Anomalous Melting Point of Multicharge Ionic Liquids: Structural, Electrostatic, and Orbital Properties of [Ln(NO3)6]3- (Ln = Ce, Pr) Anions.

Salts composed of multicharged cations/anions usually exhibit a large lattice energy and strong Coulomb force, which results in high melting points. However, an increasing number of highly charged ionic liquids exceed expectations based on conventional experience; even their melting points are much lower than those found for simple ionic liquids composed of monovalent ions. To further study this phenomenon, we studied a group of stable ionic liquids containing tricharged [Ce(NO3)6]3- and [Pr(NO3)6]3- anions. The structures for [C6mim]3[Ce(NO3)6] and [C6mim]3[Pr(NO3)6] were determined by single-crystal X-ray diffraction with triclinic and P1̅ space groups. The electrostatic potential density per unit ion surface and volume was proposed and calculated. Additionally, theoretical analysis based on Hirshfeld surface and charge decomposition was carried out to explore the intermolecular interaction and electronic structure of the lanthanide anions. The electrostatic and orbital properties were found to be more useful for understanding the melting points of highly charged salts compared with the sole use of lattice energy. The electrostatic potential density per unit ion surface and volume showed a linear relationship with the melting point of ionic liquids composed of monovalent to trivalent ions. These structure-melting point relationships will be beneficial for expounding new low-melting-point ionic liquids with a wide liquidus range.

Biocompatible Ionic Liquid Based on Curcumin as Fluorescence Probe for Detecting Benzoyl Peroxide without the Interference of H2O2.

Accurate estimation of the level of benzoyl peroxide (BPO) is of considerable significance because of its threat to humanity and environment. Several research efforts have been devoted to the detection of BPO by fluorescent method with high sensitivity and selectivity. However, it remains challenging to eliminate the interference of H2O2 due to its similar properties to BPO. In this work, the first demonstration of fluorescent and colorimetric probe for specific detection of BPO without the disturbance of H2O2 was achieved by curcumin-based ionic liquid (CIL) that possesses simple fabrication, good biocompatibility, and low cost. The fluorescence quenches and emission peak blue-shifts once the probe selectively interacts with BPO, whereas the other possible interfering agents, including H2O2, do not have this phenomenon. The probe CIL exhibits prominent sensitivity for BPO sensing and enables the detection limit at levels as ultralow as 10 nM. The local detection of BPO in practical samples is realized by visualization using a portable device derived from CIL-based liquid atomizer.

Hydrogen-Bonding-Driven Ion-Pair Formation in Protic Ionic Liquid Aqueous Solution.

Protic ionic liquids (PILs) in solution especially in water have attracted more and more attention due to their unique properties. The solvation of PILs in water is important to their properties and applications. To explore the solvation of bio-based PILs in water, acidity of 49 [AA]X amino acid ionic liquids (AAILs) consisting of 7 different cations and 7 different anions was studied as a favorable probe. The pKa values for [AA]X PILs containing same cations were obtained and discussed. The acidity strength of the [AA]X PILs varies with both cation and anion which does not follow the conventional assumption that the acidity for PILs is independent of anions. The acidic discrepancy of [AA]X PILs aqueous solution is probably mediated by the formation of ion pairs according to a revised solvation model of PILs. Quantum-chemistry calculation was employed to unpuzzle anion's different effects on the acid balance of cations where cation-anion hydrogen bonds play an important role. Such difference in acidity allows us to understand the formation of solvated ion pairs. This work provides an insight into the fundamental solvation of PILs from acid perspective and their influence on acidity properties for the first time.

Fluorescigenic Magnetofluids Based on Gadolinium, Terbium, and Dysprosium-Containing Imidazolium Salts.

