Can cholinium chloride form eutectic solvents with organic chloride-based salts?

The high melting point of a large number of organic salts with potential ionic liquid-like properties, hinders their applicability as solvents. Considering the success of cholinium chloride on lowering the melting temperature of several substances and its success on forming deep eutectic solvents, this work studies its mixing with organic chlorides to lower their melting points producing eutectic ionic liquids. The solid-liquid phase diagrams for binary mixtures composed of cholinium chloride and ten organic halides were experimentally measured. Surprisingly, cholinium chloride presented, for all these systems, significant positive deviations from ideal liquid behaviour that restricted its ability to lower the melting points of these mixtures. Only for mixtures with ammonium chloride, tetramethylammonium chloride, bis(2-hydroxyethyl)dimethylammonium chloride or cholinium bromide was cholinium chloride able to significantly lower the melting point of the mixture, but without reaching values close to room temperature (298 K). For a better understanding of the results obtained, the solid-liquid phase diagrams of four alkylammonium chloride-based mixtures were experimentally assessed and used to show that these compounds are better than cholinium chloride at inducing negative deviations from ideality, leading to greater melting point depressions.This work was developed in the scope of the project CICECO e Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (Ref. FCT UID/CTM/50011/2013) and Associate Laboratory LSRELCM, POCI-01-0145-FEDER-006984 (Ref. FCT UID/EQU/50020/2019), and project MultiBiorefinery (POCI-01-0145-FEDER-016403), all financed by national funds through the FCT/MCTES (PIDDAC) and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. FCT is also acknowledged for funding the project DeepBiorefinery (PTDC/AGRTEC/1191/2014). The authors acknowledge the European Research Council under the European Union's Seventh Framework Programme (FP7/ 2007 e 2013)/ERC grant agreement no. 337753. M.A.R.M. acknowledges financial support from NORTE-01-0145-FEDER-000006 - funded by NORTE2020 through PT2020 and ERDF. L.P.S. acknowledges FCT for her PhD grant (SFRH/BD/135976/2018).info:eu-repo/semantics/publishedVersio

Indirect assessment of the fusion properties of choline chloride from solid-liquid equilibria data

The temperature and enthalpy of fusion of choline chloride -[Ch]Cl- are not directly measurable since this compound decomposes upon melting. Yet, given the wide use of this compound in the preparation of deep eutectic solvents (DES), its thermophysical fusion properties are very important for a better understanding of these mixtures and the thermodynamic description of their solid-liquid phase diagrams. In this work, the fusion properties of choline chloride were estimated using the solubility curves of choline chloride in ten different ionic compounds, forming simple binary eutectic mixtures with quasi-ideal liquid phases. Experimental solid-liquid equilibria data for these systems -[Ch] Cl + ionic compounds- were measured, and the ideality of the systems assessed through the quantification of the activity coefficients and their comparison in each pair of binary solutions. The values estimated for the fusion properties of choline chloride are T fus,[Ch]Cl = 597 ± 7 K and Δ fus H [Ch]Cl = 4300 ± 600 J mol −1 . These were additionally checked by thermodynamic consistency tests and by the prediction of the solid-liquid curves with COSMO-RS model. The results obtained with both procedures allow us to guarantee the usefulness and robustness of the estimated data.This work was developed in the scope of the project CICECOAveiro Institute of Materials, POCI-01-0145-FEDER-007679 (Ref. FCT UID/CTM/50011/2013) and Project POCI-01-0145-FEDER- 006984 e Associate Laboratory LSRE-LCM, both funded by FEDER through COMPETE2020 - Programa Operacional Competitividade e Internacionalizaç~ao (POCI) e and by national funds through FCT - Fundaç~ao para a Ci^encia e a Tecnologia. M.A.R.M acknowledges FCT for her PhD grant (SFRH/BD/87084/2012). J.O. and L.F. thank the financing provided by the Spanish Government, Ministerio de Economia y Competitividad (MINECO), under the project CTQ2012- 37114 and the short-stay grant EEBB-I-16-11792.info:eu-repo/semantics/publishedVersio

KREAP: An automated Galaxy platform to quantify in vitro re-epithelialization kinetics

Background: In vitro scratch assays have been widely used to study the influence of bioactive substances on the processes of cell migration and proliferation that are involved in re-epithelialization

Ocular accommodation and wavelength: The effect of longitudinal chromatic aberration on the stimulus–response curve

