Manganese-based nanomaterials promote synergistic photo-immunotherapy: green synthesis, underlying mechanisms, and multiple applications.

Single phototherapy and immunotherapy have individually made great achievements in tumor treatment. However, monotherapy has difficulty in balancing accuracy and efficiency. Combining phototherapy with immunotherapy can realize the growth inhibition of distal metastatic tumors and enable the remote monitoring of tumor treatment. The development of nanomaterials with photo-responsiveness and anti-tumor immunity activation ability is crucial for achieving photo-immunotherapy. As immune adjuvants, photosensitizers and photothermal agents, manganese-based nanoparticles (Mn-based NPs) have become a research hotspot owing to their multiple ways of anti-tumor immunity regulation, photothermal conversion and multimodal imaging. However, systematic studies on the synergistic photo-immunotherapy applications of Mn-based NPs are still limited; especially, the green synthesis and mechanism of Mn-based NPs applied in immunotherapy are rarely comprehensively discussed. In this review, the synthesis strategies and function of Mn-based NPs in immunotherapy are first introduced. Next, the different mechanisms and leading applications of Mn-based NPs in immunotherapy are reviewed. In addition, the advantages of Mn-based NPs in synergistic photo-immunotherapy are highlighted. Finally, the challenges and research focus of Mn-based NPs in combination therapy are discussed, which might provide guidance for future personalized cancer therapy.

Spent Lithium-Ion Batteries Derived Co3O4 for Electrocatalytic Polyethylene Terephthalate Plastic Recycling.

Spent lithium-ion batteries (LIBs) are an essential secondary resource containing valuable metal elements. Transforming spent LIBs into efficient catalysts through a simple process presents a promising strategy to address both metal resource scarcity and clean energy challenges. Herein, a deep eutectic solvent-assisted synthesis of Co3O4 material from spent LIBs is proposed. The obtained Co3O4 material possesses efficient and stable electrocatalytic activity for converting raw polyethylene terephthalate (PET) bottles into high-purity formic acid and terephthalic acid products under ambient conditions. As expected, the Co3O4 catalyst exhibits a high FE of 92 % with a concentration of produced potassium formate of 23.6 mM under alkaline conditions. This study presents a waste-treating-waste strategy for the simultaneous recovery of spent LIBs and PET waste in a greener manner.

Quantification of alkalinity of deep eutectic solvents based on (H-) and NMR.

Alkaline deep eutectic solvents (DESs) have been widely employed across diverse fields. A comprehensive understanding of the alkalinity data is imperative for the comprehension of their performance. However, the current range of techniques for quantifying alkalinity is constrained. In this investigation, we formulated a series of alkaline DESs and assessed their basicity properties through a comprehensive methodology of Hammett functions alongside 1H NMR analysis. A correlation was established between the composition, structure and alkalinity of solvents. Furthermore, a strong linear correlation was observed between the Hammett basicity (H-) of solvents and initial CO2 adsorption rate. Machine learning techniques were employed to predict the significant impact of alkaline functional components on alkalinity levels and CO2 capture capacity. This study offers valuable insights into the design, synthesis and structure-function relationship of alkaline DESs.

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.

Roles of Apigenin and Nepetin in the Assembly Behavior and Cytotoxicity of Prion Neuropeptide PrP106-126.

Development of potential inhibitors to prevent prion protein (PrP) fibrillation is a therapeutic strategy for prion diseases. The prion neuropeptide PrP106-126, a research model of abnormal PrP (PrPSc), presents similar physicochemical and biochemical characters to PrPSc, which is also a target of potential inhibitors against prion deposition. Many flavones have antioxidant, anti-inflammatory, and antibacterial properties, and they are applied in treating prion disorder and other amyloidosis as well. However, the inhibition mechanism of flavones on PrP106-126 fibrillation is still unclear. In the current work, apigenin and nepetin were used to suppress the aggregation of PrP106-126 and to alleviate the peptide-induced cytotoxicity. The results showed that apigenin and nepetin impeded the fibril formation of PrP106-126 and depolymerized the preformed fibrils. They were bound to PrP106-126 predominantly by hydrophobic and hydrogen bonding interactions. In addition, both flavones upregulated cell viability and decreased membrane leakage through reducing peptide oligomerization. The differences in inhibition and cell protection between the two small molecules were presumably attributed to the substitution of hydroxyl and methoxy groups in nepetin, which demonstrated the significant structure-function relationship of flavones with prion neuropeptide and the prospect of flavonoids as drug candidates against prion diseases.

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.