Multistimuli responsive soft materials are urgently needed in many different fields, such as anticounterfeiting technology and microdroplet manipulation. Herein, the straightforward preparation of fluorescigenic magnetofluids by the introduction of the paramagnetic metal ions Gd3+, Tb3+, and Dy3+ into alkylimidazolium-based ionic liquids (ILs) is reported. Bright visible fluorescence was observed under UV irradiation for Tb- and Dy-containing ILs. Either pure samples or papers coated with these ILs exhibited pronounced magnetic responses. Consistent and stable structures of these salts were confirmed by systematical characterizations. Because of the competition of nitrate ligands, structural water in the precursors was eliminated easily under a vacuum. For Tb- and Dy-containing ILs, featured electronic transitions were observed and were assigned in the fluorescence spectra. The long lifetimes of these transitions were also confirmed. The field-cooling experiments showed that all of these ILs display paramagnetism at room temperature. At low temperature, small deviations from the Curie Law indicate the occurrence of antiferromagnetic coupling and spin canting in these ILs. Temperature-induced differences in magnetic properties were further verified by field-dependent magnetic susceptibility measurements carried out at 5 and 300 K.

Bio-based ionic liquid filter with enhanced electrostatic attraction for outside filtration and inside collection of viral aerosols.

Hazardous biological pathogens in the air pose a significant public environmental health concern as infected individuals emit virus-laden aerosols (VLAs) during routine respiratory activities. Mask-wearing is a key preventive measure, but conventional filtration methods face challenges, particularly in high humidity conditions, where electrostatic charge decline increases the risk of infection. This study introduces a bio-based air filter comprising glycine ionic liquids (GILs) and malleable polymer composite (GILP) with high polarity and functional group density, which are wrapped around a melamine-formaldehyde (MF) resin skeleton, forming a conductive, porous GIL functionized ionic network air filter (GILP@MF). When subjected to low voltage, the GILP@MF composite efficiently captures VLAs including nanoscale virus particles through the enhanced electrostatic attraction, especially in facing high humidity bioaerosols exhaled by human body. The filtration/collection efficiency and quality factor can reach 98.3% and 0.264 Pa-1 at 0.1 m s-1, respectively. This innovative filter provides effective VLA protection and offers potential for non-invasive respiratory virus sampling, advancing medical diagnosis efforts.

Low-melting multicharge ionic liquids with [Ln(NO3)5]2- (Ln = Ho-Lu): structural, electrostatic, thermochemical, and fluorescence properties.

A series of green and safe heavy-rare-earth ionic liquids were obtained using a straightforward method. The stable structures of these ionic liquids, characterized by high-coordinating anions, were confirmed by nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and single crystal X-ray diffraction (XRD). These ionic liquids exhibited wide liquid phase intervals and excellent thermal stability. The bidentate nitrato ligands occupied a sufficient number of coordination sites on the lanthanide ions, resulting in the formation of water-free 10-coordination structures. To explain the anomalous melting points observed in these multi-charged ionic liquids, a combination of experimental data and theoretical studies was employed to investigate the relationship between the electrostatic properties and the melting point. The electrostatic potential density per unit ion surface and volume were proposed and utilized for melting point prediction, demonstrating good linearity. Furthermore, the coordinating spheres of the lanthanide ions in these ionic liquids were devoid of luminescence quenchers such as O-H and N-H groups. Notably, the ionic liquids containing Ho3+, Er3+, and Tm3+ exhibited long lifetime near-infrared (NIR) and blue emissions, respectively. The UV-vis-NIR spectra revealed numerous electronic transitions of the lanthanide ions, which were attributed to their unique optical properties.

Arthrocolins Synergizing with Fluconazole Inhibit Fluconazole-Resistant Candida albicans by Increasing Riboflavin Metabolism and Causing Mitochondrial Dysfunction and Autophagy.

