Renaissance of Chlorine Evolution Reaction: Emerging Theory and Catalytic Materials.

Chlorine (Cl2) is one of the most important commodity chemicals that has found widespread utility in chemical industry. Most Cl2 is currently produced via the chlorine evolution reaction (CER) at the anode of chlor-alkali electrolyzers, for which platinum group-metal (PGM)-based mixed metal oxides (MMOs) have been used for more than half a century. However, MMOs suffer from the use of expensive and scarce PGMs and face selectivity problems due to the parasitic oxygen evolution reaction. Over the last decade, the field of CER catalysis has seen dramatic advances in both the theory and discovery of new catalysts. Theoretical approaches have enabled a fundamental understanding of CER mechanisms and provided catalyst design principles. The exploration of new materials has led to the discovery of CER catalysts other than MMOs, including non-PGM oxides, atomically dispersed single-site catalysts, and organic molecules, with some of which following novel reaction pathways. This minireview provides an overview of the recent advances in CER electrocatalyst research and suggests future directions for this revitalized field.

Steering Catalytic Selectivity with Atomically Dispersed Metal Electrocatalysts for Renewable Energy Conversion and Commodity Chemical Production.

Electrocatalysis is a key driver in promoting the paradigm shift from the current fossil-fuel-based hydrocarbon economy to a renewable-energy-driven hydrogen economy. The success of electrocatalysis hinges primarily on achieving high catalytic selectivity along with maximum activity and sustained longevity. Many electrochemical reactions proceed through multiple pathways, requiring highly selective catalysts.Atomically dispersed metal catalysts have emerged as a new frontier in heterogeneous catalysis. In addition to the widely perceived advantages of maximized active site utilization and substantially reduced metal content, they have shown different catalytic selectivities in some electrocatalytic reactions compared to the traditional nanoparticle (NP)-based catalysts. Although there have been significant advances in their synthesis, the highly energetic nature of a single atomic site has made the preparation of atomically dispersed metal catalysts rely on empiricism rather than rational design. Consequently, the structural comprehension of a single atomic site and the understanding of its unusual electrocatalytic selectivity remain largely elusive.In this Account, we describe our endeavors toward developing general synthetic approaches for atomically dispersed metal catalysts for the discovery of new selective and active electrocatalysts and to understand their catalytic nature. We introduce synthetic approaches to produce a wide range of nonprecious- and precious-metal-based atomically dispersed catalysts and control their coordination environments. Metallomacrocyclic-compound-driven top-down and metal salt/heteroatom layer-based bottom-up strategies, coupled with a SiO2-protective-layer-assisted method, have been developed that can effectively generate single atomic sites while mitigating the formation of metallic NPs. The low-temperature gas-phase ligand exchange method can reversibly tune the coordination structure of the atomically dispersed metal sites. We have used the prepared atomically dispersed metal catalysts as model systems to investigate their electrocatalytic reactivity for renewable energy conversion and commodity chemical production reactions, in which high selectivity is important. The reactions of our interest include the following: (i) the oxygen reduction reaction, where O2 is reduced to either H2O or H2O2 via the four-electron or two electron pathway, respectively; (ii) the CO2 reduction reaction, which should suppress the hydrogen evolution reaction; and (iii) the chlorine evolution reaction, which competes with the oxygen evolution reaction. The type of metal center to which the reactant is directly bound is found to be the most important in determining the selectivity, which originates from the dramatic changes in the binding energy of each metal center with the reactants. The coordination structure surrounding the metal center also has a significant effect on the selectivity; its control can modulate the oxidation state of the metal center, thereby altering the binding strength with the reactants.We envisage that future advances in the synthesis of atomically dispersed metal catalysts, combined with the growing power of computational, spectroscopic, and microscopic methods, will bring their synthesis to the level of rational design. Elaborately designed catalysts can overcome the current limits of catalytic selectivity, which will help establish the field of atomically dispersed metal catalysts as an important branch of catalysis.

