Synthesis of water soluble metalloporphyrin-cored amphiphilic star block copolymer photocatalysts for an environmental application

Two series of water-soluble metalloporphyrin-cored amphiphilic star block copolymers were synthesized by controlled radical polymerizations such as atom transfer radical polymerization (ATRP) and reversible addition fragmentation chain transfer (RAFT), which gave eight amphiphilic block copolymer arm chains consisting of poly(n-butyl acrylate-b-poly(ethylene glycol) methyl ether methacylate) (PnBA-b-PEGMEMA, M_n,GPC = 78,000, M_w/M_n = 1.2, 70 wt% of PPEGMEMA) and poly(styrene-b-2-dimethylamino ethyl acrylate) (PS-b-PDMAEA, M_n,GPC = 83,000, M_w/M_n = 1.2, 67 wt% of PDMAEA), yielding porphyrin(Pd)-(PnBA-b-PPEGMEMA)₈ and porphyrin(Pd)-(PS-b-PDMAEA)₈, respectively. Obtained metalloporphyrin polymer photocatalysts were homogeneously solubilized in water to apply to the removal of chlorophenols in water, and was distinguished from conventional water-insoluble small molecular metalloporphyrin photocatalysts. Notably, we found that the water-soluble star block copolymers with hydrophobic–hydrophilic core–shell structures more effectively decomposed the chlorophenol, 2,4,6-trichlorophenol (2,4,6-TCP), in water under visible light irradiation (k = 1.39 h^?1, t_1/2 = 0.5 h) in comparison to the corresponding water-soluble star homopolymer, because the hydrophobic core near the metalloporphyrin effectively captured and decomposed the hydrophobic chlorophenols in water.     

Silylation of sodium silicate-based silica aerogel using trimethylethoxysilane as alternative surface modification agent

Trimethylethoxysilane (TMES) has been recognized as a good co-precursor to increase the degree of hydrophobicity during the synthesis of a silica aerogel because of its methyl groups. Therefore, some physical properties of silica aerogels, including the contact angle and porosity, were investigated using TMES as a co-precursor at different molar ratios with the main precursor such as tetramethoxysilane (TMOS) or tetraethoxysilane (TEOS). In contrast to TMES, most silylating agents such as hexamethyldisilazane (HMDZ) and trimethylchlorosilane (TMCS) have been used for surface modification because of their ability to enhance the hydrophobicity of the aerogel surface. This work examines the silylation effect, which includes increasing hydrophobicity by TMES to determine the possibility of using it as an alternative silylating agent during ambient pressure drying in the synthesis of sodium silicate-based silica aerogel. In addition, the physical properties of sodium silicate-based silica aerogels with silylation under different TMES/TMCS volume ratio are investigated. The physical properties of sodium silicate-based aerogels can be changed by the TMES/TMCS volume ratio during the surface modification step. Aerogels with a high specific surface area (458?m²/g), pore volume (3.215?cm³/g), porosity (92.7%), and contact angle (131.8°) can be obtained TMES/TMCS volume ratio of 40/60.

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Spontaneous reductive decomposition behavior of hydrogen permanganate in water for chemical decontamination of nuclear power plants

The spontaneous reductive decomposition behavior of HMnO₄ in water as a function of the initial HMnO₄ concentration and reaction temperature was investigated. The decomposition of HMnO₄ was fast in the early stage of the reaction and thereafter slowed down significantly, regardless of the initial HMnO₄ concentration. The loss of HMnO₄ by spontaneous reductive decomposition increased with increasing reaction temperature. Based on the experimental results and the classical nucleation theory, a mathematical model was developed using a combination of two first-order reactions representing the nucleation and crystal growth of MnO₂ to predict the spontaneous reductive decomposition behavior of HMnO₄.     

Pertechnetate removal from aqueous solution using activated carbon modified with oxidizing and reducing agents

Journal of Radioanalytical and Nuclear Chemistry - The adsorption mechanism of pertechnetate on activated carbon (AC) has been studied. For this work, the surface of commercial AC was modified...     

Reversible cyanovinylcarbazole-based polymer gel via photo-cross-linking reaction

A polymeric gel was prepared from a bis(3-cyanovinylcarbazole)-based derivative and a thymine-bearing calix[4]arene derivative via photo-cross-linking between 3-cyanovinylcarbazole and thymine groups by irradiation with 365 nm UV light, a novel and facile method to obtain a soft material. Values for storage and loss moduli of the bis(3-cyanovinylcarbazole)-based derivative and the thymine-bearing calix[4]arene derivative gradually increased during photoirradiation. This gel was transformed back to the solution state by decomposition of the polymer network to the monomers via irradiation with 312 nm UV light.     

