Henley's Recipes

January 5, 2015

Scientists are taught to always cite primary sources in their research papers. I doubt that many astronomers still cite Copernicus in publishing a paper on Solar System studies, but citations are a good measure of what's considered to be important in any field of science. Last year marked the 50th anniversary of the Science Citation Index, a service that tracks citations in scientific papers, often to the dismay of academics who are often evaluated by how frequently their papers are cited. A recent article in Nature has reviewed the hundred most cited scientific papers.[1]

What's interesting about this list is that many of the papers are not the ones you would expect. Certainly, Watson and Crick's DNA paper should be there, and at least one of Einstein's fundamental papers, right? These are absent. I've highlighted a few of these top hundred papers, below, selected because of their relevance to my fields of study. You can see from the most cited paper and many of the rest that most highly cited papers involve methods.

•  O.H. Lowry, N.J. Rosebrough, A.L. Farr, and R.J. Randall, "Protein measurement with the folin phenol reagent," J. Biol. Chem., vol. 193 (1951), pp. 265-275. This paper has the most citations (305,148), and you can see from its title that it's an assay to determine the amount of protein in a solution.

•  R. D. Shannon, "Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides," Acta Crystallographica Section A, vol. 35, no. 5 (September, 1976), pp. 751-767. I've cited this paper myself. It has 28,658 citations, and it's ranked twenty-second. Robert Shannon, the paper's author, was a scientist with Dupont, Wilmington, Delaware.

•  S. Iijima, "Helical microtubules of graphitic carbon," Nature, vol. 354, no. 6348 (November 7, 1991), pp. 56 - 58. This is the carbon nanotube paper, ranked thirty-sixth with 22,899 citations.

•  N. Metropolis, A.W. Rosenbluth, M.N. Rosenbluth, A.H. Teller, and E. Teller, "Equation of state calculations by fast computing machines," J. Chem. Phys. vol. 21 (1953), pp. 1087-1092. This paper, which has its own Wikipedia page, is ranked fifty-eighth with 15,902 citations. It describes Monte Carlo calculations using what's now known as the Metropolis algorithm. I wrote about Nicholas Metropolis in a previous article (Nicholas Metropolis, June 11, 2010).

•  K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, and A. A. Firsov, "Electric Field Effect in Atomically Thin Carbon Films," Science, vol. 306, no. 5696 (October 22, 2004), pp. 666-669. This is the graphene paper, ranked sixty-fifth with 15,022 citations. As the authors state in their abstract, "We describe monocrystalline graphitic films, which are a few atoms thick but are nonetheless stable under ambient conditions, metallic, and of remarkably high quality."

•  A. Bondi, "Van der Waals volumes and radii," J. Phys. Chem., vol. 68, no. 3 (March, 1964), pp. 441-451. Another useful list of atomic parameters along the lines of the previously cited Shannon paper. This paper is ranked eighty-third with 13,417 citations. This paper is used as a reference for the Atomic radii of the elements (data page) on Wikipedia.

•  S. Kirkpatrick, C.D. Gelatt, and M.P. Vecchi, "Optimization by simulated annealing," Science, vol. 220, no. 4598 (May 13, 1983), pp. 671-680. This paper is ranked eighty-sixth with 13,293 citations. As its authors write, "A detailed analogy with annealing in solids provides a framework for optimization of the properties of very large and complex systems." I'm a member of the small group that's done both actual annealing and simulated annealing.

•  Donald W. Marquardt, "An algorithm for least-squares estimation of nonlinear parameters," Journal of the Society for Industrial and Applied Mathematics, vol. 11, no. 2 (1963), pp. 431-441. This paper ranks eight-eighth with 13,258 citations. Many useful methods, such as this, appeared in the early days of computing. This is sometimes called the Levenberg–Marquardt algorithm, since it was apparently first published by Kenneth Levenberg under the title, "A Method for the Solution of Certain Non-Linear Problems in Least Squares" in the Quarterly of Applied Mathematics.

•  B. O'Regan and M. Grätzel, "A low-cost, high-efficiency solar-cell based on dye-sensitized colloidal TiO2 films," Nature, vol. 353, no. 6346 (October 24, 1991), pp. 737-740. This paper, ranked ninetieth with 12,873 citations, is about dye-sensitized solar cells. I wrote about these in a previous article (Dye-Sensitized Solar Cells, June 23, 2010).

•  S. Brunauer, P.H. Emmett, and E. Teller, "Adsorption of gases in multimolecular layers," J. Am. Chem. Soc., vol. 60, no. 2 (February 1938), pp. 309–319. This paper is ranked ninety-ninth with 12,252 citations. It's applied as a popular method for measuring the surface area of solids.

