G. D. Patterson

Carnegie Mellon University | CMU · Department of Chemistry

The natural philosophy of chemistry grew slowly until the articulation of the axiom of chemical atoms by John Dalton in the early nineteenth century. Sir John F. W. Herschel was one of the leading natural philosophers of the nineteenth century and published his own monograph, in which he listed the ten key axioms of chemistry. Later in that decade,...

In 2020 the Cellulose and Renewable Materials Division (CELL) of the American Chemical (ACS) society celebrates its 100th anniversary. The following paper is based on a chapter from the book commissioned by the Division (Patterson, 2021). CELL is one of the most successful and dynamic Divisions in the ACS. It has evolved throughout its history to r...

A brief history of the founding of New England is presented. The key players are introduced in more detail, and the arrival of John Winthrop, Jr., is placed context. The role of alchemy in 17th century New England is explained and placed in the context of the Puritan Commonwealth.

The history and philosophy of Puritanism is presented and related to John Winthrop, Jr. The scientific world of Francis Bacon is also presented. Winthrop was fully committed to both of these programs for human flourishing.

Contrary to a later period in the history of Harvard University, the seventeenth century produced many practicing physicians. They also served as Puritan ministers. This chapter tells their story. The three Presidents of Harvard University, Henry Dunster, Charles Chauncy and Leonard Hoar, were all physicians. They mentored budding iatrochemists dur...

John Winthrop, Jr., was a prodigious correspondent. In addition to his English and European correspondence, many volumes of his American letters have been collected by the Massachusetts Historical Society. A discussion of his primary correspondents is presented: Thomas Shepherd, Robert Child, George Stirk, Richard Leader, Jonathan Brewster, Gershom...

One of the most important things John Winthrop, Jr., did for New England was to found new towns. His first venture was a fishing village near Salem on Cape Ann, Agawam (later Ipswich). The land needed to be cleared, surveyed, parceled and houses built. Winthrop did his part, both in manual labor and in detailed planning and in political organizatio...

A short essay on both chemistry in seventeenth century New England and the history of chemistry itself is presented. John Winthrop, Jr., relied primarily on his extensive reading and his careful empirical work to produce both needed chemicals and good recipes for others to follow. The story told in these pages is much more interesting and substanti...

After John Winthrop, Jr., had been relieved of his responsibilities for the ironworks, he was free to pursue his dream of creating a utopian plantation in Connecticut. This is a complicated story, but it illustrates all the excellencies of Winthrop. He founded a flourishing town of New London. He established an iatrochemical practice that all the l...

The life of John Winthrop, the Younger, is presented in the context of his progress as an alchemical adept. He collected the finest library in New England in the 17th century and alchemical books were the dominant genre. He was in communication with most of the working alchemists of his time and especially admired John Dee. He traveled throughout t...

One of the great needs of the Colonial enterprise was a local source of ironware. John Winthrop, Jr., traveled to England to raise the capital and recruit iron workers. While the political situation in England was unsettled, he visited alchemical friends in Europe and honed his iatrochemical skills. There was a vibrant intellectual world in England...

After the restoration of Charles II, John Winthrop, the Younger, traveled to London to obtain a Royal Charter for Connecticut. While it took a long time and required a large sum of money, Winthrop showed both political skill and patience in obtaining his desired end. He also used his copious free time in London to pursue his scientific interests am...

This book explores the lively chemistry culture that arose during the 17th century in Colonial New England. This was chiefly due to the efforts of John Winthrop, Jr. who brought both chemical knowledge and the largest library of chemical books in the New World to Boston. He founded towns, such as Ipswich and New London, and industrial enterprises,...

William Henry was a model preceptor of Chemistry. He created a coherent paradigm for all of Chemistry in the early 19th century based on the notion of Daltonian atoms. His classic text, The Elements of Experimental Chemistry, was used throughout the world for more than 50 years. He taught everyone from Natural Philosophers to Pharmacist Assistants....

Herman Mark is widely considered to be one of the greatest scientists of the 20th century. He chose to solve problems with multidisciplinary teams, rather than build a solitary reputation. He lived at a time and in a place where it was highly unlikely that he would receive the national support needed for a Nobel Prize. His reward was to be one of t...

In the 1950s, the discovery of a class of 'living' polymerization reaction revolutionized the field of polymer science by providing a way of controlling the molecular-weight distribution of polymers. The effects reverberate to this day.

Carl Shipp Marvel (1894-1988) took the mantle left by Wallace Carothers . It is not surprising that he also came from the University of Illinois. The towering figure at Illinois in this period was Roger Adams (1889-1971). He was Department Head from 1916-1954. Adams was from a famous New England family and attended Harvard University.