The longitudinal chromatic aberration (LCA) of the eye creates a chromatic blur on the retina that is an important cue for accommodation. Although this mechanism can work optimally in broadband illuminants such as daylight, it is not clear how the system responds to the narrowband illuminants used by many modern displays. Here, we measured pupil and accommodative responses as well as visual acuity under narrowband light-emitting diode (LED) illuminants of different peak wavelengths. Observers were able to accommodate under narrowband light and compensate for the LCA of the eye, with no difference in the variability of the steady-state accommodation response between narrowband and broadband illuminants. Intriguingly, our subjects compensated more fully for LCA at nearer distances. That is, the difference in accommodation to different wavelengths became larger when the object was placed nearer the observer, causing the slope of the accommodation response curve to become shallower for shorter wavelengths and steeper for longer ones. Within the accommodative range of observers, accommodative errors were small and visual acuity normal. When comparing between illuminants, when accommodation was accurate, visual acuity was worst for blue narrowband light. This cannot be due to the sparser spacing for S-cones, as our stimuli had equal luminance and thus activated LM-cones roughly equally. It is likely because ocular LCA changes more rapidly at shorter wavelength and so the finite spectral bandwidth of LEDs corresponds to a greater dioptric range at shorter wavelengths. This effect disappears for larger accommodative errors, due to the increased depth of focus of the eye

A noninvasive multi-analyte diagnostic assay: Combining protein and DNA markers to stratify bladder cancer patients

Purpose: The authors recently reported the development of a noninvasive diagnostic assay using urinary matrix metalloproteinases (MMPs) as monitors of disease-free status and bladder cancer in high-risk populations. Using an approach called clinical intervention determining diagnostic (CIDD), they identified with high confidence those patients who could be excluded from additional intervention. To maximize performance, MMPs were combined with DNAbased markers and CIDD was applied to a population of patients undergoing monitoring for recurrence. Patients and methods: Urine samples were obtained from 323 patients, 48 of whom had a recurrence and 275 of whom did not have cancer upon cytoscopic evaluation. Twist1 and Nid2 methylation status was determined using methylation-specific polymerase chain reaction, FGFR3 mutational status by quantitative PCR, and MMP levels by enzyme-linked immunosorbent assay. Results: Using a combination of these DNA and protein markers, the authors identified with high confidence (97% negative predicted value) those patients who do not have cancer. Cutoffs were adjusted such that at 92% sensitivity, 51% of disease-free patients might be triaged from receiving further tests. Conclusion: The multi-analyte diagnostic readout assay described here is the first to combine protein and DNA biomarkers into one assay for optimal clinical performance. Using this approach, the detection of FGFR3 mutations and Twist1 and Nid2 methylation in the urine of patients undergoing bladder cancer recurrence screening increase the sensitivity and negative predictive value at an established MMP protein cutoff. This noninvasive urinary diagnostic assay could lead to the more efficient triage of patients undergoing recurrence monitoring

Characterization and Modeling of the Liquid Phase of Deep Eutectic Solvents Based on Fatty Acids/Alcohols and Choline Chloride

The solid-liquid equilibria phase diagrams of eight eutectic systems formed by choline chloride and fatty acids, or fatty alcohols, were measured to characterize the nonideality of the liquid phase of these systems, commonly reported in the literature as examples of type III deep eutectic solvents (DESs), and to evaluate the best modeling approaches to their description. Most of these systems are shown to present only slight deviations from ideal behavior, resulting from a fine balance of the hydrogen bonding between the hydroxyl/carboxylic groups with the chloride anion and the interactions present in the pure compounds. The phase diagrams measured were modeled with an associative equation of state (EoS) and a g E model. As an EoS, the perturbed-chain statistical associating fluid theory (PC-SAFT) was used, and this model was able to accurately describe the experimental data and to provide reliable estimates of the eutectic points using just a single binary temperature-dependent interaction parameter that often correlates with the acid/alcohol chain length. The performance of PC-SAFT was further compared with the g E model, a non-random two-liquid model (NRTL), and was found to provide a better description of the experimental data, especially for the more nonideal systems. Ultimately, the data gathered, and the molecular modeling, allowed the discussion of the behavior of fatty acids or fatty alcohols as hydrogen bond donors in choline chloride-based DESs.This work was developed in the scope of Projects POCI-01- 0145-FEDER-007679 - CICECO - Aveiro Institute of Materials (ref. FCT UID/CTM/50011/2013), POCI-01-0145-FEDER- 006984 - Associate Laboratory LSRE-LCM both funded by European Regional Development Fund (ERDF) through COMPETE2020 - Programa Operacional Competitividade e Internacionalização (POCI), and by national funds through FCT - Fundação para a Ciência e a Tecnologia. This work is also a result of project “AIProcMat@N2020 - Advanced Industrial Processes and Materials for a Sustainable Northern Region of Portugal 2020”, with the reference NORTE-01-0145- FEDER-000006, supported by Norte Portugal Regional Operational Programme (NORTE 2020), under the Portugal 2020 Partnership Agreement, through ERDF. M.A.R.M acknowledges FCT for her Ph.D. grant (SFRH/BD/87084/2012). C.H. gratefully acknowledges financial support of Max- Buchner Research Foundation.info:eu-repo/semantics/publishedVersio

