Zirconium and hafnium catalyzed C-C single bond hydroboration.

Selective cleavage and subsequent functionalization of C-C single bonds present a fundamental challenge in synthetic organic chemistry. Traditionally, the activation of C-C single bonds has been achieved using stoichiometric transition-metal complexes. Recently, examples of catalytic processes were developed in which use is made of precious metals. However, the use of inexpensive and Earth-abundant group IV metals for catalytic C-C single-bond cleavage is largely underdeveloped. Herein, the zirconium-catalyzed C-C single-bond cleavage and subsequent hydroboration reactions is realized using Cp2ZrCl2 as a catalytic system. A series of structures of various γ-boronated amines are readily obtained, which are otherwise difficult to obtain. Mechanistic studies disclose the formation of a N-ZrIV species, and then a ß-carbon elimination route is responsible for C-C single bond activation. Besides zirconium, hafnium exhibits a similar performance for this transformation.

Experimental-Computational Investigation of the Elastic Modulus of Mortar under Sulfate Attack.

External sulfate attack is an important factor causing a decrease in the mechanical properties of cement-based materials. In this paper, a computational prediction model of elastic modulus, considering the characteristics of sulfate corrosion from outside to inside and the influence of the interface transition zone (ITZ), was established to predict the elastic modulus of mortar under the external sulfate attack. Firstly, the backscattered electron (BSE) images of mortar and the algorithm of image threshold segmenting were used to determine a reasonable thickness of corroded ITZ. Secondly, the nanoindentation test was adopted to acquire the microscopic elastic parameters of phases (sand, cement, and ITZ) in corroded mortar. Moreover, the mortar mix proportion and Lu and Torquato's model were adopted to calculate the volume fractions of phases. Finally, a computational prediction model of elastic modulus of mortar under sulfate attack was proposed with homogenization methods. The results indicate that the thickness of corroded ITZ is 20 mm, and the error values of elastic modulus between the theoretical prediction results and the experimental results are within 8%, indicating that the macroscopic elastic modulus of corroded mortar can be precisely predicted by the computational prediction model of elastic modulus.

Anion-substitution interfacial engineering to construct C@MoS2 hierarchical nanocomposites for broadband electromagnetic wave absorption.

Developing an effective strategy to regulate the interfacial properties of hierarchical structure is of great significance for preparation of high-performance electromagnetic wave absorption (EMA) materials. Ion-substitution can change intrinsic structure and properties of a materials, but its effect on the interfacial properties of hierarchical structure remained to be explored. Herein, we first constructed a C@MoS2 hierarchical structure via simple hydrothermal reaction, then used the ion-substitution strategy to replace the S atoms in MoS2 with O, F and Se, and finally obtained anion-substituted hierarchical structure (C@X-MoS2, X = O, F, Se). The results show that ion-substitution destroys the MoS2 crystal structure and realizes tunable dielectric properties of C@MoS2, which leads to further enhancement of overall interfacial polarization. After optimization, the absorption strength and width of C@O-MoS2 has been significantly improved. The minimum reflection loss (RLmin) reaches -62.17 dB, and the maximum effective absorption bandwidth (EABmax) is 7.0 GHz. The simulation results show the obtained absorbent can greatly reduce the radar cross section of target, indicating it has broad application potential. Therefore, this work provides a novel method for regulation of EMA performance of hierarchical structure and preparation of high-performance absorbents.

Si-B Functional Group Exchange Reaction Enabled by a Catalytic Amount of BH3: Scope, Mechanism, and Application.

Functional group exchanges based on single-bond transformation are rare and challenging. In this regard, functional group exchange reactions of hydrosilanes proved to be more problematic. This is because this exchange requires the cleavage of the C-Si bond, while the Si-H bond is relatively easily activated for hydrosilanes. Herein, we report the first Si-B functional group exchange reactions of hydrosilanes with hydroboranes simply enabled by BH3 as a catalyst. Our methodology works for various aryl and alkyl hydrosilanes and different hydroboranes with the tolerance of general functional groups (up to 115 examples). Control experiments and density functional theory (DFT) studies reveal a distinct reaction pathway that involves consecutive C-Si/B-H and C-B/B-H σ-bond metathesis. Further investigations of using more readily available chlorosilanes, siloxane, fluorosilane, and silylborane for Si-B functional group exchanges, Ge-B functional group exchanges, and depolymerizative Si-B exchanges of polysilanes are also demonstrated. Moreover, the regeneration of MeSiH3 from polymethylhydrosiloxane (PMHS) is achieved. Notably, the formal hydrosilylation of a wide range of alkenes with SiH4 and MeSiH3 to selectively produce (chiral)trihydrosilanes and (methyl)dihydrosilanes is realized using inexpensive and readily available PhSiH3 and PhSiH2Me as gaseous SiH4 and MeSiH3 surrogates.

