Hydrogenation of Quinones to Hydroquinones under Atmospheric Pressure Catalyzed by a Metal-Ligand Bifunctional Iridium Catalyst.

A general method for the hydrogenation of quinones to hydroquinones under atmospheric pressure has been developed. In the presence of [Cp*Ir(2,2'-bpyO)(H2O)] (0.5-1 mol %), a range of products were obtained in high yields. Furthemore, the expansion of this catalytic system to the hydrogenation of 1,4-benzoquinone diimines was also presented. Functional groups in the bpy ligand were found to be crucial for the catalytic activity of iridium complexes.

The Association Between Environmental Cadmium Exposure and Parathyroid Hormone Levels.

Cadmium exposure is associated with renal dysfunction and bone damage. Chronic kidney disease and bone loss are also related to parathyroid hormone (PTH). However, whether cadmium exposure affect PTH level is not completely understood. In this study, we observed the association between environmental cadmium exposure and PTH levels in a Chinese population. A ChinaCd study was performed in China in 1990s which included 790 subjects living in heavily, moderately and low cadmium polluted area. 354 of them (121 men and 233 women) also had the data of serum PTH. The cadmium levels in blood (BCd) and urine (UCd) were determined by flame atomic absorption spectrometry. Serum PTH was detected by immunoradiometric assay. Renal function was assessed based on urinary N-acetyl-ß-d-glucosaminidase (UNAG), ß2-microglobulin (UBMG) and urinary albumin (UALB). The median BCd and UCd levels were 4.69 µg/L and 5.50 µg/g creatinine. The BCd, UCd, UNAG, UBMG and UALB levels in subjects with low PTH (< 5.0 ng/L) were significantly higher than those with PTH ≥ 5.0 ng/L (p < 0.05 or p < 0.01). Spearman correlation analysis also showed that UCd level was negatively correlated to PTH levels (r = -0.17, p = 0.008) in women. A weak correlation was also observed between PTH level and BCd in women (r = -0.11, p = 0.09) and UBMG in total population (r = -0.114, p = 0.07). Univariable and mutivariable logistic regression analysis both demonstrated that high BCd (> 10 µg/L) (odds ratio (OR) = 2.26, 95% confidence interval (CI):1.10-4.63; OR = 2.36, 95%CI: 1.11-5.05) and UCd level (> 20 µg/g cr) (OR = 2.84, 95% CI:1.32-6.10; OR = 2.97, 95%CI: 1.25-7.05) were associated with high risk of low PTH. Our data showed that environmental cadmium exposure was associated with low PTH level.

Construction of artificial light-harvesting systems based on a variety of polyelectrolyte materials and application in photocatalysis.

In the present work, we designed and synthesized a cationic cyano-substituted p-phenylenevinylene derivative (PPTA), which can form supramolecular assemblies through electrostatic interaction with a type of polyelectrolyte material anionic guar gum (GP5A). A polyelectrolyte-based artificial light-harvesting system (LHS) was constructed by selecting a fluorescent dye sulforhodamine 101 (SR101) that matched its energy level as an energy acceptor. The energy harvested by the acceptors was used in the aqueous phase cross dehydrogenation coupling (CDC) reaction with a yield of up to 87%. In addition, the general applicability of polyelectrolyte materials to build artificial LHS was demonstrated by three other polyelectrolyte materials sodium polyphenylene sulfonate (RSS), sodium carboxymethyl cellulose (CMC), and sodium polyacrylate (PAAS), in which the CDC reaction was also carried out by these three LHSs and obtained high yields. This work not only provides a new method to construct LHSs by using polyelectrolyte materials, but also provides a beneficial exploration for further applying the energy harvested in LHSs to the field of photocatalysis in an aqueous solution.

Novel Strategy of Constructing Artificial Light-Harvesting System with Two-Step Sequential Energy Transfer for Efficient Photocatalysis in Water.

An efficient artificial light-harvesting system with a two-step sequential energy transfer was fabricated in the aqueous solution based on the host-guest interactions between cyano-substituted p-phenylenevinylene derivative (PPTA) and a water-soluble pillar[5]arene (WP5). PPTA-WP5 complex could self-assemble into nanoparticles, and two fluorescent dyes eosin Y (EY) and Nile Red (NIR) are employed as acceptors to realize sequential energy transfer. The PPTA-WP5-EY-NIR system could achieve efficient two-step sequential energy transfer process from PPTA-WP5 to EY and then to NIR (67% for the first step and 66% for the second step). Moreover, to make full use of the harvested energy, the hydrophobic microenvironment in the assembled nanoparticles is used to promote the aerobic cross-dehydrogenative coupling (CDC) reaction in aqueous medium with 88% yield after 12 h of irradiation. To our knowledge, this is the first example of artificial LHS with two-step energy transfer used to catalyze the CDC reaction in aqueous medium. This work directly mimics the function of photosynthesis in nature of converting solar energy into chemical energy in aqueous solution.

