Preparation and gas sensing activity of La and Y co-doped titania nanoparticles

Journal of Sol-Gel Science and Technology - A novel gas sensing material, La–Y co-doped TiO2 nanoparticles, was synthesized by sol–gel method and applied to detect organic pollutants...     

The Effect of Metal‐Ligand Affinity on Fe3O4_Supported Co–Rh Catalysts for Dicyclopentadiene Hydroformylation

The catalytic performances of Co‐Rh/Fe₃O₄ catalysts modified with phosphine ligands (PPh₃) and its analogues on dicyclopentadiene hydroformylation were evaluated. Among these catalysts, Co‐Rh/Fe₃O₄ modified with tris(p‐trifluoromethylphenyl)phosphine was determined to be effective for monoformyltricyclodecanes production, whereas Co‐Rh/Fe₃O₄ modified with PPh₃ or tri‐p‐tolylphosphine was effective for the diformyltricyclodecanes production. To investigate the ligand effects, the complex catalyst system (Co‐Rh/Fe₃O₄ and phosphine ligand) was subjected to pretreatment with syngas and then characterized by thermogravimetry and differential thermal analysis (TG‐DTA). It was determined that the threshold decomposition temperature reflected the corresponding Rh‐phosphine interaction strength, affecting the catalytic selectivity toward different products. A weak Rh‐phosphine interaction was desirable to produce monoformyltricyclodecanes with fast reaction kinetics, whereas a strong Rh‐phosphine complex was required for the synthesis of diformyltricyclodecanes. In addition to the selectivity rule shown in the PPh₃ series, experiments with other ligands also demonstrated similar selectivity trends.     

Design and development of self-repairable and recyclable crosslinked poly(thiourethane-urethane) via enhanced aliphatic disulfide chemistry

Thermoset polymer elastomers that are capable of autonomous repairability upon physical damage at ambient temperature are highly desirable because of their thermal and environmental resistance, outstanding mechanical toughness and stability. To aim at this goal, we demonstrated that tris(diethylamino)phosphine was initially proven as an efficient catalyst for the aliphatic disulfide exchange at mild condition. By making use of the aliphatic disulfide bond reshuffling and elasticity of polyurethane elastomers, the inherently cross-linked polysulfide-based poly(thiourethane-urethane) elastomers were prepared and exhibited the ability to mend without extrinsic stimuli in the presence of phosphorus catalyst at room temperature after artificially damaged. The self-healing efficiency via the mechanical recovery approach was investigated to be mainly dependent upon the cross-linking density of polysulfide and hard segments chemistry, which in turns determined the molecular chain diffusion and reshuffling that was corroborated by the stress-relaxation study. The thermoset elastomer based on asymmetric diisocynate showed a maximum self-healing efficiency of 85.6% compared to 71.6% for the elastomer with symmetric monomer building blocks. The self-healable polymer was confirmed to be recyclable and reprocessable through a cut-compression processing cycle under a quite mild pressure and temperature thanks to the disulfide bond reshuffling. Meanwhile, the recycled thermoset elastomer well maintained the mechanical properties to its original material.     

Multipolar Porphyrin-Triazatruxene Arrays for Two-Photon Fluorescence Cell Imaging

Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP) _n (n=1–3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40–0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT-ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δ_TPA values of TAT-(ZnP)₂ and TAT-(ZnP)₃ further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π-conjugated quadrapole/octupole molecules and the extension of D -π-A-D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin-based TPEF materials by the construction and extension of D -π-A-D multipolar array.     

Highly Conjugated π-Systems Arising from Cannibalistic Hexadehydro-Diels–Alder Couplings: Cleavage of C−C Single and Triple Bonds

We have investigated the cannibalistic self-trapping reaction of an ortho-benzyne derivative generated from 1,11-bis(p-tolyl)undeca-1,3,8,10-tetrayne in an HDDA reaction. Without adding any specific trapping agent, the highly reactive benzyne is trapped by another bisdiyne molecule in at least three different modes. We have isolated and characterized the resulting products and performed high-level calculations concerning the reaction mechanism. During the cannibalistic self-trapping process, either a C≡C triple bond or an sp–sp³ C−C single bond is cleaved. Up to seven rings and nine C−C bonds are formed starting from two 1,11-bis(p-tolyl)undeca-1,3,8,10-tetrayne molecules. Our experiments and calculations provide considerable insight into the variety of reaction pathways which the ortho-benzyne derivative, generated from a bisdiyne, can take when reacting with another bisdiyne molecule.     

Silica microbeads capture fetal nucleated red blood cells for noninvasive prenatal testing of fetal ABO genotype

ABO hemolytic disease of the newborn (ABO-HDN), which may cause neonatal jaundice and polycythemia, or even stillbirth or neonatal death, is widespread in China. Prenatal testing for the fetal ABO blood group can reduce unnecessary concerns or ensure prompt treatment. Herein, we presented a method to employ high-density silica microbeads (SiO₂ MBs) for capturing fetal nucleated red blood cells (fnRBCs) in maternal peripheral blood, and we detected the ABO genotype of the fetus using these captured cells. We evaluated 52 patients using the SiO₂ MBs. Among 26 pregnant women with type O blood, 8 (30.8%) of the fetuses had type A blood, 5 (19.2%) had type B blood, and 13 (50%) had type O blood. SRY genes were detected in all 27 male fetuses. This study represents a simple and effective method for noninvasive prenatal detection of the fetal ABO genotype. We believe that this method has great potential for noninvasive prenatal testing of the fetal Rh blood group and other fetal diseases as well.     

Design and synthesis of the honeycomb PtSnNa/ZSM-5 monolithic catalyst for propane dehydrogenation

A novel PtSnNa/ZSM-5 monolithic catalyst was designed and synthesized for the propane dehydrogenation reaction, which was a significant transformation in industry. Experimental results showed that although the propane conversion and the propylene selectivity gradually fell down along with the reaction time, the descent speed of the PtSnNa/ZSM-5 monolithic catalyst was slower than that of the granule catalyst and the propane conversion and propylene selectivity of the reaction with monolithic catalyst still remained at a high level after 12 hr. The monolithic catalyst had regular pore structure that facilitated the separation of the product from the catalyst and reduced the limitation on internal and external diffusion and mass transfer, and led to the high catalytic activity and stability. The catalyst could be easily fabricated and was of highly industrial application potential.     

Nickel Oxide/Graphene Composites: Synthesis and Applications

Nickel oxide (NiO) has emerged as one of the most promising transition-metal oxides (TMOs) for electrochemical capacitors, batteries, catalysis, and electrochromic films, owing to its cost-effectiveness, abundance, and well-defined electrochemical properties. Recent studies have identified that mixing NiO with graphene or graphene derivatives results in novel composites with synergistic effects and superior electrochemical performance. This review summarizes the latest advances in composites of NiO with graphene or graphene derivatives. The synthetic strategies, morphologies, and electrochemical performance of these composites are introduced, as well as their electrochemical applications in supercapacitors, batteries, sensors, catalysis, and so forth. Finally, tentative conclusions and assessments regarding the opportunities and challenges for the future development of these composites and other TMOs/graphene or graphene-derived composites are presented.