Enhancing the stability, BBB permeability and neuroprotective activity of verbascoside in vitro using lipid nanocapsules in combination with menthol.

Verbascoside (VER) shows promising neuroprotective activity. However, the instability and low permeability in crossing the blood-brain barrier (BBB) greatly hinder its application. In the present study, verbascoside was encapsulated into lipid nanocapsules (LNC) by reverse micelle (RM) to increase its stability. Besides, we used VER-RM-LNC combined with an envoy drug, menthol, to improve its BBB permeability and neuroprotective activity. VER-RM-LNC was prepared by the phase inversion temperature method, resulting in an encapsulation efficiency of nearly 85 %. The formulated VER-RM-LNC was stable for 6 months at 4 °C. VER encapsulated into LNC possessed enhanced stability and a reduced release profile. Menthol increased the cellular uptake and the permeability of VER-RM-LNC in the BBB model in vitro. In addition, the improved neuroprotective activity of VER through incubation with menthol and VER-RM-LNC was verified in the neurotoxic human brain microvascular endothelial cells model induced by Aß25-35.

Eucommia ulmoides male flower as a remarkable edible floral resource exerts lifespan/healthspan-promoting effects on Caenorhabditis elegans.

Natural products, especially phytochemicals, can effectively improve the health of various model organisms and ultimately prolong their lifespan. As an emerging resource of plant-based food, edible flowers have potential anti-aging effects. Here, we showed that twelve out of 30 drug-food homologous flowers' extracts significantly extended the lifespan of C. elegans, and the Eucommia ulmoides male flower was screened out by comparing centrally. The lifespan of C. elegans increased by 18.61% under the treatment of 100 µg mL-1 floral extract (EUFE). Interestingly, this effect was attenuated when EUFE was administered late or at higher concentrations. Significantly, EUFE improved health indicators that decline with aging including pharyngeal pumping, mobility, muscle morphology, and lipofuscin accumulation. EUFE also enhanced the resistance of C. elegans to oxidative/heat stress. The longevity-extending effect of EUFE was dependent on transcription factor DAF-16 and mitochondrial function. Moreover, EUFE triggered the nuclear translocation of DAF-16 and promoted downstream LGG-1 and SOD3 protein expression. In body-wall muscles, EUFE stimulated mitochondrial fission and mitophagy to mitigate age-related mitochondrial impairments. The transcriptional checkpoints of daf-16, drp-1, eat-3, lgg-1, and dct-1 further showed that EUFE regulated DAF-16 signaling and mitochondrial homeostasis. Finally, the interpretation of the EUFE components by correlation analysis, UHPLC-QE-MS, and verification experiments showed that aucubin, geniposide, and asperuloside are the main active compounds. We revealed the excellent lifespan/healthspan-promoting efficacy of EUFE and highlighted that edible flowers are worthy of further investigation as anti-aging dietary resources. Meanwhile, related mechanisms enriched the hypothesis that mitochondria might be involved in the healthspan modulation of longevity pathways.

Titanium-Catalyzed Exhaustive Reduction of Oxo-Chemicals.

Catalytic reduction of carboxylic acids and derivatives all the way to their corresponding methyl-compounds is very rare and still challenging for homogeneous transition-metal catalysis. Herein, we report an unprecedented and general catalytic exhaustive reduction of carboxylic functional group straightforwardly to a methyl group. This reaction was achieved using earth-abundant and readily available titanium as a catalyst. Our system has broad functional group tolerance and works for various other types of oxo-chemicals such as alcohols, aldehydes, ketones, lactones, and carboxylates (>100 examples). Preliminary mechanistic studies revealed that the in situ-generated TiIII -H species was vital for this transformation.

Stigmasterol attenuates inflammatory response of microglia via NF-κB and NLRP3 signaling by AMPK activation.

