Charge transport in highly acidic glass-forming protic ionic liquids tailored by zwitterionic precursors.

Highly acidic protic ionic liquids (PILs) are promising materials for potential electrochemical applications due to their high proton conductivity and excellent thermal stability. Still, little is known about the correlation between charge transport and structural dynamics as well as the proton transport mechanism despite the large body of literature on this topic. Here, we have examined the charge transport and structural dynamics by employing broadband dielectric spectroscopy in two highly acidic PILs in their supercooled liquid and glassy states, which included the same anion [TfO]- and different cations, [Tau]+ vs [Ahs]+. Unlike many other ionic liquids, the conductivity relaxation time τe of two studied PILs is substantially faster than the structural relaxation time τα. The decoupling behavior between charge transport and structural dynamics of two materials, which is manifested by a decoupling index Rτ, varies between 0.3 and 2.3 over the temperature range above Tg. Moreover, "Walden" plots of the molar conductivity vs the viscosity qualify both compounds as "Super ILs." All findings support the physical picture of large, polar, and orientationally correlated ion clusters, where the slow α-relaxation can be identified as structural relaxation associated with cooperative reorientations of the cluster macrodipole. In contrast, the shortest timescale for diffusive charge transport, τe, is 1-2 decades shorter than τα, implying that proton hopping is triggered by "single particle" (ions or ion pair) rotations and jumps on a sub-length scale of the cluster size, a dynamics being present even in the glassy state as indicated by a strong ß-relaxation. These results demonstrate the practicality of employing highly acidic PILs in electrochemical fields.

Ex situ Generation of Thiazyl Trifluoride (NSF3 ) as a Gaseous SuFEx Hub.

Sulfur(VI)-fluoride exchange (SuFEx) chemistry, an all-encompassing term for substitution events that replace fluoride at an electrophilic sulfur(VI), enables the rapid and flexible assembly of linkages around a SVI core. Although a myriad of nucleophiles and applications works very well with the SuFEx concept, the electrophile design has remained largely SO2 -based. Here, we introduce S≡N-based fluorosulfur(VI) reagents to the realm of SuFEx chemistry. Thiazyl trifluoride (NSF3 ) gas is shown to serve as an excellent parent compound and SuFEx hub to efficiently synthesize mono- and disubstituted fluorothiazynes in an ex situ generation workflow. Gaseous NSF3 was evolved from commercial reagents in a nearly quantitative fashion at ambient conditions. Moreover, the mono-substituted thiazynes could be extended further as SuFEx handles and be engaged in the synthesis of unsymmetrically disubstituted thiazynes. These results provide valuable insights into the versatility of these understudied sulfur functionalities paving the way for future applications.

Chemistry of Pentafluorosulfanyl Derivatives and Related Analogs: From Synthesis to Applications.

Pentafluorosulfanyl (SF5 )-containing compounds and corresponding analogs are a highly valuable class of fluorine-containing building blocks owing to their unique properties. The reason for that is the set of peculiar and tremendously beneficial characteristics they can impart on molecules once introduced onto them. Despite this, their application in distinct scientific fields remains modest, given the extremely harsh reaction conditions needed to access such compounds. The recent synthetic approaches via S-F, and C-SF5 bond formation as well as the use of SF5 -containing building blocks embody a "stairway-to-heaven" loophole in the synthesis of otherwise-inaccessible chemical scaffolds only a few years ago. Herein, we report and evaluate the properties of the SF5 group and analogs, by summarizing synthetic methodologies available to access them as well as following applications in material science and medicinal chemistry since 2015.

Correction: SuFEx-enabled, chemoselective synthesis of triflates, triflamides and triflimidates.

[This corrects the article DOI: 10.1039/D1SC06267K.].

SuFEx-enabled, chemoselective synthesis of triflates, triflamides and triflimidates.

Sulfur(vi) Fluoride Exchange (SuFEx) chemistry has emerged as a next-generation click reaction, designed to assemble functional molecules quickly and modularly. Here, we report the ex situ generation of trifluoromethanesulfonyl fluoride (CF3SO2F) gas in a two chamber system, and its use as a new SuFEx handle to efficiently synthesize triflates and triflamides. This broadly tolerated protocol lends itself to peptide modification or to telescoping into coupling reactions. Moreover, redesigning the SVI-F connector with a S[double bond, length as m-dash]O → S[double bond, length as m-dash]NR replacement furnished the analogous triflimidoyl fluorides as SuFEx electrophiles, which were engaged in the synthesis of rarely reported triflimidate esters. Notably, experiments showed H2O to be the key towards achieving chemoselective trifluoromethanesulfonation of phenols vs. amine groups, a phenomenon best explained-using ab initio metadynamics simulations-by a hydrogen bonded termolecular transition state for the CF3SO2F triflylation of amines.

