Hydrogen Bonding in Ionic Liquids Probed by Linear and Nonlinear Vibrational Spectroscopy

Three imidazolium-based ionic liquids of the type [Cnmim][NTf2] with varying alkyl chain lengths (n = 1, 2 and 8) at the 1 position of the imidazolium ring were studied applying IR, linear Raman, and multiplex CARS spectroscopy. The focus has been on the CH-stretching region of the imidazolium ring, which is supposed to carry information about a possible hydrogen bonding network in the ionic liquid. The measurements are compared to calculations of the corresponding anharmonic vibrational spectra for a cluster of [C2mim][NTf2] consisting of four ion pairs. The results support the hypothesis of weak hydrogen bonding involving the C(4)-H and C(5)-H groups and somewhat stronger hydrogen bonds of the C(2)-H groups.Comment: revised manuscript, accepted for publication in New J. Phy

‘Everything’s from the inside out with PCOS’:exploring women’s experiences of living with Polycystic Ovary Syndrome (PCOS) and co-morbidities through Skype™ interviews

Polycystic ovary syndrome is an endocrine disorder affecting 1 in 10 women. Women with polycystic ovary syndrome can experience co-morbidities, including depressive symptoms. This research explores the experience of living with polycystic ovary syndrome and co-morbidities. Totally, 10 participants with polycystic ovary syndrome took part in Skype™ interviews and analysed using thematic analysis. Four themes emerged from the data: change (to life plans and changing nature of condition); support (healthcare professionals, education and relationships); co-morbidities (living with other conditions and depression, self-harm and suicidal ideation) and identity (feminine identity and us and them). The findings highlight the need for screening of women with polycystic ovary syndrome for depressive disorders

Noise-Corrected, Exponentially Weighted, Diffusion-Weighted MRI (niceDWI) Improves Image Signal Uniformity in Whole-Body Imaging of Metastatic Prostate Cancer.

Purpose: To characterize the voxel-wise uncertainties of Apparent Diffusion Coefficient (ADC) estimation from whole-body diffusion-weighted imaging (WBDWI). This enables the calculation of a new parametric map based on estimates of ADC and ADC uncertainty to improve WBDWI imaging standardization and interpretation: NoIse-Corrected Exponentially-weighted diffusion-weighted MRI (niceDWI). Methods: Three approaches to the joint modeling of voxel-wise ADC and ADC uncertainty (σADC) are evaluated: (i) direct weighted least squares (DWLS), (ii) iterative linear-weighted least-squares (IWLS), and (iii) smoothed IWLS (SIWLS). The statistical properties of these approaches in terms of ADC/σADC accuracy and precision is compared using Monte Carlo simulations. Our proposed post-processing methodology (niceDWI) is evaluated using an ice-water phantom, by comparing the contrast-to-noise ratio (CNR) with conventional exponentially-weighted DWI. We present the clinical feasibility of niceDWI in a pilot cohort of 16 patients with metastatic prostate cancer. Results: The statistical properties of ADC and σADC conformed closely to the theoretical predictions for DWLS, IWLS, and SIWLS fitting routines (a minor bias in parameter estimation is observed with DWLS). Ice-water phantom experiments demonstrated that a range of CNR could be generated using the niceDWI approach, and could improve CNR compared to conventional methods. We successfully implemented the niceDWI technique in our patient cohort, which visually improved the in-plane bias field compared with conventional WBDWI. Conclusions: Measurement of the statistical uncertainty in ADC estimation provides a practical way to standardize WBDWI across different scanners, by providing quantitative image signals that improve its reliability. Our proposed method can overcome inter-scanner and intra-scanner WBDWI signal variations that can confound image interpretation

Solutions of ionic liquids with diverse aliphatic and aromatic solutes – Phase behavior and potentials for applications:A review article

This article principally reviews our research related to liquid–liquid and solid–liquid phase behavior of imidazolium- and phosphonium-based ionic liquids, mainly having bistriflamide ([NTf2]−) or triflate ([OTf]−) anions, with several aliphatic and aromatic solutes (target molecules). The latter include: (i) diols and triols: 1,2-propanediol, 1,3-propanediol and glycerol; (ii) polymer poly(ethylene glycol) (PEG): average molecular mass 200, 400 and 2050 – PEG200 (liquid), PEG400 (liquid) and PEG2050 (solid), respectively; (iii) polar aromatic compounds: nicotine, aniline, phenolic acids (vanillic, ferulic and caffeic acid,), thymol and caffeine and (iv) non-polar aromatic compounds (benzene, toluene, p-xylene). In these studies, the effects of the cation and anion, cation alkyl chain and PEG chain lengths on the observed phase behaviors were scrutinized. Thus, one of the major observations is that the anion – bistriflamide/triflate – selection usually had strong, sometimes really remarkable effects on the solvent abilities of the studied ionic liquids. Namely, in the case of the hydrogen-bonding solutes, the ionic liquids with the triflate anion generally exhibited substantially higher solubility than those having the bistriflamide anion. Nevertheless, with the aromatic compounds the situation was the opposite – in most of the cases it was the bistriflamide anion that favoured solubility. Moreover, our other studies confirmed the ability of PEG to dissolve both polar and non-polar aromatic compounds. Therefore, two general possibilities of application of alternative, environmentally acceptable, solvents of tuneable solvent properties appeared. One is to use homogeneous mixtures of two ionic liquids having [NTf2]− and [OTf]− anions as mixed solvents. The other, however, envisages the application of homogeneous and heterogeneous (PEG + ionic liquid) solutions as tuneable solvents for aromatic solutes. Such mixed solvents have potential applications in separation of the aforesaid target molecules from their aqueous solutions or in extraction from original matrices. From the fundamental point of view the phase equilibrium studies reviewed herein and the diversity of the pure compounds – ionic liquids and target molecules – represent a good base for the discussion of interactions between the molecules that exist in the studied solutions