Intermetallic PtCu Nanoframes as Efficient Oxygen Reduction Electrocatalysts.

Nanoframe alloy structures represent a class of high-performance catalysts for the oxygen reduction reaction (ORR), owing to their high active surface area, efficient molecular accessibility, and nanoconfinement effect. However, structural and chemical instabilities of nanoframes remain an important challenge. Here, we report the synthesis of PtCu nanoframes constructed with an atomically ordered intermetallic structure (O-PtCuNF/C) showing high ORR activity, durability, and chemical stability. We rationally designed the O-PtCuNF/C catalyst by combining theoretical composition predictions with a silica-coating-mediated synthesis. The O-PtCuNF/C combines intensified strain and ligand effects from the intermetallic PtCu L11 structure and advantages of the nanoframes, resulting in superior ORR activity to disordered alloy PtCu nanoframes (D-PtCuNF/C) and commercial Pt/C catalysts. Importantly, the O-PtCuNF/C showed the highest ORR mass activity among PtCu-based catalysts. Furthermore, the O-PtCuNF/C exhibited higher ORR durability and far less etching of constituent atoms than D-PtCuNF/C and Pt/C, attesting to the chemically stable nature of the intermetallic structure.

Schisandrin C Affects Glucose-Stimulated Insulin Secretion in Pancreatic ß-Cells and Glucose Uptake in Skeletal Muscle Cells.

The aim of our study was to investigate the effect of three lignans (schisandrol A, schisandrol B, and schisandrin C) on insulin secretion in rat INS-1 pancreatic ß-cells and glucose uptake in mouse C2C12 skeletal muscle cells. Schisandrol A and schisandrin C enhanced insulin secretion in response to high glucose levels with no toxic effects on INS-1 cells. The effect of schisandrin C was superior to that of gliclazide (positive control), a drug commonly used to treat type 2 diabetes (T2D). In addition, western blot analysis showed that the expression of associated proteins, including peroxisome proliferator-activated receptor γ (PPARγ), pancreatic and duodenal homeobox 1 (PDX-1), phosphatidylinositol 3-kinase (PI3K), Akt, and insulin receptor substrate-2 (IRS-2), was increased in INS-1 cells after treatment with schisandrin C. In addition, insulin secretion effect of schisandrin C were enhanced by the Bay K 8644 (L-type Ca2+ channel agonist) and glibenclamide (K+ channel blocker), were abolished by the nifedipine (L-type Ca2+ channel blocker) and diazoxide (K+ channel activator). Moreover, schisandrin C enhanced glucose uptake with no toxic effects on C2C12 cells. Western blot analysis showed that the expression of associated proteins, including insulin receptor substrate-1 (IRS-1), AMP-activated protein kinase (AMPK), PI3K, Akt, glucose transporter type 4 (GLUT-4), was increased in C2C12 cells after treatment with schisandrin C. Schisandrin C may improve hyperglycemia by enhancing insulin secretion in pancreatic ß-cells and improving glucose uptake into skeletal muscle cells. Our findings may provide evidence that schisandrin C may be beneficial in devising novel anti-T2D strategies.

Reversible Ligand Exchange in Atomically Dispersed Catalysts for Modulating the Activity and Selectivity of the Oxygen Reduction Reaction.

Rational control of the coordination environment of atomically dispersed catalysts is pivotal to achieve desirable catalytic reactivity. We report the reversible control of coordination structure in atomically dispersed electrocatalysts via ligand exchange reactions to reversibly modulate their reactivity for oxygen reduction reaction (ORR). The CO-ligated atomically dispersed Rh catalyst exhibited ca. 30-fold higher ORR activity than the NHx -ligated catalyst, whereas the latter showed three times higher H2 O2 selectivity than the former. Post-treatments of the catalysts with CO or NH3 allowed the reversible exchange of CO and NHx ligands, which reversibly tuned oxidation state of metal centers and their ORR activity and selectivity. DFT calculations revealed that more reduced oxidation state of CO-ligated Rh site could further stabilize the *OOH intermediate, facilitating the two- and four-electron pathway ORR. The reversible ligand exchange reactions were generalized to Ir- and Pt-based catalysts.