Cocomposing an Aesthetic Self Through Play: Toward a Transformative Framework for Dementia Care.

BACKGROUND AND OBJECTIVES: Aging and deterioration mark a new phase in many older adults' life, highlighting the importance of creativity and imagination. This article introduces the implementation of an innovative program, Play Intervention for Dementia, at a nursing home in Hong Kong, with emphasis on its contribution to the conceptual framework for understanding the selfhood of older adults with dementia. RESEARCH DESIGN AND METHODS: As a community-based participatory action research project, this study democratized knowledge production by integrating voices of practitioners with diverse backgrounds through video-based methods. RESULTS: Play, as an activity replete with free expressions and impulsive interactions, is an ideal realm for exploring and establishing selfhood with older adults with dementia. It has been found that "aesthetic self," an alternative self emerging from immediate aesthetic experience and carrying transformative power within the caring relationship, is a necessary element of self-construction in life with dementia. DISCUSSION AND IMPLICATIONS: Integrating theories and practice, this framework provides a new lens for understanding and responding to selfhood, disease, and life.

Melatonin ameliorates cerebral ischemia-reperfusion injury in diabetic mice by enhancing autophagy via the SIRT1-BMAL1 pathway.

Diabetic brains are more vulnerable to ischemia-reperfusion injury. Previous studies have proved that melatonin could protect against cerebral ischemia-reperfusion (CIR) injury in non-diabetic stroke models; however, its roles and the underlying mechanisms against CIR injury in diabetic mice remain unknown. Streptozotocin-induced diabetic mice and high-glucose-cultured HT22 cells were exposed to melatonin, with or without administration of the autophagy inhibitor 3-methyladenine (3-MA) and the specifically silent information regulator 1 (SIRT1) inhibitor EX527, and then subjected to CIR or oxygen-glucose deprivation/reperfusion operation. We found that diabetic mice showed aggravated brain damage, increased apoptosis and oxidative stress, and deficient autophagy following CIR compared with non-diabetic counterparts. Melatonin treatment exhibited improved histological damage, neurological outcomes, and cerebral infarct size. Intriguingly, melatonin markedly increased cell survival, anti-oxidative and anti-apoptosis effects, and significantly enhanced autophagy. However, these effects were largely attenuated by 3-MA or EX527. Additionally, our cellular experiments demonstrated that melatonin increased the SIRT1-BMAL1 pathway-related proteins' expression in a dose-dependent manner. In conclusion, these results indicate that melatonin treatment can protect against CIR-induced brain damage in diabetic mice, which may be achieved by the autophagy enhancement mediated by the SIRT1-BMAL1 pathway.

[Effect and Mechanism of Foliar Application Nano-MnO2 on Cadmium Enrichment of Rice].

Cadmium (Cd) is easily enriched in rice, resulting in an excessive Cd content in the grain, which seriously threatens human health. Manganese (Mn) is an essential element of plants. In a field experiment on Cd-contaminated acid soils, we investigated the effectiveness and mechanism of Mn in minimizing Cd accumulation in rice via foliar spraying using 0.1%, 0.3%, and 0.5% nano-MnO2 solutions at an early stage of heading. Compared with a control treatment, foliar spraying effectively reduced the Cd content of rice leaves, husks, and brown rice; increased the Mn content of all rice organs; but had no effect on rice yield. Foliar application of nano-MnO2 alleviated the plant stress induced by Cd by improving leaf photosynthesis, inhibiting lipid peroxidation, and increasing the content of the oxidative stress protein kinase. In addition, foliar application of nano-MnO2 limited the absorption of Cd by roots by increasing the content of iron-manganese plaque on the surfaces of rice roots and strengthening its adsorption/co-precipitation of Cd. Therefore, foliar application of nano-MnO2 during the early stages of rice heading is an effective measure to increase the Mn content and reduce the Cd content of brown rice.

Enrichment of cadmium in rice (Oryza sativa L.) grown under different exogenous pollution sources.

