is found that the covalent gel containing β-CD can efficiently remove SDS from the BSA/SDS complex. The gel is not permeable to BSA but it can encapsulate SDS, thus yielding the free protein in solution and allowing recovery of the native protein conformation. Collectively, the accrued knowledge supports potential applications in protein purification biotechnological processes.

This national survey investigated the clinical practice of psychologists in Canada with particular reference to the usage of progress monitoring (PM) measures. Data from 1,668 registered psychologists were collected on demographic characteristics, years of experience, years since graduation, degree, professional activities, primary clientele, theoretical orientations as well as familiarity with PM measures, usage of PM measures, and usage of other methods to monitor client progress. Survey results indicated that more than 2 thirds of psychologists were unfamiliar with PM measures and only 12% of psychologists were using these measures. Profiles of psychologists based on awareness and usage of PM measures are presented. Implications for practicing clinicians are discussed.