Controlling Supramolecular Structures of Drugs by Light.

Controlling physicochemical properties of light-unresponsive drugs, by light, prima facie, a paradox approach. We expanded light control by ion pairing light-unresponsive salicylate or ibuprofen to photoswitchable azobenzene counterions, thereby reversibly controlling supramolecular structures, hence the drugs' physicochemical and kinetic properties. The resulting ion pairs photoliquefied into room-temperature ionic liquids under ultraviolet light. Aqueous solutions showed trans-cis-dependent supramolecular structures under a light with wormlike aggregates decomposing into small micelles and vice versa. Light control allowed for permeation through membranes of cis-ibuprofen ion pairs within 12 h in contrast to the trans ion pairs requiring 72 h. In conclusion, azobenzene ion-pairing expands light control of physicochemical and kinetic properties to otherwise light-unresponsive drugs.

Excitation-independent dual emissions of carbon dots synthesized by plasma irradiation of ionic liquids: Ratiometric fluorometric determination of norfloxacin and mercury(II).

The capacitively coupled plasma (CCP) discharge of an ionic liquid solution of citric acid produces carbon dots (CDs) with excitation-independent fluorescent dual-emissions peaking at 410 nm and 480 nm. The intensity of the purple photoluminescence at 410 nm increases with (a) the flow rate of O2 plasma gas supply from 2.0 to 30 standard cubic centimeters per minute (sccm), (b) the 2-h exposure of the CDs to 254 nm light, and (c) the 8-h immersion of the CDs in a solution of NaBH4. The UV exposure and the hydride immersion reduce the fluorescence intensity peaking at 480 nm, which is highest at 5.0 and 10 sccm. The two emissive states were revealed by UV-vis absorption, XPS spectra, and time-resolved fluorescence. Control of the O2 flow rate can simply tune the ratiometric fluorescence of the CCP-CDs. The CDs obtained from 5 and 30 sccm O2 supplies present a high-intensity ratio (I480 nm/I410 nm ≈ 3.35) and a low one (≈ 0.48), respectively. The 480 nm fluorescence of the former CDs is quenched by mercury(II) ions in the 0.2 to 50 µM concentration range. The 410 nm fluorescence of the latter CDs is enhanced by norfloxacin in the 25 nM to 1.0 µM concentration range. The detection limits are 75 nM for Hg(II) and 7.3 nM for norfloxacin. Graphical abstract Schematic presentation of the effect of the oxygen flow rate in capacitively coupled radio frequency (RF) plasma on the formed CDs. The emission can be quenched by Hg2+ or enhanced by norfloxacin.

Radiation stability of cations in ionic liquids. 5. Task-specific ionic liquids consisting of biocompatible cations and the puzzle of radiation hypersensitivity.

In 1953, an accidental discovery by Melvin Calvin and co-workers provided the first example of a solid (the α-polymorph of choline chloride) showing hypersensitivity to ionizing radiation: under certain conditions, the radiolytic yield of decomposition approached 5 × 10(4) per 100 eV (which is 4 orders of magnitude greater than usual values), suggesting an uncommonly efficient radiation-induced chain reaction. Twenty years later, the still-accepted mechanism for this rare condition was suggested by Martyn Symons, but no validation for this mechanism has been supplied. Meanwhile, ionic liquids and deep eutectic mixtures that are based on choline, betainium, and other derivitized natural amino compounds are presently finding an increasing number of applications as diluents in nuclear separations, where the constituent ions are exposed to ionizing radiation that is emitted by decaying radionuclides. Thus, the systems that are compositionally similar to radiation hypersensitive solids are being considered for use in high radiation fields, where this property is particularly undesirable! In Part 5 of this series on organic cations, we revisit the phenomenon of radiation hypersensitivity and explore mechanistic aspects of radiation-induced reactions involving this class of task-specific, biocompatible, functionalized cations, both in ionic liquids and in reference crystalline compounds. We demonstrate that Symons' mechanism needs certain revisions and rethinking, and suggest its modification. Our reconsideration suggests that there cannot be conditions leading to hypersensitivity in ionic liquids.

Time-dependent density functional theory for ion diffusion in electrochemical systems.

