The scientific legacy of Howard Vincent Malmstadt

Spectrochimica Acta Part B 61 (2006) 602 – 618 www.elsevier.com/locate/sab

The scientific legacy of Howard Vincent Malmstadt ☆ Gary Horlick ⁎ Department of Chemistry, University of Alberta, Edmonton, AB, Canada T6G 2G2 Received 16 May 2006; accepted 17 May 2006

Abstract Howard Malmstadt was a true giant of Analytical Chemistry and clearly one of the most influential analytical chemists of the last 50 years. Howard, through his own work and that of his students (first generation) and their students (second generation) and their students' students (third generation) changed the course of Analytical Chemistry. His research interests were broad and ranged from analytical solution chemistry (titrimetry and reaction rates) and electrochemistry to atomic and molecular spectroscopy, chemical instrumentation, clinical chemistry and automation. Howard was also one of the most innovative and influential educators of our time. He changed forever the analytical curriculum through his many books on Electronics for Scientists, most written in conjunction with Chris Enke and Stan Crouch. Their texts and short courses went from pioneering the application of tube-based analog electronics (servo systems and operational amplifiers) in scientific measurements to the impact that integrated circuits and digital electronics would have on laboratory measurements. He strongly believed in the importance of “handson” in education. To this end, he expended considerable personal effort and time to see not only the development and commercialization of an effective laboratory infrastructure to support education in analog and digital electronics, but also oversaw the development of modular instrumentation for spectroscopy. Over the years he received many awards from the Analytical Chemistry community for his outstanding efforts and contributions to teaching and research. Many of Howard's students went on into academia. They and their students now represent the ongoing legacy for analytical chemistry that evolved from Howard's laboratory at Illinois. A remarkable diversity of research programs are underway in their laboratories. Topics range from atomic, laser, mass, and Raman spectroscopy to detection technology, analytical education, micro-fabricated instrumentation, and intercellular analytical measurements.

Keywords: Howard V. Malmstadt; Chemical instrumentation; Chemical education

1. Introduction At the Pittsburgh Conference held in Chicago, Illinois in March of 2004, a symposium was held in honor of Howard V. Malmstadt. The symposium was entitled “Howard V. Malmstadt: His Ongoing Legacy for Analytical Chemistry”. Planning for the symposium was well underway a year earlier, in March of 2003, with the full intent that Howard would be present at the symposium. Unfortunately, Howard passed away on July 7, 2003 in Hawaii. Howard Malmstadt had that hard-to-define component of leadership that fostered independence, creativity and great enthu☆

This article is published in a special honor issue of Spectrochimica Acta Part B dedicated to the memory of Prof. Howard V. Malmstadt, in recognition of his many outstanding contributions to spectrochemical analysis, in areas of research, leadership, and teaching. ⁎ Tel.: +1 780 492 5552; fax: +1 780 492 8231. E-mail address: [email protected].

doi:10.1016/j.sab.2006.05.008

siasm in those that worked with him and many truly innovative research ideas and papers emanated from his laboratory at the University of Illinois. Through his own work and that of his students (first generation), their students (second generation) and ongoing generations, the course of Analytical Chemistry was changed. He was a true giant of Analytical Chemistry and clearly one of the most influential analytical chemists of the last 50 years. In this paper (based on a presentation at the symposium for Howard [1]) some highlights of Howard's career will be presented along with an outline of the legacy for Analytical Chemistry that has evolved from the research of the first and ongoing generations that make up the Malmstadt family of students. 2. The beginning (Wisconsin and the Navy) First, a brief look at the past. The scientific family tree for Howard V. Malmstadt is shown in Fig. 1. The tree extends back

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Fig. 1. Historical scientific family tree for Howard V. Malmstadt.

through T.W. Richards (Harvard University), to both French and German institutions. Richards, regarded by many as the first Analytical Chemist in North America, received the Nobel Prize for his accurate determinations of atomic weights. Brief accounts of his research and that of Vauquelin, Thenard, Berthollet, Liebig, and Guy-Lussac can be found in reference [2] along with images of these scientists as they have appeared on postage stamps. Howard attended the University of Wisconsin, Madison for both his undergraduate and graduate degrees. However, this beginning to his scientific career was interrupted by World War II. After graduation with his undergraduate degree he was

commissioned in the U.S. Navy. He attended navel electronics and radar schools and served, from 1944 to 1945, as a navy lieutenant (radar officer) on a destroyer in the Pacific Fleet. Upon returning, he was supervisor for the Department of Electronic Fundamentals at the Naval Radar School on Treasure Island, California. As a result of this military service during W.W. II, he became highly trained in the state-of-the-art electronics for the era. This expertise that he gained in electronics provided him with unique insight into the impact that the development of modern electronics would have on how scientific measurements would be carried out. In many ways this experience set the

Fig. 2. Abstract for Malmstadt PhD research paper (Anal. Chem. 22 (1950) 734–742).

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Fig. 3. Abstract for first paper of Malmstadt from research at the University of Illinois (Anal. Chem. 26 (1954) 442–445).

tone for his research for the rest of his life, as he focused much of his career on the wide-ranging aspects of applying electronics to scientific measurements. In addition, the teaching environment in the naval schools (professional, hands-on, short and intense) strongly influenced his educational approach to teaching scientific electronics. Howard became one of the most innovative and influential educators of our time. In particular, he changed forever the analytical curriculum through his many books on Electronics for Scientists, his strong belief in the importance of “hands-on” education and the need to move quickly from the lecture to the laboratory environment. But, we are getting ahead of ourselves. After being discharged from the Navy, he returned to the University of Wisconsin. He carried out his PhD research under the direction of Walter J. Blaedel, working in the area of high-frequency titrations. He had several publications in this area (see reference list) and the abstract for one of them [Malmstadt Publication 3]

is shown in Fig. 2. Clearly, the electronic and instrumental tone to his research had already begun. 3. The Illinois years (1951–1964) Upon graduation from the University of Wisconsin, he was recruited by Herb Laitinen to the Department of Chemistry at the University of Illinois in Champaign-Urbana. He joined the Department in 1951. His first work at Illinois was concentrated in the area of titrimetry, with an emphasis on automating the titration process. The title and abstract of the first paper from his research at Illinois is shown in Fig. 3. His work in automating the titration process progressed rapidly and soon he and his students had developed automatic, differential potentiometric [Malmstadt Publication 9] and spectrophotometric [Malmstadt Publication 14] titrators. The circuit diagram for the differential titrator [Malmstadt Publication 9] is shown in Fig. 4. A commercial

Fig. 4. Circuit for auto-titrator (Anal. Chem. 26 (1954) 1348–1351).

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Fig. 5. Analytical Chemistry advertisement for the Sargent–Malmstadt automatic titrator.

titrator was developed based on the concepts that he developed and was known as the Sargent-Malmstadt Automatic Titrator. An advertisement for this titrator that appeared in the journal Analytical Chemistry in the mid-1950s is shown in Fig. 5. When Laitinen recruited Malmstadt to Illinois, he actually asked Howard to expand his research program into the area of

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analytical atomic spectroscopy. Emission spectroscopy underwent dramatic development during W.W. II, particularly with the development of the photomultiplier tube-based, directreading spectrometers and Laitinen felt that the field should be part of the teaching and research program at Illinois. To this end, Howard spent some time in the early 1950s learning about the techniques and instrumentation of emission spectroscopy at the Applied Research Laboratories (ARL) in Southern California under the mentorship of Maurice Hasler. It is interesting to note that many years later at the 1995 Pittsburgh Conference in New Orleans, Howard would be the recipient of the Maurice F. Hasler Award. Howard's first paper in emission spectroscopy [Malmstadt Publication 12], co-authored with R.G. Scholz, was titled “Emission spectrochemical analysis of vanadium and iron in titanium tetrachloride. Spark-in-spray excitation method”. The abstract for this paper (reproduced from Analytical Chemistry) is shown in Fig. 6 and Figure 1 from that paper is shown in Fig. 7. Over the years, atomic spectroscopy became a long-term research area and a focus for the research of many graduate students. Perhaps the pinnacles of his work in this area were the stunningly detailed and high quality research carried out by John Walters on the emission characteristics of the high voltage spark discharge [Malmstadt Publication 49] in the early to mid-1960s and the uniquely definitive work carried out by Gary Hieftje clarifying processes in flame spectrometric analysis utilizing an elegant isolated droplet technique [Malmstadt Publication 58] in the late 1960s. Finally during this early part of his career, he developed his interests in reaction rate methods of analysis and clinical

Fig. 6. Abstract for Malmstadt's first paper in emission spectroscopy (Anal. Chem. 27 (1955) 881–883).

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Fig. 7. Diagram of spark-in-spray apparatus (Anal. Chem. 27 (1955) 881–883).

chemistry, particularly glucose determinations. One of his first papers in this area, co-authored by G.P. Hicks [Malmstadt Publication 35], was the “Determination of glucose in blood serum by a new rapid and specific automatic system”. The new system was based on automatically measuring the initial reaction rate of a coupled enzymatic oxidation of glucose. With the right conditions the initial reaction rate was directly proportional to concentration (Fig. 8). Many students worked in this area, including Pardue, Hadjiioannou and Crouch. A summary of the evolution of his research interests during his first decade and a half at Illinois is provided by the listing of his graduate students and their thesis titles as presented in Table 1.