Ordered Mesoporous Carbons with Graphitic Tubular Frameworks by Dual Templating for Efficient Electrocatalysis and Energy Storage.

Ordered mesoporous carbons (OMCs) have attracted considerable interest owing to their broad utility. OMCs reported to date comprise amorphous rod-like or tubular or graphitic rod-like frameworks, which exhibit tradeoffs between conductivity and surface area. Here we report ordered mesoporous carbons constructed with graphitic tubular frameworks (OMGCs) with tunable pore sizes and mesostructures via dual templating, using mesoporous silica and molybdenum carbide as exo- and endo-templates, respectively. OMGCs simultaneously realize high electrical conductivity and large surface area and pore volume. Benefitting from these features, Ru nanoparticles (NPs) supported on OMGC exhibit superior catalytic activity for alkaline hydrogen evolution reaction and single-cell performance for anion exchange membrane water electrolysis compared to Ru NPs on other OMCs and commercial catalysts. Further, the OMGC-based full-carbon symmetric cell demonstrates excellent performances for Li-ion capacitors.

Nanocrevasse-Rich Carbon Fibers for Stable Lithium and Sodium Metal Anodes.

Metallic lithium (Li) and sodium (Na) anodes have received great attention as ideal anodes to meet the needs for high energy density batteries due to their highest theoretical capacities. Although many approaches have successfully improved the performances of Li or Na metal anodes, many of these methods are difficult to scale up and thus cannot be applied in the production of batteries in practice. In this work, we introduce nanocrevasses in a carbon fiber scaffold which can facilitate the penetration of molten alkali metal into a carbon scaffold by enhancing its wettability for Li/Na metal. The resulting alkali metal/carbon composites exhibit stable long-term cycling over hundreds of cycles. The facile synthetic method is enabled for scalable production using recycled metal waste. Thus, the addition of nanocrevasses to carbon fiber as a scaffold for alkali metals can generate environmentally friendly and cost-effective composites for practical electrode applications.

Isolinderalactone Induces Cell Death via Mitochondrial Superoxide- and STAT3-Mediated Pathways in Human Ovarian Cancer Cells.

The mortality rate of ovarian cancer (OC) worldwide increases with age. OC is an often fatal cancer with a curative rate of only 20-30%, as symptoms often appear after disease progression. Studies have reported that isolinderalactone (ILL), a furanosesquiterpene derivative extracted from the dried root of Lindera aggregata, can inhibit several cancer cell lines' growth. However, the molecular mechanisms underlying ILL activities in human OC cells remain unexplored. This study investigated the antitumor activities of ILL in human OC cells by inducing mitochondrial superoxide (mtSO) and JAK-signal transducer and activator of transcription 3 (STAT3)-dependent cell death. ILL caused cell death in SKOV-3 and OVCAR-3 cells and increased the cell proportion in the subG1 phase. Additionally, ILL significantly induced mtSO production and reduced ROS production. Moreover, ILL downregulated mitochondrial membrane potential and the expression levels of anti-apoptotic Bcl-2 family proteins and superoxide dismutase (SOD)2. Results showed that ILL decreased phosphorylation of serine 727 and tyrosine 705 of STAT3 and expression of survivin, a STAT3-regulated gene. Furthermore, ILL-induced cell death was reversed by pretreatment of Mito-TEMPO, a mitochondria-specific antioxidant. These results suggest that ILL induces cell death by upregulation of mtSO, downregulation of mitochondrial SOD2, and inactivation of the STAT3-mediated pathway.

Hollow nanoparticles as emerging electrocatalysts for renewable energy conversion reactions.

