Heavy metal removal from water/wastewater by nanosized metal oxides: a review.

A new class of organic nanoparticles (CN-MBE nanoparticles) with a mean diameter of ca. 30−40 nm, which exhibit a strongly enhanced fluorescence emission, were prepared by a simple reprecipitation method. CN-MBE (1-cyano-trans-1,2-bis-(4‘-methylbiphenyl)ethylene) is very weakly fluorescent in solution, but the intensity is increased by almost 700 times in the nanoparticles. Enhanced emission in CN-MBE nanoparticles is attributed to the synergetic effect of intramolecular planarization and J-type aggregate formation (restricted excimer formation) in nanopaticles. On/off fluorescence switching for organic vapor was demonstrated with CN-MBE nanoparticles.

Enhanced Emission and Its Switching in Fluorescent Organic Nanoparticles

Organometal halide perovskites are inexpensive materials with desirable characteristics of color-tunable and narrow-band emissions for lighting and display technology, but they suffer from low photoluminescence quantum yields at low excitation fluencies. Here we developed a ligand-assisted reprecipitation strategy to fabricate brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots with absolute quantum yield up to 70% at room temperature and low excitation fluencies. To illustrate the photoluminescence enhancements in these quantum dots, we conducted comprehensive composition and surface characterizations and determined the time- and temperature-dependent photoluminescence spectra. Comparisons between small-sized CH3NH3PbBr3 quantum dots (average diameter 3.3 nm) and corresponding micrometer-sized bulk particles (2–8 μm) suggest that the intense increased photoluminescence quantum yield originates from the increase of exciton binding energy due to size reduction as well a...

Brightly Luminescent and Color-Tunable Colloidal CH3NH3PbX3 (X = Br, I, Cl) Quantum Dots: Potential Alternatives for Display Technology.

Spiropyrans and Spirooxazines for Memories and Switches

The chemistry of copper is extremely rich because it can easily access Cu0, CuI, CuII, and CuIII oxidation states allowing it to act through one-electron or two-electron processes. As a result, both radical pathways and powerful two-electron bond forming pathways via organmetallic intermediates, similar to those of palladium, can occur. In addition, the different oxidation states of copper associate well with a large number of different functional groups via Lewis acid interactions or π-coordination. In total, these feature confer a remarkably broad range of activities allowing copper to catalyze the oxidation and oxidative union of many substrates.

Oxygen is a highly atom economical, environmentally benign, and abundant oxidant, which makes it ideal in many ways.1 The high activation energies in the reactions of oxygen require that catalysts be employed.2 In combination with molecular oxygen, the chemistry of copper catalysis increases exponentially since oxygen can act as either a sink for electrons (oxidase activity) and/or as a source of oxygen atoms that are incorporated into the product (oxygenase activity). The oxidation of copper with oxygen is a facile process allowing catalytic turnover in net oxidative processes and ready access to the higher CuIII oxidation state, which enables a range of powerful transformations including two-electron reductive elimination to CuI. Molecular oxygen is also not hampered by toxic byproducts, being either reduced to water, occasionally via H2O2 (oxidase activity) or incorporated into the target structure with high atom economy (oxygenase activity). Such oxidations using oxygen or air (21% oxygen) have been employed safely in numerous commodity chemical continuous and batch processes.3

However, batch reactors employing volatile hydrocarbon solvents require that oxygen concentrations be kept low in the head space (typically <5–11%) to avoid flammable mixtures, which can limit the oxygen concentration in the reaction mixture.4,5,6 A number of alternate approaches have been developed allowing oxidation chemistry to be used safely across a broader array of conditions. For example, use of carbon dioxide instead of nitrogen as a diluent leads to reduced flammability.5 Alternately, water can be added to moderate the flammability allowing even pure oxygen to be employed.6 New reactor designs also allow pure oxygen to be used instead of diluted oxygen by maintaining gas bubbles in the solvent, which greatly improves reaction rates and prevents the build up of higher concentrations of oxygen in the head space.4a,7 Supercritical carbon dioxide has been found to be advantageous as a solvent due its chemical inertness towards oxidizing agents and its complete miscibility with oxygen or air over a wide range of temperatures.8 An number of flow technologies9 including flow reactors,10 capillary flow reactors,11 microchannel/microstructure structure reactors,12 and membrane reactors13 limit the amount of or afford separation of hydrocarbon/oxygen vapor phase thereby reducing the potential for explosions.