A Prehistory of Polymer Science ended with Hermann Staudinger well ensconced at Freiburg and basking in the success of the Faraday Discussion on Polymerization [1]. But better days were not ahead. Most of his best collaborators were either going or gone. The conditions in Germany were not going to get better and all scientists were expected to serv...

The period from 1935-1953 was a very profitable and dynamic era in the history of polymer science. The worldwide community that coalesced in 1935 was very active in identifying the key phenomena and forging satisfying qualitative and quantitative theories. The state of the community in 1953 will be surveyed from several perspectives.

Many other scientists committed a major part of their work to the study and understanding of macromolecules. In this chapter, brief surveys of these emerging leaders are given.

After the triumphant Faraday Society Meeting of 1935, Herman Mark (1895-1992) went back to Vienna and started preparing a monograph summarizing the current paradigms in polymer science.

1935 was a very good year for polymer science. More than 200 scientists, engineers and technologists had gathered in Manchester to present and discuss the field of polymerization and the discipline of polymer science.

Although Wallace Carothers (1896-1937) was not alive to personally interact with the ongoing polymer science community, he left a legacy of publication that was quickly collected and edited by Herman Mark (1895-1992) and G. Stafford Whitby (1887-1972).

One of the great French explorers of the eighteenth century was Charles Marie de la Condamine (1701–1774).

Another lens through which to view the birth of polymer science is the foremost community of physical chemists in the early twentieth century, The Faraday Society.

The formation of a viable research paradigm requires many factors to be aligned. There needs to be a coherent collection of observable phenomena that requires the paradigm in order to comprehend the facts. Since there are polymers everywhere in the natural world, what set of observations provoked a search for an appropriate paradigm? The discovery...

The synthesis, spectral properties, and electropolymerization of hybrid gold nanoparticle core/carbazole dendron shells are reported. Ligand exchange of short-chain alkane thiol stabilized Au-NP is compared with direct synthesis using peripheral carbazole dendron ligands. Optical spectra, light scattering, TEM, and electron diffraction data confirm...

There have been occasions when the publication of a particular book has had a singular impact on the conceptual world of the chemist. Sometimes the publication occurs near the beginning of a major change in discourse, and sometimes more near the end. Jean Perrin published Les Atomes in 1913 as the culmination of a century-long controversy over the...

A series of episodes in the historical development of our view of chemical atoms are presented. Emphasis is placed on the key observations that drove chemists and physicists to conclude that atoms were real objects and to envision their structure and properties. The kinetic theory of gases and measurements of gas transport yielded good estimates fo...

IntroductionMichael Faraday (1791–1867)James Clerk Maxwell (1831–79)John William Strutt (1842–1919)NotesReferences

An Evangelical Natural PhilosophyAn Evangelical AnthropologyReferences

IntroductionOrigenNewtonConclusions References

One of the central dogmas of modern science is that the world around us can be understood in terms of microscopic chemical entities known as atoms. It may come as a surprise that this notion has only been widely acknowledged since the 1910s. The French physicist Jean Perrin had a hand in many of the key developments that led to the emergence of the...

Written by a chemical physicist specializing in macromolecular physics, this book brings to life the definitive work of celebrated scientists who combined multidisciplinary perspectives to pioneer the field of polymer science. The author relates firsthand the unique environment that fostered the experimental breakthroughs underlying some of today's...

The light scattering structure factor S(q, c) has been measured for a series of concentrations near the overlap value c* for solutions of high molecular weight poly(-methyl styrene) in the good solvent toluene. Scattering functions near and above overlap are characterized by a maximum as a function of scattering vector q. Scattering functions have...

The full range of relaxation processes present in optically pure poly-(n-hexyl methacrylate) (PHMA) was studied using Rayleigh–Brillouin and photon correlation spectroscopy (PCS). Brillouin shifts, linewidths, and Landau–Placzek ratios (LPR) were measured over the temperature range from −11 to 21 °C. The Brillouin splitting and linewidth were consi...

The enzyme beta-galactosidase has been immobilized through incorporation into a selectively soluble microgel, prepared from DNA, biotinylated peptide nucleic acid (PNA), and the protein avidin. The enzyme was conjugated to avidin, allowing it to be integrated directly into the microgel network. Efficient hydrolysis of a small-molecule substrate occ...

Multifunctional molecules were designed to produce microgels with specific structures. Both static light scattering and dynamic light scattering were employed to determine the fractal dimension of the microgels. The protein, avidin, was strongly bound to four biotin moieties. Biotin was attached covalently to specifically engineered peptide nucleic...