Supramolecular polymers based on host-guest interactions for the construction of artificial light-harvesting systems.

In the present work, artificial light-harvesting systems with a fluorescence resonance energy transfer (FRET) process were successfully obtained in the aqueous solution. We designed and synthesized an amphiphilic pyrene derivative with two 4-vinylpyridium arms (Pmvb), which can interact with cucurbit[8]uril (CB[8]) to form supramolecular polymer through host-guest interactions in aqueous solution. The formation of supramolecular polymers results in a significant enhancement of fluorescence, which makes Pmvb-CB[8] an ideal energy donor to construct artificial light-harvesting systems in the aqueous solution. Subsequently, two different fluorescence dyes Rhodamine B (RhB) and Sulforhodamine 101 (SR101) were introduced as energy acceptors into the solution of Pmvb-CB[8] respectively, to fabricate two different artificial light-harvesting systems. The obtained artificial light-harvesting systems can achieve an efficient energy transfer process from Pmvb-CB[8] to RhB or SR101 with high energy transfer efficiency.

Supramolecular assemblies working as both artificial light-harvesting system and nanoreactor for efficient organic dehalogenation in aqueous environment.

In this work, three artificial light-harvesting systems are constructed by a supramolecular approach in aqueous environment. The water-soluble bipyridinium derivatives (DPY1, DPY2, and DPY3) were self-assembled with cucurbit[7]uril (CB[7]) to form the host-guest DPY-CB[7] complexes, which can highly disperse in water as small nanoparticles. The excited DPY-CB[7] assemblies can transfer energy to the sulfo-rhodamine 101 (SR101) molecules at a high donor/acceptor ratio. With the help of hydrophobic cavity of CB[7], the DPY-CB[7] + SR101 systems can works as a nanoreactor for effective dehalogenation of α-bromoacetophenone and its derivatives in aqueous medium under white light irradiation. Such light-harvesting systems has greatly potential applications to realize some organic photocatalytic synthesis in aqueous environment.

The construction of an artificial light-harvesting system with two-step sequential energy transfer based on supramolecular polymers.

An artificial light-harvesting system with two-step sequential energy transfer was constructed in aqueous media based on cyano-substituted p-phenylenevinylene derivative (PPTA) and bis-(p-sulfonatocalix[4]arenes) (BSC4) supramolecular polymers formed through host-guest interactions, in which two different fluorescent dyes, eosin Y (EY) and sulforhodamine (SR101), were employed as energy acceptors. The obtained artificial light-harvesting system can achieve an efficient two-step energy transfer process from PPTA-BSC4 to EY and then to SR101 with high energy-transfer efficiencies of up to 36.6% and 40.8%, respectively. More importantly, the harvested energy from the PPTA-BSC4 + EY + SR101 system can be used to promote the dehalogenation of α-bromoacetophenone with a yield of 89% in aqueous solution.

Transfer Hydrogenation of Ketones and Imines with Methanol under Base-Free Conditions Catalyzed by an Anionic Metal-Ligand Bifunctional Iridium Catalyst.

An anionic iridium complex [Cp*Ir(2,2'-bpyO)(OH)][Na] was found to be a general and highly efficient catalyst for transfer hydrogenation of ketones and imines with methanol under base-free conditions. Readily reducible or labile substituents, such as nitro, cyano, and ester groups, were tolerated under present reaction conditions. Notably, this study exhibits the unique potential of anionic metal-ligand bifunctional iridium catalysts for transfer hydrogenation with methanol as a hydrogen source.

Monitoring mitochondrial pH with a hemicyanine-based ratiometric fluorescent probe.

Mitochondria as essential organelles play critical roles in cellular metabolism. Mitochondrial pH is a vital parameter that directly affects the unique function of mitochondria. Herein, we present a new ratiometric fluorescent probe M-pH for monitoring the pH within the mitochondria. M-pH consists of a stable and large π-electron conjugated merocyanine system. The lipophilic cationic benzyl group will facilitate the accumulation of M-pH in mitochondria. The phenol unit is the recognition moiety, achieving the ratiometric sensing of pH changes. The experimental results indicate that M-pH displays ratiometric fluorescence response to different pH values. Meanwhile, M-pH shows negligible response to common species, and has high stability and low cytotoxicity. In biological experiments, M-pH can solely accumulate in mitochondria and visualize the pH changes during mitophagy and cell apoptosis. We thus believe that M-pH has great potential as a practical tool for real-time monitoring of pH changes of mitochondria, contributing to revealing the pathogenesis of mitochondrial pH associated diseases.