While the realization of clean and sustainable energy conversion systems primarily requires the development of highly efficient catalysts, one of the main issues had been designing the structure of the catalysts to fulfill minimum cost as well as maximum performance. Until now, noble metal-based nanocatalysts had shown outstanding performances toward the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). However, the scarcity and high cost of them impeded their practical use. Recently, hollow nanostructures including nanocages and nanoframes had emerged as a burgeoning class of promising electrocatalysts. The hollow nanostructures could expose a high proportion of active surfaces while saving the amounts of expensive noble metals. In this review, we introduced recent advances in the synthetic methodologies for generating noble metal-based hollow nanostructures based on thermodynamic and kinetic approaches. We summarized electrocatalytic applications of hollow nanostructures toward the ORR, OER, and HER. We next provided strategies that could endow structural robustness to the flimsy structural nature of hollow structures. Finally, we concluded this review with perspectives to facilitate the development of hollow nanostructure-based catalysts for energy applications.

Active Edge-Site-Rich Carbon Nanocatalysts with Enhanced Electron Transfer for Efficient Electrochemical Hydrogen Peroxide Production.

A highly efficient, metal-free carbon nanocatalyst is presented that possesses abundant active, oxygenated graphitic edge sites. The edge site-rich nanocarbon catalyst exhibits about 28 times higher activity for H2 O2 production than a basal plane-rich carbon nanotube with a H2 O2 selectivity over 90 %. The oxidative treatment further promotes the H2 O2 generation activity to reach close to the thermodynamic limit. The optimized nanocarbon catalyst shows a very high H2 O2 production activity, surpassing previously reported catalysts in alkaline media. Moreover, it can stably produce H2 O2 for 16 h with Faradaic efficiency reaching 99 % and accumulated H2 O2 concentration of 24±2 mm. Importantly, we find that the heterogeneous electron transfer kinetics of the carbon-based catalyst is closely related to the electrocatalytic activity, suggesting that first outer-sphere electron transfer to O2 is an important step governing the H2 O2 production rate.

Ni@Ru and NiCo@Ru Core-Shell Hexagonal Nanosandwiches with a Compositionally Tunable Core and a Regioselectively Grown Shell.

The development of highly active electrocatalysts is crucial for the advancement of renewable energy conversion devices. The design of core-shell nanoparticle catalysts represents a promising approach to boost catalytic activity as well as save the use of expensive precious metals. Here, a simple, one-step synthetic route is reported to prepare hexagonal nanosandwich-shaped Ni@Ru core-shell nanoparticles (Ni@Ru HNS), in which Ru shell layers are overgrown in a regioselective manner on the top and bottom, and around the center section of a hexagonal Ni nanoplate core. Notably, the synthesis can be extended to NiCo@Ru core-shell nanoparticles with tunable core compositions (Ni3 Cox @Ru HNS). Core-shell HNS structures show superior electrocatalytic activity for the oxygen evolution reaction (OER) to a commercial RuO2 black catalyst, with their OER activity being dependent on their core compositions. The observed trend in OER activity is correlated to the population of Ru oxide (Ru4+ ) species, which can be modulated by the core compositions.

Pharmacokinetics of tafamidis, a transthyretin amyloidosis drug, in rats.

1. We characterized the pharmacokinetics of tafamidis, a novel drug to treat transthyretin-related amyloidosis, in rats after intravenous and oral administration at doses of 0.3-3 mg/kg. In vitro Caco-2 cell permeability and liver microsomal stability, as well as in vivo tissue distribution and plasma protein binding were also examined. 2. After intravenous injection, systemic clearance (CL), volumes of distribution at steady state (Vss) and half-life (T½) remained unaltered as a function of dose, with values in the ranges of 6.41-7.03 mL/h/kg, 270-354 mL/kg and 39.5-46.9 h, respectively. Following oral administration, absolute bioavailability was 99.7-104% and was independent of doses from 0.3 to 3 mg/kg. In the urine and faeces, 4.36% and 48.9% of tafamidis, respectively, were recovered. 3. Tafamidis was distributed primarily in the liver and not in the brain, kidney, testis, heart, spleen, lung, gut, muscle, or adipose tissue. Further, tafamidis was very stable in rat liver microsomes, and its plasma protein binding was 99.9%. 4. In conclusion, tafamidis showed dose-independent pharmacokinetics with intravenous and oral doses of 0.3-3 mg/kg. Tafamidis undergoes minimal first-pass metabolism, distributes mostly in the liver and plasma, and appears to be eliminated primarily via biliary excretion.