We introduce a generic form of time-dependent density functional theory (TDDFT) to describe ion diffusion in electrochemical systems to account for steric effects and electrostatic correlations neglected in the Poisson-Nernst-Planck equations. An efficient numerical algorithm is proposed to analyze the charging kinetics of electric double layers in model electrochemical systems that consist of spherical ions in a dielectric continuum confined between two planar electrodes. By comparing the theoretical predictions from TDDFT and conventional electrokinetic methods for constant-voltage charging of the model electrochemical cells, we demonstrate that thermodynamic non-ideality plays a pivotal role in electrodiffusion even at relatively low electrolyte concentrations, and this effect cannot be captured by the lattice-gas model for the excluded volume effects. In particular, TDDFT predicts 'wave-like' variation of the ionic density profiles that has not been identified in previous investigations. At conditions where there are no significant correlations between electric double layers from opposite electrodes, the charging kinetics follows an exponential behavior with a linear dependence of the relaxation time on the cell thickness in excellent agreement with the equivalent circuit model. However, the conventional electrokinetic model breaks down when the electrodes are at small separation, in particular for systems with low ionic strength or high charging voltage. We also find that ionic screening retards the charging kinetics at low salt concentrations, but has the opposite effect at large salt concentrations.

Effect of a bias electric field on the structure and dielectric response of the ferroelectric smectic-A liquid crystal in thin planar cells.

The phenomenological continuum model is used to study the director structure and dielectric response of the ferroelectric smectic-A phase in thin planar cells. The frequency of the phase mode and the dielectric permittivity are calculated numerically as a function of the bias external DC electric field, cell thickness, the strength of polar surface anchoring, and the ratio between the bend and splay elastic constants. The theoretically obtained dependencies are in agreement with the recently reported experimental measurements, which show that in thin planar cells both the phase mode frequency and the dielectric permittivity decrease with increasing external bias electric field.

TiO2 nanoparticles: low-temperature hydrothermal synthesis in ionic liquids/water and the photocatalytic degradation for o-nitrophenol.

The well-crystallized anatase TiO2-IL nanoparticles were synthesized by one-step routes under low-temperature using room temperature ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate as an additional solvent with water. The photocatalytic properties of TiO2 nanoparticles were evaluated by photocatalytic degradation experiments of o-nitrophenol. The TiO2 nanoparticles show a higher photocatalytic activity than the TiO2 with pure water and commercial TiO2 (P25), which may be related to the high crystallinity. The TiO2-IL nanoparticles still hold a high photocatalytic activity after the catalyst was recycled nine times. Chemical oxygen demand removal was achieved under optimum experimental conditions.

Selective conversion of cellulose to levulinic acid via microwave-assisted synthesis in ionic liquids.

A highly selective approach to produce levulinic acid from cellulose was developed via microwave-assisted synthesis in SO3H-functionalized ionic liquids (SFILs). The effects of reaction conditions and ionic liquid structures on the yield of levulinic acid have been investigated, where the highest yield of 55.0% was obtained. The catalytic activities of SFILs depend on the anions and decrease in the order: HSO4->CH3SO3->H2PO4-, which is in good agreement with their acidity order. The SFILs are efficient catalysts for cellulose conversion into levulinic acid and the subsequent esterification, which facilitates the separation of product and reuse of ionic liquids.

Ultrasound and ionic liquid: an efficient combination to tune the mechanism of alkenes epoxidation.

In this proof of concept study, the advantageous properties of both H(2)O(2)/NaHCO(3)/imidazole/Mn(TPP)OAc oxidation system and MOPyrroNTf(2) ionic liquid have been combined under ultrasonic irradiation to give an exceptionally favorable environment for Mn(TPP)OAc catalyzed olefin oxidations. The results reveal the crucial role played by the ultrasonic irradiations that influence drastically the oxidation process. In MOPyrroNTf(2) and under ultrasonic irradiation, the mechanism probably involves an oxo-manganyl intermediate at the expense of the classical bicarbonate-activated peroxide route.

Measurement of evaporation rates of different kind of aqueous solutions under microwave irradiation.

The evaporation rate of water is, of course, different under the same heating conditions of different aqueous solutions. Under conventional heating conditions, the evaporation rate of water is much higher than the evaporation rate of water of aqueous solutions of different kinds of solute materials, which is well accordance with the classical Raoult's law. The results obtained in this study have clearly shown that the chemical characteristics of dissolved materials in water very seriously affect the evaporation rates of water under the microwave heating. This generally causes contradictory results to Raoult's law and this can be explained with the additional microwave energy absorption by the ionic or molecular solute materials found in the solutions other than the microwave energy absorption by water molecules themselves.

A convenient and efficient protocol for the synthesis of acylals catalyzed by Brønsted acidic ionic liquids under ultrasonic irradiation.