Transfer Hydrogenation of Aldehydes and Ketones with Isopropanol under Neutral Conditions Catalyzed by a Metal-Ligand Bifunctional Catalyst [Cp*Ir(2,2'-bpyO)(H2O)].

A Cp*Ir complex bearing a functional bipyridonate ligand [Cp*Ir(2,2'-bpyO)(H2O)] was found to be a highly efficient and general catalyst for transfer hydrogenation of aldehydes and chemoselective transfer hydrogenation of unsaturated aldehydes with isopropanol under neutral conditions. It was noteworthy that many readily reducible or labile functional groups such as nitro, cyano, ester, and halide did not undergo any change under the reaction conditions. Furthermore, this catalytic system exhibited high activity for transfer hydrogenation of ketones with isopropanol. Notably, this research exhibited new potential of metal-ligand bifunctional catalysts for transfer hydrogenation.

N-Methylation of Amines with Methanol Catalyzed by a Cp*Ir Complex Bearing a Functional 2,2'-Bibenzimidazole Ligand.

A new type of Cp*Ir complex bearing a functional 2,2'-bibenzimidazole ligand was designed, synthesized, and found to be a highly effective and general catalyst for the N-methylation of a variety of amines with methanol in the presence of a weak base (0.3 equiv of Cs2CO3).

Acceptorless Dehydrogenative Cyclization of o-Aminobenzyl Alcohols with Ketones to Quinolines in Water Catalyzed by Water-Soluble Metal-Ligand Bifunctional Catalyst [Cp*(6,6'-(OH)2bpy)(H2O)][OTf]2.

The strategy for acceptorless dehydrogenative cyclization of o-aminobenzyl alcohols with ketones to quinolines in water has been accomplished. In the presence of [Cp*Ir(6,6'-(OH)2bpy)(H2O)][OTf]2, a series of desirable products were obtained in high yields. Notably, this research exhibits the potential for the construction of heterocycles via acceptorless dehydrogenative reactions in water catalyzed by water-soluble metal-ligand bifunctional catalysts.

Synthesis of a-Alkylated Ketones via Tandem Acceptorless Dehydrogenation/a-Alkylation from Secondary and Primary Alcohols Catalyzed by Metal-Ligand Bifunctional Iridium Complex [Cp*Ir(2,2'-bpyO)(H2O)].

A new strategy for the synthesis of α-alkylated ketones via tandem acceptorless dehydrogenation/α-alkylation from secondary and primary alcohols was proposed and accomplished. In the presence of metal-ligand bifunctional iridium complex [Cp*Ir(2,2'-bpyO)(H2O)], various desirable products were obtained in high yields. Compared with previous methods for the direct dehydrogenative coupling of secondary alcohols with primary alcohols to α-alkylated ketones, this protocol has obvious advantages including complete selectivity for α-alkylated ketones and more environmentally benign conditions. Notably, the study also exhibited the potential to develop tandem reactions catalyzed using a metal-ligand bifunctional iridium complex.

Decay kinetic properties of atoms in photonic crystals with absolute gaps.

Decay kinetic properties of a two-level atom near the band edges of photonic crystals (PCs) with absolute gaps are studied based on the Green's function expression for the evolution operator. The local coupling strength between the photons and an atom is evaluated by an exact numerical method. It is found that the decay behavior of an excited atom can be fundamentally changed by the variation of the atomic position: Weisskopf-Wigner and non-Weisskopf-Wigner decay phenomena occur at different atomic positions in the PCs as a result of a significant difference in the local coupling strength. Our finding implies that it is possible to engineer the luminescence spectrum by controlling the atomic position.

Decay distribution of spontaneous emission from an assembly of atoms in photonic crystals with pseudogaps.

Spontaneous decay behaviors from an assembly of atoms (or molecules) in 3D photonic crystals (PC's) with pseudogaps are investigated. Theoretically, a lifetime distribution function for these atoms or molecules is defined to reveal decay kinetics. Our calculations show that quite wide or narrow lifetime distributions can occur for different spread configurations of the atoms (or molecules). The pure PC effect may lead to coexistence of both accelerated and inhibited decay processes. These results provide theoretical clarification for substantial discrepancies in the recent reported experiments.