Alzheimer's disease (AD) is the most common cause of dementia in the elderly. Although its pathogenesis remains unclear, studies have indicated microglia-mediated neuroinflammation playing an important role. Phytosterols are a class of natural compounds presented in food, and have anti-inflammatory abilities. Recent studies suggested that phytosterols can traverse the blood-brain barrier and enter the brain, however, it remains largely unknown that whether phytosterols affect neuroinflammation in the AD pathogenesis. Here, we used APPswe/PS1dE9 mice as the animal model of AD, and found that stigmasterol treatment attenuated cognitive deficits, and decreased Aß42 concentration in cortex and hippocampus. Stigmasterol treatment also suppressed neuroinflammation, by reducing pro-inflammatory cytokine levels and microglia activation. Next, we simulated BV2 cells with Aß42 oligomers, which induced inflammatory responses of microglia. Stigmasterol protected BV2 cells against Aß42 oligomers induced inflammation, and mediated secretion of pro-inflammatory cytokines via NF-κB and NLRP3 signaling pathways by AMPK activation. Stigmasterol also alleviated the M1 polarization of BV2 cells. In general, our study demonstrates that stigmasterol ameliorated neuroinflammation in APP/PS1 mice, and suppressed inflammatory response of microglia to Aß42 oligomers via AMPK/NF-κB and AMPK/NLRP3 signaling, which provides a mechanistic insight for stigmasterol in anti-inflammation and AD therapy.

Visible-Light-Promoted Unsymmetrical Phosphine Synthesis from Benzylamines.

Herein, by applying visible-light photoredox catalysis, we have achieved the catalytic deaminative alkylation of diphenylphosphine and phenyl phosphine with benzylamine-derived Katritzky salts at room temperature. The use of Eosin Y as photoredox catalyst and visible light can largely promote the reaction. A series of unsymmetrical tertiary phosphines were successfully synthesized, including phosphines with three different substituents that are otherwise difficult to obtain.

Exploration of Osmanthus fragrans Lour.'s composition, nutraceutical functions and applications.

Osmanthus fragrans (Thunb.) Lour. has been cultivated in China for over 2500 years. Due to the unique and strong fragrance, O. fragrans flowers have long been added into food, tea, and beverages. Not only the O. fragrans flowers, but also leaves, barks, roots, and fruits possess some beneficial effects such as relieving pain and alleviating cough in Traditional Chinese Medicine. Modern pharmacological researches demonstrated that O. fragrans possesses a broad spectrum of biological activities including antioxidant, neuroprotective, antidiabetic and anticancer activities etc. A large number of phytochemicals identified in O. fragrans are responsible for its health promoting and disease preventing effects. The components of volatile compounds in O. fragrans are complex but the content is less abundant. The present review mainly focuses on the bioactive ingredients identified from O. fragrans, the therapeutic effects of O. fragrans and its applications in food, cosmetics and medicines.

Linking phytosterols and oxyphytosterols from food to brain health: origins, effects, and underlying mechanisms.

Phytosterols and their oxidation products, namely oxyphytosterols, are natural compounds present in plant foods. With increased intake of phytosterol-enriched functional food products, the exposure of both phytosterols and oxyphytosterols is rising. Over the past ten years, researches have been focused on their absorption and metabolism in human body, as well as their biological effects. More importantly, recent studies showed that phytosterols and oxyphytosterols can traverse the blood-brain barrier and accumulate in the brain. As brain health problems resulting from ageing being more serious, attenuating central nervous system (CNS) disorders with active compounds in food are becoming a hot topic. Phytosterols and oxyphytosterols have been shown to implicated in cognition altering and the pathologies of several CNS disorders, including Alzheimer's disease and multiple sclerosis. We will overview these findings with a focus on the contents of phytosterols and oxyphytosterols in food and their dietary intake, as well as their origins in the brain, and illustrate molecular pathways through which they affect brain health, in terms of inflammation, cholesterol homeostasis, oxidative stress, and mitochondria function. The existing scientific gaps of phytosterols and oxyphytosterols to brain health in knowledge are also discussed, highlighting research directions in the future.

Site-Fixed Hydroboration of Terminal and Internal Alkenes using BX3 /i Pr2 NEt*.

