GPR40 agonist ameliorates neurodegeneration and motor impairment by regulating NLRP3 inflammasome in Parkinson's disease animal models.

Parkinson's disease (PD) is characterized by the progressive degeneration of dopaminergic neurons in the substantia nigra (SN) and accumulation of intracellular α-synuclein (ɑ-syn) aggregates known as Lewy bodies and Lewy neurites. Levels of polyunsaturated fatty acids (PUFAs) have previously been shown to be reduced in the SN of PD patients. G protein-coupled receptor 40 (GPR40) serves as a receptor for PUFAs, playing a role in neurodevelopment and neurogenesis. Additionally, GPR40 has been implicated in several neuropathological conditions, such as apoptosis and inflammation, suggesting its potential as a therapeutic target in PD. In this study, we investigated the neuroprotective effects of the GPR40 agonist, TUG469 in PD models. Our results demonstrated that TUG469 reduces the neurotoxicity induced by 6-OHDA in SH-SY5Y cells. In 6-OHDA-induced PD model mice, TUG469 treatment improved motor impairment, preserved dopaminergic fibers and cell bodies in the striatum (ST) or SN, and attenuated 6-OHDA-induced microgliosis and astrogliosis in the brain. Furthermore, in a PD model involving the injection of mouse ɑ-syn fibrils into the brain (mPFFs-PD model), TUG469 treatment reduced the levels of pSer129 ɑ-syn, and decreased microgliosis and astrogliosis. Our investigation also revealed that TUG469 modulates inflammasome activation, apoptosis, and autophagy in the 6-OHDA-PD model, as evidenced by the results of RNA-seq and western blotting analyses. In summary, our findings highlight the neuroprotective effects of GPR40 agonists on dopaminergic neurons and their potential as therapeutic agents for PD. These results underscore the importance of targeting GPR40 in PD treatment, particularly in mitigating neuroinflammation and preserving neuronal integrity.

Hydrogen bonding in 2,2,2-trifluoroethanol.

CONTEXT: 2,2,2-Trifluoroethanol (TFE) is known as a membrane mimetic solvent. The IR spectrum, 1H NMR spectrum, 13C NMR spin‒lattice relaxation times (T1), and nuclear Overhauser effect (NOE) data are consistent with extensive hydrogen bonding in TFE, but do not lead to structural features of the hydrogen bonding. Hence, DFT computations were carried out. The results predict the existence of a set of H-bonded dimers and trimers. The bond lengths and dihedral angles in these complexes are obtained, together with their dissociation energies. Computations were also performed for the geometry of the two conformers of the isolated monomer. The structure of one of the dimers consists of a 7-member cyclic fragment with a free CF3CH2 side chain. One set of the trimer structures involves the OH of a third monomer H-bonding to one of the F atoms in the CF3 group of the side chain of this dimer, thereby creating three trimer isomers. A fourth trimer cluster is formed from three monomers in which three OH∙∙∙O bonds create a cyclic fragment with three CF3CH2 side chains. The high dissociation energy (with respect to three monomers) indicates the high stability of the trimer complexes. The structural features of the trimer complexes resemble the structure of a conventional liquid crystal molecule and are postulated to resemble the latter in properties and function in solution, but at a much shorter timescale because of the noncovalent bonding. This hydrogen bonding phenomenon of TFE may be related to its function as a membrane memetic solvent. METHODS: Initially, IR and NMR spectroscopic methods were used. Standard procedures were followed. For the computations, a hybrid DFT method with empirical dispersion, ωB97X-D, was used. The basis set, 6-311++G**, is of triple-ζ quality, in which polarization functions and diffuse functions were added for all atoms.

Solvation Regulation Reinforces Anion-Derived Inorganic-Rich Interphase for High-Performance Quasi-Solid-State Li Metal Batteries.