Interventional radiology virtual simulator for liver biopsy

Purpose Training in Interventional Radiology currently uses the apprenticeship model, where clinical and technical skills of invasive procedures are learnt during practice in patients. This apprenticeship training method is increasingly limited by regulatory restrictions on working hours, concerns over patient risk through trainees’ inexperience and the variable exposure to case mix and emergencies during training. To address this, we have developed a computer-based simulation of visceral needle puncture procedures. Methods A real-time framework has been built that includes: segmentation, physically based modelling, haptics rendering, pseudo-ultrasound generation and the concept of a physical mannequin. It is the result of a close collaboration between different universities, involving computer scientists, clinicians, clinical engineers and occupational psychologists. Results The technical implementation of the framework is a robust and real-time simulation environment combining a physical platform and an immersive computerized virtual environment. The face, content and construct validation have been previously assessed, showing the reliability and effectiveness of this framework, as well as its potential for teaching visceral needle puncture. Conclusion A simulator for ultrasound-guided liver biopsy has been developed. It includes functionalities and metrics extracted from cognitive task analysis. This framework can be useful during training, particularly given the known difficulties in gaining significant practice of core skills in patients

Factors Affecting Bubble Size in Ionic Liquids

This study reports on understanding the formation of bubbles in ionic liquids (ILs), with a view to utilising ILs more efficiently in gas capture processes. In particular, the impact of the IL structure on the bubble sizes obtained has been determined in order to obtain design principles for the ionic liquids utilised. 11 ILs were used in this study with a range of physico-chemical properties in order to determine parametrically the impact on bubble size due to the liquid properties and chemical moieties present. The results suggest the bubble size observed is dictated by the strength of interaction between the cation and anion of the IL and, therefore, the mass transport within the system. This bubble size – ILs structure–physical property relationship has been illustrated using a series of QSPR correlations. A predictive model based only on the sigma profiles of the anions and cations has been developed which shows the best correlation without the need to incorporate the physico-chemical properties of the liquids. Depending on the IL, selected mean bubble sizes observed were between 56.1 and 766.9 μm demonstrating that microbubbles can be produced in the IL allowing the potential for enhanced mass transport and absorption kinetics in these systems

A qualitative investigation of the impact of peer to peer online support for women living with Polycystic Ovary Syndrome

Background: Polycystic Ovary Syndrome is a common, chronic condition which affects women living with the condition both physically and psychologically. Social support may be beneficial to sufferers in coping with chronic conditions and the Internet is becoming a common place for accessing social support and information. The aim of this study was to consider the experiences of women living with Polycystic Ovary Syndrome who access and participate in an online support group discussion forum dedicated to issues surrounding this condition. Methods: Fifty participants responded to a series of open-ended questions via an online survey. Results: Thematic analysis revealed a number of empowering and disempowering experiences associated with online support group participation. The empowering processes reported by members of the group included: Connecting with others who understand; Access to information and advice; Interaction with healthcare professionals; Treatment-related decision making; Improved adjustment and management. In terms disempowering processes, only two were described by group participants: Reading about the negative experiences of others and Feeling like an outsider. Conclusions: For women living with Polycystic Ovary Syndrome, participation within an online support group may help to empower them in a range of important ways however, there may be some disempowering consequences

Alkyltributylphosphonium chloride ionic liquids: synthesis, physicochemical properties and crystal structure

[EN] A series of alkyltributylphosphonium chloride ionic liquids, prepared from tributylphosphine and the respective 1-chloroalkane, CnH2n+1Cl (where n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12 or 14), is reported. This work is a continuation of an extended series of tetraalkylphosphonium ionic liquids, where the focus is on the variability of n and its impact on the physical properties, such as melting points/glass transitions, thermal stability, density and viscosity. Experimental density and viscosity data were interpreted using QPSR and group contribution methods and the crystal structure of propyl(tributyl) phosphonium chloride is detailed.This work was funded by Cytec Canada, Inc. G.A. would like to thank Dr Douglas Harris (Cytec) for fruitful comments and advice at the beginning of this work; Prof. Chris Strauss, Dr Markus Fanselow and Dr Giulia Fiorani for microwave assistance and helpful guidance, and Prof. P.R. Raithby for the X-ray diffraction data collection. L.P.N.R. thanks Fundacao para a Ciencia e Tecnologia, Portugal, for support under grants PTDC/QUI-QUI/101794/2008 and PTDC/QUI/71331/2006.Adamova, G.; Gardas, RL.; Nieuwenhuyzen, M.; Vaca Puga, A.; Rebelo, LPN.; Robertson, AJ.; Seddon, KR. (2012). Alkyltributylphosphonium chloride ionic liquids: synthesis, physicochemical properties and crystal structure. Dalton Transactions. 41(27):8316-8332. doi:10.1039/c1dt10466gS83168332412