Project description:The reactions of two cyclic germylene phosphane adducts with monosubstituted acetylenes caused the formation of spirocyclic germanes, which is postulated to occur by double acetylene insertion into germylene attached bonds. Further insertion of the formed cyclic divinylgermylene into transannular Si-Si or Si-Ge bonds provides the spirocyclic germanes. Thermal treatment of two germacyclopropenes, formed by the reaction of the two cyclic germylene phosphane adducts with tolane, also produced spirocyclogermanes. The structures of the latter require, however, a more complicated mechanistic proposal.
Project description:Removal of toxic dyes from wastewater has become a hot topic in both academic and industrial fields since there is growing concern about the threat of sewage to human health. Herein, we demonstrate that the three-dimensional porous polyacrylamide-phytic acid-polydopamine (termed as PAAM/PA/PDA) hydrogel can be served as reusable adsorbent with high efficiency for either anionic or cationic dyes. Using methyl blue (MB), methylene blue (YMB), methyl violet (MV) and neutral red (NR) as model dyes, we investigate the effect of pH, temperature, dye concentration, and PAAM/PA/PDA hydrogel mass on the adsorption. The experimental maximum adsorption capacities are more than 350.67?mg?g-1 for four selected dyes. Adsorption kinetic and thermodynamic analysis suggests that the dyes are adsorbed on the PAAM/PA/PDA hydrogel through the strong ?-? stacking and anion-cation interaction, and the adsorption process satisfies a pseudo-second-order model. Furthermore, the free-standing PAAM/PA/PDA hydrogel can be easily removed from water after adsorption process, and regenerated by adjusting solution pH values.
Project description:The efficient and straightforward syntheses of silylthioethers and disulfides are presented. The synthetic methodologies are based on new rhodium complexes containing bulky N-heterocyclic carbene (NHC) ligands that turned out to be efficient catalysts in thiol and thiol-silane coupling reactions. These green protocols, which use easily accessible reagents, allow obtaining compounds containing S-Si and S-S bonds in solvent-free conditions. Additionally, preliminary tests on coupling of mono- and octahydro-substituted spherosilicates with selected thiols have proved to be very promising and showed that these catalytic systems can be used for the synthesis of a novel class of functionalized silsesquioxane derivatives.
Project description:A novel, simple and efficient strategy for fabricating a magnetic metal-organic framework (MOF) as sorbent to remove organic compounds from simulated water samples is presented and tested for removal of methylene blue (MB) as an example. The novel adsorbents combine advantages of MOFs and magnetic nanoparticles and possess large capacity, low cost, rapid removal and easy separation of the solid phase, which makes it an excellent sorbent for treatment of wastewaters. The resulting magnetic MOFs composites (also known as MFCs) have large surface areas (79.52 m(2) g(-1)), excellent magnetic response (14.89 emu g(-1)), and large mesopore volume (0.09 cm(3) g(-1)), as well as good chemical inertness and mechanical stability. Adsorption was not drastically affected by pH, suggesting π-π stacking interaction and/or hydrophobic interactions between MB and MFCs. Kinetic parameters followed pseudo-second-order kinetics and adsorption was described by the Freundlich isotherm. Adsorption capacity was 84 mg MB g(-1) at an initial MB concentration of 30 mg L(-1), which increased to 245 mg g(-1) when the initial MB concentration was 300 mg L(-1). This capacity was much greater than most other adsorbents reported in the literature. In addition, MFC adsorbents possess excellent reusability, being effective after at least five consecutive cycles.
Project description:We report the first example of enantioselective, intermolecular diarylcarbene insertion into Si-H bonds for the synthesis of silicon-stereogenic silanes. Dirhodium(II) carboxylates catalyze an Si-H insertion using carbenes derived from diazo compounds where selective formation of an enantioenriched silicon center is achieved using prochiral silanes. Fourteen prochiral silanes were evaluated with symmetrical and prochiral diazo reactants to produce a total of 25 novel silanes. Adding an ortho substituent on one phenyl ring of a prochiral diazo enhances enantioselectivity up to 95:5 er with yields up to 98%. Using in situ IR spectroscopy, the impact of the off-cycle azine formation is supported based on the structural dependence for relative rates of diazo decomposition. A catalytic cycle is proposed with Si-H insertion as the rate-determining step, supported by kinetic isotope experiments. Transformations of an enantioenriched silane derived from this method, including selective synthesis of a novel sila-indane, are demonstrated.