Solid-state polymer lithium metal batteries are an important strategy for achieving high safety and high energy density. However, the issue of Li dendrites and inherent inferior interface greatly restricts practical application. Herein, this study introduces tris(2,2,2-trifluoroethyl)phosphate solvent with moderate solvation ability, which can not only complex with Li+ to promote the in-situ ring-opening polymerization of 1,3-dioxolane (DOL), but also build solvated structure models to explore the effect of different solvation structures in the polymer electrolyte. Thereinto, it is dominated by the contact ion pair solvated structure with pDOL chain segments forming less lithium bonds, exhibiting faster kinetic process and constructing a robust anion-derived inorganic-rich interphase, which significantly improves the utilization rate of active Li and the high-voltage resistance of pDOL. As a result, it exhibits stable cycling at ultra-high areal capacity of 20 mAh cm-2 in half cells, and an ultra-long lifetime of over 2000 h in symmetric cells can be realized. Furthermore, matched with LiNi0.9Co0.05Mn0.05O2 cathode, the capacity retention after 60 cycles is as high as 96.8% at N/P value of 3.33. Remarkably, 0.7 Ah Li||LiNi0.9Co0.05Mn0.05O2 pouch cell with an energy density of 461 Wh kg-1 can be stably cycled for five cycles at 100% depth of discharge.

Durable photobioreactor antibiofouling coatings for microalgae cultivation by photoreactive poly(2,2,2-trifluoroethyl methacrylate).

To improve the durability of the photobioreactor antibiofouling surface for microalgal cultivation, a series of photoreactive poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) were successfully synthesized and used to modify ethylene-vinyl acetate (EVA) films by a surface coating and UV light grafting method. Fourier transform infrared (FT-IR) spectra, X-ray photoelectron spectroscopy analysis (XPS) and fluorescence microscopy results indicated that PTFEMA were fixed successfully onto the EVA film surface through a covalent bond. During the microalgal adhesion assay, the number of EVA-PTFEMA film-adhered microalgae was 41.4% lower than that of the EVA film. Moreover, the number of microalgae attached to the EVA-PTFEMA film decreased by 61.7% after cleaning, while that of EVA film decreased by only 49.1%. It was found that the contact angle of EVA-PTFEMA film surface increased, and remained stable when immersed in acid and alkali solution for up to 90 days.HIGHLIGHTSDurable photobioreactor antibiofouling surfaces for microalgal cultivation were prepared successfully.The contact angle of antibiofouling coating surface remained stable in acid and base environment for 90 days.The attached microalgae on antibiofouling surface decreased 41.4% than those of unmodified surface.The attached microalgae on antibiofouling surface could be cleaned by 61.7% through changing the flow velocity of microalgal suspension.

Modeling 1-Cyano-4-Dimethylaminopyridine Tetrafluoroborate (CDAP) Chemistry to Design Glycoconjugate Vaccines with Desired Structural and Immunological Characteristics.

Glycoconjugation is a well-established technology for vaccine development: linkage of the polysaccharide (PS) antigen to an appropriate carrier protein overcomes the limitations of PS T-independent antigens, making them effective in infants and providing immunological memory. Glycoconjugate vaccines have been successful in reducing the burden of different diseases globally. However, many pathogens still require a vaccine, and many of them display a variety of glycans on their surface that have been proposed as key antigens for the development of high-valency glycoconjugate vaccines. CDAP chemistry represents a generic conjugation strategy that is easily applied to PS with different structures. This chemistry utilizes common groups to a large range of PS and proteins, e.g., hydroxyl groups on the PS and amino groups on the protein. Here, new fast analytical tools to study CDAP reaction have been developed, and reaction conditions for PS activation and conjugation have been extensively investigated. Mathematical models have been built to identify reaction conditions to generate conjugates with wanted characteristics and successfully applied to a large number of bacterial PSs from different pathogens, e.g., Klebsiella pneumoniae, Salmonella Paratyphi A, Salmonella Enteritidis, Salmonella Typhimurium, Shighella sonnei and Shigella flexneri. Furthermore, using Salmonella Paratyphi A O-antigen and CRM197 as models, a design of experiment approach has been used to study the impact of conjugation conditions and conjugate features on immunogenicity in rabbits. The approach used can be rapidly extended to other PSs and accelerate the development of high-valency glycoconjugate vaccines.

