Size modulation of MIL-125 nanocrystals to promote the catalytic performance towards oxidative desulfurization.

The Ti-based metal-organic framework (Ti-MOF) MIL-125 with tunable crystalline size in the range of ca. 50 nm to 1500 nm was synthesized by the coordination modulation method using trans-cinnamic acid (CA) as a modulator. The coordination modulation also induced hierarchical porosity and structure defects on the nanocrystals. A significant size-dependent catalytic activity towards the oxidative desulfurization (ODS) reaction was observed for these MIL-125 nanocrystals. In particular, the MIL-125 nanocrystals with a mean size of ca. 50 nm exhibit dramatically enhanced catalytic performance for the bulky sulfur compound 4,6-dimethyldibenzothiophene (4,6-DMDBT) compared to the microcrystals. It is demonstrated that the size modulation of MIL-125 is an effective approach to promote its performance for the catalysis of bulky molecules.

Shape-controlled synthesis of the metal-organic framework MIL-125 towards a highly enhanced catalytic performance for the oxidative desulfurization of 4,6-dimethyldibenzothiophene.

Nanoscale MIL-125 crystals with truncated octahedral shape were synthesized through the coordination modulation method using butyric acid as the modulator. Compared to the traditional MIL-125 crystals with dominant {001} facets, the truncated octahedral crystals are dominated by {101} facets as the exposed crystal facets. The MIL-125 crystals with different morphology exhibit significant facet-dependent catalytic activity for the oxidative desulfurization (ODS) reaction. The truncated octahedral MIL-125 crystals show remarkably enhanced catalytic performance towards oxidative desulfurization of the most refractory sulfur compound 4,6-dimethyldibenzothiophene (4,6-DMDBT). It is demonstrated that the shape-controlled synthesis of nanoscale MIL-125 is a promising way to promote its catalytic performance towards the reaction involving bulky molecules.

Template Thermolysis to Create a Carbon Dots-Embedded Mesoporous Titanium-Oxo Sulfate Framework for Visible-Light Photocatalytic Applications.

An organo-templated titanium-oxo sulfate of the formulation (H2nep)[TiO(SO4)2] (denoted as TiOS, nep = N-ethylpiperazine) was synthesized under solvent-free conditions. The framework of TiOS is assembled from the [TiO(SO4)2]n2n- infinite chains interconnected by the H2nep cations through H-bond networks. After thermal treatment under vacuum conditions, the organic template H2nep was partially decomposed and converted into N-doped carbon dots (N-CDs), resulting in the N-CDs@TiOS composite material with retained crystallinity of the parent TiOS. The thermolysis of organic templates generates meso-cavities in the framework, rendering N-CDs@TiOS with a mesoporous structure. Photoelectrochemical and photocatalytic experiments show that the presence of N-CDs substantially improved visible-light-driven photocatalytic activity of N-CDs@TiOS compared to that of TiOS. The template thermolysis strategy gives an effective approach to construct the CDs-sensitized Ti-based mesoporous open-framework materials for visible-light photocatalytic applications.

Construction of Highly Catalytic Porous TiOPC Nanocomposite Counter Electrodes for Dye-Sensitized Solar Cells.

Developing low-cost, durable, and highly catalytic counter electrode (CE) materials based on earth-abundant elements is essential for dye-sensitized solar cells (DSSCs). In this study, we report a highly active nanostructured compositional material, TiOPC, which contains titanium, oxygen, phosphorus, and carbon, for efficient CE in I3-/I- electrolyte. The TiOPC nanocomposites are prepared from carbon thermal transformation of TiP2O7 in an atmosphere of nitrogen at high temperature, and their catalytic performance is regulated by changing the carbon content in the nanocomposites. The TiOPC with appropriate 24.6 wt % carbon and porous structure exhibits an enhanced electrocatalytic activity in the reduction of I3-, providing a short-circuit current density of 16.64 mA cm-2, an open-circuit potential of 0.78 V, and an energy conversion efficiency of 8.65%. The photovoltaic performance of TiOPC CE-based DSSC is even superior to that of a Pt CE-based cell (13.80 mA cm-2, 0.79 V, and 6.66%). The enhanced catalytic activity of TiOPC is attributed to the presence of predominant Ti-O-P-C structure along with the continuous conductive carbon network and the porous structure.

Distribution of Th17 cells and Th1 cells in peripheral blood and cerebrospinal fluid in chronic inflammatory demyelinating polyradiculoneuropathy.

Chronic inflammatory demyelinating polyradiculoneuropathy (CIDP) is an immune-mediated demyelinating disease of the peripheral nervous system. Th17 and Th1 cells contribute to the pathogenesis of most autoimmune diseases, but little is known about their distribution and reciprocal relationship in CIDP. In this study, we analyzed the distribution of Th17, Th1, and Th17/Th1 cells in the peripheral blood and cerebrospinal fluid (CSF). The results showed that the frequency of Th17 cells was significantly higher in the peripheral blood mononuclear cell (PBMCs) and CSF of active CIDP in comparison with remitting CIDP or to other non-inflammatory neurological diseases (ONDs), accompanied by similar findings for Th17/Th1 cells. Both active and remitting CIDP have higher percentage of Th1 cells in the CSF than OND. CSF protein levels positively correlated with the frequencies of Th17 cells either in the PBMCs or CSF of active CIDP, while there was no significant correlation with Th1 cells. In line with these observations, the levels of interleukin-17 (IL-17) in plasma and transcript factors retinoic acid receptor-related orphan receptor (ROR)γt expressed by PBMCs were significantly higher in the active CIDP than remitting CIDP or OND. In summary, our preliminary findings suggest that elevated numbers of inflammatory T cells, especially for Th17 cells, might be an important determinant in the evolution of CIDP.

Development of microsatellite markers from tartary buckwheat.

A genomic library enriched with (gT)(n) repeats from tartary buckwheat (Fagopyrum tataricum) was constructed using 5'-anchored PCR for the development of microsattellite markers. Sequencing analysis of 5 clones from the library showed that they all contained microsatellites (totally 10 loci), and each was unique. An additional locus-specific primer was designed according to flanking sequence. Two of the microsatellite loci of 10 tartary buckwheat varieties were amplified using an anchored primer and a locus-specific primer, which revealed a clear polymorphic pattern. The data confirmed that the degenerate primer was reliably anchoring at the 5'-end of the microsatellite, and the primers developed based on this technology could be used for diversity analysis of tartary buckwheat.