Yet another perspective on hole interactions, part II: lp-hole vs. lp-hole interactions.

Most of the experimental and theoretical work in hole interactions (HIs) is mainly focused on exploiting the nature and characteristics of σ and π-holes. In this perspective, we focus our attention on understanding the origin and properties of lone-pair holes. These holes are present on an atom opposite to its lone-pair region. Utilizing some new and old examples, such as X3N/P⋯F- (X = F/Cl/Br/I), F-Cl/Br/I⋯H3P⋯NCH and H3B-NBr3 along with other molecular systems, we explored to what extent these lp-holes participate in lp-hole interactions, if they participate at all.

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.

Deep insights into the viscosity of deep eutectic solvents by an XGBoost-based model plus SHapley Additive exPlanation.

Deep eutectic solvents (DESs) are emerging as novel green solvents for the processes of mass transport and heat transfer, in which the viscosity of DESs is important for their industrial applications. However, for DESs, the measurement of viscosity is time-consuming, and there are many factors influencing the viscosity, which impedes their wider application. This study aims to develop a data-driven model which could accurately and rapidly predict the viscosity of diverse DESs at different temperatures, and furthermore boost the design and screening of novel DESs. In this work, we collected 107 DESs with 994 experimental values of viscosity from published works. Given the significant effect of water on viscosity, the water content of each collected DES was labeled. The Morgan fingerprint was first employed as a feature to describe the chemical environment of DESs. And four machine learning algorithms were used to train models: support vector regression (SVR), random forest (RF), neural network (NN), and extreme gradient boosting (XGBoost), and XGBoost showed the best predictive performance. In combination with the powerful interpretation method SHapley Additive exPlanation (SHAP), we further revealed the positive or negative effect of features on viscosity. Overall, this work provides a machine learning model which could predict viscosity precisely and facilitate the design and application of DESs.

Deep Eutectic Solvent-Induced In Situ Etching and Phosphorization to Form Nickel Phosphides for Electrooxidation of 5-Hydroxymethylfurfural.

The development of catalysts with relatively high current densities at low potentials for the electrooxidation of 5-hydroxymethylfurfural (HMF) is still challenging. In this study, an in situ deep eutectic solvent (DES) etching phosphorization strategy is developed to prepare nickel phosphides encapsulated in P,O-codoped carbon nanosheets (Ni-P@POC). The DES serves not only as an etchant to extract Ni2+ from the nickel foam, but also as a phosphorus source to form nickel phosphides in situ uniformly embedded in the carbon films to produce a sheet structure. The electrooxidation performance is further greatly improved by implementing an electrochemical activation step to transform Ni-P@POC into NiOOH/Ni-P@POC (t-Ni-P@POC). t-Ni-P@POC exhibits a low onset potential of 1.20 V vs. RHE and a high current density of 200 mA cm-2 at 1.33 V vs. RHE for HMF electrooxidation, outperforming most reported catalysts. The as-developed DES etching phosphorization strategy offers a facile, flexible, and universal route for the design of high-performance catalysts with specific nanostructures.

Magnetic deep eutectic solvents: formation and properties.

Deep eutectic solvents (DESs) are well-known as novel solvents due to their unique properties, which are indispensable for the development of green chemistry in the future. CoCl2·6H2O and NiCl2·6H2O-based DESs, which could be called magnetic DESs (MDESs) for short in view of their responsive behavior to an external magnetic field, have been widely used in many industrial applications, such as biomass treatment, electrolytes, and material preparation. For better application and full-scale development of these MDESs in various fields, eleven MDESs were prepared in this work by using CoCl2·6H2O and NiCl2·6H2O as hydrogen bond acceptors (HBAs) with alcohols, carboxylic acids and amides as hydrogen bond donors (HBDs), respectively. The intermolecular interactions between the components of MDESs were characterized via FTIR, 1H NMR and DSC analysis. In addition, physicochemical properties including density, viscosity, conductivity, ionicity, pH values, surface tension, thermostability and solvatochromic parameters were investigated. All MDESs exhibit acid characteristics and have good conductivity comparable with ionic liquids (ILs) and other DESs used for electrolytes. The results show that stronger H-bonding networks in Ni-based MDESs make them have higher density, viscosity, polarity and surface tension values than Co-based MDESs. Moreover, all prepared MDESs possess a good conductivity behavior which could be comparable to that of common organic solvents and ILs. According to this work, we could better comprehend the behavior of Co/Ni-based MDESs and choose the appropriate one for particular applications.

A Weak Acidic and Strong Coordinated Deep Eutectic Solvent for Recycling of Cathode from Spent Lithium-Ion Batteries.