Spiroketones and a Biphenyl Analog from Stems and Leaves of Larrea nitida and Their Inhibitory Activity against IL-6 Production.

Bioactivity-guided fractionation for the stems of leaves of Larrea nitida Cav., using interleukin-6 (IL-6) inhibitory assay in human mast cells (HMC-1), led to the isolation of three new compounds with an unprecedented skeleton in nature (1-3) and three known compounds (4-6). Their structures were elucidated through extensive spectroscopic analysis. The three new compounds were elucidated as two new spiroketones, nitidaones A (1), and B (2) and one new biphenyl analog, nitidaol (3). The known compounds were identified as nordihydroguaiaretic acid (4), 7,3',4'-tri-O-methylquercetin (5) and ayanin (6). All the isolates were tested for their inhibitory activity against IL-6 production in HMC-1 cells. Of them, compounds 1, 3-6 showed potent anti-inflammatory activity, with IC50 values of 12.8, 17.5, 14.9, 22.9, and 17.8 µM, respectively.

Cactus-Like Hollow Cu2-x S@Ru Nanoplates as Excellent and Robust Electrocatalysts for the Alkaline Hydrogen Evolution Reaction.

The development of Pt-free electrocatalysts for the hydrogen evolution reaction (HER) recently is a focus of great interest. While several strategies are developed to control the structural properties of non-Pt catalysts and boost their electrocatalytic activities for the HER, the generation of highly reactive defects or interfaces by combining a metal with other metals, or with metal oxides/sulfides, can lead to notably enhanced catalytic performance. Herein, the preparation of cactus-like hollow Cu2-x S@Ru nanoplates (NPs) that contain metal/metal sulfide heterojunctions and show excellent catalytic activity and durability for the HER in alkaline media is reported. The initial formation of Ru islands on presynthesized Cu1.94 S NPs, via cation exchange between three Cu+ ions and one Ru3+ , induces the growth of the Ru phase, which is concomitant with the dissolution of the Cu1.94 S nanotemplate, culminating in the formation of a hollow nanostructure with numerous thin Ru pillars. Hollow Cu2-x S@Ru NPs exhibit a small overpotential of 82 mV at a current density of -10 mA cm-2 and a low Tafel slope of 48 mV dec-1 under alkaline conditions; this catalyst is among state-of-the-art HER electrocatalysts in alkaline media. The excellent performance of hollow Cu2-x S@Ru NPs originates from the facile dissociation of water in the Volmer step.

Alterations in Pharmacokinetics of Gemcitabine and Erlotinib by Concurrent Administration of Hyangsayukgunja-Tang, a Gastroprotective Herbal Medicine.

Gemcitabine and erlotinib are the chemotherapeutic agents used in the treatment of various cancers and their combination is being accepted as a first-line treatment of advanced pancreatic cancer. Hyangsayukgunja-tang (HYT) is a traditional oriental medicine used in various digestive disorders and potentially helpful to treat gastrointestinal adverse effects related to chemotherapy. The present study was aimed to evaluate the effect of HYT on the pharmacokinetics of gemcitabine and erlotinib given simultaneously in rats. Rats were pretreated with HYT at an oral dose of 1200 mg/kg/day once daily for a single day or 14 consecutive days. Immediately after pretreatment with HYT, gemcitabine and erlotinib were administered by intravenous injection (10 mg/kg) and oral administration (20 mg/kg), respectively. The effects of HYT on pharmacokinetics of the two drugs were estimated by non-compartmental analysis and pharmacokinetic modeling. The pharmacokinetics of gemcitabine and erlotinib were not altered by single dose HYT pretreatment. However, the plasma levels of OSI-420 and OSI-413, active metabolites of erlotinib, were significantly decreased in the multiple dose HYT pretreatment group. The pharmacokinetic model estimated increased systemic clearances of OSI-420 and OSI-413 by multiple doses of HYT. These data suggest that HYT may affect the elimination of OSI-420 and OSI-413.

