Improved antioxidant activity and delivery of peppermint oil Pickering emulsion stabilized by resveratrol-grafted zein covalent conjugate/quaternary ammonium chitosan nanoparticles.

Novel nanoparticles (Z-R/H) were successfully fabricated by a resveratrol-grafted zein covalent conjugate (Z-R) combined with quaternary ammonium chitosan (HTCC), which were used as stabilizers to prepare peppermint oil (PO) Pickering emulsions with antioxidant activity. HTCC effectively adjusted wettability of Z-R conjugate, and three-phase contact angle of Z-R/H3:1 was moderate (95.01°). The influencing factors of Pickering emulsion formation, including volume fraction of PO, concentration of Z-R/H, and mass ratio of Z-R to HTCC, were evaluated by droplet size, ζ-potential, microscopic observation, and stability index analysis. Pickering emulsions stabilized by Z-R/H3:1 showed excellent physical stability under heat treatment. Z-R/H nanoparticles adsorbed on the oil-water interface yielded a dense filling layer as a physical barrier to improve the emulsion stability, which was validated by confocal laser-scanning microscopy. After 4 weeks of storage, retention rate of PO in Pickering emulsion stabilized by Z-R/H3:1 remained high (72.1 %). Electronic nose analysis showed that Z-R/H3:1-stabilized emulsion effectively prevented volatilization of PO aroma components. Additionally, PO and Z-R/H nanoparticles provided an additive antioxidant effect of Pickering emulsions against DPPH and ABTS free radicals. In summary, these novel Z-R/H nanoparticle offer promising applications as a stabilizer with great potential in preparing functional Pickering emulsions to improve essential oil delivery.

Preparation of alginate-whey protein isolate and alginate-pectin-whey protein isolate composites for protection and delivery of Lactobacillus plantarum.

Probiotics are sensitive to external conditions, resulting in low survival rates after being ingested or during food production, transportation and storage. In order to improve the survival rate of Lactobacillus plantarum (LP) during gastrointestinal digestion, storage, and freeze-drying, alginate-whey protein isolate (ALG-WPI) and alginate-pectin-whey protein isolate (ALG-PEC-WPI) composites were employed to encapsulate LP. The encapsulation efficiency of ALG-WPI-LP and ALG-PEC-WPI-LP beads both reached more than 99 %. Scanning electron microscopy (SEM) indicated that dense and rough aggregates were formed on the surface of both composites, and attached LP cells could be observed inside the beads. The ALG-WPI and ALG-PEC-WPI composites can protect the viability of LP in simulated gastric fluid (SGF) and release the probiotics in simulated intestinal fluid (SIF). The storage stability of LP at 4 °C was improved by about 15 % in comparison with bare LP and the survival rates of LP in ALG-WPI-LP and ALG-PEC-WPI-LP powders after freeze-drying were increased by 65.37 % and 72.06 %, respectively. The formation mechanism of ALG-WPI and ALG-PEC-WPI composites was further explored by fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The ALG-WPI and ALG-PEC-WPI composites have great potential to protect and deliver probiotics in food systems.

Preparation of zein-lecithin-EGCG complex nanoparticles stabilized peppermint oil emulsions: Physicochemical properties, stability and intelligent sensory analysis.

Peppermint oil emulsions were prepared by using zein-lecithin-EGCG (Z-L/E) complex nanoparticles as emulsifiers. The preparation conditions of emulsions were optimized via measuring the particle size, surface tension and stability of emulsions, and peppermint oil of 3% (particle size = 375 nm, polydispersity index (PDI) = 0.45), the zein:lecithin ratio of 4:1 (w/w) (particle size = 396 nm), and the zein:EGCG ratio of 10:1 (w/w) (surface tension = 47.32 N/m) was the optimal condition. The rapid stability analysis showed that the instability mechanism of emulsions was ascribed to creaming and stratification, and the stability mechanism of emulsions was explored, indicating that the complex nanoparticles adsorbed on the surface of oil droplets to give Pickering emulsions. Electronic tongue experiments showed that the Z-E/L4:1 stabilized emulsion was distinguished from the other three samples due to its good stability. The electronic nose experiment could distinguish the emulsions with different droplet sizes.