Our previous study reported that seminaturally occurring arthrocolins A to C with unprecedented carbon skeletons could restore the antifungal activity of fluconazole against fluconazole-resistant Candida albicans. Here, we showed that arthrocolins synergized with fluconazole, reducing the fluconazole minimum and dramatically augmenting the survivals of 293T human cells and nematode Caenorhabditis elegans infected with fluconazole-resistant C. albicans. Mechanistically, fluconazole can induce fungal membrane permeability to arthrocolins, leading to the intracellular arthrocolins that were critical to the antifungal activity of the combination therapy by inducing abnormal cell membranes and mitochondrial dysfunctions in the fungus. Transcriptomics and reverse transcription-quantitative PCR (qRT-PCR) analysis indicated that the intracellular arthrocolins induced the strongest upregulated genes that were involved in membrane transports while the downregulated genes were responsible for fungal pathogenesis. Moreover, riboflavin metabolism and proteasomes were the most upregulated pathways, which were accompanied by inhibition of protein biosynthesis and increased levels of reactive oxygen species (ROS), lipids, and autophagy. Our results suggested that arthrocolins should be a novel class of synergistic antifungal compounds by inducing mitochondrial dysfunctions in combination with fluconazole and provided a new perspective for the design of new bioactive antifungal compounds with potential pharmacological properties. IMPORTANCE The prevalence of antifungal-resistant Candida albicans, which is a common human fungal pathogen causing life-threatening systemic infections, has become a challenge in the treatment of fungal infections. Arthrocolins are a new type of xanthene obtained from Escherichia coli fed with a key fungal precursor toluquinol. Different from those artificially synthesized xanthenes used as important medications, arthrocolins can synergize with fluconazole against fluconazole-resistant Candida albicans. Fluconazole can induce the fungal permeability of arthrocolins into fungal cells, and then the intracellular arthrocolins exerted detrimental effects on the fungus by inducing fungal mitochondrial dysfunctions, leading to dramatically reduced fungal pathogenicity. Importantly, the combination of arthrocolins and fluconazole are effective against C. albicans in two models, including human cell line 293T and nematode Caenorhabditis elegans. Arthrocolins should be a novel class of antifungal compounds with potential pharmacological properties.

Molecular and immunological characteristics of patients with CMTM6 low expression colorectal cancer.

CKLF-like MARVEL transmembrane domain-containing 6 (CMTM6), a regulator of programmed cell death ligand 1 (PD-L1), has attracted extensive attention due to its role in tumors. However, research on the expression of CMTM6 in colorectal cancer (CRC) and its relationship with PD-L1 expression and immune cell infiltration is limited. We used The Cancer Genome Atlas database to mine and analyze data from patients with CRC using bioinformatics methods. We investigated the expression of CMTM6 in CRC and its relationship with PD-L1 expression and immune cell infiltration. Immunohistochemistry and PCR were performed to detect CMTM6 and PD-L1 expression in CRC tissues. Differential gene expression analysis was performed using the edgeR package in R and immune cell infiltration analysis was performed using the ssGSEA algorithm. Additionally, GO and KEGG enrichment analyses were conducted to identify the biological processes and pathways associated with low CMTM6 expression. Our study found that CMTM6 expression was significantly upregulated in CRC tissues compared to that in adjacent normal tissues. Patients with high CMTM6 expression exhibited significantly increased levels of PD-L1 expression and higher levels of tumor-infiltrating immune cells compared to patients with low CMTM6 expression. GO and KEGG analyses suggested that CMTM6 may be involved in multiple immune regulatory pathways in CRC.

Hydrogen-bonding and "π-π" interaction promoted solution-processable mixed matrix membranes for aromatic amines detection.

Detection of hazardous compounds can alleviate risk to human health. However, it remains a challenge to develop easy-to-use testing tools for carcinogenic aromatic amines. Herein, we presented a conjugated molecule-based aniline detector, mixed matrix membranes (MMMs), through the solution-processable strategy. The pentacene-based dispersed phase is achieved using the state-of-the-art ionic liquids (ILs) as the continuous phase, based on which MMMs are easily manufactured by a solution process. Moreover, molecular dynamics (MD) simulations and quantum mechanical calculations suggested that hydrogen bonding and π-π interaction between ILs cations and pentacene could promote the dissolution. These prepared MMMs can offer easy-operation and on-site detection of carcinogenic primary aromatic amines with eye-readable fluorescence signal. This work provides a paradigm for the design of a portable testing device for various hazardous compounds.

Ultralow-cost portable device for cesium detection via perovskite fluorescence.

Public anxiety and concern from cesium pollution in oceans have been back on the agenda since tons of nuclear waste water were announced to be poured into oceans. Cesium ion can easily enter organisms and bioaccumulate in animals and plants, thus its harm is chronic to humans through food chains. Here we showed a kind of hybrid ionic liquid membrane (HILM) for detection of cesium ion in seawater through CsPbBr3 perovskite fluorescence. With sustainability in mind, HILM was built frugally. The lowest cost of HILM is below 3 cents per piece. The HILM can detect cesium ion quickly with eye-readable fluorescence signal. Ultracheap, portable, easy-to-use on-site detection device could offer benefit for personal security and applications in environment science and ecology in the future decades.