Formation of extended polyiodides at large cation templates.

By studying the structures of (µ-1,4,10,13-tetrathia-7,16-diazacyclooctadecane)bis[iodidopalladium(II)] diiodide penta(diiodine), [Pd2I2(C12H26N2S4)](I)2·5I2 or [Pd2I2([18]aneN2S4)](I)2·(I2)5, and 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane triiodide iodide hemipenta(diiodine) dichloromethane monosolvate, C18H38N2O62+·I3-·I-·2.5I2·CH2Cl2 or [H2([2.2.2]cryptand)](I3)(I)(I2)2.5·CH2Cl2, we confirm the structural variety of extended polyiodides achievable upon changing the shape, charge and dimensions of the cation template, by altering the synthetic strategy adopted and/or the experimental conditions. Although it is still often difficult to characterize discrete [I2m+n]n- polyiodides higher than I3- on the basis of structural parameters, such as I-I bond distances, FT-Raman spectroscopy appears to identify them as aggregates of I2, I- and (symmetric or slightly asymmetric) I3- building blocks linked by I...I interactions of varying strengths. However, because FT-Raman spectroscopy carries no information about the topological features of extended polyiodides, the two techniques should therefore be applied in combination to enhance the analysis of this kind of compounds.

Enantioselective Construction of Tetrahydroindole Skeletons by Rh-Catalyzed [2+2+2] Cycloaddition of Homopropargyl Enamides with Alkynes.

We have developed the Rh-catalyzed enantioselective [2+2+2] cycloaddition of homopropargyl enamides (tosylamide-tethered 1,6-enynes) with alkynes to construct tetrahydroindole skeletons found in natural alkaloids and pharmaceuticals. This cycloaddition proceeds at room temperature in high yields and regio- and enantioselectivity with a broad substrate scope. The preparative scale reaction followed by substituent conversion on the nitrogen atom and the diastereoselective [4+2] cycloaddition with singlet O2 affords hexahydroindole-diols bearing three stereogenic centers and variable substituents on the nitrogen. Mechanistic studies have revealed that the substituents of the enynes change the ratio of intramolecular and intermolecular rhodacycle formation when using terminal alkynes, varying the ee values of the cycloadducts.

Variant of uncertain significance Arg866Cys enhances disorderedness of h-BRCA1 (759-1064) region.

High structural flexibility has been reported in the central region of BRCA1, which hinders the structural and functional evaluations of mutations identified in the domain. Additionally, the need to categorize variants of unknown significance (VUS) has increased due to the growth in the number of variants reported in clinical settings. Therefore, unraveling the disease-causing mechanism of VUS identified in different functional domains of BRCA1 is still challenging. The current study uses a multidisciplinary approach to assess the structural impact of BRCA1 Arg866Cys mutation discovered in the central domain of BRCA1. The structural alterations have been characterized using Circular-Dichroism spectroscopy, nano-DSF, and molecular-dynamics simulations. BRCA1 Arg866Cys mutant demonstrated more flexibility and lesser affinity to DNA than the wild-type protein. The BRCA1(759-1064) wild-type protein was shown to be a ßII-rich protein with an induced D-O transition in the presence of DNA and 2,2,2-Trifluoroethanol (TFE). The protein's alpha-helical composition did not significantly change in the presence of TFE, besides an increase in ß-turns and loops. Under Transmission Electron Microscopes (TEM), amyloid-like fibrils structure was detected for Arg866Cys mutant whereas the wild-type protein showed amorphous aggregates. An increased ThT fluorescence indicated ß-rich composition and aggregation-prone behaviour for BRCA1 wild-type protein, while the fluorescence intensity was significantly quenched in the Arg866Cys mutant. Furthermore, increased conformational flexibility in the Arg866Cys variant was observed by principal component analysis. This work aims to comprehend the inherently disordered region of BRCA1 as well as the impact of missense mutations on folding patterns and binding to DNA for functional aspects.