Exploration of the Microstructure and Rheological Properties of Sodium Alginate-Pectin-Whey Protein Isolate Stabilized Β-Carotene Emulsions: To Improve Stability and Achieve Gastrointestinal Sustained Release.

Sodium alginate (SA)-pectin (PEC)-whey protein isolate (WPI) complexes were used as an emulsifier to prepare ß-carotene emulsions, and the encapsulation efficiency for ß-carotene was up to 93.08%. The confocal laser scanning microscope (CLSM) and scanning electron microscope (SEM) images showed that the SA-PEC-WPI emulsion had a compact network structure. The SA-PEC-WPI emulsion exhibited shear-thinning behavior and was in a semi-dilute or weak network state. The SA-PEC-WPI stabilized ß-carotene emulsion had better thermal, physical and chemical stability. A small amount of ß-carotene (19.46 ± 1.33%) was released from SA-PEC-WPI stabilized ß-carotene emulsion in simulated gastric digestion, while a large amount of ß-carotene (90.33 ± 1.58%) was released in simulated intestinal digestion. Fourier transform infrared (FTIR) experiments indicated that the formation of SA-PEC-WPI stabilized ß-carotene emulsion was attributed to the electrostatic and hydrogen bonding interactions between WPI and SA or PEC, and the hydrophobic interactions between ß-carotene and WPI. These results can facilitate the design of polysaccharide-protein stabilized emulsions with high encapsulation efficiency and stability for nutraceutical delivery in food and supplement products.

Fabrication and characterization of oil-in-water pickering emulsions stabilized by ZEIN-HTCC nanoparticles as a composite layer.

In this work, the ZEIN-HTCC nanoparticles formed by zein and N-(2-hydroxy)propyl-3-trimethylammonium chitosan chloride (HTCC) were used as stabilizers to prepare oil-in-water (O/W) Pickering emulsions. The preparation conditions including shearing time, volume fraction of corn oil, mass ratio of ZEIN:HTCC and total concentration of ZEIN-HTCC of emulsions were optimized by measuring the droplet size, zeta potential, PDI and surface tension of emulsions. The ZEIN-HTCC emulsions are stable at the pH range of 4-9 and in the low salt ion concentrations up to 0.2 mol L-1, and can keep stable up to 21 d during low temperature storage. Fourier transform infrared spectroscopy (FTIR), the confocal laser scanning microscope (CLSM) and scanning electron microscopy (SEM) were used to analyze the interaction between emulsion components, revealing that zein and HTCC form a composite layer by flocculation to adsorb on the surface of oil droplets, thus preventing emulsion droplets from aggregation. This novel, long-term stable, surfactant-free, and edible zein-based Pickering emulsion could be used as potential carriers for lipophilic nutrients delivery.

The regulation of sodium alginate on the stability of ovalbumin-pectin complexes for VD3 encapsulation and in vitro simulated gastrointestinal digestion study.

The ovalbumin (OVA)-pectin (PEC)-sodium alginate (SA)-Vitamin D3 (VD3) complex nanoparticles were fabricated by antisolvent precipitation method, and the excellent encapsulation efficiency and loading capacity of VD3 were obtained by 96.6% and 2.8%, respectively. Compared with ternary OVA-PEC-VD3 complexes, the addition of SA with strong negative charge effectively regulated the OVA-PEC complexes and significantly improved the stability of OVA-PEC-SA-VD3 complex nanoparticles with preferable size as small as 126 nm. The storage stability was also investigated after low temperature storage for 31 d, and the particle size of quaternary complexes was increased only 40 nm. In vitro digestion results elucidated that the complex nanoparticles had good stability in the simulated gastric fluid, and almost completely released in the simulated intestinal fluid confirmed by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) experiments and scanning electron microscope (SEM) images. The release kinetics study clarified that it was close to Fick release. Fluorescence and Fourier transform infrared spectroscopy (FTIR) experiments showed that quaternary complex nanoparticles were mainly combined by electrostatic, hydrophobic and hydrogen bonding interactions. The novel quaternary protein-polysaccharide complexes have excellent stability and great sustained-release performance for VD3, which may be helpful for the digestion and absorption of vitamin by human body, thus have potential applications in the food and drug industry.