Somewhat arbitrarily I have used the graduation years from 1955 to 1964 to designate his first group of PhDs. Among these, one recognizes several names well known to the analytical chemistry community, including Jim Winefordner (University of Florida), Themis Hadjiioannou (University of Athens), Harry Pardue (Purdue University), Willard Harrison (University of Florida) and J.P. Walters (University of Wisconsin/St. Olaf College). Photographs of Howard from this time frame are shown in Figs. 9 and 10. Howard Malmstadt was intensely interested in teaching. He spent a considerable portion of his career in the development of course material (texts and equipment) in the areas of electronics, chemical instrumentation and spectroscopy. His teaching philosophy also had a strong emphasis on the intensive short course and hands-on learning, moving quickly from the lecture to the teaching laboratory environment. His now-legendary book Electronics for Scientists (see Book List), published in 1962, co-authored with Chris Enke and with the assistance of Cliff Toren, changed the course of education in our field. It was sub-titled Principles and Experiments for Those Who Use Instruments and nicknamed the black book. In this initial book, they pioneered the application of tube-based analog electronics (servo systems and operational amplifiers) to scientific measurements. This book, along with the hands-on experiments made possible by the Heath-built Instrumentation Station (Fig. 11), resulted in the adoption of this program at hundreds of institutions all over the world. Malmstadt was particularly fond of the intensive short-course format for the presentation of this material. The three-week summer course presented at Champaign-Urbana for many years was as legendary as the book. The normal full 15-week semester course was presented in 15 days to 75 participants in two daily shifts of lectures and three (morning, afternoon and evening) daily shifts of laboratory. The short course provided a rich training ground for many of Howard's students who served as teaching assistants. It was an intense experience for both the teaching assistants and students.

Fig. 8. Chart recorder output illustrating the concept of the initial reaction rate method of analysis (Anal. Chem. 32 (1960) 394–398).

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Table 1 The first group of PhD students, 1955–1964 Student

Year

Thesis title

E.R. Fett C.B. Roberts P.A. Vassallo J.D. Winefordner A.L. Schalge W.E. Chambers A.W. Cordes T.P. Hadjiioannou P.P-L. Ho H.L. Pardue E.C. Toren, Jr. W.W. Harrison W.W. Lanier J.P. Walters

1955 1956 1958 1958 1959 1960 1960 1960 1960 1961 1961 1964 1964 1964

Automatic potentiometric titrations Automatic spectrophotometric titrations Automatic potentiometric and spectrophotometric titrations Precision null-point potentiometry (PNPP) Emission spectrochemical analysis by the spark-in-spray solution technique Precision null-point atomic absorption spectrometry Dielectric behavior in polar solvents EDTA titrations with automatic spectrophotometric end-point Automatic turbidimetric titrations Precision null-point potentiometry (PNPP) and reaction rate methods Potentiometric reaction rate methods Quantitative atomic absorption spectroscopy Precision spectrophotometry Time-resolved spark spectroscopy: a study of the sampling step in the point-to-plane spectrochemical analysis of aluminum base alloys

And these were not your ordinary summer students. The “summer student” included many senior scientists from industry and government laboratories, as well as many professors from a wide-ranging number of universities and colleges, many wanting to learn the material so as to be able to take the course back to their own institution. Indeed, Walter Blaedel, Malmstadt's thesis professor, was one of the participants in the late 1960s. All-in-all, it was a unique experience to be part of teaching this course in the summer. It is remarkable that in parallel to all the developments with respect to the electronics course, Malmstadt and Enke also developed equipment to support laboratory instruction in the rapidly-evolving “Instrumental Analysis” courses that were appearing in chemistry programs. This included the Heath– Malmstadt–Enke pH recording electrometer and controlled potential polarography system. They were remarkably versatile yet low-cost systems. Photographs of Malmstadt and Enke from this time frame are shown in Fig. 12. Many people have assumed that Chris Enke

was one of Howard's students. He was, in fact, a PhD student at Illinois but he carried out his research under the direction of Herb Laitinen. One of the first major awards of the many that Howard was to receive came in 1963. That year he received the ACS Award in Chemical Instrumentation at the meeting in Los Angeles. The notation for the award is shown in Fig. 13. It is hard to imagine anyone fitting these criteria better than Howard Malmstadt. In addition to the 1963 symposium honoring Howard (“New Instrumental Methods and Techniques”), there was also a fullday symposium at the meeting entitled “Operational Amplifiers in Analytical Instrumentation”. This was the heyday for new

Fig. 9. Photograph of Howard Malmstadt from the time frame of his early years at Illinois.

Fig. 10. Photograph of Howard Malmstadt from the time frame of his early years at Illinois.

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Fig. 11. The Heath electronic station.

applications of operational amplifiers (OAs) in chemical instrumentation. Both Howard and Chris Enke were strong proponents of OAs, and their controlled-potential polarography system, mentioned earlier, was based on an OA design. In addition to papers presented by Howard and Chris at the symposium, several other papers were presented by a veritable who's-who of analytical chemists including Donald DeFord, Galen Ewing, Irving Shain, Robert Osteryoung, Richard Buck, Donald Smith, and Royce Murray. Topics ranged from discussions of the basic OA as an electronic device to current and potential control in electrochemical measurements, cyclic voltammetry, a.c. polarography, chronopotentiometry, and square-wave polarography. Howard would have been one of the first to state that it really is the people that he was associated with that form his true scientific legacy. He was always very proud of the accomplishments of his “academic children”. It is a remarkable part of his scientific legacy that many of his people have gone on to receive several of the awards that he too received. This is particularly true for the Award in Chemical Instrumentation presented by the

ACS Division of Analytical Chemistry. In addition to Howard in 1963, Chris Enke (Michigan State University/University of New Mexico) received the award in 1974, Jim Winefordner (University of Florida) in 1978, John Walters (University of Wisconsin/St. Olaf College) in 1979, Harry Pardue (Purdue University) in 1982, Gary Hieftje (Indiana University) in 1985, Bonner Denton (University of Arizona) in 1989, and Stan Crouch (Michigan State University) in 2001. Now secondgeneration students have started to receive the award. These include Jonathan Sweedler (University of Illinois) in 2002 (a Denton student) and Mike Ramsey (Oak Ridge National Laboratory/University of North Carolina) in 2003 (a Hieftje student). Thus, in a period of about four decades, ten “Malmstadt People” have received this award, a quarter of all the awards made in that time frame. 4. The Illinois years (1965–1972) The dramatic development of integrated circuits and digital electronics that occurred in the mid- to late 1960s certainly did

Fig. 12. Photographs of Howard Malmstadt (left) and Chris Enke (right), during the early years of collaboration.

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Fig. 15. ADD unit reality! Fig. 13. Citation for ACS Award in Chemical Instrumentation.

not go unnoticed by Malmstadt and Enke. They sensed early, and with remarkable perception, the impact that integrated circuits, digital electronics and computers would have on laboratory measurements. Howard's vision in this area was decades ahead of what was to come in the now so-called “digital world” of today's advertisements. In addition to recognizing the importance of the development of digital electronics, they also saw the need to develop new texts and laboratory equipment and experiments in order to present state-of-the-art courses in electronics to a new generation of students. A new text, the so-called red book, entitled Digital Electronics for Scientists, co-authored with Chris Enke, appeared in 1969 (see Book List). Almost simultaneously, new teaching hardware was developed, again in cooperation with Heath, in the form of the first generation ADD (Analog Digital Designer) unit (Fig. 14). This unit allowed one to quickly patch-wire a remarkably wide range of both digital and analog circuits. It fostered great creativity among students, although ADD unit reality sometimes looked like that shown in Fig. 15. Along with the ADD unit, Malmstadt, Enke and the Heath Company developed a Universal Digital Instrument (UDI) that was capable of carrying out a wide range of digital counting measurements. With simple push-button controls, one could use it as a basic digital counter, for frequency measurements, period

Fig. 14. The original analog digital designer (ADD Unit) from Heath.

measurements, time-interval measurements, and frequencyratio measurements, and voltage measurements using either a voltage-to-frequency converter or a voltage-to-time interval converter. It was a versatile and effective system for both teaching and research. Amazingly, and in parallel to all these developments in digital electronics, Malmstadt inspired the development of a complete line of instrumentation for research and teaching in spectroscopy. The core unit was a 0.35-meter Czerny–Turner scanning monochromator (Fig. 16). At the symposium for Howard at Pittcon 2004, John Walters [3] gave a fascinating account of the development of the Heath monochromator. As he said, “Howard Malmstadt directed the academic side of the project, with Jack Haynes, Chris Enke and myself (Walters) doing the mechanical, electronic and optical design, respectively. Niel Shimp and Wayne Kooy, of the Heath Company, directed the industrial side of the project…Raymond Vogel did analytical methods development…The effort was one of the more exciting and rewarding aspects of my (Walters) career and represents well the way that Howard could bring people together to bring out their best.” The “Heath Monochromator” was, and still is, an excellent monochromator and can be seen to this day in colleagues' laboratories incorporated into active research and teaching setups. Support equipment for the spectroscopy system included a photomultiplier module,

Fig. 16. The “Heath monochromator”.