Structural implications of amyloidogenic rare variants Ser282Leu and Gln356Arg identified in h-BRCA1.

Preliminary studies have shown BRCA1 (170-1600) residues to be intrinsically disordered with unknown structural details. However, thousands of clinically reported variants have been identified in this central region of BRCA1. Therefore, we aimed to characterize h-BRCA1(260-553) to assess the structural basis for pathogenicity of two rare missense variants Ser282Leu, Gln356Arg identified from the Indian and Russian populations respectively. Small-angle X-ray scattering analysis revealed WT scores Rg -32 Å, Dmax -93 Å, and Rflex-51% which are partially disordered, whereas Ser282Leu variant displayed a higher degree of disorderedness and Gln356Arg was observed to be aggregated. WT protein also possesses an inherent propensity to undergo a disorder-to-order transition in the presence of cruciform DNA and 2,2,2-Trifluoroethanol (TFE). An increased alpha-helical pattern was observed with increasing concentration of TFE for the Gln356Arg mutant whereas Ser282Leu mutant showed significant differences only at the highest TFE concentration. Furthermore, higher thermal shift was observed for WT-DNA complex compared to the Gln356Arg and Ser282Leu protein-DNA complex. Moreover, mature amyloid-like fibrils were observed with 30 µM thioflavin T (ThT) at 37°C for Ser282Leu and Gln356Arg proteins while the WT protein exists in a protofibril state as observed by TEM. Gln356Arg formed higher-order aggregates with amyloidogenesis over time as monitored by ThT fluorescence. In addition, computational analyses confirmed larger conformational fluctuations for Ser282Leu and Gln356Arg mutants than for the WT. The global structural alterations caused by these variants provide a mechanistic approach for further classification of the variants of uncertain clinical significance in BRCA1 into amyloidogenic variants which may have a significant role in disease pathogenesis.

Efficient Synthesis of Chiral Aryl Alcohol with a Novel Kosakonia radicincitans Isolate in Tween 20/L-carnitine: Lysine-Containing Synergistic Reaction System.

Chiral trifluoromethyl alcohols as vital intermediates are of great interest in fine chemicals and especially in pharmaceutical synthesis. In this work, a novel isolate Kosakonia radicincitans ZJPH202011 was firstly employed as biocatalyst for the synthesis of (R)-1-(4-bromophenyl)-2,2,2-trifluoroethanol ((R)-BPFL) with good enantioselectivity. By optimizing fermentation conditions and bioreduction parameters in aqueous buffer system, the substrate concentration of 1-(4-bromophenyl)-2,2,2-trifluoroethanone (BPFO) was doubled from 10 to 20 mM, and the enantiomeric excess (ee) value for (R)-BPFL increased from 88.8 to 96.4%. To improve biocatalytic efficiency by strengthening the mass-transfer rate, natural deep-eutectic solvents, surfactants and cyclodextrins (CDs) were introduced separately in the reaction system as cosolvent. Among them, L-carnitine: lysine (C: Lys, molar ratio 1:2), Tween 20 and γ-CD manifested higher (R)-BPFL yield compared with other same kind of cosolvents. Furthermore, based on the excellent performance of both Tween 20 and C: Lys (1:2) in enhancing BPFO solubility and ameliorating cell permeability, a Tween 20/C: Lys (1:2)-containing integrated reaction system was then established for efficient bioproduction of (R)-BPFL. After optimizing the critical factors involved in BPFO bioreduction in this synergistic reaction system, BPFO loading increased up to 45 mM and the yield reached 90.0% within 9 h, comparatively only 37.6% yield was acquired in neat aqueous buffer. This is the first report on K. radicincitans cells as new biocatalyst applied in (R)-BPFL preparation, and the developed Tween 20/C: Lys-containing synergistic reaction system has great potential for the synthesis of various chiral alcohols.

