Mechanistic Insights into Copper‐Catalyzed Sonogashira–Hagihara‐Type Cross‐Coupling Reactions: Sub‐Mol % Catalyst Loadings and Ligand Effects

An efficient catalytic system for Sonogashira–Hagihara‐type reactions displaying ligand acceleration in the copper‐catalyzed formation of C(sp²)? C(sp) bonds is described. The structure of the ligand plays a key role for the coupling efficiency. Various copper sources show excellent catalytic activity, even in sub‐mol % quantities. A wide variety of substituents is tolerated in the substrates. Mechanistic details have been revealed by kinetic measurements and DFT calculations.     

Microwave‐Induced In Situ Synthesis of Zn2GeO4/N‐Doped Graphene Nanocomposites and Their Lithium‐Storage Properties

Zn₂GeO₄/N‐doped graphene nanocomposites have been synthesized through a fast microwave‐assisted route on a large scale. The resulting nanohybrids are comprised of Zn₂GeO₄ nanorods that are well‐embedded in N‐doped graphene sheets by in situ reducing and doping. Importantly, the N‐doped graphene sheets serve as elastic networks to disperse and electrically wire together the Zn₂GeO₄ nanorods, thereby effectively relieving the volume‐expansion/contraction and aggregation of the nanoparticles during charge and discharge processes. We demonstrate that an electrode that is made of the as‐formed Zn₂GeO₄/N‐doped graphene nanocomposite exhibits high capacity (1463 mAh g^?1 at a current density of 100 mA g^?1), good cyclability, and excellent rate capability (531 mAh g^?1 at a current density of 3200 mA g^?1). Its superior lithium‐storage performance could be related to a synergistic effect of the unique nanostructured hybrid, in which the Zn₂GeO₄ nanorods are well‐stabilized by the high electronic conduction and flexibility of N‐doped graphene sheets. This work offers an effective strategy for the fabrication of functionalized ternary‐oxide‐based composites as high‐performance electrode materials that involve structural conversion and transformation.     

Expanded Organic Building Units for the Construction of Highly Porous Metal–Organic Frameworks

Two new organic building units that contain dicarboxylate sites for their self‐assembly with paddlewheel [Cu₂(CO₂)₄] units have been successfully developed to construct two isoreticular porous metal–organic frameworks (MOFs), ZJU‐35 and ZJU‐36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST‐1. Because the organic linkers in ZJU‐35 and ZJU‐36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8 Å in HKUST‐1 to 14.4 Å in ZJU‐35 and 16.5 Å in ZJU‐36, thus leading to their higher porosities with Brunauer–Emmett–Teller (BET) surface areas of 2899 and 4014 m² g^?1 for ZJU‐35 and ZJU‐36, respectively. High‐pressure gas‐sorption isotherms indicate that both ZJU‐35 and ZJU‐36 can take up large amounts of CH₄ and CO₂, and are among the few porous MOFs with the highest volumetric storage of CH₄ under 60 bar and CO₂ under 30 bar at room temperature. Their potential for high‐pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU‐35 and ZJU‐36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH₄ under 60 bar and CO₂ under 30 bar at room temperature are those self‐assembled from organic tetra‐ and hexacarboxylates that contain m‐benzenedicarboxylate units with the [Cu₂(CO₂)₄] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self‐assembly with [Cu₂(CO₂)₄] units has provided great promise for the exploration of a large number of new tetra‐ and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated into the frameworks to tune their porosities, pore structures, and framework densities, thus targeting some even better performing MOFs for very high gas storage and efficient gas separation under high pressure and at room temperature in the near future.     

Synthesis of aryloxyazetidine derivatives by CuI/l-proline catalyzed coupling reaction of arylboronic acid with 1-Boc-3-iodoazetidine

A novel CuI/l-proline catalyzed coupling reaction of 1-Boc-3-iodoazetidine with various arylboronic acids which produced aryloxyazetidine derivatives in moderate to good yields was investigated.     

Cucurbit[7]uril promoting PdCl2-catalyzed cross-coupling reaction of benzyl halides and arylboronic acids in aqueous media

The research provides a novel approach for producing diarylmethane derivatives using CB[7]–NaCl–PdCl₂ catalyzed Suzuki cross-coupling reaction of benzyl chloride derivatives and arylboronic acids in ethanol aqueous solution.     