Fermi-edge singularities in linear and non-linear ultrafast spectroscopy

We discuss Fermi-edge singularity effects on the linear and nonlinear transient response of an electron gas in a doped semiconductor. We use a bosonization scheme to describe the low energy excitations, which allows to compute the time and temperature dependence of the response functions. Coherent control of the energy absorption at resonance is analyzed in the linear regime. It is shown that a phase-shift appears in the coherent control oscillations, which is not present in the excitonic case. The nonlinear response is calculated analytically and used to predict that four wave-mixing experiments would present a Fermi-edge singularity when the exciting energy is varied. A new dephasing mechanism is predicted in doped samples that depends linearly on temperature and is produced by the low-energy bosonic excitations in the conduction band.Comment: long version; 9 pages, 4 figure

Exciton Spin Dynamics in Semiconductor Quantum Wells

In this paper we will review Exciton Spin Dynamics in Semiconductor Quantum Wells. The spin properties of excitons in nanostructures are determined by their fine structure. We will mainly focus in this review on GaAs and InGaAs quantum wells which are model systems.Comment: 55 pages, 27 figure

Phase diagram of the La1−x_{1-x}Cax_{x}MnO3_{3} compound for 0.5≤x≤0.90.5\leq x\leq 0.9

We have studied the phase diagram of La$_{1-x}$Ca$_{x}$MnO$_{3}$ for $0.5\leq x\leq 0.9$ using neutron powder diffraction and magnetization measurements. At 300 K all samples are paramagnetic and single phase with crystallographic symmetry $Pnma$. As the temperature is reduced a structural transition is observed which is to a charge-ordered state only for certain x. On further cooling the material passes to an antiferromagnetic ground state with Neel temperature $T_N$ that depends on x. For $0.8\leq x\leq 0.9$ the structural transformation occurs at the same temperature as the magnetic transition. Overall, the neutron diffraction patterns were explained by considering four phase boundaries for which La$_{1-x}$Ca$_x$MnO$_3$ forms a distinct phase: the CE phase at $x=0.5-0.55$, the charge-ordered phase at x=2/3, the monoclinic and C-type magnetic structure at $x=0.80-0.85$ and the G-type magnetic structure at x=1. Between these phase boundaries the magnetic reflections suggest the existence of mixed compounds containing both phases of the adjacent phase boundaries in a ratio determined by the lever rule

Diagnosis features of pediatric Gaucher disease patients in the era of enzymatic therapy, a national-base study from the Spanish Registry of Gaucher Disease

Background: The enzymatic replacement therapy (ERT) availability for Gaucher disease (GD) has changed the landscape of the disease, several countries have screening programs. These actions have promoted the early diagnosis and avoided many complications in pediatric patients. In Spain ERT has been available since 1993 and 386 patients have been included in the Spanish Registry of Gaucher Disease (SpRGD). The aim of this study is to analyze the impact of ERT on the characteristics at time of diagnosis and initial complications in pediatric Gaucher disease patients. Aim: To analyze the impact of ERT on the characteristics at time of diagnosis and initial complications in pediatric Gaucher disease patients. Methods: A review of data in SpRGD from patients'' diagnosed before 18 years old was performed. The cohort was split according the year of diagnosis (=1994, cohort A; =1995, cohort B). Results: A total of 98 pediatric patients were included, GD1: 80, GD3: 18; mean age: 7.2 (0.17-16.5) years, 58 (59.2%) males and 40 (40.8%) females. Forty-five were diagnosed = 1994 and 53 = 1995. Genotype: N370S/N370S: 2 (2.0%), N370S/L444P: 27 (27.5%), N370S/other: 47 (48%), L444P/L444P: 7 (7.1%), L444P/D409H: 2 (2.0%), L444P/other: 3 (6.2%), other/other: 10 (10.2%). The mean age at diagnosis was earlier in patients diagnosed after 1995 (p < 0.001) and different between the subtypes, GD1: 8.2 (0.2-16.5) years and GD3: 2.8 (0.17-10.2) years (p < 0.001). There were more severe patients in the group diagnosed before 1994 (p = 0.045) carrying L444P (2), D409H (2), G377S (1), G195W (1) or the recombinant mutation. The patients'' diagnosed =1994 showed worse cytopenias, higher chance of bone vascular complications at diagnosis and previous spleen removal. The patients started ERT at a median time after diagnosis of 5.2 years [cohort A] and 1.6 years [cohort B] (p < 0.001). Conclusions: The early diagnosis of Gaucher disease in the era of ERT availability has permitted to reduce the incidence of severe and irreversible initial complication in pediatric patients, and this has permitted better development of these patients. This is the largest pediatric cohort from a national registry