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Table 2 The second group of PhD students, 1965–1972 Student

Year

Thesis title

R.M. Barnes E.H. Piepmeier S.R. Crouch P.J. Zanzucchi J.M. Baldwin A.V. Nowak L.J. Cline M.L. Franklin

1966 1966 1967 1967 1968 1968 1969 1969

G.M. Hieftje A.C. Javier

1969 1969

G. Horlick E.D. Jackson J.W. Kirkpatrick K-P. Li

1970 1970 1970 1970

J.A. Reeve C.J. Delaney M.B. Denton E.D. Iracki E.C. Stanley

1971 1972 1972 1972 1972

Submicrosecond time-resolved spark emission spectroscopy Time- and spatially-resolved emission and atomic absorption measurements on laser plumes Automatic reaction rate methods Direct solution analysis with a new hollow cathode discharge system Alkali-metals–halogen interactions in the sensitized flame ionization flame photometric detector A selective gas-chromatographic detector utilizing emitted radiation from a sensitized flame Signal-to-noise considerations in laser-Raman spectrometry Submicrosecond time- and spacially-resolved investigations of atomic emission produced from an Al target by a megawatt pulsed laser with and without auxiliary spark excitation Investigations into flame spectrometric processes and methods using an isolated droplet technique Investigations of the mechanism of the 12-molybdophosphoric acid reaction and application to a rapid quantitative reaction-rate procedure for phosphate Basic and practical considerations in utilizing a Fourier transform spectrometer for spectral measurements New approaches to precision spectrophotometry Emission spectrometric determination of the nitrogen isotope ratio Fundamental considerations of the photon counting technique and its application in a comparison of flame spectrophotometric techniques Quadrupole mass filter as a detector for gas chromatography employing a high capacity sampling system An automated spectrophotometric stopped-flow system for reaction-rate measurements Considerations in laser-excited atomic fluorescence spectroscopy and related investigations A computer-controlled automated spectrophotometric system for reaction-rate measurements Analysis of gases utilizing sensitive and precise ultraviolet absorption spectrophotometry

photometric readout module, log/linear current module, atomic absorption–emission–fluorescence spectrophotometer, UV– visible single-beam spectrophotometer, sample-cell module and UV–visible light source module. Throughout all these developments, Howard continued to direct a vigorous and wide-ranging research program. A list of what one could call his second group of PhD students (1966–1972) is presented in Table 2. Nineteen students graduated in that time frame and their research areas were clearly wide-ranging. Several have had notable academic careers and are well known today by their papers and conference presentations. These include Ray Barnes (University of Massachusetts), Stan Crouch (Michigan State University), Gary Hieftje (Indiana University), Gary Horlick (University of Alberta), and Bonner Denton (University of Arizona). 5. The later Illinois years and beyond The Malmstadt–Enke team never seemed to lose momentum in the development of new texts, approaches, and hardware for electronics education. In the first half of the 1970s, now teamed up with Stan Crouch of Michigan State University, they published a series of four modular texts. This Instrumentation for Scientists Series consisted of Module 1: Electronic Analog Measurements and Transducers, Module 2: Control of Electrical Quantities in Instrumentation, Module 3: Digital and Analog Data Conversions, and Module 4: Optimization of Electronic Measurements, this last module with Gary Horlick (University of Alberta) added as the fourth co-author. The modules were published with and without experiments and together as a single volume entitled Electronic Measurements for Scientists (see Book List).

Developments continued to flow through the 1970s, 1980s and into the 1990s. The Analog Digital Designer line of Heath was taken over by E and L Instruments, the ADD unit was redesigned by E and L into the ADD-8000, and new workbooks appeared as well as a new text in 1981 entitled Electronics and Instrumentation for Scientists. By the 1990s a new approach emerged along with, yet again, a new text. Malmstadt–Enke–Crouch developed a 2–3 day short course in Electronics for Scientists that could be presented the weekend before a national conference such as an ACS Meeting or the Pittsburgh Conference. The new text was entitled Microcomputers and Electronic Instrumentation: Making the Right Connections and a small, low-cost breadboarding system allowed hands-on experiments by each participant at the conference site. The course is also supported by audio and video cassettes and it was presented well into this century by the Malmstadt–Enke–Crouch team. Stan Crouch covered a number of these developments in his talk at Pittcon 2004 [4]. During all these evolutions of Electronics for Scientists, Howard's research pace remained in high gear. A list of his 3rd group of PhD students (1974–1982) is presented in Table 3 along with the titles of their theses. This group numbers 31, making a total of 64 PhD students. Again a wide range of research areas was investigated, including atomic spectroscopy, mass spectroscopy, fluorescence (atomic and molecular) spectroscopy, automation, microprocessors, reaction-rate methods, and clinical analytical determinations. He maintained throughout his career an uncanny ability to inspire creative work from students in a wide variety of research areas. The 1970s also saw a major change of direction to Howard's career. In the late 1970s and into the 1980s, he

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Table 3 The third group of PhD students, 1973–1982 Student

Year

Thesis title

R.W. Crane W.C. Fuller L.A. Green R.G. Kaley J.D. Lowry R.B. Timmer P.C. Dryden D.C. Harrington P-K. Kuo K.R. O'Keefe B.W. Renoe R.W. Spillman J.D. Defreese T.A. Woodruff M.F. Bryant R.P. Gregory D.V. Lovse J.A. Perry J.P. Avery S.D. Brunk D.L. Krottinger S.J. Martin M.S. McCracken M.J. Simmons M. Dancziger G.B. Wengert, Jr. A.H. Wu P.R. Bross K.M. Walczak M.D. Ruth M.W. Warren

1974 1974 1974 1974 1974 1974 1975 1975 1975 1975 1975 1975 1976 1976 1977 1977 1977 1977 1978 1978 1978 1978 1978 1978 1978 1980 1980 1981 1981 1982 1982

An automated molecular fluorescence/absorption analyzer with laser source The application of Fourier transform techniques to multi-element atomic fluorescence determinations The application of quadrupole mass spectrometry to nitrogen isotope analysis An atom reservoir for automated flame atomic fluorescence spectrometry An automated approach to some basic sample handling concepts Wavelength modulation and noise reduction using a minicomputer controlled UV–VIS–NIR recording spectrophotometer A new nanosecond gated optical detection system for spectrochemical analysis A versatile tunable dye laser for spectrochemical fluorescence methods Application of hollow cathode lamps in a programmed high current mode for fluorescence and absorption molecular spectrometry An automated spectrometer for the investigation of chemical reactions and application to the study of the Jaffe reaction Development and evaluation of an automated sample and reagent handling system for analytical and clinical applications The development and application of an automated multielement atomic emission atomic fluorescence flame spectrometer A simultaneous split beam ratiometric system for spectrochemical analysis An automated flame spectrometer system An automated dye laser spectrofluorometer for obtaining corrected excitation and emission spectra on the nanosecond time scale Development and application of a microprocessor-controlled multichannel pipetting system for clinical/analytical chemistry A microprocessor-controlled photodiode array system for analytical spectrometers Atomic fluorescence and absorption spectrometry with a microprocessor-controlled dye laser Microprocessors in analytical chemistry: application to analytical spectrometry Enzyme immunoassay methodology: new instrumental and chemical procedures for serum drug assays Automated clinical/analytical methodologies developed for a stopped-flow spectrophotometric system Critical evaluation of some atom reservoirs for atomic fluorescence spectroscopy Automated reaction rate methods for the determination of protein nitrogen and phosphorus Fluorescence measurements on a minidisc centrifugal analyzer with a pulsed nitrogen laser source An automated titrator for studies of incremental and continuous modes of endpoint determination A multichannel centrifugal analyzer: simultaneous determination of multiple constituents in clinical samples Microcomputer controlled titrimetry and spectrophotometric systems Quantitative photoacoustic reaction-rate measurements under microcomputer control Automated analysis by stopped-flow methodology Investigations of an automated system for profiling of serum constituents in neonatal blood samples Quantitative analysis by room-temperature phosphorescence

teamed up with Loren Cunningham, founder of Youth With a Mission, to plan, build and run a mission-oriented university. The site was Kailua-Kona on the island of Hawaii and the university became known as the Pacific and Asia Christian University. Howard played a major role in the design and construction of the physical infrastructure of the university and in setting up its approach to teaching, often based on his modular, intensive short course approach to instruction. In fact, Howard, Chris and Stan taught a one-week version of the summer electronics course called Laboratory Electronics at the Kona campus in 1987 and 1988. Also, he would come to scientific meetings that made their way to Hawaii to touch bases with his former students. Two such conferences were the 1984 International Chemical Congress of Pacific Basin Societies (see Fig. 17) and the 1986 Winter Conference on Plasma Spectrochemistry. This latter conference, organized by Ray Barnes, one of Howard's former students, was held at Kailua-Kona and Howard opened the Conference with a welcoming address. Over the years Pacific and Asia Christian University became the University of the Nations (headquartered in Kona), which now has a network of about 300 branch locations in 90 nations, offering hundreds of different courses in the arts, Christian ministries, communications, counseling and health care, education, humanities and international studies, and science and technology. He served

