Organic ammonium ion-occluded flexible coordination polymers: Thermal activation, structure transformation and proton transfer

Solvothermal reactions of 1,3,5-benzenetricarboxylic acid (H₃btc) with cadmium acetate or zinc acetate yielded two compounds formulated as (Me₂NH₂)[Cd(btc)]·DMA (1) (btc = 1,3,5-benzenetricarboxylate, DMA = N,N-dimethylacetamide) and (Me₂NH₂)[Zn(btc)]·DMF (2) (DMF = N,N-dimethylformamide). Both are 3-D frameworks with the rutile topology, which are constructed from six-connected dimeric metal cores and three-connected btc linkers. The solvent molecules and counter cations are located in the 1-D channels of the frameworks. A slight difference between the two compounds is the different connectivity modes of the metal atoms with the carboxylate groups of the ligands. However, this slight difference results in distinct flexibilities of the two frameworks. Variable-temperature powder X-ray diffraction studies revealed that the framework of 1 collapses when heated at 180 °C with loss of the guest species, but compound 2 undergoes two structural transformations below 380 °C. Thermogravimetry-infrared spectroscopy analysis for 2 showed that the two structural transformations are induced by separate losses of solvent molecules and counter cations, and that the dimethylammonium cations are eliminated as neutral dimethylamine molecules. IR spectroscopy demonstrated that the protons are transferred from the counter cations onto the uncoordinated carboxylate oxygen atoms on the channel walls. Sorption and proton conduction studies have also been performed for the compounds.     

Silica Microspheres for SPE and Determination of Fungicides in Water by LC

A new method has been developed for the determination of metalaxyl, myclobutanil, and tebuconazole in environmental water samples with preconcentration by cartridges packed with SiO₂ microspheres prior to LC. Several parameters such as the volume and composition of eluent, sample flow rate, sample pH, and sample volume were optimized. Under the optimal conditions, excellent detection limits (S/N = 3) and precision (RSD, n = 6) were 0.02 ng mL^?1, 1.3% for metalaxyl, 0.02 ng mL^?1, and 2.4% for myclobutanil and 0.08 ng mL^?1 and 4.3% for tebuconazole, respectively. The method was applied to the analysis of real-water samples, and satisfactory results were obtained. The average spiked recoveries were in the range of 86.3–97.5%. These results indicate that SiO₂ microspheres have great potential to be used as a novel solid phase extraction adsorbent that could have wide applications in the environmental field.     

Influence of viscosity on the phase transformation of amorphous calcium carbonate in fluids: An understanding of the medium effect in biomimetic mineralization

Biological mineral generation via an amorphous precursor is a topic of great current interest. Various factors such as the temperature, solution composition and presence of organic molecules can influence this important inorganic process. Here we demonstrate that this mineral transformation can actually readily be regulated by solution viscosity, a fundamental but often overlooked property. In our experiment, amorphous calcium carbonate (ACC), a key model compound in biomimetic mineralization studies, is synthesized and dispersed into inert dispersants with different viscosities and the crystallization process is examined by using FT-IR spectroscopy and XRD. It is found that the inhibition of the transformation of ACC becomes more significant with increasing fluid viscosity. This phenomenon can be explained by the differences in ion diffusion in different media. Furthermore, the resulting crystals always have different morphologies and size distributions although they all have the calcite structure. This study implies that the importance of the fluid medium cannot be ignored in building a complete understanding of biological control of biomimetic crystallizations.     

A novel multi-functional magnetic Fe-Ti-V spinel catalyst for elemental mercury capture and callback from flue gas

A novel magnetic Fe-Ti-V spinel catalyst showed an excellent performance for elemental mercury capture at 100 °C, and the formed HgO can be catalytically decomposed by the catalyst at 300 °C to reclaim elemental mercury and regenerate the catalyst.     

Diastereoselective silver-catalyzed 1,3-dipolar cycloaddition of azomethine ylides with fluorinated imine

We described hereby an instance of diastereoselective silver-catalyzed 1,3-dipolar cycloaddition of azomethine ylides with imine compounds. This new method provided synthetically useful, highly substituted tetrahydroimidazole derivatives with efficiency and high diastereoselectivity. We can conveniently obtain fluorinated dihydroimidazole, imidazole, and diamino esters through simple modification.     

In silico identification of conserved microRNAs and their target transcripts from expressed sequence tags of three earthworm species

MicroRNAs are a recently identified class of small regulatory RNAs that target more than 30% protein-coding genes. Elevating evidence shows that miRNAs play a critical role in many biological processes, including developmental timing, tissue differentiation, and response to chemical exposure. In this study, we applied a computational approach to analyze expressed sequence tags, and identified 32 miRNAs belonging to 22 miRNA families, in three earthworm species Eisenia fetida, Eisenia andrei, and Lumbricus rubellus. These newly identified earthworm miRNAs possess a difference of 2-4 nucleotides from their homologous counterparts in Caenorhabditis elegans. They also share similar features with other known animal miRNAs, for instance, the nucleotide U being dominant in both mature and pre-miRNA sequences, particularly in the first position of mature miRNA sequences at the 5' end. The newly identified earthworm miRNAs putatively regulate mRNA genes that are involved in many important biological processes and pathways related to development, growth, locomotion, and reproduction as well as response to stresses, particularly oxidative stress. Future efforts will focus on experimental validation of their presence and target mRNA genes to further elucidate their biological functions in earthworms.     

Quantitative characterization of membrane formation process of alginate–chitosan microcapsules by GPC

The semi-permeable membrane of alginate–chitosan (AC) microcapsules has been proven important to control the microcapsule stability and selective substance diffusion rate. Therefore, a novel and operable methodology based on gel permeation chromatography (GPC) was established for quantitative characterization of the membrane formation process, so as to provide guidance on performance improvement of AC microcapsules in biomedical applications. Not only the molecular weight (M_w) and its distribution of chitosan can be obtained by GPC, but also the area integral of molecular weight peaks can be linearly correlated to chitosan concentration in certain range. The dynamic membrane formation process was then obtained by quantitatively analyzing reaction amount of chitosan with time, which showed that for chitosan molecules with wide M_w distribution, only parts of molecules bind with alginate to form microcapsule membrane. Moreover, the contribution of chitosan molecules participating in the membrane formation process was also different. These new findings, therefore, are helpful for adjusting and controlling the membrane formation process and properties of microcapsule membrane.