From Humble Beginnings

Handbook of Green Chemistry Volume 9 Designing Safer Chemicals, First Edition. Edited by Robert Boethling and Adelina Voutchkova. 

8% l -valeric acid [6]. Nevertheless, by 1912, early experiments into asymmetric organocatalysis were being conducted by Bredig and Fiske, who achieved low levels of asymmetric induction [up to 20% enantiomeric excess ( )] in cyanohydrin formation from benzaldehyde, catalyzed by quinine and also quinidine [7], and it can be confidently stated that the era of asymmetric organocatalysis had begun. 

Examples of nonasymmetric organocatalysts that were introduced in the 1950s include analogs of thiamine reported by Breslow in 1957 as an alternative to cyanide as a catalyst for the benzoin condensation [8]. Asymmetric versions of these thiazolium catalysts were used in organocatalytic benzoin condensations by Sheehan and Hunneman in 1966 [9]. In another important development, in 1969 the nucleophilic catalyst 4-(dimethylamino)pyridine (DMAP), which is now widely used for difficult esterifications, was reported by Steglich [10]. 

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Despite the argument that in terms of trade it is commercial specifications which are most important, it is probably more convenient to discuss these groups in descending order of scope, i.e. from the international downwards. In practice of course, a new test method usually proceeds in the opposite direction from humble beginnings in particular laboratories via national recognition to international status, often becoming much modified on the way. 

While many metal centers can be reversibly cycled between two (or more) oxidation states, few organic moieties can match such reversibility especially in protic media. Nevertheless, the first supramolecular example of an electroswitch-able luminescent device involved the benzoquinone-hydroquinone couple. The luminescence of 55 " is switched off due to PET in the benzoquinone state of the redox couple. Electrochemical or chemical reduction of the benzoquinone under protic conditions to hydroquinone recovers the luminescence of the tris(2,2 -bipyridyl) Ru(II) unit. It is noted that the luminescence of tris(2,2 -bipyridyl) Ru(Il) itself is electroswitchable. Indeed tris(2,2 -bipyridyl) Ru(II) came to fame as a solar energy material from more humble beginnings as a luminescent redox indicator. However 55 achieves the same switching at a lower magnitude of reduction potential. Here lies the advantage of the supramolecular design. Like tris(2,2 -bipyridyl) Ru(II), many lumophores show electroswitchable luminescence. An... 

From the humble beginnings described, coking operations have been developed that can be considered modern processes, for some are still operating today. 

Toronto had gained international reputations as major research institutions before the Second World War. Although some research was carried out prior to 1950 at about 20 universities across Canada, the majority of the significant research was done in the laboratories of the National Research Council of Canada (NRC) in Ottawa. From its humble beginnings in 1916, the NRC developed into a research organization which by the 1960s operated some of the premier research laboratories in the world. 

With this vision in mind, Sheldon was one of the original founders of the American Association for Aerosol Research (AAAR). From its humble beginning as a small group in Santa Monica in 1982, the Association has grown to nearly 1000 members. Along with the European Aerosol Association, the AAAR has become a flagship of a network of aerosol associations worldwide. Sheldon served as President of AAAR during 1984-1986, and remained active in the association nntil the time of his death. 

The development of potential components for molecular computers started from not so humble beginnings. The enlightening research performed by... 

Nuclear magnetic resonance (NMR) spectroscopy is arguably the most important analytical technique available to chemists. From its humble beginnings in 1945, the area of NMR spectroscopy has evolved into many overlapping subdisciplines. Luminaries have been awarded several recent Nobel prizes, including Richard Ernst in 1991 and Kurt Wiithrich in 2002. 

The radioactivity of naturally occurring and artificially produced isotopes, nuclear fission (the reactions involved in commercial nuclear reactors) and nuclear fusion (the source of the sun s power) are all examples of nuclear reactions (Fig. 21.1). Radioactivity started as a scientific curiosity. From these humble beginnings developed nuclear power (the main provider of power for the generation of electricity in some countries) and the awesome power of nuclear warheads. 

OLe Kirk Christiansen, a carpenter from Denmark, designed the first interlocking blocks in 1947. He called his first blocks Automatic Binding Bricks. Mr. Christiansen s workshop was the humble beginning of the now world-... 

Amazon.com, one ofthe most successful pure Internet retailers, has grown from a book reseller to a retailing giant on the Internet. Amazon.com reported its net profit in 2005 as 359 million on 8.49 billion in net sales (Finfacts Team, 2006). From its humble beginnings using one distribution center in Seattle, Amazon.com has expanded to seven distribution centers across the United States as listed in Table 1. 

From these humble beginnings emerged a vast international effort to expand the horizons of the methodology. These efforts rapidly became diversified in order to address the numerous challenges as they were identified. A study of the relevant literature reveals many of these motivating trends, including ... 

Our story has now been brought up to date. From its humble beginnings as a set of isolated triads of elements, the periodic system has grown to embody well more than 100 elements and has survived various discoveries such as that of isotopes and the quantum mechanical revolution in the study of matter. Rather than being swept aside, it has continued to provide a challenge to the development of ever more accurate means of calculating the basic properties of the atoms of the chemical elements. The central role of the periodic system in modem chemistry has been consolidated rather than eroded. 

Ceramic engineering has come a long vray from its humble beginnings in the 1800 s. Various government s encies, universities, businesses, and the general public have contributed to, or benefited from, the innovations made in advanced ceramics. The North American market for advanced structural ceramics was worth 2.7 million in 2007 and is... 

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