Improved Stability and Targeted Cytotoxicity of Epigallocatechin-3-Gallate Palmitate for Anticancer Therapy.

Although with high antioxidant activity, epigallocatechin-3-gallate (EGCG) was restricted by its poor chemical stability in practical applications. One of EGCG derivatives, EGCG palmitate, was synthesized with EGCG and palmitoyl chloride to overcome instability of EGCG. However, uncertainties still exist in chemical stability and cytotoxicity of EGCG palmitate, which are essential for further exploration in anticancer therapy. Our work aims to analyze the resistance of EGCG palmitate to oxidation and summarize its targeted inhibition efficiency on cancerous cells and normal cells. High-performance liquid chromatography analysis confirmed that EGCG palmitate remained stable in air and Dulbecco's modified eagle medium (DMEM) for a longer time than EGCG. Antioxidative and pro-oxidative effects of EGCG palmitate on treated cells are proposed through reactive oxygen species (ROS) detection, respectively. It reveals that pro-oxidants by H2O2 production can exert antiproliferative and proapoptotic effects on cancerous cells and stimulate autophagy, while an antioxidant relieves oxidative stress caused by superoxide as compared to normal cells. Consequently, targeted cytotoxicity is adopted by EGCG palmitate-treated cancerous cells. Results above manifest that EGCG palmitate possesses potential to serve as a promising prodrug in anticancer treatment.

Duo of (-)-epigallocatechin-3-gallate and doxorubicin loaded by polydopamine coating ZIF-8 in the regulation of autophagy for chemo-photothermal synergistic therapy.

To achieve highly systemic therapeutic efficacy, chemotherapy is combined with photothermal therapy for chemo-photothermal synergistic therapy; however, this strategy suffers from high toxicity and unsatisfactory sensitivity for cancer cells. Herein, we developed a pH- and photothermal-responsive zeolitic imidazolate framework (ZIF-8) compound for loading a dual-drug in the tumor site and improving their curative effects. Since autophagy always accompanies tumor progression and metastasis, there is an unmet need for an anticancer treatment related to the regulation of autophagy. Green tea polyphenols, namely, (-)-epigallocatechin-3-gallate (EGCG) and doxorubicin (DOX), both of which exhibit anticancer activity, were dual-loaded via polydopamine (PDA) coating ZIF-8 (EGCG@ZIF-PDA-PEG-DOX, EZPPD for short) through hierarchical self-assembly. PDA could transfer photothermal energy to increase the temperature under near-infrared (NIR) laser irradiation. Due to its pH-response, EZPPD released EGCG and DOX in the tumor microenvironment, wherein the temperature increased with the help of PDA and NIR laser irradiation. The duo of DOX and EGCG induced autophagic flux and accelerated the formation of autophagosomes. In a mouse HeLa tumor model, photothermal-chemotherapy could ablate the tumor with a significant synergistic effect and potentiate the anticancer efficacy. Thus, the results indicate that EZPPD renders the key traits of a clinically promising candidate to address the challenges associated with synergistic chemotherapy and photothermal utilization in antitumor therapy.

A combined experimental and theoretical study on the structures, interactions and volumetric properties of guanidinium-based ionic liquid mixtures.