in many capacities, including International Provost and VicePresident of Academic Affairs, Dean of the College of Science and Technology, International Chancellor and ultimately, simply known as the University of the Nations Founding Father (Fig. 18). 6. More awards Even as he was winding down his group, taking early retirement from the University of Illinois and starting a new career (as just outlined), awards and scientific recognition continued to flow to Howard. He received the ACS Award in Analytical Chemistry: the Fisher Award at the ACS Centennial Meeting in New York in 1976. A large symposium was held in his honor with 18 of his former students presenting papers in three different areas: chemical instrumentation, analytical and clinical methodology and analytical spectroscopy. As was the case with the ACS Award in Chemical Instrumentation, some of his students have also received this award. Jim Winefordner (University of Florida) received the Fisher Award in 1973, Gary Hieftje (Indiana University) in 1987 and Harry Pardue (Purdue University) in 1995. The Chemical Institute of Canada (CIC) has a similar achievement award in Analytical Chemistry and it is also known as the Fisher Award. Gary Horlick (University of Alberta) received this award in 1987 and Mike

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Fig. 17. Photograph of Howard Malmstadt at the 1984 International Chemical Congress of Pacific Basin Societies in Honolulu.

Blades (University of British Columbia), a Horlick student, received the award in 1994. Howard received the ACS Analytical Division Award for Excellence in Teaching at the St. Louis ACS Meeting in 1984. The citation for the award is shown in Fig. 19. As with the ACS Award in Chemical Instrumentation, one would be hard pressed to find a candidate more fitting for this teaching award than Howard Malmstadt. As was mentioned earlier, Howard had an intense interest in teaching and always challenged his own students to aspire to be

Fig. 18. Howard V. Malmstadt, Founder of the University of Nations.

outstanding teachers. This certainly proved to be the case as John Walters (University of Wisconsin/St. Olaf College) received this same teaching award in 1993 as did Jim Winefordner (University of Florida) in 1995, Stan Crouch (Michigan State) in 1996, and Gary Hieftje (Indiana University) in 1998. The 1987 FACSS Meeting in Detroit provides a remarkable demonstration of the outstanding people legacy that has come out of Howard's research groups from Illinois. At this meeting, Howard received the ANACHEM Award from the Association of Analytical Chemists (Detroit). Previous to him, Jim Winefordner received the ANACHEM Award in 1980 and Gary Hieftje in 1984. Following shortly after Howard, Harry Pardue received the award in 1989. Now back to the 1987 FACSS Meeting. The Lester Strock Award Recipient is honored yearly at FACSS and that year the award was received by Richard Sacks (University of Michigan) who was a student of John Walters. The first FACSS Thomas Hirschfeld Awards given to outstanding graduate students, went to Jonathan Sweedler (Denton), Brad Tenge (Honigs, Hieftje) and Peter Wentzell (Crouch). The General Chairman of this FACSS Meeting was David Coleman and the Program Chairman was John Beaty, both students of John Walters. So now, second (academic grand children) and third (academic great grand children) generations of students are being awarded for their contributions to the field of analytical chemistry. Finally at the 1987 FACSS Meeting in Detroit, 20% of the papers (126 out of 632 papers) presented at the Conference were authored or co-authored by “Malmstadt People”. 7. Pittcon connections Howard had a long and fruitful association with the Pittsburgh Conference. For his graduate students, it was likely the first conference that they would attend and he insisted that talks be well prepared, rehearsed and rehearsed, and well presented. For his own part, he attended almost every Pittcon since 1950. The remarkable presence of Malmstadt and his students at Pittcon is summarized in Table 4. Howard received a number of awards at Pittcon. The first award presented to him was the Outstanding Analytical Chemist Award presented by the Society for Analytical Chemists of Pittsburgh at the 1978 Pittcon in Cleveland. As stated, “This award will honor

Fig. 19. Citation for the ACS Analytical Division Award for Excellence in Teaching.

G. Horlick / Spectrochimica Acta Part B 61 (2006) 602–618 Table 4 The Malmstadt presence at Pittcon • Howard attended almost every Pittcon since 1950. • “Malmstadt People” have been listed as Authors and Co-Authors over 1000 times from 1973 to 2003. • In the decade 1994 to 2003 “Malmstadt People” have been listed as Authors and Co-Authors an average of 57 times each year and 86 times in 2004. • One former student (Hieftje), along with his students, have presented about 175 papers. • The one year record is Sweedler with 21 listings in 2004, replacing Hieftje who had 17 listings in 1986. • Many “Malmstadt People” are on the exhibit floor (i.e. in the booth) at Pittcon every year. • AND…Dan A. Wilson (Hieftje), President, Pittcon 2005.

Professor Malmstadt for his many achievements in the field of analytical instrumentation and his impact on the education of analytical chemists”. Howard was the inaugural recipient of the award and, in fact, it was initiated by the Society for Analytical Chemists of Pittsburgh so that they could honor him before his early retirement took effect at Illinois. This award has gone on to be called the Pittsburgh Analytical Chemistry Award and is now one of the most prestigious awards presented at Pittcon. Again, some students have followed in his footsteps, Gary Hieftje (Indiana University) received this award in 1986, Jim Winefordner (University of Florida), in 1991 and at the most recent Pittcon (2006) in Orlando, Mike Ramsey (Oak Ridge National Laboratory/ University of North Carolina), a Hieftje student, received the award. At the 1994 Pittcon in Chicago, Howard was honored in a symposium entitled “Pioneers in Analytical Chemistry”. His topic was” “Reflecting on the Past: Creating for the Future”. Some flavor of where he had been and where he was headed can be seen in his abstract, which is reproduced below: Reflecting on the past; creating for the future Howard V. Malmstadt, University of the Nations, KailuaKona, HI 96740 Powerful and elegant analytical methods and instruments are used daily in industry, hospitals, R & D laboratories and process control systems. Major improvements in sensitivity, detectability, accuracy, speed and reliability provide the necessary data for dramatic breakthroughs in science and technology. I want to reflect on some of these developments in which I have been fortunate to help pioneer. By retracing some steps in the past five decades, I hope to illustrate certain principles that can prove valuable in the exciting years ahead. The story behind the story often starts with a simple question or comment. Why wouldn't this work? There must be a better way! What would be the “ideal” way? It takes too much time to do it that way! How can we make it available to others? Several examples are cited wherein such questions and comments started the author on a search for answers and subsequently resulted in improved analytical methods and instrumentation.

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There is a powerful incentive to learn and to find effective ways to do things when it is “a matter of life and death”. Likewise, projects that are especially relevant and serve others tend to motivate. Research projects and course developments that have been influenced significantly by these considerations are described. Modern microcomputer-based analytical instruments often provide push-button analyses. However, it is also important to master these new instruments, to understand the data flow and transformations that yield measurements and control our systems. It is shown how a small investment of time and effort can provide a sound, working knowledge of the new instruments, and how this experience can improve on-thejob efficiency and lead to creative solutions for projects. Education and training for the future must become a high priority. Recognizing the needs, working in unity, and adhering to the highest standards of integrity can provide innovative methods. A potential student movement that would motivate and feed environmental data into an internal data bank is considered as an example. Also, the relationship of science and technology to community development is evaluated, and the ingredients for local, national and international development are assessed. The final award that he received at Pittcon was the Maurice F. Hasler Award, which was alluded to earlier in the paper. He received this award at the 1995 Pittcon in New Orleans. This award “recognizes and encourages notable achievements in spectroscopy which have resulted in significant applications of broad utility”. A tribute session was held entitled “The Malmstadt Legacy: Towards the Future of Spectroscopy”. So now we have come full circle to the Memorial Symposium for Howard V. Malmstadt that was presented at Pittcon 2004 in Chicago [5]. As was mentioned earlier, Howard, through his own work and that of his students (first generation) and their students (second generation) changed the course of Analytical Chemistry in the USA and Canada and, indeed, throughout the world. In this symposium, his ongoing scientific legacy was highlighted in research talks presented by first, second and third generation students. A remarkable diversity of research is currently underway in these various laboratories with topics ranging from atomic, laser, mass, and Raman spectroscopy to detection technologies, analytical education and microfabricated instrumentation. Chris Enke (University of New Mexico) opened the symposium with a talk highlighting both Howard's charisma and his chemistry. Gary Horlick (University of Alberta) provided some highlights of Howard's career and then outlined the legacy for Analytical Chemistry that has been created by the first and ongoing generations that make up the Malmstadt family of students, a talk that became the basis for this paper. Jim Winefordner (University of Florida) related how his own research evolved from potentiometry to laser spectroscopy and emphasized the highly positive and encouraging approach that Howard took in motivating and mentoring his students in research.

