Can fluorine chemistry be green chemistry?

The roles of the element fluorine and its compounds in relationship to green chemistry and clean chemical manufacturing are considered.     

Combination of electrochemistry and the concurrent reduction and substitution chemistry to provide a facile and versatile tool for preparing functional polyanilines

Polyaniline as the first commercially available conducting polymer has recently received great attention from both academic and industrial communities. Although there have been quite a few reports on substituted polyanilines, none of them are concerning about the amino- and alkylthio-substituted polyanilines. Unlike other substituted polyanilines, the attempts in synthesizing poly(alkylthioaniline) directly from the alkylthioaniline monomer via chemical and electrochemical oxidative-coupling chemistry were all fail. On the other hand,we have recently discovered that the amino and alkylthio functional groups can be easily introduced to the backbone of emeraldine polyaniline via the concurrent reduction and substitution chemistry. Further combination of electrochemistry and the concurrent reduction and substitution chemistry can provide us a facile and versatile tool for preparing functional polyanilines. Different functional groups can be introduced sequentially to the same polymer backbone. The concentrations of each substituents can be easily controlled. This new process provides us a useful utility for tailoring the molecular and the electronic structures of polyanilines to render them with appropriate and possibly new material properties suitable for many different potential applications.     

Single-molecular detection in solution: a new tool for analytical chemistry

Single-molecule detection (SMD) is becoming more and more popular in the scientific community and is on the threshold to become a technique for laboratory use. Therefore, conceivable applications as well as optimized conditions for SMD will be discussed. To point out the possibilities of SMD, the signal-to-background ratio and the detection efficiency, in combination with the probability of misclassification, will be contemplated.     

Single-molecule detection in solution: a new tool for analytical chemistry

Single-molecule detection (SMD) is becoming more and more popular in the scientific community and is on the threshold to become a technique for laboratory use. Therefore, conceivable applications as well as optimized conditions for SMD will be discussed. To point out the possibilities of SMD, the signal-to-background ratio and the detection efficiency, in combination with the probability of misclassification, will be contemplated.     

Combinatorial chemistry: a tool for the discovery of new catalysts

The discovery of new reactions and catalysts has always presented an intriguing challenge to scientists. With the rise of combinatorial chemistry, a new method has emerged that holds considerable promise to facilitate the task since it allows for the simultaneous generation and testing of a large number of compounds. The crucial difficulty lies in establishing general technologies for rapid and reliable screening of libraries to determine the catalytic activity of their members. Several recent publications have addressed this question by using infrared thermography, colorimetric assays and fluorescence spectroscopy. These techniques have not only been applied successfully to the high-throughput screening of parallel compound arrays but also to the screening of one-bead-one-compound libraries. This demonstrates that combinatorial chemistry possesses indeed the potential to establish itself as a powerful tool for the discovery of new catalysts. This review describes the methodologies used so far for the detection of catalytic events and will place particular emphasis on the on-bead screening of one-bead-one-compound libraries.     

From synthetic organic chemistry to electrochemistry

The paper describes the change of the author??s research from synthetic organic chemistry to electrochemistry and the advantages and disadvantages of having been trained in organic synthesis rather than in electrochemistry. The described research in electrochemistry includes, among other projects, oxidations in non-aqueous solvents, reduction of azomethine derivatives and heterocyclic compounds, synthesis of heterocyclic compounds, reduction of graphite, electrocatalytic reductions, electron transfer in nucleophilic substitutions and additions, determination of redox potentials of short-lived radicals, and electrochemical formation of Grignard compounds having reducible groups. At the end, some considerations after 60?years of research are included.     

