Rigid probe solutes in a smectic-A liquid crystal: An unconventional route to the latter's positional order parameters

Biphenylene and pyrene were dissolved in the nematic and smectic-A phases of the liquid crystal 4,4’-di-n-heptyl-azoxybenzene and the orientational order parameters of both solutes and solvent measured via proton and deuteron nuclear-magnetic-resonance spectroscopy. This new data set was then merged with the one previously obtained, formed by 4,4’-di-chloro-benzene and naphthalene as solutes in the same solvent, and the resulting overall data set analyzed with a statistical thermodynamic density-functional theory to provide positional-orientational distribution functions of the various solutes along with the smectic solvent’s positional order parametersM.E.D.P. is grateful to the European Commission, the European Social Fund, and the Regione Calabria for cofunding her Ph.D. scholarship. M.E.D.P., G.C., and G.D.L. thank the University of Calabria and MIUR PRIN 2009 for financial support. G.C. acknowledges the financial support of the Spanish Ministry of Research via a Raóon y Cajal research fellowshi

Correction: Conformational features of 4-(N)-squalenoyl-gemcitabine in solution: a combined NMR and molecular dynamics investigation

Correction for 'Conformational features of 4-(N)-squalenoyl-gemcitabine in solution: a combined NMR and molecular dynamics investigation' by Ceruti Maurizio et al., New J. Chem., 2015, 39, 3484–3496

Insights into the Effect of Lithium Doping on the Deep Eutectic Solvent Choline Chloride: Urea

Choline-based deep eutectic solvents (DESs) are potential candidates to replace flammable organic solvent electrolytes in lithium-ion batteries (LIBs). The effect of the addition of a lithium salt on the structure and dynamics of the material needs to be clarified before it enters the battery. Here, the archetypical DES choline chloride:urea at 1:2 mole fraction has been added with lithium chloride at two different concentrations and the effect of the additional cation has been evaluated with respect to the non-doped system via multinuclear NMR techniques. 1H and 7Li spin-lattice relaxation times and diffusion coefficients have been measured between 298 K and 373 K and revealed a decrease in both rotational and translational mobility of the species after LiCl doping at a given temperature. Temperature dependent 35Cl linewidths reflect the viscosity increase upon LiCl addition, yet keep track of the lithium complexation. Quantitative indicators such as correlation times and activation energies give indirect insights into the intermolecular interactions of the mixtures, while lithium single-jump distance and transference number shed light into the lithium transport, being then of help in the design of future DES electrolytes

Reinforcing the Electrode/Electrolyte Interphases of Lithium Metal Batteries Employing Locally Concentrated Ionic Liquid Electrolytes

Lithium metal batteries (LMBs) with nickel-rich cathodes are promising candidates for next-generation high-energy-density batteries, but the lack of sufficiently protective electrode/electrolyte interphases (EEIs) limits their cyclability. Herein, trifluoromethoxybenzene is proposed as a cosolvent for locally concentrated ionic liquid electrolytes (LCILEs) to reinforce the EEIs. With a comparative study of a neat ionic liquid electrolyte (ILE) and three LCILEs employing fluorobenzene, trifluoromethylbenzene, or trifluoromethoxybenzene as cosolvents, it is revealed that the fluorinated groups tethered to the benzene ring of the cosolvents not only affect the electrolytes’ ionic conductivity and fluidity, but also the EEIs’ composition via adjusting the contribution of the 1-ethyl-3-methylimidazolium cation (Emim$^+$) and bis(fluorosulfonyl)imide anion. Trifluoromethoxybenzene, as the optimal cosolvent, leads to a stable cycling of LMBs employing 5 mAh cm$^{−2}$ lithium metal anodes (LMAs), 21 mg cm$^{−2}$ LiNi$_{0.8}$Co$_{0.15}$Al$_{0.05}$ (NCA) cathodes, and 4.2 µL mAh$^{−1}$ electrolytes for 150 cycles with a remarkable capacity retention of 71%, thanks to a solid electrolyte interphase rich in inorganic species on LMAs and, particularly, a uniform cathode/electrolyte interphase rich in Emim$^+$-derived species on NCA cathodes. By contrast, the capacity retention under the same condition is only 16%, 46%, and 18% for the neat ILE and the LCILEs based on fluorobenzene and benzotrifluoride, respectively

Locally Concentrated Ionic Liquid Electrolyte with Partially Solvating Diluent for Lithium/Sulfurized Polyacrylonitrile Batteries

The development of Li/sulfurized polyacrylonitrile (SPAN) batteries requires electrolytes that can form stable electrolyte/electrode interphases simultaneously on lithium-metal anodes (LMAs) and SPAN cathodes. Herein, a low-flammability locally concentrated ionic liquid electrolyte (LCILE) employing monofluorobenzene (mFBn) as the diluent is proposed for Li/SPAN cells. Unlike non-solvating diluents in other LCILEs, mFBn partially solvates Li$^+$, decreasing the coordination between Li$^+$ and bis(fluorosulfonyl)imide (FSI$^−$). In turn, this triggers a more substantial decomposition of FSI$^−$ and consequently results in the formation of a solid electrolyte interphase (SEI) rich in inorganic compounds, which enables a remarkable Coulombic efficiency (99.72%) of LMAs. Meanwhile, a protective cathode electrolyte interphase (CEI), derived mainly from FSI$^−$ and organic cations, is generated on the SPAN cathodes, preventing the dissolution of polysulfides. Benefiting from the robust interphases simultaneously formed on both the electrodes, a highly stable cycling of Li/SPAN cells for 250 cycles with a capacity retention of 71% is achieved employing the LCILE and only 80% lithium-metal excess