Mixtures of ionic liquids (ILs) have shown their potential in both physical and chemical processes, regarded as alternatives to common ILs. In this work, four guanidinium-based ILs, 2-ethyl-1,1,3,3-tetramethylguanidinium ethyl sulfate ([TMG(C2)][C2OSO3]) and bis(trifluoromethylsulfonyl)imide ([TMG(C2)][NTf2]), and 2,2-diethyl-1,1,3,3-tetramethylguanidinium ethyl sulfate ([TMG(C2)2][C2OSO3]) and bis(trifluoromethylsulfonyl)imide ([TMG(C2)2][NTf2]), are employed to investigate the structures, interactions and properties of four systems of IL-IL binary mixtures, including [TMG(C2)][C2OSO3]x[NTf2]1-x, [TMG(C2)]x[TMG(C2)2]1-x[C2OSO3], [TMG(C2)]x[TMG(C2)2]1-x[NTf2] and [TMG(C2)2][NTf2]x[C2OSO3]1-x. Combining experiments with theory, the relationships among H-bond interactions, structures and volumetric properties have been revealed. 1H NMR characterizations show the changes of H-bond interactions in the IL-IL mixtures in relation to composition, and DFT calculations reveal significant cation-anion interactions through the active hydrogen atom (N+-H) and the methyl groups in the cations with the anions in the manner of HO and HF. The ethyl group in the [C2OSO3]- anion hardly forms interactions with other components. The size effect of the calculated system has been evaluated for the IL-IL clusters with 2, 4 and 8 ions. Different structures due to variation of cationic and anionic species have remarkable influence on the volumetric properties of the IL-IL mixtures. Negative excess molar volume (VEm) is found in [TMG(C2)]x[TMG(C2)2]1-x[C2OSO3], and it is caused by the close packing of ions. Positive VEm values indicate that interaction loss occurs in the other three systems, where a linear arrangement or square packing of ions with low space utilization is found.

DFT studies on mechanistic origins of ligand-controlled selectivity in Pd-catalyzed non-decarbonylative and decarbonylative reductive conversion of acyl fluoride.

The mechanisms and origins for ligand-controlled non-decarbonylative and decarbonylative conversions of acyl fluorides catalyzed by palladium catalysts with different ligands tricyclohexylphosphine (PCy3) and 1,2-bis(dicyclohexylphosphino)ethane (DCPE) have been investigated by density functional theory (DFT) calculations. In the case of the DCPE ligand, the favorable catalytic cycle contains four steps, oxidative addition, decarbonylation, transmetallation and reductive elimination. In the case of the PCy3 ligand, the favorable catalytic cycle proceeds by three steps, oxidative addition, transmetallation and reductive elimination. Distortion/interaction analysis indicated that decarbonylation does not occur for PCy3 owing to the repulsive interaction between PCy3 and substrates. Present calculations agree with the experimental observations and understanding these surprising ligand-controlled non-decarbonylative and decarbonylative selectivity reactions could provide important insights into the development of selective catalyst systems.

Non-innocent PNN ligand is important for CO oxidation by N2O catalyzed by a (PNN)Ru-H pincer complex: insights from DFT calculations.

Milstein et al. developed an efficient and mild method for CO oxidation by N2O to give CO2 and N2 catalyzed by a (PNN)Ru-H pincer complex. To gain mechanistic information on this catalytic transformation, the reaction mechanism has been studied using density functional theory (DFT) calculations. It was found that the catalytic cycle for CO oxidation by N2O proceeds in three stages: N2O activation to form a (PNN)Ru-OH intermediate, CO insertion into the Ru-OH bond to form a (PNN)Ru-COOH intermediate and CO2 release from (PNN)Ru-COOH. In the CO2 release stage, CO2 is not released via a ß-H elimination mechanism as proposed in experiments, instead it is released via a deprotonation mechanism. The calculations demonstrated that the Ru-H bond of the catalyst plays an important role in facilitating the activation of N2O, which is the rate-determining step for the whole catalytic cycle, and the non-innocent PNN ligand is very important for CO oxidation by N2O. Our theoretical results are consistent with the experimental observations and could help design highly efficient catalysts for N2O activation.