Transition-metal-free,atom-economical cascade synthesis of novel 2-sulfonated-benzo[f][1,7]naphthyridines and their cytotoxic activities

An efficient, transition-metal-free cascade synthetic method has been developed for new 2-aryl/heteroaryl sulfonated benzo[f][1,7]naphthyridines. It is tert-butyl hydroperoxide (TBHP) mediated highly regioselective sulfonylation?cyclization?aromatization process between N-(3-aryl/heteroarylprop-2-yn-1-yl)quinolin-3-amines and aryl/heteroaryl sulfonylhydrazides. This synthetic protocol offers one-step strategy for CS and CC bond formations with a broad range of functional group tolerance. It is a simple, mild, and atom-economical route for the synthesis of various valuable functionalized 1, 2-aryl/heteroaryl sulfonated benzo[f][1,7]naphthyridines in moderate yields. Since the core motif of 2-sulfonated benzo[f][1,7]naphthyridines are biologically and pharmaceutically important (TLR activity 7, 8 modulators). Additionally, the synthesized derivatives were evaluated for their in vitro cytotoxic activities against six human cancer cell lines including lung (NCIH23), colon (HCT15), gastric (NUCG-3), renal (ACHN), prostate (PC-3), and breast (MDA-MB-231) cell lines. These compounds displayed significant cytotoxic activities against all tested human cancer cell lines.     

A Crosslinked Nucleic Acid Nanogel for Effective siRNA Delivery and Antitumor Therapy

Functional siRNAs are employed as cross‐linkers to direct the self‐assembly of DNA‐grafted polycaprolactone (DNA‐g‐PCL) brushes to form spherical and nanosized hydrogels via nucleic acid hybridization in which small interfering RNAs (siRNAs) are fully embedded and protected for systemic delivery. Owing to the existence of multivalent mutual crosslinking events inside, the crosslinked nanogels with tunable size exhibit not only good thermostability, but also remarkable physiological stability that can resist the enzymatic degradation. As a novel siRNA delivery system with spherical nucleic acid (SNA) architecture, the crosslinked nanogels can assist the delivery of siRNAs into different cells without any transfection agents and achieve the gene silencing effectively both in vitro and in vivo, through which a significant inhibition of tumor growth is realized in the anticancer treatment.     

Green solvents from ionic liquids and deep eutectic solvents to natural deep eutectic solvents

Natural deep eutectic solvents (NADESs) are defined as mixtures of certain molar ratios of natural compounds such as sugars, organic acids, amino acids, and organic bases that are abundant in organisms. The melting points of these mixtures are considerably lower than those of their individual ingredients and far below ambient temperature. The first publications on the NADES concept in 2011 created a great expectation regarding their potential as green solvents that could replace conventional organic solvents in a wide range of applications. This was largely because many of the drawbacks of conventional synthetic ionic liquids (ILs) and deep eutectic solvents (DESs), particularly their toxicity and environmental hazards, could be solved using NADESs. Throughout the last 7 years, the interest in NADESs has increased enormously as reflected by the exponential growth of the number of related publications. The research on NADESs has rapidly expanded particularly into the evaluation of the feasibility of their application in diverse fields such as the extraction of (targeted) bioactive compounds from natural sources, as media for enzymatic or chemical reactions, preservatives of labile compounds, or as vehicles of non–water-soluble compounds for pharmaceutical purposes. Along with the exploration of these potential applications, there have been a large number of other studies related to their physicochemical features, the search for new NADESs, the research into the interactions between NADES components or with solutes, the recovery of solutes from NADES solutions, and the ways of circumventing inherent problems of NADESs such as their high viscosity and the consequent difficulties in handling them. This article contains a review of the applications of NADESs as extraction solvents, reaction media, and preservative, providing also a perspective of their future.     

High-performance fiber-optic temperature sensor using low-coherence interferometry

A temperature-sensor system based on low-coherence interferometry with a fiber Mach-Zehnder interferometer as a phase modulator was implemented. A measurement range of 20 to 800 degrees C with a resolution of 0.025 degrees C (corresponding to 0.0004 fringe) was achieved with a 1-mm-long fiber Fabry-Perot interferometer as the sensing element.     

Resonant enhancement of low-contrast electro-optic effects

Ferroelectric liquid crystals can be optimized for speed, but such materials tend to have small switching angles and consequently low contrast in the smectic A(*) phase. We describe a method whereby such a low-contrast but fast-switching effect can be enhanced, in theory giving the same contrast as a material with a switching angle of 22.5 degrees . This method therefore promises liquid-crystal modulators of high contrast and with speeds of the order of hundreds of nanoseconds. The theoretical basis of this method and initial results that support this analysis are presented.