Kinetics and Products of Air Plasma Induced Oxidation in Water of Imidacloprid and Thiamethoxam Treated Individually and in Mixture

Imidacloprid (I) and thiamethoxam (T) are widely used neonicotinoid insecticides with high persistence in the environment and thus included in the watch list of substances for European Union-wide monitoring reported in the Decision 2015/495/EU. In this work aqueous solutions of I, T and I?+?T were subjected to advanced oxidation by air plasma produced by negative DC corona discharges above the liquid surface. The oxidative degradation of each pollutant was investigated by monitoring the rate and the products of its decay when treated alone and in the presence of variable amounts of the other compound. The results show that both I and T are readily degraded and that mineralization can be achieved in this process, as proven by the measurement of the residual organic carbon and by the quantitative conversion of chlorine and sulfur into inorganic chloride and sulfate, respectively. The major organic intermediates formed during the complex stepwise oxidation of I and T were identified and monitored by HPLC–MS/MS analysis. The results of kinetic studies show that both for I and T the reaction rate depends inversely on the insecticide initial concentration, that I and T have similar reactivities and that they do not interfere reciprocally in any specific way when treated in mixture at a total concentration of ca 1?×?10^?4 M. Based on literature data and on previous results with the same reactor, it is reasonable to propose that the oxidation of I and T is initiated by the reaction with OH radicals.

     

Robust Superhydrophobic/Superoleophilic Wrinkled Microspherical MOF@rGO Composites for Efficient Oil–Water Separation

Graphene/MOF‐based composite materials in three‐dimensional (3D) architectures are promising for the treatment of oil‐containing wastewater by absorption owing to their intrinsic properties of graphene and metal‐organic frameworks (MOFs), such as high porosity, ultralow density, and facilely tailored superwettability. In this study, novel wrinkled 3D microspherical MOF@rGO composites with both superhydrophobic and superoleophilic properties were developed by embedding MOF nanoparticles between graphene oxide (GO) nanosheets, followed by high‐temperature reduction self‐assembly. The microspherical composites feature a unique micro/nano hierarchy consisting of crumpled reduced GO (rGO) nanosheets intercalated with well‐dispersed MOF nanoparticles. Combined with the superwettability and abundant meso/microporosity, the peculiar architectures of wrinkled ZIF‐8@rGO microspheres show very fast absorption rates and high sorption selectivity for organic solvents and oils from water.     

Spleen SORT LNP Generated in situ CAR T Cells Extend Survival in a Mouse Model of Lymphoreplete B Cell Lymphoma

Chimeric Antigen Receptor (CAR) T cell immunotherapy is revolutionizing treatment for patients suffering from B-cell lymphoma (BL). However, the current method of CAR T cell production is complicated and expensive, requiring collection of patient blood to enrich the T cell population, ex vivo engineering/activation, and quality assessment before the patient can receive the treatment. Herein we leverage Spleen Selective ORgan Targeted (SORT) Lipid Nanoparticles (LNPs) to produce CAR T cells in situ and bypass the extensive and laborious process currently used. Optimized Spleen SORT LNPs containing 10 % 18 : 1 PA transfected CD3+, CD8+, and CD4+ T cells in wild-type mice. Spleen SORT LNPs delivered Cre recombinase mRNA and CAR encoding mRNA to T cells in reporter mice and in a lymphoreplete B cell lymphoma model (respectively) after intravenous injection without the need for active targeting ligands. Moreover, in situ CAR T cells increased the overall survival of mice with a less aggressive form of B cell lymphoma. In addition, in situ transfected CAR T cells reduced tumor metastasis to the liver by increasing tumor infiltrating lymphocytes. Overall, these results offer a promising alternative method for CAR T cell production with pre-clinical potential to treat hematological malignancies.     