In order to unravel the cadmium (Cd) enrichment patterns in rice (Oryza sativa L.) grown under different exogenous exposure pathways, the pot experiment was conducted in a greenhouse. Cd was added to the soil-rice system via mixing soil with Cd-containing solution, irrigating the pots with Cd-containing water and leaf-spraying with Cd solution to simulate soil pollution (SPS), irrigation water pollution (IPS), and atmospheric deposit pollution sources (APS), respectively. No significant (p > 0.05) differences in plant height and rice grain yield were observed among all treatments including three different Cd pollution sources and control. The contents of Cd in rice plants significantly (p < 0.05) increased with increase in Cd concentrations in three pollution sources. The distribution pattern of Cd in the rice plant organs treated with SPS and IPS followed the order: roots > stems > leaves > husk > brown rice, while it was leaves > roots > stems > husk > brown rice treated with APS. At the same level of treatment, the highest concentration of Cd was observed in rice organs (except for middle and high concentrations treatment roots) grown under APS, followed by IPS and SPS, suggesting that the Cd bioavailability from different pollution sources followed the order of APS > IPS > SPS. It is concluded that the atmospheric pollution contributed more enrichment of rice with Cd. Therefore, in field environment, air deposits should also be analyzed for toxic metals during assessment of food chain contamination and health risk.

Spontaneous Formation of Moiré Patterns through Self-Assembly of Janus Nanoparticles.

Two periodic two-dimensional lattices overlap with each other with a twisted angle can result in moiré patterns (MPs). In this in silico study, we show that by using amphiphilic Janus nanoparticles (JNPs) as a building block, the MPs of JNPs emerge spontaneously via direct self-assembly in dilute solution without additional complicated operation. The formation of MPs is attributed to the hydrophobicity of the nanoparticles (and the so-induced "force strings" at the membrane rim) together with suitable grafted hydrophilic and hydrophobic chain lengths. The mass production of MPs with controlled size can be fulfilled by adding stabilizers that effectively reduce the line tension at the rim of membranes with MPs.

Microscopic characteristics of Janus nanoparticles prepared via a grafting-from reaction at the immiscible liquid interface.

The dynamic process of synthesizing Janus nanoparticles (JNPs) at a water/oil two-phase interface using a grafting-from reaction is investigated via dissipative particle dynamics simulations. We find that the interfacial tension, the initial monomer concentration, and the reaction probability can greatly influence the microscopic characteristics of JNP structure. It is difficult to synthesize a symmetric JNP with an equal volume ratio between hydrophilic and hydrophobic parts by grafting-from methods unless the physical chemical conditions in the two phases are strictly symmetric, and there is always a disordered domain on the JNP at a two immiscible solvents interface. Interestingly, for certain routes for synthesizing JNPs with a grafting-from method, the higher interfacial tension between the water and oil phases may enhance the degree of disorder of the grafted chains. The asymmetric initial monomer concentration in solution and the reaction probability can be used to control the syntheses of asymmetric JNPs.

Organocatalytic Asymmetric Mannich Addition of 3-Fluorooxindoles to Dibenzo[b,f][1,4]oxazepines: Highly Enantioselective Construction of Tetrasubstituted C-F Stereocenters.

3-Fluorooxindoles and the dibenzo[b,f][1,4]oxazepane scaffolds are important pharmacophores that have important application in medicinal chemistry. An organocatalyzed asymmetric Mannich reaction of 3-fluorooxindoles with dibenzo[b,f][1,4]oxazepines affording various seven-member cyclic amines containing chiral tetrasubstituted C-F stereocenters was developed. These reactions which were catalyzed by a bifunctional Cinchona alkaloid-derived thiourea catalyst afforded a wide range of substrates in moderate to high yields with excellent diastereo- and enantioselectivities (up to 88% yield, >20:1 dr and >99% ee). A feasible reaction mechanism was also proposed.

Squaramide-catalyzed asymmetric Mannich reactions between 3-fluorooxindoles and pyrazolinone ketimines.

An enantioselective Mannich reaction between 3-fluorooxindoles and pyrazolinone ketimines has been developed for the construction of amino-pyrazolone-oxindoles containing stereogenic C-F units. Based on this new protocol that allows for the generation of two adjacent tetrasubstituted stereocenters, a variety of structurally diverse fluorinated amino-pyrazolone-oxindoles were obtained in good to excellent yields with excellent diastereoselectivities and enantioselectivities (up to 98% yield, >20 : 1 dr and >99% ee). What's more, good yield and high stereoselectivities were obtained in the gram-scale reaction.