A General Approach to Preferential Formation of Active Fe-Nx Sites in Fe-N/C Electrocatalysts for Efficient Oxygen Reduction Reaction.

Iron-nitrogen on carbon (Fe-N/C) catalysts have emerged as promising nonprecious metal catalysts (NPMCs) for oxygen reduction reaction (ORR) in energy conversion and storage devices. It has been widely suggested that an active site structure for Fe-N/C catalysts contains Fe-Nx coordination. However, the preparation of high-performance Fe-N/C catalysts mostly involves a high-temperature pyrolysis step, which generates not only catalytically active Fe-Nx sites, but also less active large iron-based particles. Herein, we report a general "silica-protective-layer-assisted" approach that can preferentially generate the catalytically active Fe-Nx sites in Fe-N/C catalysts while suppressing the formation of large Fe-based particles. The catalyst preparation consisted of an adsorption of iron porphyrin precursor on carbon nanotube (CNT), silica layer overcoating, high-temperature pyrolysis, and silica layer etching, which yielded CNTs coated with thin layer of porphyrinic carbon (CNT/PC) catalysts. Temperature-controlled in situ X-ray absorption spectroscopy during the preparation of CNT/PC catalyst revealed the coordination of silica layer to stabilize the Fe-N4 sites. The CNT/PC catalyst contained higher density of active Fe-Nx sites compared to the CNT/PC prepared without silica coating. The CNT/PC showed very high ORR activity and excellent stability in alkaline media. Importantly, an alkaline anion exchange membrane fuel cell (AEMFC) with a CNT/PC-based cathode exhibited record high current and power densities among NPMC-based AEMFCs. In addition, a CNT/PC-based cathode exhibited a high volumetric current density of 320 A cm-3 in acidic proton exchange membrane fuel cell. We further demonstrated the generality of this synthetic strategy to other carbon supports.

Crystal structure and activity of Francisella novicida UDP-N-acetylglucosamine acyltransferase.

The first step of lipid A biosynthesis in Escherichia coli (E. coli) is catalyzed by LpxA (EcLpxA), an acyltransferase selective for UDP-N-acetylglucosamine (UDP-GlcNAc) and R-3-hydroxymyristoyl-acyl carrier protein (3-OH-C14-ACP), and is an essential step in majority of Gram-negative bacteria. Since the majority of lipid A species isolated from F. novicida contains 3-OH-C16 or 3-OH-C18 at its C3 and C3' positions, FnLpxA was thought to be selective for longer acyl chain (3-OH-C16 and 3-OH-C18) over short acyl chain (3-OH-C14, 3-OH-C12, and 3-OH-C10). Here we demonstrate that Francisella novicida (F. novicida) lpxA functionally complements an E. coli lpxA knockout mutant and efficiently transfers 3-OH-C14 as well as 3-OH-C16 in E. coli. Our results implicate that the acyl chain length of lipid A is determined by several factors including acyl chain selectivity of LpxA and downstream enzymes, as well as the composition of the acyl-ACP pool in vivo. We also report the crystal structure of F. novicida LpxA (FnLpxA) at 2.06 Å. The N-terminal parallel beta-helix (LßH) and C-terminal alpha-helical domain are similar to other reported structures of LpxAs. However, our structure indicates that the supposed ruler residues for hydrocarbon length, 171L in one monomer and 168H in the adjacent monomer in a functional trimer of FnLpxA, are located just 3.8 Å apart that renders not enough space for binding of 3-OH-C12 or longer acyl chains. This implicates that FnLpxA may have an alternative hydrophobic pocket, or the acyl chain may bend while binding to FnLpxA. In addition, the FnLpxA structure suggests a potential inhibitor binding site for development of antibiotics.