Difluorobenzene‐Based Locally Concentrated Ionic Liquid Electrolyte Enabling Stable Cycling of Lithium Metal Batteries with Nickel‐Rich Cathode

Lithium metal batteries (LMBs) with nickel-rich cathodes are promising candidates for next-generation, high-energy batteries. However, the highly reactive electrodes usually exhibit poor interfacial compatibility with conventional electrolytes, leading to limited cyclability. Herein, a locally concentrated ionic liquid electrolyte (LCILE) consisting of lithium bis(fluorosulfonyl)imide (LiFSI), 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EmimFSI), and 1,2-difluorobenzene (dFBn) is designed to overcome this challenge. As a cosolvent, dFBn not only promotes the Li$^{+}$ transport with respect to the electrolyte based on the ionic liquid only, but also has beneficial effects on the electrode/electrolyte interphases (EEIs) on lithium metal anodes (LMAs) and LiNi$_{0.8}$Mn$_{0.1}$Co$_{0.1}$O$_{2}$ (NMC811) cathodes. As a result, the developed LCILE enables dendrite-free cycling of LMAs with a coulombic efficiency (CE) up to 99.57% at 0.5 mA cm$^{-2}$ and highly stable cycling of Li/NMC811 cells (4.4 V) at C/3 charge and 1 C discharge (1 C = 2 mA cm−2) for 500 cycles with a capacity retention of 93%. In contrast, the dFBn-free electrolyte achieves lithium stripping/plating CE, and the Li/NMC811 cells’ capacity retention of only 98.22% and 16%, respectively under the same conditions. The insight into the coordination structure, promoted Li$^{+}$ transport, and EEI characteristics gives fundamental information essential for further developing (IL-based) electrolytes for long-life, high-energy LMBs

Urinary Metabolic Profile of Patients with Transfusion-Dependent β-Thalassemia Major Undergoing Deferasirox Therapy

Introduction: Renal dysfunction is a frequent complication in patients suffering from β-thalassemia major (β-TM). The aim of this study was to analyze the renal function and urine metabolomic profile of β-TM patients undergoing transfusions and deferasirox (DFX) therapy, in order to better characterize and shed light on the pathogenesis of renal disease in this setting. Methods and Subjects: 40 patients affected by β-TM treated with DFX and 35 age- and gender-matched healthy controls were enrolled in the study. Renal function was assessed. Glomerular filtration rate (GFR) was estimated with CKD-EPI and Schwartz formula for adults and children, respectively. Renal tubular function and maximal urine concentration ability were tested. Urine specimens were analyzed by nuclear magnetic resonance spectroscopy to identify the urinary metabolite profiles. Results: The study of renal function in β-TM patients revealed normal estimated (e)GFR mean values and the albumin-to-creatinine ratio was <30 mg/g. The analysis of tubular function showed normal basal plasma electrolyte levels; 60% of patients presented hypercalciuria and many subjects showed defective urine concentration. Several amino acids, N-methyl compounds, and organic acids were overexcreted in the urine of thalassemic patients compared with controls. Discussion: The major finding of this work is that β-TM patients and controls exhibit different concentrations of some metabolites in the urine. Early recognition of urinary abnormalities may be useful to detect and prevent kidney damage

The Complex Story Behind a Deep Eutectic Solvent Formation as Revealed by L‑Menthol Mixtures with Butylated Hydroxytoluene Derivatives.

An in-depth study of the hydrophobic eutectic mixtures formed by L-menthol (MEN) with the butylated hydroxytoluene (BHT), 2-tert-butyl-pcresol (TBC), and p-cresol (PC) compounds has been carried out, where TBC and PC are analogous to the BHT species but with a different degree of steric hindrance around the hydroxyl group. Thermal characterization evidenced that the BHT/MEN system can be classified as an ideal eutectic, while the TBC/MEN and PC/MEN mixtures behave as type V deep eutectic solvents (DESs) for a wide range of compositions around the eutectic point. As shown by an array of experimental and theoretical methods, in the BHT/MEN mixtures the establishment of hydrogen-bond (H-bond) interactions between the components is dramatically hampered because of the steric hindrance in the BHT molecule, so that the achievement of a liquid phase at room temperature for the eutectic composition is driven by apolar−apolar attractions among the alkyl functional groups of the constituents. Differently, the TBC-MEN donor−receptor H-bond is the main driving force for the formation of a type V DES and derives from a concurrence of electronic and steric factors characterizing the TBC molecule. Finally, the absence of steric hindrance around the hydroxyl group allows the self-association among PC molecules through H-bonded networks already in the pristine compound, but the replacement with the more favorable PC-MEN H-bond provides a type V DES upon mixing of these components. Our combined approach, together with the peculiarity of the inspected systems, delivered an archetypal study able to shed light onto the various contributions ruling the structure− properties relationship in DESs and possibly deepening the currently accepted view of these inherently complex media