Latest ArticlesThe biogeochemical transformation of gold (Au), i.e. its dissolution and re-precipitation, is critical in supergene transport of Au and formation of Au granules. Besides biogenic reduction, the formation Au granules can also be driven by chemical processes. Previous studies have showed the formation of Au nanoparticles (AuNPs) from ionic Au(Ⅲ) can be mediated by dissolved organic matter under sunlight. In this letter, we further demonstrated that these AuNPs can further slowly (in years) grow into visible Au granules. Different sized nano-flower and fractal dendrite-like branched gold structures (from tens of nanometres to over 100 μm) were observed in the Au granule sample. This growth of AuNPs into visible Au granules may play a critical role in the supergene mineralization and enrichment of secondary Au and drive the biogeochemical cycle of Au.
Rh/ZhaoPhos-catalyzed asymmetric hydrogenation of a series of (E)-2-(chroman-4-ylidene)acetates was successfully developed to prepare various chiral 4-substituted chromanes with high yields and excellent enantioselectivities (up to 99% yield, 98% ee). Moreover, the gram-scale hydrogenation could be performed well in the presence of 0.02 mol% catalyst loading (TON = 5000), the hydrogenation product was easily converted to access other important compounds, which demonstrated the synthetic utility of this asymmetric catalytic methodology.
A new paradigm to remove toxic chromate anions from aqueous solution by crystallization of chromatewater clusters with imine-linked guanidinium cationic ligands is introduced. The guanidium-based cationic ligand was easily prepared through the imine condensation of an aldehyde and aminoguanidine hydrochloride. The cationic imine-linked guanidinium ligand (BBIG-Cl) showed a high removal capacity (292.5 mg/g) in the solutions. Rapid decontamination of chromate anions from the wastewater by this cationic ligand was resulted from an instantaneous crystallization. The produced guanidium chromate salts have an extremely low solubility (Ksp, BBIG = 8.19×10-9). Such superior removal performance of these materials was attributed to the charge-assisted hydrogen bonding between the cationic ligand and chromate-water hydrate anions, which was revealed by the single-crystal X-ray diffraction analysis and density functional theory (DFT) calculations. In addition, the successful recovery of the guanidium-based ligand makes it more attractive for real-world applications.
Robust normalization is a prerequisite for reliable metabonomic analysis especially when intervention treatments cause drastic metabolomic changes or when spot urinary samples are employed without knowing the drinking water quantity. With the simulated and real datasets, here, we report a probabilistic quotient normalization method based on the mode-of-quotients (mPQN) which is suitable for metabonomic analysis of both NMR and LC-MS data with little and/or drastic metabolite changes. When applied to metabonomic analysis of both animal plasma samples and human urinary samples, this newly proposed method has clearly shown better robustness than all classical normalization methods especially when drastic changes of some metabolites occur.
The controlled self-assembly of discrete metal-organic nanocapsules (MONCs), and metal-organic frameworks (MOFs) based on the MONCs are achieved. Specifically, the solvothermal reaction of nickel nitrate hexahydrate and C-methylpyrogallol[4]arene in mixed DMF/MeOH solution leads to the unexpected form of discrete nickel-seamed hexameric pyrogallol[4]arene MONCs, and MONC-based three-dimensional (3D) MOF. Notably, the latter MOF is constructed from the aforementioned nickelseamed MONC building blocks and formate linkers in-situ generated from the hydrolysis of DMF solvent. Interestingly, introducing pyridine and formic acid in the reaction conditions leads to the controlled assemblies of the discrete MONC and MONC-based 3D MOF structures. Moreover, the variabletemperature magnetic susceptibilities of both the abovementioned compounds have been investigated, indicating typical antiferromagnetic interactions between the metal centers.
A novel BODIPY (boradiazaindacene) dye denoted as BODIPY-DT containing terpyridine unit has been designed and characterized. The dye is found to be selective and visual solvatochromic sensor toward DMF among test organic solvents. The sensing process displays time-controllable, dynamic signal outputs in the emission colors including red, purple, yellow and even white emission colors. It is presented that selective free radical oxidation reaction happens during the recognition process.
Insulin fibrillation poses a variety of problems in biomedical and biotechnological applications of insulin. Inhibiting insulin fibrillation is highly on demand to address those problems. We herein demonstrate the capability of amphiphilic sulfonatocalixarene to inhibit insulin fibrillation. The amphiphilic assembly of p-sulfonatocalix[4]arene tetra dodecyl ether exhibits much better efficiency on inhibiting insulin fibrillation, with respect to p-sulfonatocalix[4]arene and sodium dodecyl benzenesulphonate. The pronounced inhibition effect results from both the preorganized scaffold of calixarene and the amphiphilic assembly.
A metal-free photocatalytic oxidative decarboxylation reaction at room temperature was developed for the synthesis of aromatic aldehydes and ketones from the corresponding arylacetic acids. The reaction was realized under blue-light irradiation by adding 1 mol% of 4CzIPN as photocatalyst and air as oxidant. This reaction represents a novel decarboxylation of a sp3-hybridized carboxylic acids without traditional heating, additional oxidants, and metal reagents under mild conditions.
Fluorescence anisotropy (FA) assay in homogenous solution is simple, sensitive and reproducible. Here, we reported an aptamer structure switch FA assay for detection of aflatoxin B1 (AFB1), one of the most toxic mycotoxins, by using tetramethylrhodamine (TMR)-labeled aptamer probe and its complementary DNA (cDNA) with tandem G bases extension, to meet the demand in sensitive and selective detection of AFB1. The hybridization of aptamer and cDNA drew TMR close to the repeated guanine (G) bases, and a high FA value was induced due to TMR-G interaction and restricted local rotation of TMR. In the presence of AFB1, aptamer bound to AFB1 instead of the cDNA due to competition. Thus, the TMR-G interaction was eliminated, and FA value of TMR decreased. This assay enabled the detection of AFB1 with detection limit of 125 pmol/L and dynamic range from 125 pmol/L to 31.2 nmol/L
4H-silicon carbides deposited by diamond films have wide applications in many fields such as semiconductor heterojunction, heat sink and mechanical sealing. Nucleation plays a critical role in the deposition of the diamond film on 4H-silicon carbides. Nevertheless, as a typical polar material, the fundamental mechanism of diamond nucleation on different faces of 4H-silicon carbides has not been fully understood yet. In this contribution, nucleation of diamond was performed on the carbon- and silicon-faces of 4H-silicon carbides in a direct current chemical vapor deposition device. The nucleation density on the carbon-face is higher by 2-3 orders of magnitude compared to the silicon-face. Transmission electron microscopy verifies that there are high density diamond nuclei on the interface between the carbon-face and the diamond film, which is different from columnar diamond growth structure on the silicon-face. Transition state theory calculation reveals that the unprecedented distinction of the nucleation density between the carbon-face and the silicon-face is attributed to different desorption rates of the absorbed hydrocarbon radicals. In addition, kinetic model simulations demonstrate that it is more difficult to form CH2(s)-CH2(s) dimers on silicon-faces than carbon-faces, resulting in much lower nucleation densities on silicon-faces.