Synthesis, acaricidal activity, and structure-activity relationships of novel phenyl trifluoroethyl thioether derivatives containing substituted benzyl groups.

BACKGROUND: To discover and develop novel acaricidal compounds, a series of 2-fluoro-4-methyl/chlorine-5-((2,2,2-trifluoroethyl)thio)aniline/phenol compounds containing N/O-benzyl moieties were synthesized based on lead compound LZ-1. RESULTS: The activity of these compounds against carmine spider mites (Tetranychus cinnabarinus) was determined using the leaf-spray method. Bioassays indicated that most of the designed target compounds possessed moderate to excellent acaricidal activity against adult T. cinnabarinus. The median lethal concentrations of 25b and 26b were 0.683 and 2.448 mg L-1 against adult mites, respectively; exceeding those of bifenazate (7.519 mg L-1 ) and lead compound LZ-1(3.658 mg L-1 ). Compound 25b exhibited 100% mortality in T. cinnabarinus larvae at 10 mg L-1 . CONCLUSION: Continuing the study of these compounds in field trials, we compared the efficacy of mite killing by compound 25b with the commercial pesticide spirodiclofen and showed that mite control achieved 95.9% and 83.0% lethality at 10 and 22 days post-treatment. In comparison, spirodiclofen showed 92.7% lethality at 10 days and 77.2% lethality at 22 days post-treatment at a concentration of 100 mg L-1 . Results showed that 25b produced more facile and long-lasting control against T. cinnabarinus than the commercial acaricide spirodiclofen. Density functional theory analysis and electrostatic potential calculations of various molecular substitutions suggested some useful models to achieve other highly active miticidal compounds. © 2023 Society of Chemical Industry.

Molecular mechanism of the common and opposing cosolvent effects of fluorinated alcohol and urea on a coiled coil protein.

Alcohols and urea are widely used as effective protein denaturants. Among monohydric alcohols, 2,2,2-trifluoroethanol (TFE) has large cosolvent effects as a helix stabilizer in proteins. In contrast, urea efficiently denatures ordered native structures, including helices, into coils. These opposing cosolvent effects of TFE and urea are well known, even though both preferentially bind to proteins; however, the underlying molecular mechanism remains controversial. Cosolvent-dependent relative stability between native and denatured states is rigorously related to the difference in preferential binding parameters (PBPs) between these states. In this study, GCN4-p1 with two-stranded coiled coil helices was employed as a model protein, and molecular dynamics simulations for the helix dimer and isolated coil were conducted in aqueous solutions with 2 M TFE and urea. As 2 M cosolvent aqueous solutions did not exhibit clustering of cosolvent molecules, we were able to directly investigate the molecular origin of the excess PBP without considering the enhancement effect of PBPs arising from the concentration fluctuations. The calculated excess PBPs of TFE for the helices and those of urea for the coils were consistent with experimentally observed stabilization of helix by TFE and that of coil by urea. The former was caused by electrostatic interactions between TFE and side chains of the helices, while the latter was attributed to both electrostatic and dispersion interactions between urea and the main chains. Unexpectedly, reverse-micelle-like orientations of TFE molecules strengthened the electrostatic interactions between TFE and the side chains, resulting in strengthening of TFE solvation.

Evaluation of the Stability of a 1,8-Cineole Nanoemulsion and Its Fumigant Toxicity Effect against the Pests Tetranychus urticae, Rhopalosiphum maidis and Bemisia tabaci.