Three New Coordination Compounds with Neodymium Based on Tetrazole Containing Carboxylic Acid Ligands

Reactions of three tetrazole containing carboxylic acid ligands, namely, Hpztza, Htzpya, and Hpytza [Hpztza = 5‐(2‐pyrazinyl)tetrazole‐2‐acetic acid, Htzpya = 3‐(5‐tetrazolyl)pyridine‐1‐acetic acid, Hpytza = 5‐(3‐pyridyl)tetrazole‐2‐acetic acid] with NdCl₃ · 6H₂O under hydrothermal conditions, afforded the complexes [Nd(pztza)₂(H₂O)₆] · pztza · 3H₂O ( 1 ), [Nd₂(tzpya)₂(H₂O)₁₂]Cl₄ · 2H₂O ( 2 ), and [Nd(pytza)₂Cl(H₂O)₂] ( 3 ). The compounds were structurally characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. X‐ray diffraction analyses revealed that compound 1 displays a mononuclear structure, 2 shows a dinuclear structure, and 3 features a 1D polymeric chain structure via pytza as linker. Furthermore, the luminescent properties investigated at room temperature in the solid state show that compound 2 has an obvious decrease in its luminescence, when compared to the ligand.     

Highly efficient N-glycoproteomic sample preparation by combining C18 and graphitized carbon adsorbents

Conventional N-glycoproteome analysis usually applies C₁₈ reversed-phase (RP) adsorbent for sample purification, which will lead to unavoidable sample loss due to the high hydrophilicity of N-glycopeptides. In this study, a porous graphitized carbon (PGC) absorbent was combined with a C₁₈ adsorbent for N-glycopeptide purification in comprehensive N-glycoproteome analysis based on the hydrophobic and polar interactions between carbon and N-glycans. It was observed that the small hydrophilic N-glycopeptides that cannot retain onto C₁₈ adsorbent can be captured by the graphitized carbon, while the large hydrophobic N-glycopeptides that cannot retain onto the graphitized carbon can be feasibly captured by the C₁₈ adsorbent. Comparing with sample purification by using C₁₈ adsorbent only, 28.5 % more N-glycopeptides were identified by combining both C₁₈ and PGC adsorbents. The C₁₈-PGC strategy was further applied for both sample purification and pre-fractionation of a complex protein sample from HeLa cell. After hydrophilic interaction chromatography enrichment, 1,484 unique N-glycopeptides with 1,759 unique N-glycosylation sites were finally identified.

Determination of manganese (VII), chromium (VI) and nickel (II) in medicinal herb samples by cloud-point extraction and high-performance liquid chromatography

A highly sensitive method for the determination of manganese (VII), chromium (VI) and nickel (II) in medicinal herb samples is proposed. The method is based on analytes reacted with ammonium pyrrolidinedithiocarbamate (APDC) to give hydrophobic chelates (M–APDC), which were separated and enriched by cloud-point extraction (CPE) with non-ionic surfactant Tergitol TMN-6 as extractant. The surfactant-rich phase containing the chelates is determined with a high-performance liquid chromatography system. To achieve the best CPE method, the Box–Behnken design was used to study the concentration of Tergitol TMN-6, equilibrium temperature, equilibrium time as well as their interaction. What followed was the individual research for the pH of the sample solutions and the concentration of APDC. What is more, in the given optimized experimental conditions, calibration plots were found to be linear in the range of 0.0200–0.500 mg/L for Mn (VII) and Cr (VI), meanwhile 0.0500–1.00 mg/L for Ni (II), the linear correlation coefficients were between 0.996 and 0.999, the recoveries ranged from 91.8 to 97.8 % and the relative standard deviations were between 1.09 and 2.30 % (n = 3). The limits of detection were 0.164 μg/L for Mn (VII), 0.562 μg/L for Cr (VI) and 5.12 μg/L for Ni (II), respectively. The proposed method was applied to determine manganese (VII), chromium (VI) and nickel (II) in medicinal herb samples with satisfactory results.     

Transformations of iodine species inside elliptical channels of AlPO4‐11 crystals at low temperature: a Raman study

Raman spectra of iodine species confined in one‐dimensional elliptical channels of AlPO₄‐11 (AEL) crystals have been studied from room temperature down to −196 °C. As temperature decreases, thermal fluctuations of individual iodine molecules confined in AEL channels are slowed down and they prefer to rotate to channel axis direction, which increases the population of iodine molecules along channel axis (i.e., lying molecules and chains). Such temperature‐driven orientation transformation of iodine molecules is found to be reversible upon heating up to room temperature. The experimental observations are in good agreement with our theoretical simulations by molecular dynamics on low density iodine‐filled AEL crystals. We thus provide a new way to modulate the orientation of iodine molecules in nanochannels, which may have implications in low‐temperature‐sensitive nanoscale devices. Copyright © 2015 John Wiley & Sons, Ltd.     

Aluminum fluoride-18-labelled indocyanine green as a potential PET imaging agent for hepatic function reserve

Journal of Radioanalytical and Nuclear Chemistry - This study evaluated the potential of Al18F-labelled restrained complexing agent (RESCA)-ICG to assess hepatic function reserve on PET/CT imaging....