FA-PEG decorated MOF nanoparticles as a targeted drug delivery system for controlled release of an autophagy inhibitor.

A zeolitic imidazolate framework (ZIF-8) with high loading capacity and pH-responsive properties, an important subclass of metal-organic frameworks (MOFs), has become a promising material for drug delivery. A multifunctional drug delivery system (DDS) was designed in this work for effective targeting delivery of chloroquine diphosphate (CQ) as an autophagy inhibitor. The ZIF-8 nanoparticles encapsulating CQ (CQ@ZIF-8 NPs) were fabricated by a simple one-pot method and were then decorated with methoxy poly(ethylene glycol)-folate (FA-PEG), a special identifier of cancer cells, to form FA-PEG/CQ@ZIF-8. The target identification of FA-PEG/CQ@ZIF-8 NPs, compared with CQ@ZIF-8 NPs, leads to an increasing number of NPs being internalized into HeLa cells, which decreases the loss of drugs and results in high cytotoxicity of CQ for cancer cells. The lower viabilities of HeLa cells (cancer cells) and higher viabilities of HEK293 cells (healthy cells) treated with FA-PEG/CQ@ZIF-8 NPs show that the special target for cancer cells results from the combinations of folic acid and folate receptors on the surface of HeLa cells. The quantitative measurements of autophagy-related proteins and the detection of autophagy flux in HeLa cells suggest that the autophagosome formation and autophagy flux are appreciably blocked after the cells are treated with FA-PEG/CQ@ZIF-8 NPs. The ZIF-8 can disintegrate only under low pH conditions, resulting in fast and full release of CQ. The pH-responsive and tumor-targeted properties of the NPs can control the drug release and enhance the efficiency of autophagy inhibition. It indicates that the FA-PEG/CQ@ZIF-8 NPs combining target identification with controlled drug release can be used as a novel model for discussing targeted cancer therapy and inhibiting the autophagy of cancer cells.

Derivative of Epigallocatechin-3-gallatea Encapsulated in ZIF-8 with Polyethylene Glycol-Folic Acid Modification for Target and pH-Responsive Drug Release in Anticancer Research.

Epigallocatechin-3-gallatea (EGCG), a key component of tea, has been found to have anticancer activity but poor stability. To improve its antioxidative stability and widen the application of EGCG in anticancer therapy, a kind of EGCG derivative, EGCG palmitate (PEGCG), was synthesized and encapsulated in ZIF-8 nanoparticles with functionalization of folic acid (FA), which is commonly used as pH-responsive drug carrier. PEGCG encapsulated in polyethylene glycol (PEG)-FA/ZIF-8 nanoparticles (PEG-FA/PEGCG@ZIF-8 NPs) exhibits sixfold improvement of stability compared to that of free PEGCG. With target recognition between folic acid (FA) on the surface of NPs and overexpressed FA receptor (FR) in cancer cells, the NPs can be efficiently internalized into cells and present targeted effects of inhibition growth on HeLa cells (cancer cells) compared with HEK 293 cells (normal cells), consistent with the regulation of reactive oxygen species (ROS) level and the induction of autophagy. The detection of autophagy flux and the measurement of autophagy marked proteins in cells suggest that autophagy flux and the autophagosome formation are appreciably induced when the cells were treated with PEG-FA/PEGCG@ZIF-8 NPs. It indicates that pH-responsive PEG-FA/PEGCG@ZIF-8 NPs with target identification for cancer cells can be used as highly efficient drug carriers in targeting cancer chemotherapy.

MOF Nanoparticles with Encapsulated Autophagy Inhibitor in Controlled Drug Delivery System for Antitumor.

