Fluorine Induced In Situ Formation of High Valent Nickel Species for Ultra Low Potential Electrooxidation of 5-Hydroxymethylfurfural.

The Nickel-based catalysts have a good catalytic effect on the 5-hydroxymethylfurfural electrooxidation reaction (HMFOR), but limited by the conversion potential of Ni2+ /Ni3+ , 1.35 V versus RHE, the HMF electrooxidation potential of nickel-based catalysts is generally greater than 1.35 V versus RHE. Considering fluorine has the highest Pauling electronegativity and similar atomic radius of oxygen, the introduction of fluorine into the lattice of metal oxides might promote the adsorption of intermediate species, thus improving the catalytic performance. F is successfully doped into the lattice structure of NiCo2 O4 spinel oxide by the strategy of hydrothermal reaction and low-temperature fluorination. As is confirmed by in situ electrochemical impedance spectroscopy and Raman spectroscopy, the introduction of F weakens the interaction force of metal-oxygen covalent bonds of the asymmetric MT -O-MO backbone and improves the valence of Ni in tetrahedra structure, which makes it easier to be oxidized to higher valence active Ni3+ under the action of electric field and promotes the adsorption of OH- , while the decrease of Co valence enhances the adsorption of HMF with the catalyst. Combining the above reasons, F-NiCo2 O4 shows superb electrocatalytic performance with a potential of only 1.297 V versus RHE at a current density of 20 mA cm-2 , which is lower than the most catalyst.

Metabolomic and transcriptomic studies of improvements in myocardial infarction due to Pycr1 deletion.

Myocardial infarction (MI) remains a major challenge to cardiovascular health worldwide, with poor healing leaving a direct impact on patients' quality of life and survival. Metabolic abnormalities after MI are receiving increasing attention. Our previous studies showed that enhancing proline catabolism ameliorates hypoxic damage to myocardial cells; therefore, we sought to determine whether reducing the synthesis of endogenous proline also affects MI. We analysed GEO datasets associated with MI and western blot of mouse heart tissue in an MI model to demonstrate pyrroline-5-carboxylate reductase 1 (Pycr1) expression level after MI. We constructed Pycr1 KO mice by CRISPR/Cas9 technology to explore the effect of Pycr1 gene KO after MI using transcriptomic and metabolomic techniques. In this study, we found reduced mRNA and protein expression levels of Pycr1 in the hearts of mice after MI. We observed that Pycr1 gene KO has a protective effect against MI, reducing the area of MI and improving heart function. Using transcriptomics approaches, we found 215 upregulated genes and 247 downregulated genes after KO of the Pycr1 gene, indicating that unsaturated fatty acid metabolism was affected at the transcriptional level. Metabolomics results revealed elevated content for 141 metabolites and decreased content for 90 metabolites, among which the levels of fatty acids, glycerol phospholipids, bile acids, and other metabolites increased significantly. The changes in these metabolites may be related to the protective effect of Pycr1 KO on the heart after MI. Pycr1 gene KO has a protective effect against MI and our research will lay a solid foundation for the development of future Pycr1-related drug targets.

Operando Forming of Lattice Vacancy Defect in Ultrathin Crumpled NiVW-Layered Metal Hydroxides Nanosheets for Valorization of Biomass.

The 2D layered metal hydroxides (LMHs) have been developed for electrooxidation of 5-hydroxymethylfurfural (HMF). In this work, an effective strategy is proposed to tailor the electronic structure of active sites at the atomic level, which is by introducing defects into the lattice structure. As an example, a series of ultrathin crumpled ternary NiVW-LMH electrocatalysts with abundant lattice vacancies (denoted as NiVWv -LMH) are prepared in this way. The introduction of tungsten (W) endows the catalyst with a special crumpled structure, which promotes the generation of lattice vacancies and thus exposes more unsaturated Ni activity sites. The NiVWv -LMH displays superb performance in the electrooxidation of HMF. The Tafel slope for electrodehydrogenation of Ni2+ OH bond to Ni(OH)O species is 12.04 mV dec-1 . The current density at 1.43 V versus reversible hydrogen electrode (RHE) toward the oxidation reaction of HMF reaches about 193 mA cm-2 , which is better than most of the common electrocatalysts, with an 5.37-fold improvement compared with Ni(OH)2 electrode. The preparation strategy demonstrates in this work can be useful for developing highly efficient electrocatalysts.

Analysis of the oxygen evolution activity of layered double hydroxides (LDHs) using machine learning guidance.