An unprecedented and general hydroboration of alkenes with BX3 (X=Br, Cl) as the boration reagent in the presence of i Pr2 NEt is reported. The addition of i Pr2 NEt not only suppresses alkene polymerization and haloboration side reactions but also provides an "H" source for hydroboration. More importantly, the site-fixed installation of a boryl group at the original position of the internal double bond is readily achieved in contrast to conventional transition-metal-catalyzed hydroboration processes. Further application to the synthesis of 1,n-diborylalkanes (n=3-10) is also demonstrated. Preliminary mechanistic studies reveal a major reaction pathway that involves radical species and operates through a frustrated Lewis pair type single-electron-transfer mechanism.

Effects of soil amendments on fractions and stability of soil organic matter in saline-alkaline paddy.

Soil amelioration is an effective practice to alleviate the adverse effects of soil salinization. However, increasing the fertility of salt-affected soils has been challenging, particularly in coastal saline-alkaline paddy soils. Here, we carried out a 45-day incubation experiment to evaluate the impacts of soil amendments on fractions and stability of soil organic matter (SOM) in a saline-alkaline paddy. The experiment simulates the flooding-draining practice and consists of CaCO3, gypsum and biochar amendments using different fertility soils. We measured dissolved organic carbon (DOC) and nitrogen (DON) in supernatant liquids, water-soluble cations, water extractable organic carbon (WEOC) and nitrogen (WEON), and microbial biomass carbon (MBC) and nitrogen (MBN) in soils after the incubation. Results showed that water soluble sodium (Na+) was significantly decreased under all amendments (by 17%-32%), except in high fertility soil. We found a significant decrease in DOC (by 36%-47%) under gypsum treatment, but in DON (by 18%-59%) under biochar treatment. However, there was no significant effect on DOC or DON under CaCO3 treatment. Gypsum treatment led to decreased WEOC content (by 0.067%-5.4%), but increased MBC (by 0.16%-44%) and MBN (by 8.3%-37%) in all soils. Biochar treatment caused a decrease in the ratios of WEOC to soil organic carbon (SOC) and WEON to total nitrogen (TN), and an increase in MBC:SOC and MBN:TN ratios. These results suggest that gypsum and biochar amendments can enhance SOM stability in the saline-alkaline paddy. However, SOM stability was not enhanced under CaCO3 treatment, probably due to the presence of a large amount of Na+ in these soils. Our study highlights that soil amelioration has different effects on soil carbon and nitrogen cycles in the saline-alkaline paddy soils, which is associated with water-logged condition.

Catalytic Boration of Alkyl Halides with Borane without Hydrodehalogenation Enabled by Titanium Catalyst.

An unprecedented and general titanium-catalyzed boration of alkyl (pseudo)halides (alkyl-X, X=I, Br, Cl, OMs) with borane (HBpin, HBcat) is reported. The use of titanium catalyst can successfully suppress the undesired hydrodehalogenation products that prevail using other transition-metal catalysts. A series of synthetically useful alkyl boronate esters are readily obtained from various (primary, secondary, and tertiary) alkyl electrophiles, including unactivated alkyl chlorides, with tolerance of other reducing functional groups such as ester, alkene, and carbamate. Preliminary studies on the mechanism revealed a possible radical reaction pathway. Further extension of our strategy to aryl bromides is also demonstrated.

Natural P-gp inhibitor EGCG improves the acteoside absorption in Caco-2 cell monolayers and increases the oral bioavailability of acteoside in rats.

Acteoside is one of the most widespread phenylethanoid glycosides with pharmacological activities, including antioxidant, neuroprotective property, etc. However, its bioavailability is poor due to the low absorption and P-gp efflux. This study aimed to select food derived P-gp inhibitors for promoting the acteoside absorption and investigate whether the inhibitors could increase the bioavailability and stability of acteoside. Results showed that EGCG and quercetin significantly decreased the BL-to-AP efflux and promoted the AP-to-BL influx of acteoside across Caco-2 monolayers with optimum concentrations of 320 µM EGCG or 240 µM quercetin adding to 320 µM acteoside. EGCG increased the bioavailability of acteoside to 1.43-fold, but quercetin had no such effect. Further study showed that EGCG and quercetin had no effects on the storage and digestion stability of acteoside. This work revealed that EGCG could improve the acteoside absorption across the Caco-2 monolayers and enhance the bioavailability of acteoside in rats.

Visible-Light-Promoted Photoredox Dehydrogenative Coupling of Phosphines and Thiophenols.