High porosities, large surface areas, and tunable functionalities made metal-organic frameworks (MOFs) as effective carriers for drug delivery. One of the most promising MOFs is the zeolitic imidazolate framework (ZIF-8) crystal, an advanced functional material for small-molecule delivery, due to its high loading ability and pH-sensitive degradation. As a novel carrier, ZIF-8 nanoparticles were used in this work to control the release of an autophagy inhibitor, 3-methyladenine (3-MA), and prevent it from dissipating in a large quantity before reaching the target. The cellular uptake in HeLa cells of 3-MA encapsulated in ZIF-8 (3-MA@ZIF-8 NPs) is facilitated through the nanoparticle internalization with reference to TEM observations and the quantitative analyses of zinc by ICP-MS. The autophagy-related proteins and autophagy flux in HeLa cells treated with 3-MA@ZIF-8 NPs show that the autophagosome formation is significantly blocked, which reveals that the pH-sensitive dissociation increases the efficiency of autophagy inhibition at the equivalent concentration of 3-MA. In vivo experiments, when compared to free 3-MA, 3-MA@ZIF-8 NPs show a higher antitumor efficacy and repress the expression of autophagy-related markers, Beclin 1 and LC3. It follows that ZIF-8 is an efficient drug delivery vehicle in antitumor therapy, especially in inhibiting autophagy of cancer cells.

Why different ligands can control stereochemistry selectivity of Ni-catalyzed Suzuki-Miyaura cross-coupling of benzylic carbamates with arylboronic esters: a mechanistic study.

Quantum chemistry calculations have been employed to study the mechanisms of nickel-catalyzed Suzuki-Miyaura cross-coupling reactions of benzylic carbamates with arylboronic esters, and the energy profiles have been computed to evaluate possible origins for the generation of different stereochemistry products. It has been demonstrated that the mechanism can be divided into three steps: oxidative addition, transmetallation and reduction elimination. Transmetallation is the rate-limiting step for the whole reaction cycle, and oxidative addition controls the stereoselectivity of the resulting products. Two possible pathways for the transmetallation step were proposed to consider the presence and absence of a base, and the results indicated that the former is energetically more favorable. Different ligands of nickel catalysts yield two kinds of stereochemistry products. For a phosphine ligand, an R product is afforded while for the N-heterocyclic carbene ligand, an S product is afforded. The distortion/interaction energy analysis and percent buried volume models have been performed to illustrate the origins of reaction stereoselectivity, and the interactions between catalysts and organic moieties control the stereoselectivity for both Ni(PMe3) and Ni(SIMes) catalysts.

Dehydrogenation of benzyl alcohol with N2O as the hydrogen acceptor catalyzed by the rhodium(i) carbene complex: insights from quantum chemistry calculations.

The detailed mechanisms of the dehydrogenation of benzyl alcohol with N2O as the hydrogen acceptor catalyzed by the rhodium(i) carbene complex for the formation of the corresponding carboxylic acid or ester have been investigated via density functional theory (DFT) calculations at the M06 level of theory. Three cycles were considered for the formation of benzaldehyde, benzyl benzoate and benzoic acid. On the basis of the calculations, the rate-determining step for these three cycles is involved in N2O activation by the rhodium ammine hydride complex with an activation barrier of only 22.6 kcal mol-1, which is different from the previous mechanism proposed by Gianetti and co-workers, where the hydride is transferred from the Rh atom to the oxygen atom of N2O with a barrier of 30.5 kcal mol-1. In addition, the calculations also demonstrated that one more N2O is necessary to give benzoic acid, and the reaction can only take place under anhydrous conditions. Present calculations are in good agreement with the experimental observations and provide new insights into the dehydrogenation of benzyl alcohol with N2O as the hydrogen acceptor.

Hydrophobic fractal surface from glycerol tripalmitate and the effects on C6 glioma cell growth.