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Ray Barnes (University of Massachusetts/University Research Institute for Analytical Chemistry) discussed “The Industrial– Academic Interface”. Stan Crouch, recently retired from Michigan State University, outlined the long legacy of Electronics for Scientists, with emphasis on the teaching philosophy of Howard Malmstadt and John Walters (University of Wisconsin/St. Olaf College) presented a fascinating project history on the development of the Heath Monochromator. In the mid-1960s few, if any, could have envisioned the central role mass spectrometry would evolve to take in current analytical measurements. Willard Harrison (University of Florida) was one who helped to spur this evolution and he talked about some current work involving laser desorption and discharge ionization of biomolecules using nanoparticles. Gary Hieftje, who himself has pioneered many developments in spectroscopy from his laboratory at Indiana University, talked about the requirements for an ideal atomic mass spectrometer and documented progress toward this ideal. In fact, “blue sky discussions” about the “ideal…” frequently occurred during Malmstadt research group seminars at the University of Illinois. In the 1960s the electronic acquisition of spectra and computers in every instrument were still very much on the ideal list. The blue sky discussions primed his students to be early participants in the developments that were to occur in these areas. Some of those 1960 “ideals” can now be implemented. Gary Horlick (University of Alberta) discussed an electronic database, acquired with a Fourier transform spectrometer, containing complete ICP–AES–UV and visible spectra for 70 elements on two CD ROMs and Bonner Denton (University of Arizona) discussed the revolutionary progress that has been made in the area of electronic image sensing in a talk entitled “Advanced Array Detector Technologies in Chemical Analysis”.

The Malmstadt legacy for Analytical Chemistry has been carried forward by many second generation students. Some have followed on and developed new pathways in the atomic spectrometry area favored by many of the first generation students. John Olesik (Ohio State University) showed the new insights that can be gained about atomic sources utilizing single droplets, single particles and time-resolved measurements; areas of investigation that were pioneered by Gary Hieftje and John Walters. Paul Farnsworth (Brigham Young University) discussed the nuances of an ion's trip through the ICP-MS vacuum interface. Sample introduction into plasma systems was discussed by Akbar Montaser (George Washington University) and Jim Holcombe (University of Texas at Austin). Akbar presented his results on the modeling of direct liquid sample introduction for plasma spectrometry and Holcombe (a third generation student) discussed the utilization of ETV as a sample introduction system for ICPMS. Considerable work on the utilization of glow discharges in analytical spectroscopy has been carried out for many years in the laboratories of Willard Harrison. One of his students, Ken Marcus (Clemson University), has established his own legacy in this area and talked about his research that has further developed the analytical utility of the glow discharge device. A number of other second generation students are now pursuing research at the forefront of new and emerging areas such as bio-analysis, microfluidics, and nano-science. Michael Blades (University of British Columbia) whose work has contributed much to our fundamental understanding of analytical plasmas, has now focused his research on biophysical measurements and he discussed the capability of fiber-optic linked ultraviolet resonance Raman spectroscopy for such measurements. Michael Ramsey (Oak Ridge National Laboratory/University of North Carolina) is a pioneer in the area of microfluidics and the so-called “lab-on-a-chip” concept. He discussed miniaturization of

Fig. 20. Participants in the symposium “Howard V. Malmstadt: His Ongoing Legacy for Analytical Chemistry”, held at Pittcon 2004 in Chicago, IL. First Row (Left to Right): Adelina Javier, Vassili Karanassios, Ken Marcus, Gary Horlick, Gary Hieftje, Mike Ramsey, Akbar Montaser, John Olesik, Jim Winefordner, Richard Sacks. Back Row (Left to Right): Mike Blades, Jim Holcombe, Ray Barnes, Stan Crouch, Bonner Denton, Paul Fransworth, John Walters, Jonathan Sweedler, Willard Harrison.

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chemical measurement technology as did Vassili Karanassios (University of Waterloo) in his talk entitled “Thinking Small in Analytical Instrumentation”. Richard Sacks (University of Michigan) followed on this same theme with a presentation on micro-fabricated instruments for vapor analysis. Finally, Jonathan Sweedler (University of Illinois), who is making remarkable analytical measurements on and in small systems, talked about adapting techniques to characterize peptide vesicles. The symposium participants (Fig. 20) represent, of course, only a small fraction of the legacy of scientists and analytical chemists that emanated from Howard's laboratories at the University of Illinois. Their enthusiasm for science is obvious. In their past and current projects they have pushed back the frontiers in many areas, helped to establish new frontiers, and are well noted for their ability to “think outside the box”. Clearly there is a vibrant, ongoing legacy for Analytical Chemistry in the work of the first and continuing generations of students, a testament to the inspiring enthusiasm of a remarkable man: Howard Vincent Malmstadt. Acknowledgements Sources and help with material to prepare this paper include: Web page of The University of the Nations, the journals Analytical Chemistry and Chemistry and Engineering News and booklets and manuals from the Heath Company, E and L Instruments, W.A. Benjamin Inc., and the American Chemical Society. Meeting programs from the American Chemical Society (ACS), Federation of Analytical Chemistry and Spectroscopy Societies (FACSS), Pittcon and the Winter Conference on Plasma Spectrochemistry. ACS Division of Analytical Chemistry Booklets and Newsletters. Alex Scheeline, Stan Crouch and Gary and Susan Hieftje. References [1] G. Horlick, Howard V. Malmstadt: His Ongoing Legacy for Analytical Chemistry, Paper Number 1800–200, Pittcon, Chicago, IL, 2004. [2] E. Heilbronmer, F.A. Miller, A Philatelic Ramble Through Chemistry, Verlag Helvetica Chemica Acta, Basel, Switzerland, 1998. [3] J.P. Walters, The Heath Monochromator: a True Academic/Industrial Team Project, Paper Number 1800-500, Pittcon, Chicago, IL, 2004. [4] S.R. Crouch, Electronics for Scientists: Living History, Paper Number 1800-700, Pittcon, Chicago, IL, 2004. [5] Symposium Arranged by G. Hieftje, G. Horlick, Howard V. Malmstadt: his ongoing legacy for analytical chemistry, Paper Numbers 1800-100 to 1000 and 4900-100 to 1100, Pittcon, Chicago, IL, 2004.

H.V. Malmstadt Publications List [1] W.J. Blaedel, H.V. Malmstadt, High-frequency titrations — mercurimetric determination of chloride, Anal. Chem. 22 (1950) 1410–1412. [2] W.J. Blaedel, H.V. Malmstadt, High-frequency titrations — 350megacycle titrimeter, Anal. Chem. 22 (1950) 1413–1417. [3] W.J. Blaedel, H.V. Malmstadt, High-frequency titrations. A study of instruments, Anal. Chem. 22 (1950) 734–742. [4] W.J. Blaedel, H.V. Malmstadt, Volumetric determination of thorium by high-frequency titrimetry, Anal. Chem. 23 (1951) 471–475. [5] W.J. Blaedel, H.V. Malmstadt, D.L. Petitjean, W.J. Anderson, Theory of chemical analysis by high-frequency methods, Anal. Chem. 24 (1952) 1240–1244. [6] W.J. Blaedel, H.V. Malmstadt, Direct-reading and differential frequency meter for high-frequency titrations, Anal. Chem. 24 (1952) 450–454.