Herein, by applying visible-light photoredox catalysis, we have now achieved the first example of catalytic dehydrogenative coupling of phosphines and thiophenols that proceeds at room temperature. Key to our success is the use of benzaldehyde as a soft oxidant, which avoids the issue of phosphine oxidation. Furthermore, we observed the unexpected dealkylative coupling of secondary and tertiary alkylphosphine with thiophenols.

Therapeutic potential of phenylethanoid glycosides: A systematic review.

Phenylethanoid glycosides (PhGs) are generally water-soluble phenolic compounds that occur in many medicinal plants. Until June 2020, more than 572 PhGs have been isolated and identified. PhGs possess antibacterial, anticancer, antidiabetic, anti-inflammatory, antiobesity, antioxidant, antiviral, and neuroprotective properties. Despite these promising benefits, PhGs have failed to fulfill their therapeutic applications due to their poor bioavailability. The attempts to understand their metabolic pathways to improve their bioavailability are investigated. In this review article, we will first summarize the number of PhGs compounds which is not accurate in the literature. The latest information on the biological activities, structure-activity relationships, mechanisms, and especially the clinical applications of PhGs will be reviewed. The bioavailability of PhGs will be summarized and factors leading to the low bioavailability will be analyzed. Recent advances in methods such as bioenhancers and nanotechnology to improve the bioavailability of PhGs are also summarized. The existing scientific gaps of PhGs in knowledge are also discussed, highlighting research directions in the future.

Facile fabrication of functional hydrogels consisting of pullulan and polydopamine fibers for drug delivery.

With the rapid development of biomedicine applications, more flexible and efficient fabrication strategies are required for drug delivery vehicles. Naturally resourced polymers have gained considerable attention for construction of drug carriers. Here, biocompatible hydrogel reservoir system (named PHG-PDA) based on pullulan and polydopamine (PDA) are designed and fabricated by one-pot incorporation of PDA fibers into pullulan hydrogel (PHG). The structure and performance of the PHG-PDAs can be nicely adjusted by regulating the content of PDA fibers in precursor hydrogel solutions. Crystal violet is used as a drug prototype and introduced into hydrogels via swelling-diffusion approach. We found that the drug loading process followed the pseudo-second-order model and Langmuir isotherm model, while the drug releasing process was pH-responsive, and the cumulative release reached 60.3% and 87% at pH 7.4 and 5.0, respectively. In vitro cytotoxicity studies on L929 cells demonstrated that our hydrogels were nontoxic even in a high concentration (3.4 mg/mL). In sum, these biocompatible PHG-PDAs with tunable physicochemical properties are promising systems for drug delivery.

Zirconium-Catalyzed Atom-Economical Synthesis of 1,1-Diborylalkanes from Terminal and Internal Alkenes.

A general and atom-economical synthesis of 1,1-diborylalkanes from alkenes and a borane without the need for an additional H2 acceptor is reported for the first time. The key to our success is the use of an earth-abundant zirconium-based catalyst, which allows a balance of self-contradictory reactivities (dehydrogenative boration and hydroboration) to be achieved. Our method avoids using an excess amount of another alkene as an H2 acceptor, which was required in other reported systems. Furthermore, substrates such as simple long-chain aliphatic alkenes that did not react before also underwent 1,1-diboration in our system. Significantly, the unprecedented 1,1-diboration of internal alkenes enabled the preparation of 1,1-diborylalkanes.

Phenolic acid profiles of common food and estimated natural intake with different structures and forms in five regions of China.

Phenolic acids have been reported to have many biological activities, but daily intake information is scarce. In this study, the phenolic acid contents of 116 commonly consumed food in five regions of China (Beijing, Hangzhou, Wuhan, Chongqing and Guangzhou) were analyzed by high performance liquid chromatography-mass spectrometry (HPLC-MS) and dietary intakes estimated. Tea had the highest total phenolic acids (TPA) content in all regions investigated. Phenolic acids were in esterified and bound forms, and hydroxycinnamic acids accounted for more than half of TPA content, except in tea and legumes. Average TPA intake was 193.50 mg/ day at the national level but ranged from 157.09 to 263.01 mg/ day among the regions. Rice, tea, and fruits were the main contributors to dietary intakes of TPA. Also, TPA intake in the period 2009-2013 increased 31.65 mg/ day compared with 2002, largely due to increased intakes of fruits, vegetables, and legumes.