Methods for performing parts of experiments, and for later data analysis of experimental data, are very important to experimentalists, as the preceding list shows. There are also small "tricks of the trade" that don't constitute a "least publishable unit," so these become footnotes of papers, and knowledge passed from one graduate student to another.

In my Internet research last month, I happened upon an interesting book of useful recipes published a hundred years ago and freely available on the Internet Archive.[2] The title page of this book, "Henley's twentieth century formulas, recipes and processes, containing ten thousand selected household and workshop formulas, recipes, processes and moneymaking methods for the practical use of manufacturers, mechanics, housekeepers and home workers," is pictured at the left. Although many of the recipes are for

household use, quite a few relate to useful technologies of the time, and they might, with some modification, lead to better ways to do useful laboratory tasks. I've selected a few of these, as follow.

Natural Glue for Cementing Porcelain, Crystal Glass, etc. (page 15). "The large shell snails which are found in vineyards have at the extremity of their body a small, whitish bladder filled with a substance of greasy and gelatinous aspect. If this substance extracted from the bladder is applied on the fragments of porcelain or any body whatever, which are juxtaposed by being made to touch at all parts, they acquire such adhesion that if one strives to separate them by a blow, they are more liable to break at another place than the cemented seam. It is necessary to give this glue sufficient time to dry perfectly, so as to permit it to acquire the highest degree of strength and tenacity."

A non-magnetic alloy for watch-springs, wheels, etc. (page 737). "Gold, 30 to 40 parts; palladium, 30 to 40 parts; copper, 10 to 20 parts; silver, 0.1 to 5 per cent; cobalt, 0.1 to 2.5 per cent; tungsten, 0.1 to 5 per cent; rhodium, 0.1 to 5 per cent; platinum, 0.1 to 5 per cent."

Electroplating: Brassing (page 573). "The following recipe is recommended for the bath: Copper acetate, 50 parts, by weight; dry zinc chloride, 25 parts, by weight; crystallized sodium sulphite, 250 parts, by weight; ammonium carbonate, 35 parts, by weight; potassium cyanide, 110 parts, by weight. Dissolve in 3,000 parts of water." Note - Cyanide was often used in electroplating; but, as you can imagine, its use is nowadays discouraged!

Impervious Corks (page 223). "Corks which have been steeped in petrolatum are said to be an excellent substitute for glass stoppers. Acid in no way affects them and chemical fumes do not cause decay in them, neither do they become fixed by a blow or long disuse."

Liquids for Etching Steel (page 327)."I. Iodine 2 parts Potassium iodide 5 parts Water 40 parts; II. Nitric acid 60 parts Water 120 parts Alcohol 200 parts Copper nitrate 8 parts; III. Glacial acetic acid 4 parts Nitric acid 1 part Alcohol 1 part."

Strengthened Filter Paper (page 503). "When ordinary filter paper is dipped into nitric acid (specific gravity, 1.42), thoroughly washed and dried, it becomes a tissue of remarkable properties, and one that deserves to be better known by chemists and pharmacists. It shrinks somewhat in size and in weight, and gives, on burning, a diminished ash. It yields no nitrogen, nor does it in the slightest manner affect liquids. It remains perfectly pervious to liquids, its filtering properties being in no wise affected, which, it is needless to say, is very different from the behavior of the same paper "parchmented" by sulphuric acid. It is as supple as a rag, yet may be very roughly handled, even when wet, without tearing or giving way. These qualities make it very valuable for use in filtration under pressure or exhaust. It fits closely to the funnel, upon which it may be used direct, without any supports, and it thus prevents undue access of air. As to strength, it is increased upward of 10 times."

Solder For Glass (page 662). "A compound of tin (95 parts) and zinc (5 parts) melts at 392 F., and can then be firmly united to glass. An alloy of 90 parts of tin and 10 parts of aluminum melts at 734 F., adheres, like the preceding, to glass, and is equally brilliant. With either of these alloys glass may be soldered as easily as metal, in two ways. In one, heat the pieces of glass in a furnace and rub a stick of soldering alloy over their surfaces. The alloy will melt, and can be easily spread by means of a roll of paper or a slip of aluminum. Press the pieces firmly together, and keep so until cool."

References:

1. Richard Van Noorden, Brendan Maher, and Regina Nuzzo, "The top 100 papers - Nature explores the most-cited research of all time," Nature, vol. 514, no. 7524 (October 30, 2014), pp. 550-553, doi:10.1038/514550a.
2. Gardner D. Hiscox, "Henley's twentieth century formulas, recipes and processes, containing ten thousand selected household and workshop formulas, recipes, processes and moneymaking methods for the practical use of manufacturers, mechanics, housekeepers and home workers," The Norman W. Henley Publishing Company (New York, 1914), the University Of California Library, via the Internet Archive.