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[7] W.J. Blaedel, H.V. Malmstadt, Selecting the end point in high-frequency titrations: comparison of differential and ordinary procedures, Anal. Chem. 24 (1952) 455–459. [8] H.V. Malmstadt, E.C. Gohrbandt, Automatic spectrophotometric titrations. Determination of milligram quantities of thorium, Anal. Chem. 26 (1954) 442–445. [9] H.V. Malmstadt, E.R. Fett, Automatic differential potentiometric titrator, Anal. Chem. 26 (1954) 1348–1351. [10] H.V. Malmstadt, E.R. Fett, Automatic differential potentiometric titrations-electrode systems for aqueous and nonaqueous titrations, Anal. Chem. 27 (1955) 1757–1764. [11] H.V. Malmstadt, C.B. Roberts, Automatic spectrophotometric titration with coulometrically generated titanous ion. Determination of vanadium in titanium tetrachloride, Anal. Chem. 27 (1955) 741–744. [12] H.V. Malmstadt, R.G. Scholz, Emission spectrochemical analysis of vanadium and iron in titanium tetrachloride. Spark-in-spray excitation method, Anal. Chem. 27 (1955) 881–883. [13] H.V. Malmstadt, Titration methods, Record Chem. Progr. 17 (1956) 1–17. [14] H.V. Malmstadt, C.B. Roberts, Automatic derivative spectrophotometric titrations, Anal. Chem. 28 (1956) 1408–1412. [15] H.V. Malmstadt, C.B. Roberts, Determination of iron in titanium sponge, alloys, and ores. Automatic derivative spectrophotometric titration with electrolytically generated titanous ion, Anal. Chem. 28 (1956) 1412–1416. [16] H.V. Malmstadt, E.R. Fett, J.D. Winefordner, Determination of chloride in titanium sponge by the rapid potentiometric method, Anal. Chem. 28 (1956) 1878–1882. [17] H.V. Malmstadt, C.B. Roberts, Determination of titanium in titanium ores and metal by automatic derivative spectrophotometric titration, Anal. Chem. 28 (1956) 1884–1886. [18] H.V. Malmstadt, D.A. Vassallo, Rapid and accurate titrations with a convenient and compact automatic derivative spectrophotometric titrator, Anal. Chim. Acta 16 (1957) 455–463. [19] H.V. Malmstadt, Automatic stopcock twister, Anal. Chem. 29 (1957) 1901. [20] H.V. Malmstadt, T.P. Hadjiiannou, Rapid and accurate automatic titration of calcium and magnesium in dolomites and limestones — use of EDTA titrant and automatic derivative spectrophotometric end-point termination, Anal. Chim. Acta 19 (1958) 563–569. [21] H.V. Malmstadt, Automatic differential potentiometric titrator, US Patent No. 2878106 (1959). [22] H.V. Malmstadt, J.D. Winefordner, Determination of chloride in blood serum, plasma, or other biologic fluids by a new rapid precision method, Clin. Chem. 5 (1959) 284–296. [23] H.V. Malmstadt, T.P. Hadjiioannou, Automatic titration of calcium or magnesium in blood serum, Clin. Chem. 5 (1959) 50–56. [24] H.V. Malmstadt, T.P. Hadjiiannou, Rapid and accurate automatic titration method for determination of calcium and magnesium in plant material with EDTA titrant, J. Agric. Food Chem. 7 (1959) 418–420. [25] H.V. Malmstadt, J.D. Winefordner, Precision null-point potentiometry. A simple, rapid, and accurate method for low concentration chloride determinations, Anal. Chim. Acta 20 (1959) 283–291. [26] H.V. Malmstadt, T.P. Hadjiiannou, Determination of copper and zinc in metallurgical products by automatic derivative spectrophotometric titrations, Anal. Chim. Acta 21 (1959) 41–46. [27] H.V. Malmstadt, D.A. Vassallo, Direct titration of hydrochloric–sulfuric and nitric–sulfuric acid mixtures in acetone solvent — automatic derivative potentiometric or spectrophotometric end point detection, Anal. Chem. 31 (1959) 206–210. [28] H.V. Malmstadt, D.A. Vassallo, Automatic derivative potentiometric and spectrophotometric titrations of organic acids, Anal. Chem. 31 (1959) 862–865. [29] H.V. Malmstadt, T.P. Hadjiioannou, Determination of calcium, magnesium, and total hardness by automatic spectrophotometric titration, J. Am. Water Works Assoc. 51 (1959) 411–417. [30] H.V. Malmstadt, T.P. Hadjiioannou, Automatic derivative spectrophotometric titration of excess EDTA in the determination of cobalt, copper, or iron, Anal. Chim. Acta 23 (1960) 288–293.

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[31] H.V. Malmstadt, H.L. Pardue, Microrange iodometry by combining precision null-point potentiometry and electrolytic generation of iodine, Anal. Chem. 32 (1960) 1034–1038. [32] H.V. Malmstadt, H.L. Pardue, Microdetermination of silver copper in silver–copper alloys using precision null-point potentiometry, Anal. Chem. 32 (1960) 1039–1041. [33] H.V. Malmstadt, T.P. Hadjiioannou, W.E. Chambers, Precision null-point atomic absorption spectrochemical analysis, Anal. Chem. 32 (1960) 225–232. [34] H.V. Malmstadt, J.D. Winefordner, Rapid decomposition and analysis procedure for microdeterminations of chlorine compounds in petroleum fractions, Anal. Chem. 32 (1960) 281–284. [35] H.V. Malmstadt, G.P. Hicks, Determination of glucose in blood serum by a new rapid and specific automatic system, Anal. Chem. 32 (1960) 394–398. [36] H.V. Malmstadt, G.P. Hicks, Rapid injection and automatic refill pipet, Anal. Chem. 32 (1960) 445–446. [37] H.V. Malmstadt, J.D. Winefordner, Precision null-point potentiometry. Direct microdetermination of iodide in solutions with high chloride concentrations, Anal. Chim. Acta 24 (1961) 91–96. [38] H.V. Malmstadt, H.L. Pardue, Quantitative analysis by an automatic potentiometric reaction rate method. Specific enzymic determination of glucose, Anal. Chem. 33 (1961) 1040–1047. [39] H.V. Malmstadt, H.L. Pardue, Specific enzymatic determination of glucose in blood serum or plasma by an automatic potentiometric reaction-rate method, Clin. Chem. 8 (1962) 606–615. [40] H.V. Malmstadt, H.L. Pardue, High-precision rapid injection and automatic refill pipet, Anal. Chem. 34 (1962) 299–301. [41] H.V. Malmstadt, S.I. Hadjiioannou, New automatic spectrophotometric rate method for selective determination of glucose in serum, plasma, or blood, Anal. Chem. 34 (1962) 452–455. [42] H.V. Malmstadt, T.P. Hadjiioannou, Specific enzymic determination of alcohol in blood by an automatic spectrophotometric reaction rate method, Anal. Chem. 34 (1962) 455–458. [43] H.V. Malmstadt, T.P. Hadjiioannou, Improvements on the automatic determination of micro amounts of serum calcium, Clin. Chem. 9 (1963) 423–427. [44] H.V. Malmstadt, T.P. Hadjiioannou, Specific enzymic determination of some α-amino acids by automatic spectrophotometric reaction rate method, Anal. Chem. 35 (1963) 14–16. [45] H.V. Malmstadt, T.P. Hadjiioannou, Ultramicrodetermination of iodine by a rapid automatic reaction-rate method, Anal. Chem. 35 (1963) 2157–2161. [46] H.L. Pardue, R.K. Simon, H.V. Malmstadt, An automatic potentiometric method for the determination of the absolute activity of glucose oxidase, Anal. Chem. 36 (1964) 735–737. [47] H.V. Malmstadt, A versatile and inexpensive pH recording electrometer, J. Chem. Educ. 41 (1964) 148–155. [48] H.V. Malmstadt, R.M. Barnes, P.A. Rodriguez, Multipurpose high precision recording photometer — an ionization detector-readout for gas–liquid chromatography, J. Chem. Educ. 41 (1964) 263–275. [49] J.P. Walters, H.V. Malmstadt, Emission characteristics and sensitivity in a high-voltage spark discharge, Anal. Chem. 37 (1965) 1484–1503. [50] H.V. Malmstadt, E.H. Piepmeier, pH stat with digital readout for quantitative chemical determinations, Anal. Chem. 37 (1965) 34–44. [51] J.P. Walters, H.V. Malmstadt, Derivative scanning for wavelength identification, Appl. Spectrosc. 20 (1966) 193–194. [52] J.P. Walters, H.V. Malmstadt, Oscilloscopic characterization of an electronically ignited spark source, Appl. Spectrosc. 20 (1966) 80–89. [53] H.V. Malmstadt, S.R. Crouch, Systems for automatic direct readout of rate data, J. Chem. Educ. 43 (1966) 340–353. [54] S.R. Crouch, H.V. Malmstadt, Mechanistic investigation of molybdenum blue method for determination of phosphate, Anal. Chem. 39 (1967) 1084–1089. [55] S.R. Crouch, H.V. Malmstadt, Automatic reaction rate method for determination of phosphate, Anal. Chem. 39 (1967) 1090–1093. [56] A.V. Nowak, H.V. Malmstadt, Selective gas-chromatographic detector utilizing emitted radiation from a sensitized flame, Anal. Chem. 40 (1968) 1108–1113.