[Observation on Shao's five-needle therapy as adjuvant treatment for stroke-associated pneumonia].

OBJECTIVE: To compare the therapeutic effect between Shao 's five-needle therapy combined with conventional western medical treatment and the simple conventional western medical treatment on stroke-associated pneumonia. METHODS: A total of 80 patients were randomized into an observation group and a control group, 40 cases in each group. Conventional western medication treatment i.e. anti-infection combined with rehabilitation swallowing training were adopted in the control group. On the basis of the treatment in the control group, Shao 's five-needle therapy was applied at Feishu (BL 13), Dazhui (GV 14), Fengmen (BL 12), etc. in the observation group, once a day. The treatment was given for 10 days in the both groups. The levels of inflammatory indexes [white blood cell (WBC), C-reactive protein (CRP), percentage of neutrophil (N%)] before and after treatment, the disappearance time of main clinical symptoms and signs, the scores of National Institutes of Health Stroke scale (NIHSS) and the ability of daily living (ADL) were observed, and the clinical therapeutic effect was evaluated in the both groups. RESULTS: Compared before treatment, the levels of WBC, CRP, N% and the NIHSS scores after treatment were decreased (P<0.05), the ADL scores were increased in the both groups (P<0.05), and the improvement of above indexes in the observation group was superior to the control group (P<0.05). The recovery time of temperature and rale, the duration of cough in the observation group were shorter than those in the control group (P<0.05). The effective rate was 97.5% (39/40) in the observation group, which was superior to 85.0% (34/40) in the control group (P<0.05). CONCLUSION: Shao 's five-needle therapy combined with conventional western medical treatment can effectively improve the clinical symptoms in patients with stroke-associated pneumonia, down-regulate the inflammatory indexes and improve the quality of life, the therapeutic effect is superior to the simple conventional western medical treatment.

Super impact stable TATB explosives recrystallized by bicarbonate ionic liquids with a record solubility.

Ensuring the security for long-term storage of weapons is always of the great cMehilaloncerns in the field of energetic materials. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) is a remarkable explosive applied in nuclear weapons where extreme safety is required primarily. Owing to the strong inter or intra molecular hydrogen bonding, TATB shows poor solubility in most solvents. As the result, the particle shape and size of TATB products is hard to regulate, which closely related to the weapons stability. Herein, a new recrystallization method is provided to refine TATB using bicarbonate ionic liquids. Bicarbonate ionic liquids exhibited the record solubility (26.7 wt%) for dissolving TATB explosive. The recrystallized TATB were spherical particles with uniform size and showed extremely insensitivity to impact (>100 J) and friction (>360 N). Moreover, the experimental 1H and 13C NMR spectra of TATB in solution are reported for the first time.

Designing high-performance hypergolic propellants based on materials genome.

A new generation of rocket propellants for deep space exploration, ionic liquid propellants, with long endurance and high stability, is attracting more and more attention. However, a major defect of ionic liquid propellants that restricts their application is the inadequate hypergolic reactivity between the fuel and the oxidant, and this defect results in local burnout and accidental explosions during the launch process. We propose a visualization model to show the features of structure, density, thermal stability, and hypergolic activity for estimating propellant performances and their application abilities. This propellant materials genome and visualization model greatly improves the efficiency and quality of developing high-performance propellants, which benefits the discovery of new advanced functional molecules in the field of energetic materials.

Is it Always Chemical When Amino Groups Come Across CO2? Anion-Anion-Interaction-Induced Inhibition of Chemical Adsorption.

Amino-functionalized ionic liquids (IL) are often applied to fix CO2. However, as far as we know, none of them have ever been reported to exhibit considerable physical CO2 capture. Herein, we describe an amino-functionalized room-temperature ionic liquid, 1-butyl-3-methylimidazolium 3-amino-1H-1,2,4-triazolate ([Bmim][ATZ]), with an unusual ultrafast physical CO2 capture at room temperature and atmospheric pressure. Within the time needed for a chemisorbent to reach an equilibrium, 15 adsorption and desorption cycles are finished for [Bmim][ATZ], with an accumulative molar ratio of up to 2.04. The CO2/IL ratio for one adsorption process reaches 0.14, which is 4 times the highest recorded physical CO2 solubility by [thtdp][Cl] (trihexyltetradecylphosphonium chloride). The first theoretical study on anion-anion interactions of ionic liquids is reported, which rationalizes the inhibition of chemical adsorption. These results provide a new perspective on the aspect of CO2 capture, as well as designing of ionic liquids.