Sources and availability of raw materials for fluorine chemistry

The two most important sources of fluorine are the minerals fluorite, commercially known as fluorspar, and fluorapatite, commercially known as phosphate rock.The major consumers of fluorspar are the aluminum, chemical, and steel industries. Acid-grade fluorspar, one of three commercial grades, is used primarily to make hydrogen fluoride, which is then used to produce synthetic cryolite, aluminum fluoride, fluorocarbons, and other fluorochemicals. Elemental fluorine is prepared from anhydrous hydrogen fluoride by electrolysis. Fluosilicic acid is used primarily for water fluoridation but also to make aluminum fluoride and cryolite. Reported U.S. consumption of fluorspar was 753,000 tons in 1984. U.S. demand for fluorspar was projected to increase at an average annual rate of 2.7% between 1983 and 2000.U.S. production of finished fluorspar in 1984 was 72,000 tons. Fluosilicic acid production was 61,000 tons or 107,000 tons as equivalent fluorspar. More than 85% of domestic demand was imported, primarily from Mexico and the Republic of South Africa.A U.S. Bureau of Mines investigation of major fluorspar reserves and resources in market economy countries and China found approximately 900,000 tons of demonstrated and 1,200,000 tons of identified reserves in the United States. Total world demonstrated and identified reserves were 135 million tons and 262 million tons, respectively. The potential resources of fluosilicic acid were estimated at 12 million tons of equivalent fluorspar in the United States and 360 million tons for the total world. Fluorine reserves appear adequate through the year 2000 given current projections.     

Fluorine chemistry statistics: numbers of organofluorine compounds and publications associated with fluorine chemistry

Data are presented which demonstrate the considerable growth in the numbers of new organofluorine compounds produced annually, and also the numbers of papers and patents published concerned with fluorine chemistry. An overview of some information sources of relevance to fluorine chemists is also presented.     

Fluorescence microscopy coupled to electrochemistry: a powerful tool for the controlled electrochemical switch of fluorescent molecules

The first-time coupling of fluorescence microscopy with a three-electrode electrochemical cell is described and applied to the investigation of a controlled-potential redox switch of organic fluorophores such as tetrazine derivatives.     

Aqueous microwave chemistry: a clean and green synthetic tool for rapid drug discovery

The development of "Greener Organic Chemistry" is due to the recognition that environmentally friendly products and processes will be economical in the long term as they circumvent the need for treating 'end-of-the-pipe' pollutants and by-products generated by conventional synthesis. The fundamentals and significant outcomes of microwave-assisted organic synthesis in aqueous medium are summarized in this tutorial review, which have resulted in the development of relatively sustainable and environmentally benign protocols for the synthesis of drugs and fine chemicals.     

Digital microfluidics: a versatile tool for applications in chemistry, biology and medicine

Digital microfluidics (DMF) has recently emerged as a popular technology for a wide range of applications. In DMF, nanoliter to microliter droplets containing samples and reagents can be manipulated to carry out a range of discrete fluidic operations simply by applying a series of electrical potentials to an array of patterned electrodes coated with a hydrophobic insulator. DMF is distinct from microchannel-based fluidics as it allows for precise control over multiple reagent phases (liquids and solids) in heterogeneous systems with no need for complex networks of connections, microvalves, or pumps. In this review, we discuss the most recent developments in this technology with particular attention to the potential benefits and outstanding challenges for applications in chemistry, biology, and medicine.     

Thermal analysis as a tool for investigations in metal oxide chemistry

Applications of thermoanalytical methods for the controlled preparation of metal oxides from various initial compounds (‘precursors’) as well as for investigations of physical properties and the chemical behaviour of oxidic phases as function of temperature and atmosphere are presented. Studies elucidating the course of such processes yield important contributions to the understanding of the reactivity of solids in general. Moreover, they are, e.g. in the field of heterogeneous catalysis, of practical relevance. It is shown, however, that the capability of mere thermal analysis suffers from limitations which have to be overcome by using additional, independent methods such as X-ray diffraction as well as light and electron microscopy.     

Parallel processing on minicomputers: A powerful tool for quantum chemistry

It is shown that performance of quantum chemistry program systems on minicomputers may be enhanced by a factor between 2.5 and 2.8 utilizing microprogramming techniques and a computer architecture allowing four processor activities to operate in parallel, i.e., memory access, basic arithmetic operations, and two high-speed 64-bit floating-point arithmetic units.