Layered double hydroxides (LDHs) are excellent catalysts for the oxygen evolution reaction (OER) because of their tunable properties, including chemical composition and structural morphology. An interplay between these adjustable properties and other (including external) factors might not always benefit the OER catalytic activity of LDHs. Therefore, we applied machine learning algorithms to simulate the double-layer capacitance to understand how to design/tune LDHs with targeted catalytic properties. The key factors of solving this task were identified using the Shapley Additive explanation and cerium was identified as an effective element to modify the double-layer capacitance. We also compared different modelling methods to identify the most promising one and the results revealed that binary representation is better than directly applying atom numbers as inputs for chemical compositions. Overpotentials of LDH-based materials as predicted targets were also carefully examined and evaluated, and it turns out that overpotentials can be predicted when measurement conditions about overpotentials are added as features. Finally, to confirm our findings, we reviewed additional experimental literature data and used them to test our machine algorithms to predict LDH properties. This analysis confirmed the very credible and robust generalization ability of our final model capable of achieving accurate results even with a relatively small dataset.

Abnormal network properties and fiber connections of DMN across major mental disorders: a probability tracing and graph theory study.

The default mode network (DMN) is related to brain functions and its abnormalities were associated with mental disorders' pathophysiology. To further understand the common and distinct DMN alterations across disorders, we capitalized on the probability tracing method and graph theory to analyze the role of DMN across three major mental disorders. A total of 399 participants (156 schizophrenia [SCZ], 90 bipolar disorder [BP], 58 major depression disorder [MDD], and 95 healthy controls [HC]) completed magnetic resonance imaging (MRI)-scanning, clinical, and cognitive assessment. The MRI preprocessing of diffusion-tensor-imaging was conducted in FMRIB Software Library and probabilistic fiber tracking was applied by PANDA. This study had three main findings. First, patient groups showed significantly lower cluster coefficient in whole-brain compared with HC. SCZ showed significantly longer characteristic path compared with HC. Second, patient groups showed inter-group specificity in abnormalities of DMN connections. Third, SCZ was sensitive to left_medial_superior_frontal_gyrus (L_SFGmed)-right_anterior_cingulate_gyrus (R_ACG) connection relating to positive symptoms; left_ACG-right_ACG connection was the mania's antagonistic factor in BP. This trans-diagnostic study found disorder-specific structural abnormalities in the fiber connection of R_SFGmed-L_SFGmed-R_ACG_L_ACG within DMN, where SCZ showed more disconnections compared with other disorders. And these connections are diagnosis-specifically correlated to phenotypes. The current study may provide further evidence of shared and distinct endo-phenotypes across psychopathology.

Acidity scales of deep eutectic solvents based on IR and NMR.

Acidic deep eutectic solvents (ADESs) have been utilized in various applications. Clearly, it is crucial to obtain acidity information that could reveal the relationship with performance. However, appropriate methods for measuring acidity are limited. Herein, we developed two promising approaches (without additional solvents) to identify and characterize both Lewis and Brønsted acidities by applying acetonitrile as an infrared probe and trimethylphosphine oxide (TMPO) as a nuclear magnetic resonance (NMR) probe. The acetonitrile IR approach is suitable for measuring the acidity of Lewis ADESs by monitoring the peak of ν(CN) around 2300 cm-1, and the 31P-TMPO NMR approach could identify and scale both Lewis and Brønsted acidities precisely. Moreover, a perfect linear relationship between the IR shift of ν(CN) and the effective charge density of metal cations was established, which provides a better understanding of Lewis acidity. In short, this study not only offers two efficient acidity measurement methods but also provides a molecular basis for optimizing the performance of ADESs in applications.

Eutectics: formation, properties, and applications.

Various eutectic systems have been proposed and studied over the past few decades. Most of the studies have focused on three typical types of eutectics: eutectic metals, eutectic salts, and deep eutectic solvents. On the one hand, they are all eutectic systems, and their eutectic principle is the same. On the other hand, they are representative of metals, inorganic salts, and organic substances, respectively. They have applications in almost all fields related to chemistry. Their different but overlapping applications stem from their very different properties. In addition, the proposal of new eutectic systems has greatly boosted the development of cross-field research involving chemistry, materials, engineering, and energy. The goal of this review is to provide a comprehensive overview of these typical eutectics and describe task-specific strategies to address growing demands.

Correction: Eutectics: formation, properties, and applications.

Correction for 'Eutectics: formation, properties, and applications' by Dongkun Yu et al., Chem. Soc. Rev., 2021, DOI: .

Ionicity of deep eutectic solvents by Walden plot and pulsed field gradient nuclear magnetic resonance (PFG-NMR).