[57] E.M. Cordos, R. Crouch, H.V. Malmstadt, Automatic digital readout system for reaction-rate methods, Anal. Chem. 40 (1968) 1812–1818. [58] G.M. Hieftje, H.V. Malmstadt, Unique system for studying flame spectrometric processes, Anal. Chem. 40 (1968) 1860–1867. [59] S.R. Crouch, H.V. Malmstadt, Determination of inorganic phosphate in the presence of adenosine triphosphate by the automatic reaction rate method, Anal. Chem. 40 (1968) 1901–1902. [60] A.C. Javier, S.R. Crouch, H.V. Malmstadt, Investigations of formation of 12-molybdophosphoric acid utilizing rapid reaction-rate measurements, Anal. Chem. 40 (1968) 1922–1925. [61] A.V. Nowak, H.V. Malmstadt, Versatile ionization detector system for gas chromatography, J. Chem. Educ. 45 (1968) 519–523. [62] G.M. Hieftje, H.V. Malmstadt, New approach to flame spectrometric analysis utilizing isolated droplets of sample solution, Anal. Chem. 41 (1969) 1735–1744. [63] M.L. Franklin, G. Horlick, H.V. Malmstadt, Basic and practical considerations in utilizing photon counting for quantitative spectrochemical methods, Anal. Chem. 41 (1969) 2–10. [64] A.C. Javier, S.R. Crouch, H.V. Malmstadt, Automated fast reaction-rate system for phosphate determinations in the millisecond range, Anal. Chem. 41 (1969) 239–243. [65] E.H. Piepmeier, H.V. Malmstadt, Q-switched laser energy absorption in the plume of an aluminum allow, Anal. Chem. 41 (1969) 700–707. [66] G. Horlick, H.V. Malmstadt, Basic and practical considerations for sampling and digitizing interferograms generated by a Fourier transform spectrometer, Anal. Chem. 42 (1970) 1361–1369. [67] M.B. Denton, H.V. Malmstadt, Tunable organic dye laser as an excitation source for atomic-flame fluorescence spectroscopy, App. Phys. Lett. 18 (1971) 485–487. [68] H.V. Malmstadt, C.J. Delaney, E.A. Cordos, Reaction-rate methods of chemical analysis, Crit. Rev. Anal. Chem. 2 (1972) 559–619. [69] H.V. Malmstadt, E. Cordos, Automated AF [atomic fluorescence] spectrometer for rapid multielement determinations, Am. Lab., 4 (1972) 35–36, 38–42. [70] R.B. Timmer, H.V. Malmstadt, Minicomputer-controlled UV–VIS–NIR [ultraviolet–visible–near infrared] spectrophotometer, Am. Lab. 4 (1972) 43–46, 48, 50–51. [71] M.B. Denton, H.V. Malmstadt, Ultrasonic nebulization in a low-emission flame for atomic fluorescence spectrometry, Anal. Chem. 44 (1972) 1813–1818. [72] E.S. Iracki, M.B. Denton, H.V. Malmstadt, Triac switching circuitry for eliminating interfering transients in digital logic automated systems, Anal. Chem. 44 (1972) 1924–1925. [73] E. Cordos, H.V. Malmstadt, Dual channel synchronous integration measurement system for atomic fluorescence spectrometry, Anal. Chem. 44 (1972) 2277–2282. [74] E. Cordos, H.V. Malmstadt, Programmable power supply for operation of hollow cathode lamps in an intermittent current-regulated high intensity mode, Anal. Chem. 44 (1972) 2407–2410. [75] M.B. Denton, H.V. Malmstadt, Burner and ultrasonic nebulizer improvements for atomic absorption spectrometry, Anal. Chem. 44 (1972) 241–247. [76] H.V. Malmstadt, E.A. Cordos, C.J. Delaney, Automated reaction-rate methods of analysis, Anal. Chem. 44 (1972) 26A–32A, 36A, 38A, 40A–41A. [77] H.V. Malmstadt, M.L. Franklin, G. Horlick, Photon counting for spectrophotometry, Anal. Chem. 44 (1972) 63A–64A, 66A, 68A, 71A–72A, 74A, 75A–76A.E. [78] H.V. Malmstadt, C.J. Delaney, E.A. Cordos, Instruments for rate determinations, Anal. Chem. 44 (1972) 79A–82A, 84A, 86A–89A. [79] E.S. Iracki, H.V. Malmstadt, Ratemeter interface for a minicomputercontrolled reaction-rate instrument, Anal. Chem. 45 (1973) 1766–1770. [80] E. Cordos, H.V. Malmstadt, Characteristics of hollow cathode lamps operated in an intermittent high current mode, Anal. Chem. 45 (1973) 27–32. [81] E. Cordos, H.V. Malmstadt, Programmable monochromator for accurate high-speed wavelength isolation, Anal. Chem. 45 (1973) 425–433. [82] D. Harington, H.V. Malmstadt, Digital scanning, tunable dye laser for spectroanalytical methods, International Lab. (1974) 67–70, 72–73.

G. Horlick / Spectrochimica Acta Part B 61 (2006) 602–618 [83] D. Harrington, H.V. Malmstadt, Digital scanning, tunable dye laser for spectroanalytical methods, Am. Lab. 6 (1974) 33–38. [84] E. Iracki, H.V. Malmstadt, Computer-controlled automated system for chemical rate methods, Am. Lab. 6 (1974) 56–58, 60, 62, 64–67. [85] J. Avery, R.P. Gregory IV, B.W. Renoe, T. Woodruff, H.V. Malmstadt, A centrifugal analyzer with a new all-digital measurement system, Clin. Chem. 20 (1974) 942–949. [86] R.P. Gregory IV, J. Avery, B.W. Renoe, P.C. Dryden, H.V. Malmstadt, Incorporation of a high-speed decimal data processor into a centrifugal analyzer, Clin. Chem. 20 (1974) 950–954. [87] B.W. Renoe, R.P. Gregory IV, J. Avery, H.V. Malmstadt, A versatile minidisk module for a centrifugal analyzer, Clin. Chem. 20 (1974) 955–960. [88] T.A. Woodruff, H.V. Malmstadt, High-speed charge-to-count data domain converter for analytical measurement systems, Anal. Chem. 46 (1974) 1162–1170. [89] J.D. Defreese, T.A. Woodruff, H.V. Malmstadt, New type of programmable current-regulated power supply for operation of hollow cathode lamps in a high intensity programmed mode, Anal. Chem. 46 (1974) 1471–1476. [90] T.A. Woodruff, H.V. Malmstadt, Inexpensive digital correlator for spectrophotometric and other analytical measurements, Anal. Chem. 46 (1974) 2141–2150. [91] R.M. Barnes, H.V. Malmstadt, Liquid-layer-on-solid-sample spark technique for emission spectrochemical analysis, Anal. Chem. 46 (1974) 66–72. [92] M.F. Bryant, K. O'Keefe, H.V. Malmstadt, Front-face laser fluorescence technique with microabsorption cells, Anal. Chem. 47 (1975) 2324–2326. [93] D.C. Harrington, H.V. Malmstadt, New type of spectrofluorometer with a tunable laser source and unique optical system, Anal. Chem. 47 (1975) 271–276. [94] K.R. O'Keefe, H.V. Malmstadt, Automated computer-controlled spectrophotometer system for kinetic or equilibrium methods of analysis, Anal. Chem. 47 (1975) 707–714. [95] R.W. Spillman, H.V. Malmstadt, Computer-controlled multielement AF/ AE spectrometer system, Am. Lab. 8 (1976) 89–90, 92, 94, 96–97. [96] T.P. Hadjiioannou, S.I. Hadjiioannou, S.D. Brunk, H.V. Malmstadt, Automated enzymic determination of L-lactate in serum, with use of a miniature centrifugal analyzer, Clin. Chem. 22 (1976) 2038–2041. [97] T.P. Hadjiioannou, S.I. Hadjiioannou, S.D. Brunk, H.V. Malmstadt, Automated enzymatic determination of L-lactate in serum, with use of a miniature centrifugal analyzer, Clin. Chem. 22 (1976) 2042–2045. [98] T.P. Hadjiioannou, S.I. Hadjiioannou, J. Avery, H.V. Malmstadt, Automated enzymic determination of ethanol in blood, serum, and urine with a miniature centrifugal analyzer, Clin. Chem. 22 (1976) 802–805. [99] S.D. Brunk, T.P. Hadjiioannou, S.I. Hadjiioannou, H.V. Malmstadt, Adaptation of “EMIT” technique for serum phenobarbital and diphenylhydantoin assays to the miniature centrifugal analyzer, Clin. Chem. 22 (1976) 905–907. [100] J.P. Avery, H.V. Malmstadt, Computer-controlled multichannel recording ultraviolet/visible spectrophotometer, Anal. Chem. 48 (1976) 1308–1313. [101] J.D. Defreese, H.V. Malmstadt, Simultaneous, split-beam, ratio measurement system, Anal. Chem. 48 (1976) 1530–1536. [102] R.W. Spillman, H.V. Malmstadt, Computer-controlled programmable monochromator system with automated wavelength calibration and background correction, Anal. Chem. 48 (1976) 303–311. [103] B.W. Renoe, K.R. O'Keefe, H.V. Malmstadt, Automated computercontrolled solution handling system utilizing weights of solution, Anal. Chem. 48 (1976) 661–666. [104] D.L. Krottinger, M.S. McCracken, H.V. Malmstadt, Automated clinical/ analytical spectrophotometric system, Am. Lab. 9 (1977) 51–52, 54–56, 58–59. [105] S.D. Brunk, H.V. Malmstadt, Adaptation of the EMIT serum digoxin assay to a mini-disc centrifugal analyzer, Clin. Chem. 23 (1977) 1054–1056. [106] R.M. Oteiza, D.L. Krottinger, M.S. McCracken, H.V. Malmstadt, Reaction-rate method for the determination of hydrocortisone, Anal. Chem. 49 (1977) 1586–1589.