The synthesis of acylals (1,1-diacetates) via the reactions of aldehydes with acetic anhydride was carried out in 85-97% yields at room temperature under ultrasound irradiation catalyzed by the Brønsted acidic ionic liquid [bmpy]HSO(4). This method provides several advantages, such as solvent-free conditions, operational simplicity, higher yields, and reduced environmental consequences. The ionic liquid was recovered and reused.

Synthesis of gold nanoparticles by laser ablation of an Au foil inside and outside ionic liquids.

Stable gold nanoparticles (AuNPs) were prepared by simple laser ablation of an Au foil placed inside or outside four ionic liquids (ILs), without the addition of any external chemical reagent. Irregular spherical AuNPs with a diameter range of 5 to 20 nm were produced after laser ablation of an Au foil located inside or outside the ILs 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMI·BF4), 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI·PF6) and 1-(3-cyanopropyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ((BCN)MI·NTf2). Additionally, whereas laser ablation inside the IL 1-n-butyl-3-methylimidazolium dicyanamide BMI·N(CN)2 produced flower-like shaped nanoparticles of about 50 nm in size, ablation outside this IL presented similar results to the others ILs studied, as determined by TEM and UV-Vis. The size and shape of the prepared NPs were related to where NP nucleation and growth occurred, i.e., at the IL surface or within the IL. Indeed, the chemical composition of the IL/air interface and surface ion orientation played important roles in the stabilization of the AuNPs formed by laser ablation outside the ILs.

Ultrasonically-promoted synthesis of mandelic acid by phase transfer catalysis in an ionic liquid.

An efficient and facile process to synthesize mandelic acid through phase transfer catalysis (PTC; also phase transfer catalyst) using ultrasound in an ionic liquid has been developed. Mandelic acid was synthesized from benzaldehyde with chloroform in an 89.6% yield at 60°C for 2h by using tetrabutyl ammonium bromide (TBAB) as a phase transfer catalyst. Effects of different factors, such as frequency of ultrasound, reaction temperature, kinds of PTC and solvents had been investigated to obtain the optimum condition. It was observed that the ultrasonically promoted synthesis of mandelic acid by PTC in the ionic liquid exhibited significant enhancement in reaction yields under ambient conditions.

Ultrasound-assisted solvent-free synthesis of lactic acid esters in novel SO3H-functionalized Brønsted acidic ionic liquids.

Mild and efficient Fischer esterification reactions of lactic acid with a variety of straight chain aliphatic alcohols, cyclohexanol and benzyl alcohol were successfully performed using two novel Brønsted acidic ionic liquids that bear an aromatic sulfonic acid group on the imidazolium or pyridinium cation under ultrasound irradiation. These reactions carried out smoothly with good to excellent conversion rate (78-96%) and satisfactory yields (73-92%) in shorter reaction time (4-6h) at room temperature when the amount of ionic liquids was 20 mol%. These ionic liquids could be recovered readily and recycled five times without any significant loss in their catalytic activity.

Ionic liquid [EMIM]OAc under ultrasonic irradiation towards the first synthesis of trisubstituted imidazoles.

The ionic liquid 1-ethyl-3-methylimidazole acetate ([EMIM]OAc) was found to be a mild and effective catalyst for the efficient, one-pot, three-component synthesis of 2-aryl-4,5-diphenyl imidazoles at room temperature under ultrasonic irradiation. This procedure has many obvious advantages compared to those reported in the previous literatures, including avoiding the use of harmful catalysts, reacting at room temperature, high yields, simplicity of the methodology.

Metal-free, retro-cycloaddition of fulleropyrrolidines in ionic liquids under microwave irradiation.

Quantitative cycloreversion of fulleropyrrolidines to [60]fullerene is achieved in ionic liquids within minutes under microwave irradiation without any further additives.

Gamma radiolysis of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate.

The applications of room-temperature ionic liquids in the nuclear fuel cycle and radiation chemistry depend on a comprehensive knowledge of their stability and chemical properties under radiation conditions. In this work, the effect of gamma radiation on pure ionic liquid [bmim][PF6] was investigated in detail. The radiolysis of [bmim][PF6] leads to an increase of UV-vis absorbance and a decrease of fluorescence intensity with increasing radiation dose. Raman spectra proved that gamma radiation induced significant chemical scission of the n-butyl group (e.g. C-H and C-C scission) and damage to the [PF6]- anion. When the irradiated [bmim][PF6] samples were cooled, two crystal structures were found to coexist, and they suffered a continuous destruction under irradiation; their dose dependence, however, was different.