Deep eutectic solvents (DESs) have attracted considerable attention due to their unique properties. Owing to similar structures and properties, DESs are also called "quasi-ionic liquids" or "ionic liquid analogous". However, for a deeper understanding and application of DESs, a comprehensive investigation on the ionicity of DESs is crucial. In this work, the effects of the structure and components of typical DESs on the ionicity were investigated. Moreover, the ionicity was discussed by using Walden plot, and the validity of applying it to DESs was verified using pulsed field gradient nuclear magnetic resonance (PFG-NMR). We found that the lack of free charged species and high viscosities make it difficult to achieve optimal conductivities for DESs, and thus most of them exhibit "poor ionic" nature. Fortunately, with an in-depth understanding of its microstructure and physicochemical properties, the properties of DESs can be finely tailored by selecting or even designing suitable parent compounds for functional applications. In particular, the ionicity of Li-based DESs was investigated for their potential application as electrolytes in Li-ion batteries.

Abnormal resting-state cerebral-limbic functional connectivity in bipolar depression and unipolar depression.

BACKGROUND: Distinctive patterns of functional connectivity (FC) abnormalities in neural circuitry has been reported in patients with bipolar depression (BD) and unipolar depression (UD). However, it is unclear that whether this distinct functional connectivity patterns are diagnosis specific between BD and UD. This study aimed to compare patterns of functional connectivity among BD, UD and healthy controls (HC) and determine the distinct functional connectivity patterns which can differentiate BD from UD. METHOD: Totally 23 BD, 22 UD, and 24 HC were recruited to undergo resting-state fMRI scanning. FC between each pair of brain regions was calculated and compared among the three groups, the associations of FC with depressive symptom were also analyzed. RESULTS: Both patient groups showed significantly decreased cerebral-limbic FC located between the default mode network [posterior cingulated gyrus (PCG) and precuneus] and limbic regions (hippocampus, amygdala and thalamus) than HC. Moreover, the BD group exhibited more decreased FC mainly in the cortical regions (middle temporal gyrus, PCG, medial superior frontal gyrus, inferior occipital gyrus and superior temporal gyrus), but the UD group is more associated with limbic alterations. These decreased FCs were negatively correlated with HAMD scores in both BD and UD patients. CONCLUSIONS: BD and UD patients demonstrate different patterns of abnormal cerebral-limbic FC, reflected by decreased FC within cerebral cortex and limbic regions in BD and UD, respectively. The distinct FC abnormal pattern of the cerebral-limbic circuit might be applied as biomarkers to differentiate these two depressive patient groups.

Are Ionic Liquids Chemically Stable?

Ionic liquids have attracted a great deal of interest in recent years, illustrated by their applications in a variety of areas involved with chemistry, physics, biology, and engineering. Usually, the stabilities of ionic liquids are highlighted as one of their outstanding advantages. However, are ionic liquids really stable in all cases? This review covers the chemical stabilities of ionic liquids. It focuses on the reactivity of the most popular imidazolium ionic liquids at structural positions, including C2 position, N1 and N3 positions, and C4 and C5 positions, and decomposition on the imidazolium ring. Additionally, we discuss decomposition of quaternary ammonium and phosphonium ionic liquids and hydrolysis and nucleophilic reactions of anions of ionic liquids. The review aims to arouse caution on potential decomposition of ionic liquids and provides a guide for better utilization of ionic liquids.

Thermal, electrochemical and radiolytic stabilities of ionic liquids.

Research on ionic liquids has achieved rapid progress in the last several decades. Stability is a prerequisite for the application of ionic liquids. Ionic liquids may be used at elevated temperature, as electrolytes, or under irradiation. Therefore, the thermal, electrochemical, and radiolytic stabilities of ionic liquids are important and need to be known before their usage. Many research papers and some reviews on the stabilities of ionic liquids have been published. However, new results are continuously being published and a comprehensive review and perspective on this topic are still urgently needed. In this perspective, we intend to provide a comprehensive review including characterization methods, the effects of chemical composition of the ionic liquids on the thermal, electrochemical, and radiolytic stabilities of ionic liquids, respectively. Moreover, the thermal stability of some special types of ionic liquids such as poly(ionic liquids) and mixed ionic liquids, and the thermal and electrochemical stabilities of protic ionic liquids are discussed too. For thermal stability, the interactions between ions are less important than the individual anions and cations. The decomposition temperature is mainly determined by the less-stable ion, usually the anion. For electrochemical stability, the electrochemical window is determined by both the cation and anion. The less stable ion could influence the stability by interaction between the generated species from the decomposition with the more stable ion (opposite ion). This perspective is helpful for people to avoid using unstable ionic liquids and choose suitable ionic liquids.