Light scattering in bulk polymers is due to fluctuations in the local dielectric tensor ε of the medium(1, 2) In this chapter, the types of fluctuations that occur in polymers and their manifestation in the light scattering will be presented. The features which are characteristic of polymers will be elucidated as well as the general behavior of lig...

We describe the synthesis and characterization of a thermoreversibly cross-linked biopolymer microgel based on protein, DNA, and peptide nucleic acid (PNA) components. The DNA assembles into a trifunctional three-way junction (TWJ) with single-stranded overhangs. PNA oligomers complementary to these overhangs and bearing terminal biotin groups hybr...

The synthesis of hybrid nanoparticles was conducted by the atom transfer radical polymerization (ATRP) of styrene and (meth)acrylates from colloidal surfaces. Colloidal initiators were prepared by the functionalization of silica colloids with 2-bromoisobutyrate groups. ATRP from colloidal surfaces was then performed to attach well-defined homopolym...

Anionically polymerized polystyrene standards have been characterized by static and dynamic light scattering in toluene at 25°C. The molecular weights ranged from 3000 to two million g/mol. An appropriate standard for light scattering intensity was developed and the absolute Rayleigh ratio for toluene was determined for the experimental conditions....

Multifunctional molecules were designed to produce thermoreversible microgels with specific structures. Both static and dynamic light scattering were employed to determine the fractal dimension (Df) of the microgels. Avidin binds four biotin moieties. Biotin was attached covalently to engineered peptide nucleic acid (PNA) oligomers. Three designed...

The synthesis of hybrid nanoparticles was conducted by the atom transfer radical polymerization (ATRP) of styrene and (meth)acrylates from colloidal surfaces. Colloidal initiators were prepared by the functionalization of silica colloids with 2-bromoisobutyrate groups. ATRP from colloidal surfaces was then performed to attach well-defined homopolym...

The effect of the chain constraint on the glass-transition temperature of polystyrene (pS) was studied in the context of polymer tethering to curved surfaces. The synthesis and characterization of silica-graft-polystyrene (SiO2-g-pS) hybrid nanoparticles is reported. Silica nanoparticles possessing covalently bound pS chains were prepared by the at...

Dynamic light scattering (LS) is sometimes used to determine the thickness of adsorbed layers of polymers by comparing the hydrodynamic radii determined with and without the adsorbed layer. Here we point out a number of pitfalls with this method for one particular polystyrene latex. For example, even without an adsorbed layer, the hydrodynamic diam...

Hybrid nanoparticles are a useful example of spherical brushes; the size and composition of the colloid can be precisely controlled using controlled/living radical polymerization, and inorganic cores can be selectively degraded via hydrolysis, allowing for recovery of grafted polymer chains. We report the characterization of hybrid nanoparticles co...

2-Bromoisobutyrate-functionalized silica nanoparticles were prepd. via a microemulsion process and used as initiators for the prepn. of benzyl acrylate-styrene block copolymer hybrid particles using atom transfer radical polymn. [on SciFinder(R)]

Slowly relaxing longitudinal density fluctuations in an optically perfect sample of bulk poly(n-hexyl methacrylate) (PHMA) have been studied by photon correlation spectroscopy in the temperature range 10–36°C. The glass transition temperature for this sample was measured to be Tg = −3°C by differential scanning calorimetry. The optical purity of th...

Third harmonic generation (THG) is used to study the third-order nonlinear optical properties of nematic and isotropic solutions of poly(1,4-phenylene-2,6-benzobisthiazole) and related small-molecule model compounds. Maker fringe patterns (MFP) obtained using both plane slab and wedge-shaped cells for fundamental wavelengths of 1.542 and 1.907 μm a...

Static and dynamic light scattering measurements were made of solutions of pGem1a plasmids (3730 base pairs) in the relaxed circular (nicked) and supercoiled forms. The static structure factor and the spectrum of decay modes in the autocorrelation function were examined in order to determine the salient differences between the behaviors of nicked D...

Depolarized Rayleigh scattering photometry has been employed to study the temperature dependence of the optical anisotropy for benzene, hexafluorobenzene, and carbon tetrachloride. The depolarized Rayleigh intensity from carbon tetrachloride is entirely due to scattering by pairs of density fluctuations and increases monotonically with temperature....

The basic principles of dynamic light scattering from viscoelastic fluids are explained and illustrated with specific results obtained for both simple fluids and polymers. The origin and spectral form of the dynamic central peak due to slowly relaxing longitudinal density fluctuations are discussed. The importance of measuring both the power spectr...