Handy fluorescent paper device based on a curcumin derivative for ultrafast detection of peroxide-based explosives.

We report a handy, simple and inexpensive paper device for extremely sensitive detection of peroxide-based explosives. The sensing device fabricated using a curcumin derivative was capable of ultrafast sensing of triacetone triperoxide. The detection time was below 5 s. Moreover, the sensor retained full function under storage at ambient temperature for at least 120 days.

Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids.

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous, and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes, and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation-anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303-333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands.

Insensitive ionic bio-energetic materials derived from amino acids.

Energetic salts/ionic liquids have received increasing attention as fascinating energetic materials, and the use of renewable compounds is a promising approach to developing energetic materials. Until recently, biomolecules have been used as raw materials to develop neutral energetic compounds, whereas research focused on ionic energetic materials obtained from natural bio-renewable frameworks is scarce. This work systematically investigates ionic bio-energetic materials (IBEMs) derived from sustainable natural amino acids. In addition to combustibility, high density, good thermal stability, and one-step preparation, these IBEMs demonstrated apparent hypotoxicity and insensitivity. Moreover, a theoretical examination was performed to explore their appropriate properties. The intriguing results of this study indicates that IBEMs are potential bio-based energetic materials.

Effects of acupuncture on the expression of glial cell line-derived neurotrophic factor (GDNF) and basic fibroblast growth factor (FGF-2/bFGF) in the left sixth lumbar dorsal root ganglion following removal of adjacent dorsal root ganglia.

This investigation studied the temporal changes in the expression of GDNF and FGF-2 in the left sixth lumbar (L6) dorsal root ganglion (DRG) after acupuncture in adult cats subjected to unilateral removal of adjacent DRG. The cats were divided into three groups. Group I were normal control animals. Group II cats were subjected to removal of DRG associated with the left L1-L5 and L7-S2 spinal nerves, sparing the L6 DRG. Group III cats received similar treatment as Group II ones, but in addition were subjected to acupuncture on the left side at acupuncture points (xuewei) the day after the operation. Both Groups II and III animals were perfused under anesthesia at 7 and 14 days post-operation (dpo) and their left DRG were processed for the immunohistochemical demonstration of GDNF and FGF-2. Following removal of adjacent DRG, the average number of all GDNF stained neurons in L6 DRG was decreased at 7 dpo and more so at 14 dpo. Acupuncture reversed this trend, as demonstrated in the increased average number of immunopositive small-to-medium sized neurons. FGF-2 expression was also less marked at 7 dpo but returned to normal at 14 dpo. Acupuncture significantly increased the average number of FGF-2 positive neurons compared with that in operated animals. This increase was observed in both large and small-to-medium sized neurons. In conclusion, our results demonstrated that the average number of GDNF and FGF-2 neurons in L6 DRG was decreased after unilateral removal of adjacent DRG but acupuncture could reverse some of the changes.

Long-lived luminescent soft materials of hexanitratosamarate(III) complexes with orange visible emission.

Sm(III)-based ionic liquids incorporating hexanitratosamarate(III) anions were obtained and fully characterized as novel Sm(III)-containing organic complexes. The structure of the ionic liquids was determined by single-crystal X-ray diffraction (1: monoclinic system C2/c space group with cell parameters: a = 19.5624(4) Å, b = 10.11895(18) Å, c = 33.2256(6) Å, ß = 101.2912(18)°, Z = 8). The central Sm(III) ion is 12-coordinated by six bidentate nitrate ligands with twelve oxygen donors to form a [Sm(NO3)6](3-) anion. The low melting point, high thermostability and wide liquid range of these ionic liquids were determined in detail. All the complexes 1-5 display orange luminescence, rather than red luminescence as in most Sm(III)-containing organic complexes. Three characteristic monochromatic bands and an intense emission, derived from (4)G5/2→(6)HJ (J = 5/2, 7/2, and 9/2) intraconfigurational f-f transitions, were revealed. All these complexes exhibit long luminescence lifetimes.