Betel quid chewing alters functional connectivity in frontal and default networks: A resting-state fMRI study.

PURPOSE: To explore the acute effect of betel quid (BQ) use on functional network connectivity by comparing the global functional brain networks and their subsets before and immediately after BQ chewing. MATERIALS AND METHODS: Resting-state functional magnetic resonance imaging (fMRI) was performed in 27 healthy male participants before and just after chewing BQ on a 3.0T scanner with a gradient-echo echo planar imaging sequence. Independent component analysis (ICA) was used to determine components that represent the brain's functional networks and their spatial aspects of functional connectivity. A paired t-test was used for exploring the connectivity differences in each network before and after BQ chewing. RESULTS: Sixteen networks were identified by ICA. Nine of them showed connectivity differences before and after BQ chewing (P < 0.05 false discovery rate corrected): (A) orbitofrontal, (B) left frontoparietal, (C) visual, (D) right frontoparietal, (E) anterior default mode, (F) medial frontal/anterior cingulate (G) frontotemporal, (H) occipital/parietal, (I) occipital/temporal/cerebellum. Moreover, networks A, B, C, D, G, H, and I showed increased connectivity, while networks E and F showed decreased connectivity in participants after BQ chewing compared to before chewing. CONCLUSION: The acute effects of BQ use appear to actively alter functional connectivity of frontal and default networks that are known to play a key role in addictive behavior. LEVEL OF EVIDENCE: 2 J. Magn. Reson. Imaging 2017;45:157-166.

Ionic Liquid-Assisted Synthesis and Catalytic Properties of AuPd Bimetallic Particles.

Ionic liquid-assisted synthesis of inorganic materials has been demonstrated to be an efficient synthesis route in the inorganic community. Here AuPd alloy particles are successfully synthesized with the assistance of the ionic liquid 1-octyl-3-methylimidazolium chloride ([OMIM]Cl) at room temperature. The p-nitrophenol reduction reaction using the synthesized metal particles as the catalysts indicates that the synthesized Au(1)Pd(1) particles exhibit the highest catalytic activity in comparison with the studied AuPd particles, the Au and the Pd particles. Therefore, the present synthesis route could be used as an efficient synthesis strategy for fabrication of metal alloy particles with interesting catalytic properties.

Surprising Hofmeister Effects on the Bending Vibration of Water.

The Hofmeister series, which originally described the specific ion effects on the solubility of macromolecules in aqueous solutions, has been a long-standing unsolved and exceptionally challenging mystery in chemistry. The complexity of specific ion effects has prevented a unified theory from emerging. Accumulating research has suggested that the interactions among ions, water and various solutes play roles. However, among these interactions, the binding between ions and solutes is receiving most of the attention, whereas the effects of ions on the hydrogen-bond structure in liquid water have been deemed to be negligible. In this study, attenuated-total-reflectance Fourier transform infrared spectroscopy is used to study the infrared spectra of salt solutions. The results show that the red- and blue-shifts of the water bending band are in excellent agreement with the characteristic Hofmeister series, which suggests that the ions' effects on water structure might be the key role in the Hofmeister phenomenon.

Fine regulation of cellulose dissolution and regeneration by low pressure CO2 in DMSO/organic base: dissolution behavior and mechanism.

In this study, the fine regulation of the dissolution and regeneration of microcrystalline cellulose (MCC) using very low pressure (0-0.2 MPa) CO2 in a mixed solvent of dimethyl sulfoxide (DMSO) and 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) at a very low temperature (30 °C) was achieved. The solubility of MCC in DMSO/DBU (weight ratio of DMSO WDMSO = 0.90) could reach 9.0% at 30 °C and under CO2 pressure of 0.2 MPa. A similar phenomenon was observed in the mixed solvent DMSO/1,1,3,3-tetramethylguanidine (TMG). Moreover, ATR-FTIR, NMR, UV-Vis, TGA, XRD and DFT computational analyses were used to investigate the dissolution mechanism. It was concluded that in the mixed solvent (DMSO and organic base), DMSO helped to dissociate ion-pairs into free ions by balancing the concentration of free ions and the number of hydrogen bonds at WDMSO = 0.90. Interactions between CO2 and the solvent mixture were explored, and the results indicate that the optimum CO2 pressure not only promotes the formation of ionic bonds but also accelerates the formation of covalent bonds. In this way, these interactions prevent the MCC molecules from aggregating and facilitate the dissolving of MCC. This study gives a thorough insight into the dissolution mechanism and specificity of MCC in the CO2-DMSO/organic base solvent system, which could be helpful for the utilization and transformation of cellulose.