Slow relaxing longitudinal density fluctuations in bulk syndiotactic poly (n-butyl methacrylate) [PBMA] were studied by photon correlation spectroscopy as a function of temperature from 70 to 90°C. The shape of the light-scattering relaxation function broadened as the temperature approached the glass transition (Tg = 55°C). The average relaxation t...

The various characteristic spatial and temporal scales that are involved in dynamic light scattering from polymer solutions under non-hydrodynamic conditions are reviewed and analyzed. The contributions to non-exponential decay of the decay function determined in dynamic light scattering are discussed, with comparison to experimental behavior, incl...

The scattered intensity function S(q, c) and the intermediate scattering function S(q, c, τ) of poly-(α-methyl styrene) (Mω = 5.71 × 105, 1.17 × 106, and 2.96 × 106) in toluene in the dilute concentration region were measured as functions of concentration and scattering vector q. In infinitely dilute solution, the intensity function S(q, 0) agrees...

Rayleigh-Brillouin scattering has been studied as a function of temperature in a series of globular alkanes: 2,2-dimethylpropane, 2,3-dimethylbutane, and 3,3-diethylpentane. The calculated volume viscosities are larger than the shear viscosities for these liquids. The volume viscosities are analyzed in terms of a structural contribution with magnit...

We present Rayleigh-Brillouin light scattering data of highly syndiotactic poly(n-butyl methacrylate) [PBMA] whose glass transition temperature as measured by DSC is 55°C. The Brillouin peak shifts, Brillouin peak widths, and Landau-Placzek ratios from −15 to 130°C are reported. The Brillouin peak widths decrease continuously through the glass tran...

Third-order nonlinear optical properties of lyotropic liquid crystal poly(1,4-phenylene-2,6-benzobisthiazole), PBT, solutions are studied by third harmonic generation measurements. Besides the enhancement observed for this coefficient with respect to the pure PBT, coupling is observed between the mean filed nematic director n and the incident funda...

The basic principles necessary to understand light scattering from gels are now well understood. The experimental techniques necessary to measure light scattering from gels are now highly developed. Yet there are many issues that need to be clarified in practice. The spatial correlations that exist in the polymer concentration in a gel need extensi...

Light scattering has long been established as a technique for measuring the molecular weight and radius of gyration of polymer molecules. Depolarized light scattering can be studied accurately with lassers. The theory of static and dynamic depolarized light-scattering spectroscopy is presented and illustrated with two examples of novel particles in...

Light scattering spectroscopy is a powerful tool in the study of the molecular dynamics of pure fluids. In the present review we present the theory of light scattering from pure fluids and illustrate it with results obtained in our laboratory. Local translational and orientational relaxations are examined. The coupling of molecular orientation to m...

The relaxation function obtained by photoncorrelation spectroscopy of a liquid near the glass transition has a highly nonexponential decay. This nonexponential behavior can be represented by a distribution of exponential relaxation processes. Using a real‐time, 4‐bit, 4‐sample time, 256‐channel correlator we have obtained very high quality depolari...

A solubilized form of polyacetylene (PA) has recently been created by grafting polyacetylene chains onto a polyisoprene carrier chain. The product of this grafting reaction is stable in toluene solution indefinitely. In the present paper static and dynamic light scattering is used to characterize the particles that exist in solution. Polyisoprene i...

The effective diffusivity of a solute within a pore of comparable size is frequently found to be less than its value in bulk solution. This phenomenon is known as "hindered" or "restricted" diffusion and it arises fundamentally from the fact that the characteristic dimension of the solute molecule is no longer small compared to that of the pore thr...

The Rayleigh–Brillouin spectrum of 2,4‐dimethyl pentane, 2,4,6‐trimethyl heptane, 3,5‐dimethyl heptane, 2,2,4,4‐tetramethyl pentane, and 2,2,4,4,6,6,8,8‐octamethyl nonane was measured as a function of temperature from well above the Brillouin linewidth maximum down to the glass transition region. Brillouin splittings and linewidths were determined...

Hypersonic relaxation is studied in amorphous poly(dimethylsiloxane) (PDMS) as a function of temperature from 77 to 300 K and as a function of pressure at 2.96 K. A clear loss maximum as a function of pressure was found at 296 K. The loss maximum at 1 bar was found to be at 218 K at a frequency of 5.4 GHz. This is well below the melting point of PD...

Photon correlation spectroscopy has proven to be a very useful technique for studying slowly relaxing density and optical anisotropy fluctuations in bulk polymers near the glass transition. When some of the fluctuations achieve relaxation times much longer than the typical averaging time for the intensity autocorrelation function (104 s), the resul...