Self-Supported Mesostructured Pt-Based Bimetallic Nanospheres Containing an Intermetallic Phase as Ultrastable Oxygen Reduction Electrocatalysts.

Developing highly active and stable cathode catalysts is of pivotal importance for proton exchange membrane fuel cells (PEMFCs). While carbon-supported nanostructured Pt-based catalysts have so far been the most active cathode catalysts, their durability and single-cell performance are yet to be improved. Herein, self-supported mesostructured Pt-based bimetallic (Meso-PtM; M = Ni, Fe, Co, Cu) nanospheres containing an intermetallic phase are reported, which can combine the beneficial effects of transition metals (M), an intermetallic phase, a 3D interconnected framework, and a mesoporous structure. Meso-PtM nanospheres show enhanced oxygen reduction reaction (ORR) activity, compared to Pt black and Pt/C catalysts. Notably, Meso-PtNi containing an intermetallic phase exhibits ultrahigh stability, showing enhanced ORR activity even after 50 000 potential cycles, whereas Pt black and Pt/C undergo dramatic degradation. Importantly, Meso-PtNi with an intermetallic phase also demonstrated superior activity and durability when used in a PEMFC single-cell, with record-high initial mass and specific activities.

Noncovalent Surface Locking of Mesoporous Silica Nanoparticles for Exceptionally High Hydrophobic Drug Loading and Enhanced Colloidal Stability.

Advances in water-insoluble drug delivery systems are limited by selective delivery, loading capacity, and colloidal and encapsulation stability. We have developed a simple and robust hydrophobic-drug delivery platform with different types of hydrophobic chemotherapeutic agents using a noncovalent gatekeeper's technique with mesoporous silica nanoparticles (MSNs). The unmodified pores offer a large volume of drug loading capacity, and the loaded drug is stably encapsulated until it enters the cancer cells owing to the noncovalently bound polymer gatekeeper. In the presence of polymer gatekeepers, the drug-loaded mesoporous silica nanoparticles showed enhanced colloidal stability. The simplicity of drug encapsulation allows any combination of small chemotherapeutics to be coencapsulated and thus produce synergetic therapeutic effects. The disulfide moiety facilitates decoration of the nanoparticles with cysteine containing ligands through thiol-disulfide chemistry under mild conditions. To show the versatility of drug targeting to cancer cells, we decorated the surface of the shell-cross-linked nanoparticles with two types of peptide ligands, SP94 and RGD. The nanocarriers reported here can release encapsulated drugs inside the reducing microenvironment of cancer cells via degradation of the polymer shell, leading to cell death.

Coordination Chemistry of [Co(acac)2 ] with N-Doped Graphene: Implications for Oxygen Reduction Reaction Reactivity of Organometallic Co-O4 -N Species.

Hybridization of organometallic complexes with graphene-based materials can give rise to enhanced catalytic performance. Understanding the chemical structures within hybrid materials is of primary importance. In this work, archetypical hybrid materials are synthesized by the reaction of an organometallic complex, [Co(II) (acac)2 ] (acac=acetylacetonate), with N-doped graphene-based materials at room temperature. Experimental characterization of the hybrid materials and theoretical calculations reveal that the organometallic cobalt-containing species is coordinated to heterocyclic groups in N-doped graphene as well as to its parental acac ligands. The hybrid material shows high electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media, and superior durability and methanol tolerance to a Pt/C catalyst. Based on the chemical structures and ORR experiments, the catalytically active species is identified as a Co-O4 -N structure.