[Effects of nitrogen application levels on translocation and distribution of 13C-photosynthate and 15N to fruit from leaves of apple tree]. / 氮水平对苹果叶片13Cå ‰åˆäº§ç‰©å’Œ15Nå‘æžœå®žè½¬ç§»åˆ†é çš„å½±å“.

A field experiment was carried out in a six-year old 'Fuji3'/M26/Malus hupehensis Rehd. apple with 15N and 13C labeled tracers, to understand 13C assimilation capability and the characteristics of translocation and distribution of 13C-photosynthate and 15N to fruit under different nitrogen application levels (urea 0%, 0.6%, 1.2%, 1.8%, 2.4%, CK, N1, N2, N3, N4, respectively) to smear the leaves within 20 cm around the fruit at late stage of fruit enlargement. The results showed that, with the increases of urea application, the chlorophyll content, nitrogen content, net photosynthetic rate, sorbitol and sucrose content, sorbitol 6-phosphate dehydrogenase (S6PDH) and sucrose phosphate synthase (SPS) activities, 13C assimilation capability of leaves were first increased and then decreased, with the highest value in 1.8% urea smear treatment and the lowest value with the treatment of clear water. The 13C of self retention (self leaves and self branches) was the highest in clear water (81.6%) and the lowest in 1.8% urea smear treatment (63.5%). The 13C was mainly allocated to fruit, followed by unlabeled perennial branch, and the lowest in unlabeled leaves. With the increases of urea application, the 13C absorption of fruit was first increased and then decreased, with the highest value in 1.8% urea smear treatment (1.21 mg·g-1) and the lowest value in clear water (0.51 mg·g-1). The 15N absorption of fruit was enhanced with the increases of urea application. These results indicated that foliage application of urea solution improved translocation and distribution of leaf photosynthate and nitrogen to fruit with varying degrees, which was the highest in 1.8% urea smear treatment and could avoid excessive intake of nitrogen to fruit.

Computer simulation study on the self-assembly of tethered nanoparticles with tunable shapes.

We built a tethered nanoparticle (TNP) model that is composed of a nanoparticle with a hydrophobic tethered polymer chain. The shape of the nanoparticle can be tuned from a pure rigid cube to a soft sphere, mimicking the increase of grafting density on the nanocube surfaces. With this model, we study the self-assembly of TNPs in dilute solution using a dissipative particle dynamics simulation technique, and especially focus on the influence of particle shape, tethered chain length, and grafting density on the self-assembly structures. Some intriguing aggregates such as spherical micelles, pearl-necklace-like structures, cubic columnar structures, handshake structures, core-shell-corona micelles, and four-patch micelles have been observed when varying the interactions between cubes and solvents and the lengths of tethered chain. Modifying the nanocube surface with some hydrophilic grafted chains helps the TNPs form small micelles. Increased steric repulsion due to chain overlapping at larger grafting densities results in shape transformation of the nanoparticle from a rigid cube to a soft sphere. In these cases, the self-assembled structures are characterized by the packing of nanoparticles on the micelle surface, and the typical packing mode turns from rectangular (typical for cubes) to hexagonal (typical for spheres).

Tilmicosin and tylosin have anti-inflammatory properties via modulation of COX-2 and iNOS gene expression and production of cytokines in LPS-induced macrophages and monocytes.

Macrolides have been reported to modify the host immune and inflammatory responses both in vivo and in vitro. We examined the in vitro effect of the macrolides tilmicosin and tylosin, which are only used in the veterinary clinic, on the production of nitric oxide (NO), prostaglandin E(2) (PGE(2)) and cytokines by lipopolysaccharide (LPS)-stimulated RAW264.7 macrophages and mouse peripheral blood mononuclear cells (PBMCs). Compared with 5 microg/mL, tilmicosin and tylosin concentrations of 10 microg/mL and 20 microg/mL significantly decreased the production of 6-keto-prostaglandin F(1alpha) (6-keto-PGF(1alpha)), PGE(2), NO, tumour necrosis factor-alpha (TNF-alpha), interleukin (IL)-1beta and IL-6, and increased IL-10 production. Cyclooxygenase-2 (COX-2) and inducible nitric oxide synthase (iNOS) gene expression were also significantly reduced. These results support the opinion that macrolides may exert an anti-inflammatory effect through modulating the synthesis of several mediators and cytokines involved in the inflammatory process.