Project description:Neutral hosts for the recognition of anionic guests in water remain underdeveloped due to the inherent thermodynamic barrier for desolvation. To address this challenge, we have repurposed crosslinked porous organic polymers (POPs) as hosts. This polymer architecture affords a hydrophobic environment with a densely packed array of urea hydrogen bond donors to cooperatively promote anion desolvation and recognition in water. Using the principles of supramolecular design, we demonstrate through adsorption assays that the resulting Urea-POP-1 can recognize structurally different dyes containing phosphonate, sulfonate, and carboxylate anions in water. Moreover, when compared to Methyl-POP-1, a control POP lacking hydrogen bond donors, we find that the driving force for desolvation and adsorption of each dye is achieved through hydrophobic interactions with the POP backbone and, more importantly, cooperative hydrogen bonding interactions with the urea sidechains. This starting point sets the stage to exploit the modularity of our design to build a family of neutral polymer hosts with tunable pore sizes and anion preferences for fundamental investigations and targeted applications.
Project description:In the present study, we successfully synthesized a porous three-dimensional Prussian blue-cellulose aerogel (PB-CA) composite and used it as a decorporation agent for the selective removal of ingested cesium ions (Cs+) from the gastrointestinal (GI) tract. The safety of the PB-CA composite was evaluated through an in vitro cytotoxicity study using macrophage-like THP-1 cells and Caco-2 intestinal epithelial cells. The results revealed that the PB-CA composite was not cytotoxic. An adsorption study to examine the efficiency of the decorporation agent was conducted using a simulated intestinal fluid (SIF). The adsorption isotherm was fitted to the Langmuir model with a maximum Cs+ adsorption capacity of 13.70 mg/g in SIF that followed pseudo-second-order kinetics. The PB-CA composite showed excellent stability in SIF with a maximum Cs+ removal efficiency of 99.43%. The promising safety toxicology profile, remarkable Cs+ adsorption efficacy, and excellent stability of the composite demonstrated its great potential for use as an orally administered drug for the decorporation of Cs+ from the GI tract.
Project description:A synthesized functionalized pillared porous phosphate heterostructure (PPH), surface functionalized phenyl group, has been used to remove the dye Acid Blue 113 from wastewater. X-ray photoemission spectroscopy XPS and X-ray diffraction (XRD) were used to study its structure. The specific surface area of this was 498 m²/g. The adsorption capacities of PPH and phenyl surface functionalized (Φ-PPH) were 0.0400 and 0.0967 mmol/g, respectively, with a dye concentration of 10-5 M when well fitted with SIPS and Langmuir isotherms respectively (pH 6.5, 25 °C). The incorporation of the dye to the adsorbent material was monitored by the S content of the dye. It is suggested as an alternative for Acid Blue 113 remediation.
Project description:This report deligates about the creation of porous polymeric organic framework (POF) from dialkynes and poly(alkyne) with their discovery as an efficient set of purifier. POF showed efficient physisorption for dyes-fluorescein and rhodamine B. The material POF selectively released rhodamine B and not fluorescein. The material was recyclable over number of cycles during the adsorption-release cycle. Moreover, the thiol-functionalized POF expectedly showed chemisorption for mercury. Therefore, the prime attractive cause for such a material is its ability to recycle as well as its thiol functionalization toward the removal of heavy metal such as mercury.
Project description:Porous coordination polymers have received intensive attention for pollution abatement, such as dye removal, because of their high porosity and specific surface areas. However, the commonly used water-stable porous coordination polymers are microporous and synthesized within organic solvents, which deters seriously their widespread application. In this report, we developed a facile strategy for the synthesis of mesoporous Zr-based coordination polymer (Zr-BDC-CP) within aqueous solutions. The morphology and structure of Zr-BDC-CP were characterized with scanning electron microscopy, powder X-ray diffraction, and Fourier transform infrared spectroscopy. Pore size distribution analysis confirms that the as-synthesized material is mesoporous, which allows the efficient adsorption of methylene blue, 2.6 times higher than that of the microporous coordination polymer, UiO-66. The decolorization ratio can reach higher than 93.5% in the range of 10 and 400 mg/L for methylene blue solutions. This Zr-based coordination polymer shows wonderful pH stability, where no significant loss of adsorption capacities was observed between pH values of 3 and 11. The simulation of adsorption isotherm indicates that the Freundlich model can fit the adsorption isotherm very well, which reflects that the surface of adsorbents is inhomogeneous. Fitting of kinetic curves shows that the dye adsorption by Zr-BDC-CP follows the pseudo-second-order model, which confirms that the rate-determining step may be a chemisorption process involving valence forces because of the defects within the frameworks of the mesoporous coordination polymer. Zr-BDC-CP also shows desirable recyclability without significant capacity loss. This work presents a facile and sustainable method for the preparation of mesoporous Zr-based coordination polymer for dye removal with excellent stability and recyclability, which could further push the porous coordination polymers for application in the areas of pollution abatement.