Enzymatic oxidizing systems based upon copper that exploit the many advantages and unique aspects of copper as a catalyst and oxygen as an oxidant as described in the preceding paragraphs are well known. They represent a powerful set of catalysts able to direct beautiful redox chemistry in a highly site-selective and stereoselective manner on simple as well as highly functionalized molecules. This ability has inspired organic chemists to discover small molecule catalysts that can emulate such processes. In addition, copper has been recognized as a powerful catalyst in several industrial processes (e.g. phenol polymerization, Glaser-Hay alkyne coupling) stimulating the study of the fundamental reaction steps and the organometallic copper intermediates. These studies have inspiried the development of nonenzymatic copper catalysts. For these reasons, the study of copper catalysis using molecular oxygen has undergone explosive growth, from 30 citations per year in the 1980s to over 300 citations per year in the 2000s.

A number of elegant reviews on the subject of catalytic copper oxidation chemistry have appeared. Most recently, reviews provide selected coverage of copper catalysts14 or a discussion of their use in the aerobic functionalization of C–H bonds.15 Other recent reviews cover copper and other metal catalysts with a range of oxidants, including oxygen, but several reaction types are not covered.16 Several other works provide a valuable overview of earlier efforts in the field.17 This review comprehensively covers copper catalyzed oxidation chemistry using oxygen as the oxidant up through 2011. Stoichiometric reactions with copper are discussed, as necessary, to put the development of the catalytic processes in context. Mixed metal systems utilizing copper, such as palladium catalyzed Wacker processes, are not included here. Decomposition reactions involving copper/oxygen and model systems of copper enzymes are not discussed exhaustively. To facilitate analysis of the reactions under discussion, the current mechanistic hypothesis is provided for each reaction. As our understanding of the basic chemical steps involving copper improve, it is expected that many of these mechanisms will evolve accordingly.

/pdf/aerobic-copper-catalyzed-organic-reactions-3ctljpvivz.pdf

Aerobic Copper-Catalyzed Organic Reactions

Organic microcrystals ranging from several tens nm to µm in size of several chromophores were successfully prepared by simply dispersing ethanol solutions of compounds into stirred water, i.e. by a reprecipitation method. The size of microcrystals was found to depend on concentration of ethanol solutions, dispersing conditions, temperature and so on.

https://iopscience.iop.org/article/10.1143/JJAP.31.L1132/pdf

A Novel Preparation Method of Organic Microcrystals

Perylene microcrystals with different sizes from about 50 nm to about 200 nm were prepared using the reprecipitation method. Their excitonic absorption peaks were found to shift to the high energy side with decreasing crystal size, that is to say, the shifts from that of the bulk crystal were about 500 cm-1 and 1420 cm-1 for 200 nm and 50 nm microcrystals, respectively. Moreover, strong fluorescence from the free-exciton energy level in the microcrystals was observed even at room temperature, which is not usually observed in bulk crystals.

https://iopscience.iop.org/article/10.1143/JJAP.35.L221/pdf

Size-Dependent Colors and Luminescences of Organic Microcrystals

Polydiacetylenes (PDAs) are of great interest due to their π-conjugated backbone related properties, such as linear and nonlinear optical properties. As a consequence, design and preparation of PDAs assume enormous importance today. This review deals with one aspect of PDA, that is, design and preparation of the diacetylene monomers and their polymers, PDAs having conjugated side groups. The aim of such an investigation is to produce materials which exhibit large third-order nonlinear optical susceptibilities and which consequently, can be obtained in a form to be customised for optical devices.

Novel polydiacetylenes for optical materials: beyond the conventional polydiacetylenes

Topochemical [2 + 2] cycloaddition polymerization of methyl p-phenylenediacrylate and 2,5-distyrylpyridine in nanocrystals, prepared by the reprecipitation method, were investigated in comparison with those in bulk crystals. The bulk single crystals, larger than 1 mum in size, broke into microcrystals with variety of size and shape in the course of polymerization. Interestingly, however, these nanocrystals show single-crystal-to-single-crystal transformation.

Single-crystal-to-single-crystal transformation of diolefin derivatives in nanocrystals.

In this study, we found that, in perylene microcrystals, luminescence peak position from free-exciton state was gradually shifted to high energy side with reducing the crystal size, even if the microcrystals were fabricated by different kinds of preparation techniques. The life time of luminescence from self-trapped exciton state became shorter when the crystal size reduced. The main reason was estimated to be based on the change of lattice state.

Hachiro Nakanishi

Papers

A Novel Preparation Method of Organic Microcrystals

Size-Dependent Colors and Luminescences of Organic Microcrystals

Novel polydiacetylenes for optical materials: beyond the conventional polydiacetylenes

Single-crystal-to-single-crystal transformation of diolefin derivatives in nanocrystals.

Crystal Size Dependence of Emission from Perylene Microcrystals