Transition-Metal-Free Difunctionalization of Sulfur Nucleophiles**

Efficient protocols for accessing iodo-substituted diaryl and aryl(vinyl) sulfides have been developed using iodonium salts as reactive electrophilic arylation and vinylation reagents. The reactions take place under transition-metal-free conditions, employing odorless and convenient sulfur reagents. A wide variety of functional groups are tolerated in the S-diarylation, enabling the regioselective late-stage application of several heterocycles and drug molecules under mild reaction conditions. A novel S-difunctionalization pathway was discovered using vinyliodonium salts, which proceeds under additive-free reaction conditions and grants excellent stereoselectivity in the synthesis of aryl(vinyl) sulfides. A one-pot strategy combining transition-metal-free diarylation and subsequent reduction provided facile access to electron-rich thioanilines and a direct synthesis of a potential drug candidate derivative. The retained iodo group allows a wide array of further synthetic transformations. Mechanistic insights were elucidated by isolating the key intermediate, and the relevant energy profile was substantiated by DFT calculations.     

Water Transport with Ultralow Friction through Partially Exfoliated g-C3N4 Nanosheet Membranes with Self-Supporting Spacers

Two-dimensional (2D) graphitic carbon nitride (g-C₃N₄) nanosheets show brilliant application potential in numerous fields. Herein, a membrane with artificial nanopores and self-supporting spacers was fabricated by assembly of 2D g-C₃N₄ nanosheets in a stack with elaborate structures. In water purification the g-C₃N₄ membrane shows a better separation performance than commercial membranes. The g-C₃N₄ membrane has a water permeance of 29 L m⁻² h⁻¹ bar⁻¹ and a rejection rate of 87 % for 3 nm molecules with a membrane thickness of 160 nm. The artificial nanopores in the g-C₃N₄ nanosheets and the spacers between the partially exfoliated g-C₃N₄ nanosheets provide nanochannels for water transport while bigger molecules are retained. The self-supported nanochannels in the g-C₃N₄ membrane are very stable and rigid enough to resist environmental challenges, such as changes to pH and pressure conditions. Permeation experiments and molecular dynamics simulations indicate that a novel nanofluidics phenomenon takes place, whereby water transport through the g-C₃N₄ nanosheet membrane occurs with ultralow friction. The findings provide new understanding of fluidics in nanochannels and illuminate a fabrication method by which rigid nanochannels may be obtained for applications in complex or harsh environments.     

Asymptotic approximation of a highly oscillatory integral with application to the canonical catastrophe integrals

We consider the highly oscillatory integral $F(w):={\int }_{-\infty }^{\infty }{e}^{iw(t^{K+2}+e^{i\theta }{t}^p)}g(t)dt$ for large positive values of w, , K and p positive integers with $1\le p\le K$, and $g(t)$ an entire function. The standard saddle point method is complicated and we use here a simplified version of this method introduced by López et al. We derive an asymptotic approximation of this integral when $w\to +\infty$ for general values of K and p in terms of elementary functions, and determine the Stokes lines. For $p\ne 1$, the asymptotic behavior of this integral may be classified in four different regions according to the even/odd character of the couple of parameters K and p; the special case $p=1$ requires a separate analysis. As an important application, we consider the family of canonical catastrophe integrals ${\mathrm{\Psi }}_K(x_1,x_2,\text{…},x_K)$ for large values of one of its variables, say $x_p$, and bounded values of the remaining ones. This family of integrals may be written in the form $F(w)$ for appropriate values of the parameters w, θ and the function $g(t)$. Then, we derive an asymptotic approximation of the family of canonical catastrophe integrals for large $|x_p|$. The approximations are accompanied by several numerical experiments. The asymptotic formulas presented here fill up a gap in the NIST Handbook of Mathematical Functions by Olver et al.     

Polymerization and copolymerization of styrene by Ph2Zn‐metallocene‐MAO initiator systems.

Combined systems including diphenylzinc, Ph₂Zn, a metallocene, and methylaluminoxane, MAO, have been employed to initiate styrene polymerization. These initiator systems have been also used to initiate the copolymerization of styrene with p‐alkylsubstituted styrenes and with α‐olefins. Both polymerization and copolymerization processes depend on the nature of the metallocene included in the initiator system, the presence of Ph₂Zn, the temperature and the solvent used. Titanocenes produced syndiotactic polystyrene, s‐PS, while zirconocenes gave atactic polystyrene, a‐PS, with a certain content, less the 20% of s‐PS. For copolymerizations the conversion to polymer was also influenced by the comonomer nature and its molar proportion in the initial feed, as well as the sort of metallocene, titanocene or zirconocene included.