To provide a biomimic environment for glial cell culture, glycerol tripalmitate (PPP) has been used as a raw material to prepare fractal surfaces with different degrees of hydrophobicity. The spontaneous formation of the hydrophobic fractal surfaces was monitored by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The surface morphologies were observed by a scanning electron microscope (SEM), and then the fractal dimension (FD) values of the surfaces were determined with the box-counting method. C6 glioma cells were cultured and compared on different hydrophobic PPP surfaces and poly-L-lysine (PLL)-coated surface. The cell numbers as a function of incubation time on different surfaces during the cell proliferation process were measured, and the cell morphologies were observed under a fluorescence microscope. Influences of hydrophobic fractal surfaces on the cell number and morphology were analyzed. The experimental results show that the cell proliferation rates decrease while the cell morphology complexities increase with the growth of the fractal dimensions of the PPP surfaces.

Antimicrobial activity and cytotoxicity of piperazinium- and guanidinium-based ionic liquids.

Twelve piperazinium- and guanidinium-based ionic liquids (ILs) were synthesized, and characterized by (1)H nuclear magnetic resonance (NMR), thermal gravimetric analyzer (TGA) and differential scanning calorimetry (DSC). The antimicrobial activity and cytotoxicity have been investigated to provide the information whether the newly synthesized ILs are toxic or not. The antimicrobial effects of these ILs on gram negative and gram positive bacteria are evaluated on the basis of the minimum inhibitory concentration (MIC) measurements. The membrane damages of bacteria in the presence of ILs are observed by scanning electron microscopy (SEM). The cytotoxicity data of the ILs on HEK-293 and C6 cells are obtained by MTT cell viability assay. The disruption of cell cycle is analyzed by the flow cytometry. The results show that most of the ILs exhibit low toxicity, and the ILs with tetrafluoroborate anion and with benzene ring on cation are the species with relatively high toxicity among the studied ILs. The fundamental data and results can provide some useful information for the further studies and applications of the ILs.

Oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives by nitrous oxide via selective oxygen atom transfer reactions: insights from quantum chemistry calculations.

The mechanisms for the oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives (Cp* = η(5)-C5Me5) by nitrous oxide via selective oxygen atom transfer reactions have been systematically studied by means of density functional theory (DFT) calculations. On the basis of the calculations, we investigated the original mechanism proposed by Hillhouse and co-workers for the activation of N2O. The calculations showed that the complex with an initial O-coordination of N2O to the coordinatively unsaturated Hf center is not a local minimum. Then we proposed a new reaction mechanism to investigate how N2O is activated and why N2O selectively oxidize phenyl and hydride ligands of . Frontier molecular orbital theory analysis indicates that N2O is activated by nucleophilic attack by the phenyl or hydride ligand. Present calculations provide new insights into the activation of N2O involving the direct oxygen atom transfer from nitrous oxide to metal-ligand bonds instead of the generally observed oxygen abstraction reaction to generate metal-oxo species.

Antibacterial Activity, in Vitro Cytotoxicity, and Cell Cycle Arrest of Gemini Quaternary Ammonium Surfactants.

Twelve gemini quaternary ammonium surfactants have been employed to evaluate the antibacterial activity and in vitro cytotoxicity. The antibacterial effects of the gemini surfactants are performed on Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) with minimum inhibitory concentrations (MIC) ranging from 2.8 to 167.7 µM. Scanning electron microscopy (SEM) analysis results show that these surfactants interact with the bacterial cell membrane, disrupt the integrity of the membrane, and consequently kill the bacteria. The data recorded on C6 glioma and HEK293 human kidney cell lines using an MTT assay exhibit low half inhibitory concentrations (IC50). The influences of the gemini surfactants on the cell morphology, the cell migration ability, and the cell cycle are observed through hematoxylin-eosin (HE) staining, cell wound healing assay, and flow cytometric analyses, respectively. Both the values of MIC and IC50 decrease against the growth of the alkyl chain length of the gemini surfactants with the same spacer group. In the case of surfactants 12-s-12, the MICs and IC50s are found to decrease slightly with the spacer chain length changing from 2 to 8 and again to increase at higher spacer length (s = 10-12). All of the gemini surfactants show great antibacterial activity and cytotoxicity, and they might exhibit potential applications in medical fields.