Decreased long- and short-range functional connectivity at rest in drug-naive major depressive disorder.

BACKGROUND: Abnormal functional connectivity has been observed in major depressive disorder. Anatomical distance may affect functional connectivity in patients with major depressive disorder. However, whether and how anatomical distance affects functional connectivity at rest remains unclear in drug-naive patients with major depressive disorder. METHODS: Forty-four patients with major depressive disorder, as well as 44 age-, sex- and education-matched healthy controls, underwent resting-state functional magnetic resonance imaging scanning. Regional functional connectivity strength was calculated for each voxel in the whole brain, which was further divided into short- and long-range functional connectivity strength. RESULTS: The patients showed decreased long-range positive functional connectivity strength in the right inferior parietal lobule, as well as decreased short-range positive functional connectivity strength in the right insula and right superior temporal gyrus relative to those of the controls. No significant correlations existed between abnormal functional connectivity strength and the clinical variables of the patients. CONCLUSION: The findings revealed that anatomical distance decreases long- and short-range functional connectivity strength in patients with major depressive disorder, which may underlie the neurobiology of major depressive disorder.

A Green Synthesis of Nanosheet-Constructed Pd Particles in an Ionic Liquid and Their Superior Electrocatalytic Performance.

The ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM]Ac) is investigated as a solvent for the synthesis of Pd particles. Interestingly, nanosheet-constructed Pd particles could be successfully synthesized in [EMIM]Ac without any additional reducing agent and template under ionothermal conditions. [EMIM]Ac itself works as the solvent, the reducing agent, and the template for the formation of these interesting Pd particles, making this method complementary to the well-known ionic-liquid-precursor approach. Furthermore, [EMIM]Ac can be recycled with no loss of activity for the formation of nanosheet-constructed Pd particles within our studied cycles. Specifically, the nanosheet-constructed Pd particles exhibit superior electrocatalytic activity and stability towards ethanol oxidation and formic acid oxidation compared with commercially available Pd black catalyst, thus demonstrating their promising applications in fuel-cell area. The current approach, thus, presents a green approach towards the synthesis of Pd particles, using only a simple palladium salt and an ionic liquid.

Reduced cortical thickness in right Heschl's gyrus associated with auditory verbal hallucinations severity in first-episode schizophrenia.

BACKGROUND: Auditory verbal hallucinations (AVHs) represent one of the most intriguing phenomena in schizophrenia, however, brain abnormalities underlying AVHs remain unclear. The present study examined the association between cortical thickness and AVHs in first-episode schizophrenia. METHOD: High-resolution MR images were obtained in 49 first-episode schizophrenia (FES) patients and 50 well-matched healthy controls (HCs). Among the FES patients, 18 suffered persistent AVHs ("auditory hallucination" AH group), and 31 never experienced AVHs ("no hallucination" NH group). The severity of AVHs was rated by the Auditory Hallucinations Rating Scale (AHRS). Cortical thickness differences among the three groups and their association with AVHs severity were examined. RESULTS: Compared to both HCs and NH patients, AH patients showed lower cortical thickness in the right Heschl's gyrus. The degree of reduction in the cortical thickness was correlated with AVH severity in the AH patients. CONCLUSIONS: Abnormalities of cortical thickness in the Heschl's gyrus may be a physiological factor underlying auditory verbal hallucinations in schizophrenia.

Speciation analysis of lead in marine animals by using capillary electrophoresis couple online with inductively coupled plasma mass spectrometry.

We herein reported a environment-friendly microwave-assisted extraction used to extract trace lead compounds from marine animals and a ultrasensitive method for the analysis of Pb²âº, trimethyl lead chloride (TML) and triethyl lead chloride (TEL) by using CE-ICP-MS. The extraction method is simple and has a high extracting efficiency. It can be used to completely extract both inorganic lead and organolead in marine animal samples without altering its species. The analytical method has a detection limit as low as 0.012-0.084 ng Pb/mL for Pb²âº, TML, and TEL, and can be used to determine ultratrace Pb²âº, TML, and TEL in marine animals directly without any preconcentration. With the help of above methods, we have successfully determined Pb²âº, TML, and TEL in clam and oyster tissue within 20 min with a RSD (n = 6) < 5% and a recovery of 91-104%. Our results showed that Pb²âº was the main species of lead in clam and oyster, and organolead (TML) was only found in oyster. The proposed method provides a realistic approach for the accurate evaluation of lead pollution in seafood.