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[107] R.P. Gregory IV, J.D. Lowry, H.V. Malmstadt, Multichannel pipet for parallel aliquoting of samples and reagents into centrifugal analyzer minidisks, Anal. Chem. 49 (1977) 1608–1615. [108] J.A. Perry, M.F. Bryant, H.V. Malmstadt, Microprocessor-controlled, scanning dye laser for spectrometric analytical systems, Anal. Chem. 49 (1977) 1702–1710. [109] T.P. Hadjiioannou, S.I. Hadjiioannou, J. Avery, H.V. Malmstadt, Automated catalytic ultramicrodetermination of manganese in natural waters with a miniature centrifugal analyzer, Anal. Chim. Acta 89 (1977) 231–239. [110] D.L. Krottinger, M.S. McCracken, H.V. Malmstadt, High-speed, automatic dispenser/diluter or dual pipetter/mixer, J. Automat. Chem. 1 (1978) 15–21. [111] J.D. Defreese, K.M. Walczak, H.V. Malmstadt, Microcomputer-controlled monochromator accessory module for dual wavelength spectrochemical procedures, Anal. Chem. 50 (1978) 2042–2046. [112] A.H.B. Wu, H.V. Malmstadt, Versatile microcomputer-controlled titrator, Anal. Chem. 50 (1978) 2090–2096. [113] H.V. Malmstadt, D.L. Krottinger, M.S. McCracken, Automated reactionrate methods of analysis, Top. Automat. Chem. Anal. 1 (1979) 95–137. [114] C.E. Efstathiou, H.V. Malmstadt. Microcomputer-controlled multisample rotating-disk colorimeter. Am. Lab. 11 (1979) 19–20, 22, 24, 26, 28. [115] M.S. McCracken, H.V. Malmstadt, Reaction-rate method for the determination of phosphorus in agricultural products, Talanta 26 (1979) 467–471. [116] D.L. Krottinger, M.S. McCracken, H.V. Malmstadt, Spectrometric rapid sampling/mixing system for analytical/clinical methods, Talanta 26 (1979) 549–561. [117] C. Efstathiou, E. Cordos, H.F. Malmstadt, Multisample rotating-disc module for spectrometric analytical methods, Anal. Chem. 51 (1979) 58–62. [118] M.S. McCracken, H.V. Malmstadt, Reaction-rate method for determining protein nitrogen in grains and feeds, J. Assoc. Off. Anal. Chem. 62 (1979) 23–28. [119] A.H.B. Wu, T. Rotunno, H.V. Malmstadt, Microcomputer controlled titration for determination of protein nitrogen in feeds and wheat, J. Assoc. Off. Anal. Chem. 62 (1979) 969–975. [120] M.A. Koupparis, K.M. Walczak, H.V. Malmstadt, Corticosteroid determination in skin preparations by a reaction rate method, J. Pharm. Sci. 68 (1979) 1479–1482. [121] M. Dancziger, H.V. Malmstadt, Interfacing a titrator to a microcomputer for incremental or continuous modes of operation, J. Automat. Chem. 2 (1980) 194–199. [122] M.A. Koupparis, K.M. Walczak, H.V. Malmstadt, A compact automated microprocessor-based stopped-flow analyzer, J. Automat. Chem. 2 (1980) 66–75. [123] H.V. Malmstadt, K.M. Walczak, M.A. Koupparis. An automated stoppedflow/unsegmented solution-storage analyzer. Am. Lab. 12 (1980) 27, 29– 30, 32, 34–35, 37–38, 40. [124] H.V. Malmstadt, Analytical instruments for the 1980s, Analyst 105 (1980) 1018–1031. [125] H.V. Malmstadt, K.M. Walczak, M.A. Koupparis, An automated stoppedflow/unsegmented solution-storage analyzer, International Lab. 11 (1981) 32, 35–36, 38–40, 42–45. [126] A.H.B. Wu, T. Rotunno, H.V. Malmstadt. Microcomputer-controlled photodiode array spectrophotometric titrator. Clin. Chem. 13 (1981) 16, 21–22, 24, 29–32, 34. [127] A.H.B. Wu, H.V. Malmstadt, Reactions during the titration of ammonia with hypochlorite in the presence of bromide, Anal. Chem. 53 (1981) 1725–1726. [128] A.H.B. Wu, T. Rotunno, H.V. Malmstadt. Microcomputer-controlled photodiode array spectrophotometric titrator. International Lab. 12 (1982) 16, 18, 20, 22–24, 26, 28. [129] M.A. Koupparis, E.P. Diamandis, H.V. Malmstadt, Total calcium and magnesium determined in serum with an automated stopped-flow analyzer, Clin. Chem. 28 (1982) 2149–2152. [130] M.W. Warren II, J.P. Avery, H.V. Malmstadt, Wavelength accuracy of a microprocessor-controlled ultraviolet/visible monochromator, Anal. Chem. 54 (1982) 1826–1828.

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[131] M.W. Warren, J.P. Avery, H.V. Malmstadt, Quantitative room-temperature phosphorescence with internal standard and standard addition techniques, Anal. Chem. 54 (1982) 1853–1858. [132] M.A. Koupparis, H.V. Malmstadt, Determination of water by an automated stopped-flow analyzer with pyridine-free two-component Karl Fischer reagent, Anal. Chem. 54 (1982) 1914–1917. [133] C.G. Enke, S.R. Crouch, F.J. Holler, H.V. Malmstadt, J.P. Avery, Electronics, instrumentation, and microcomputers. Principles and practice for the microcircuit age, Anal. Chem. 54 (1982) 367A–368A, 370A– 371A, 374A, 377A, 382A, 386A, 388A, 393A. [134] M.A. Koupparis, K.M. Walczak, H.V. Malmstadt, Kinetic determination of nitrite in waters by using a stopped-flow analyzer, Analyst 107 (1982) 1309–1315. [135] M.A. Koupparis, K.M. Walczak, H.V. Malmstadt, Automated determination of nitrate in waters with a reduction column in a microcomputerbased stopped-flow sample processing system, Anal. Chim. Acta 142 (1982) 119–127. [136] M.A. Koupparis, E.P. Diamandis, H.F. Malmstadt, Automated determination of crude protein, phosphorus, calcium, iron, and magnesium in feeds by using stopped-flow analyzer, J. Assoc. Off. Anal. Chem. 66 (1983) 188–196. [137] M.A. Koupparis, P. Anagnostopoulou, H.V. Malmstadt, Automated flow-injection pseudotitration of strong and weak acids, ascorbic acid and calcium, and catalytic pseudotitrations of aminopolycarboxylic acids by use of a microcomputer-controlled analyzer, Talanta 32 (1985) 411–417. [138] M.A. Koupparis, E.P. Diamandis, H.V. Malmstadt, Automated stoppedflow analyzer in clinical chemistry: determination of albumin with bromcresol green and purple, Clin. Chim. Acta 149 (1985) 225–235.

H.V. Malmstadt Book List [1] H.V. Malmstadt, C.G. Enke, with the assistance of E.C. Toren, Jr., Electronics for Scientists: Principles and Experiments for Those Who Use Instruments, W.A. Benjamin, New York, NY, 1962, 619 pages.

[2] H.V. Malmstadt, C.G. Enke, Digital Electronics for Scientists, W.A. Benjamin, New York, NY, 1969, 656 pp. [3] H.V. Malmstadt, C.G. Enke, Computer Logic: a Laboratory Workbook, W.A. Benjamin, New York, N.Y., 1970, 167 pp; Instrumentation for Scientists Series. Published as four modules in two forms, Text with Experiments and Text with Lab Summaries and as one full text containing the Text with Lab Summaries of all four modules. [4] H.V. Malmstadt, C.G. Enke, S.R. Crouch, Electronic Analog Measurements and Transducers: Module 1. Text With Experiments, W.A. Benjamin, Menlo Park, CA, 1973, 199 pp. [5] H.V. Malmstadt, C.G. Enke, S.R. Crouch, Control of Electrical Quantities in Instrumentation: Module 2. Text with Experiments, W.A. Benjamin, Menlo Park, CA, 1973, 355 pp. [6] H.V. Malstadt, C.G. Enke, S.R. Crouch, Digital and Analog Data Conversions: Module 3. Text with Experiments, W.A. Benjamin, Menlo Park, CA, 1973, 455 pp. [7] H.V. Malmstadt, C.G. Enke, S.R. Crouch, G. Horlick, Optimization of Electronic Measurements: Module 4. Text with Experiments, W.A. Benjamin, Menlo Park, CA, 1974, 203 pp. [8] H.V. Malmstadt, C.G. Enke, S.R. Crouch with G. Horlick (Module 4), Electronic Measurements for Scientists, W.A. Benjamin, Menlo Park, CA, 1974, 906 pages. [9] H.V. Malmstadt, C.G. Enke, S.R. Crouch, ADD Book ONE: Experiments in Digital and Analog Electronics, E&L Instruments, Derby, CT, 1977, 251 pp. [10] H.V. Malmstadt, C.G. Enke, S.R. Crouch, Electronics and Instrumentation for Scientists, The Benjamin/Cummings Publishing Company, Menlo Park, CA, 1981, 543 pp. [11] H.V.Malmstadt, C.G.Enke, S.R.Crouch, Microcomputers and Electronic Instrumentation: Making the Right Connections, Americal Chemical Society, Washington, DC, 1994, 452 pp.