Pest control is a main concern in agriculture. Indiscriminate application of synthetic pesticides has caused negative impacts leading to the rapid development of resistance in arthropod pests. Plant secondary metabolites have been proposed as a safer alternative to conventional pesticides. Monoterpenoids have reported bioactivities against important pests; however, due to their high volatility, low water solubility and chemical instability, the application of these compounds has been limited. Nanosystems represent a potential vehicle for the broad application of monoterpenoids. In this study, an 1,8-cineole nanoemulsion was prepared by the low energy method of phase inversion, characterization of droplet size distribution and polydispersity index (PDI) was carried out by dynamic light scattering and stability was evaluated by centrifugation and Turbiscan analysis. Fumigant bioactivity was evaluated against Tetranychus urticae, Rhopalosiphum maidis and Bemisia tabaci. A nanoemulsion with oil:surfactant:water ratio of 0.5:1:8.5 had a droplet size of 14.7 nm and PDI of 0.178. Formulation was stable after centrifugation and the Turbiscan analysis showed no particle migration and a delta backscattering of ±1%. Nanoemulsion exhibited around 50% more bioactivity as a fumigant on arthropods when compared to free monoterpenoid. These results suggest that nanoformulations can provide volatile compounds of protection against volatilization, improving their bioactivity.

Thermodynamics of modulation of interaction of α-helix inducer 2, 2, 2-trifluoroethanol with lysozyme in presence of cationic, anionic and non-ionic surfactants.

The interactions of anionic sodium dodecyl sulphate (SDS), cationic cetyltrimethylammonium bromide (CTAB) and nonionic triton X-100 (TX-100) surfactants with lysozyme at pH = 2.4 have been studied individually as well as in combination with 2,2,2-trifluoroetanol (TFE). Urea has also been used in combination with surfactants. By using these combinations, efforts have been made to obtain partially folded conformations of the protein in the presence of surfactants and effect of α-helix inducer 2,2,2-trifluoroethanol on these intermediate states. Thermodynamic analysis of all these interactions has been done employing a combination of UV-visible, fluorescence and circular dichroism spectroscopies. The results have been correlated with each other and characterized qualitatively as well as quantitatively. At lower concentration of surfactant, the thermodynamic parameters indicated the destabilizing effect of SDS, stabilizing effect of CTAB and unappreciable destabilizing impact of TX-100 on lysozyme. The enhancement in destabilization effect or reduction in stabilization effect of surfactants on lysozyme in the presence of TFE and urea has also been indicated.Communicated by Ramaswamy H. Sarma.

Intermolecular Triazene Alkene Cycloaddition via Lewis Base Catalysis: Access to Diverse Trifluoromethylated Pyrazolines.

A novel approach to chemoselective synthesis of biologically important CF3 -subsituted pyrazolines was developed via a Lewis base catalyzed intermolecular triazene cycloaddition reaction of an array of terminal/internal alkenes with CF3 CHN2 . This strategy features a catalytic amount of 1,8-diazabicyclo[5.4.0]undec-7-ene, high yields (up to 95 %), wide substrate scope and excellent functional group tolerance (54 examples). Importantly, we preformed scaffold diversification of a panel of known pharmaceuticals, natural products, and bioactive heterocycles to generate the corresponding pyrazoline derivatives with potential broad bioactivities for further development.

Tyrosylprotein sulfotransferase suppresses ABA signaling via sulfation of SnRK2.2/2.3/2.6.

Phytohormone abscisic acid (ABA) plays vital roles in stress tolerance, while long-term overactivation of ABA signaling suppresses plant growth and development. However, the braking mechanism of ABA responses is not clear. Protein tyrosine sulfation catalyzed by tyrosylprotein sulfotransferase (TPST) is a critical post-translational modification. Through genetic screening, we identified a tpst mutant in Arabidopsis that was hypersensitive to ABA. In-depth analysis revealed that TPST could interact with and sulfate SnRK2.2/2.3/2.6, which accelerated their degradation and weakened the ABA signaling. Taken together, these findings uncovered a novel mechanism of desensitizing ABA responses via protein sulfation.

Shape- and Size-Tunable Synthesis of Covalent Organic Cages through Rh-Catalyzed Regioselective [2+2+2] Cycloaddition.