The leaching and recycling of valuable metals via environmentally benign solvents is important because of the ever-increasing waste lithium-ion batteries, but it remains a challenge. Herein, a multi-functional deep eutectic solvent (DES) based on lactic acid (LA) and guanidine hydrochloride (GHC) was used to extract cobalt and lithium ions from LiCoO2 . Due to the strong acidity (protons) and abundant chlorine coordinating ions of LA/GHC, the solubility of LiCoO2 in LA/GHC could reach as high as 19.9 mg g-1 (stirred at 80 °C for 24 h), and a little LiCoO2 powder even could be dissolved at room temperature without stirring. Oxalic acid was used to strip and separate the oxalates of cobalt and lithium. Furthermore, LA/GHC could be recycled with a similar dissolving performance. This work avoided using corrosive acids and could be realized at low temperature (80 °C), making it energy-saving and cost-effective. It shows DESs have great potential in extracting strategically important metals from LiCoO2 cathodes and provides an efficient and green alternative for sustainable recycling of spent lithium-ion batteries.

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.

An emerging deep eutectic solvent based on halogen-bonds.

A new deep eutectic solvent (DES) driven by halogen bonding (XB) was exploited. A family of eutectic mixtures in the liquid state was obtained by the combination of quaternary ammonium salts and dihalogens. The formation mechanism was discussed based on experiments and DFT calculations. It not only broadens the potential DES systems but unlocks the possibility of XB complexes as solvents.

Calorimetric effect and thermokinetics in the formation process of a deep eutectic solvent.

For the first time, we report the calorimetric effect and thermokinetics in the formation process of a model deep eutectic solvent (DES), ChCl:urea. Mixing of a 1-to-2 molar ratio of choline chloride and urea shows a rapid endothermic process under stirring. The rate constants and reaction orders are determined by analyzing the thermokinetic curves at several constant temperatures. Low activation energy and activation parameters demonstrate that the formation of this DES is a rapid process. Other thermodynamic parameters are also estimated.

Correction: Eutectics: formation, properties, and applications.

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

Robust superbase-based emerging solvents for highly efficient dissolution of cellulose.

The development of robust solvent systems for cellulose dissolution is of significant importance for cellulose utilization and transformation. Herein, six kinds of novel superbase-based solvents were designed by a combination of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) with pyridine N-oxide (PyO) or 2-picoline-N-oxide (PiO) for dissolution of cellulose. It was observed that the prepared superbase-based solvents (denoted as DBN-PyO-x and DBN-PiO-4) could efficiently dissolve cellulose at mild temperatures (<80 °C). The chemical structure of the prepared superbase-based solvents and the molar ratio of the components significantly affected the solubility of cellulose, and DBN-PyO-4 showed the best performance with a cellulose solubility of 14.1 wt% 70 °C. The systematic study revealed that the good performance of the prepared superbase-based solvents on cellulose dissolution resulted from the synergistic effect of their ability to form hydrogen bonds and their polarizability.

Deep eutectic solvent-assisted synthesis of porous Ni2CO3(OH)2/SiO2 nanosheets for ultra-efficient removal of anionic dyes from water.

Wastewater treatment is a severe environment issue, especially the discharge of excessive synthetic dyestuffs in the aquatic environment. In this study, a facile binary deep eutectic solvothermal process plus silica surface modification was successfully applied for preparation of porous nanosheet Ni2CO3(OH)2/SiO2 composites. The composites show powerful anionic dyes removal ability due to the high specific surface areas, hydrogen bond connection, coordination effect and strong electrostatic interactions with anionic dyes. A maximum adsorption capacity of 2637 mg g-1 at neutral pH (ca.7) and 303 K was achieved for Ni2CO3(OH)2/SiO2 composite to adsorb Congo red, a representative anionic dye. Moreover, the composite has an excellent specificity for anionic dyes and could maintain above 95% removal efficiency after 5 cycles. Therefore, the as-prepared nanocomposites could be qualified as candidates for industrial environmental remedy. Furthermore, the proposed material preparation strategy could be extended to fabricate various advanced energy and environmental materials.

Thermal properties and cold crystallization kinetics of deep eutectic solvents confined in nanopores.

Herein, the phase behaviors of both bulk and confined deep eutectic solvents in controlled pore glasses were first investigated. Glass transition, cold crystallization and melting behaviors alter significantly in the nanopores due to the size effect and interfacial interactions. Kinetic analysis of the crystallization reveals increased effective activation energies and pre-exponential factors under nanoconfinement.