Covalent organic cages have potential applications in molecular inclusion/recognition and porous organic crystals. Bridging arene units with sp3 atoms enables facile construction of rigid isolated internal vacancies, and various prismatic arene cages have been synthesized by kinetically controlled covalent bond formation. However, the synthesis of a tetrahedral one, which requires twice as much bond formation as prismatic ones, has been limited to a thermodynamically controlled dynamic SN Ar reaction, and this reversible covalent bond formation made the resulting cage product chemically unstable. Here we report the Rh-catalyzed high-yielding and highly 1,3,5-selective room temperature [2+2+2] cycloaddition of push-pull alkynes and its application to the synthesis of chemically stable aryl ether cages of various shapes and sizes, including prismatic and tetrahedral forms. These aryl ether cages are highly crystalline and intertwine with each other to form regular packing structures. Some aryl ether cages encapsulated isolated water molecules in their hydrophobic cavity by hydrogen bonding with the multiple ester moieties.

Recent Advances of N-2,2,2-Trifluoroethylisatin Ketimines in Organic Synthesis.

The special properties of fluorine atoms and fluorine-containing groups have led to an increasing number of applications for fluorine-containing organic compounds, which are also extremely widely used in the field of new drug development. Unfortunately, naturally fluorinated organics are rare in nature, so the selective introduction of fluorine atoms or fluorine-containing groups into organic molecules is very important for pharmaceutical/synthetic chemists. N-2,2,2-trifluoroethylisatin ketimines have received the attention of many chemists since they were first developed as fluorine-containing synthons in 2015. This paper reviews the organic synthesis reactions in which trifluoroethyl isatin ketimine has been involved in recent years, focusing on the types of reactions and the stereoselectivity of products, and also provides a prospect of its application in this field.

Highly transparent, hydrophobic, and durable anisotropic cellulose films as electronic screen protectors.

Cellulose films have attracted extensive interest in the field of burgeoning electronic devices. However, it remains a challenge to simultaneously address the difficulties including facile methodology, hydrophobicity, optical transparency, and mechanical robustness. Herein, we reported a coating-annealing approach to fabricate highly transparent, hydrophobic, and durable anisotropic cellulose films, where poly(methyl methacrylate)-b-poly(trifluoroethyl methacrylate) (PMMA-b-PTFEMA) as low surface energy chemicals was coated onto regenerated cellulose films via physical (hydrogen bonds) and chemical (transesterification) interactions. The resultant films with nano-protrusions and low surface roughness exhibited high optical transparency (92.3 %, 550 nm) and good hydrophobicity. Moreover, the tensile strength of the hydrophobic films was 198.7 MPa and 124 MPa in dry and wet states, respectively, which also showed excellent stability and durability under various conditions, such as hot water, chemicals, liquid foods, tape peeling, finger pressing, sandpaper abrasion, ultrasonic treatment, and water jet. This work provided a promising large-scale production strategy for the preparation of transparent and hydrophobic cellulose-based films for electronic device protection as well as other emerging flexible electronics.

Rhodium-Catalyzed Chemo-, Regio-, Diastereo-, and Enantioselective Intermolecular [2+2+2] Cycloaddition of Three Unsymmetric 2π Components.

We have developed the Rh+ /H8 -binap-catalyzed chemo-, regio-, diastereo-, and enantioselective intermolecular [2+2+2] cycloaddition of three unsymmetric 2π components. Thus, two arylacetylenes react with a cis-enamide to yield a protected chiral cyclohexadienylamine. Moreover, replacing one arylacetylene with a silylacetylene enables the [2+2+2] cycloaddition of three distinct unsymmetric 2π components. These transformations proceed with excellent selectivity (complete regio- and diastereoselectivity and up to >99 % yield and >99 % ee). Mechanistic studies suggest the chemo- and regioselective formation of a rhodacyclopentadiene intermediate from the two terminal alkynes.