Laser light scattered from a block of polystyrene is observed to have a pattern of bright and dark regions called speckle. We observe that the speckle pattern has a lifetime consistent with that of the average relaxation lifetime 〈τ〉 of the intensity fluctuations of the medium as determined by photon correlation spectroscopy. In order to study the...

Poly(methyl methacrylate) (PMMA) has been studied by photon correlation spectroscopy in the temperature range 120–150°C. The relaxation functions for longitudinal density fluctuations were determined and analyzed using the empirical function ϕ(t) = exp[−(t/τ)β]. The average relaxation times were calculated for each temperature and compared to mecha...

Photon correlation spectroscopy is employed to study the slowly relaxing density and anisotropy fluctuations in bulk atactic polystyrene as a function of temperature from 100 to 160°C and pressure from 1 to 1330 bar. The light-scattering relaxation function is well described by the empirical function ϕ(t) = exp[−(t/τ)β], where for polystyrene β = 0...

It has recently been suggested that a mesomorphic transition in the melt of n-tetracosane can be detected using Brillouin scattering. In the present paper we report measurements of both the longitudinal Rayleigh–Brillouin spectrum and the depolarized Rayleigh spectrum as a function of temperature from the melting point to 240 °C. The spectra are di...

A report is presented of features in the Brillouin spectra of PS (polystyrene) and PMMA (polymethyl methacrylate) which the authors believe to be due to SWS. In PS they find these features to be weaker than those reported by J. K. Kruger et al. The shear wave linewidths are resolved, but a serious study of the relative widths of the longitudinal an...

Photon correlation spectroscopy is employed to study the slowly relaxing density and anisotropy fluctuations in bulk atactic polystyrene as a function of pressure at 146 °C from 1 bar to 1.33 kbar. The light scattering relaxation function observed as a function of pressure is identical in shape to that observed previously as a function of temperatu...

The central Lorentzian peak in the depolarized Rayleigh spectrum of CCl4 and GeCl4 is studied as a function of temperature using a high resolution Fabry–Perot interferometer. The results are shown to be consistent with a recent theory by Madden which attributes the depolarized spectrum to scattering by anisotropic pairs of density fluctuations. It...

Depolarized Rayleigh scattering is studied as a function of temperature in a group of small alkanes under conditions where the observed relaxation time is in the picosecond time range. The molecules studied include the n‐alkanes from pentane to nonane, 2‐methyl butane, 2,3‐dimethyl butane, 2,4‐dimethyl pentane, 2,2,4,4‐tetramethyl pentane, and 3,3‐...

Brillouin scattering is used to study hypersonic relaxation in 1,2-polybutadiene and cis-polyisoprene. The temperature of maximum loss was determined to be 125°C for a frequency of 5.0 GHz for polybutadiene and 100°C at a frequency of 5.9 GHz for polyisoprene. Hypersonic loss maxima are examined for many polymers and general conclusions are reached...

The Brillouin splitting and line width are measured for the system consisting of the solvent Cellosolve Acetate and a polyepoxide formed from glycerol and bisphenol-A with epoxide end groups. Gels were formed by end-linking the chains in solution with a low molecular weight poly(propylene glycol) with amine end groups. Addition of polymer does lead...

Problems in the collection and analysis of photon correlation data obtained near the glass transition are presented and discussed. The use of the Williams-Watts empirical relaxation function in the analysis of the data is critically examined. A proposed graphical method of analysis is also studied and found to be subject to many limitations. The av...

The mutual diffusion coefficient Dc is determined by photon correlation spectroscopy during the thermal gelation reaction of styrene and divinylbenzene. The resulting gel is then studied as a function of temperature. The present results do not differ significantly from those obtained for solutions of polystyrene in styrene reported earlier. The qua...

In order to more fully understand the viscoelastic properties of amorphous polymers, it is desireable to have dynamic mechanical data over as wide a range in frequency as possible. One useful technique for studying the high-frequency behavior of polymers is to measure the velocity and attenuation of sound waves in the polymer fluid. When the freque...

The distribution function of relaxation times underlying the nonexponential relaxation function of Williams and Watts is derived and compared with the analogous Cole–Davidson distribution function. In order to make the comparison between the two distribution functions, a simple empirical relationship between the Cole–Davidson and Williams–Watts par...

The mutual diffusion coefficient in polystyrene solutions is examined both theoretically and experimentally. The measurements are shown to be incapable of testing the scaling law predictions for the osmotic modulus and friction coefficient. Measured values of Dc in carbon tetrachloride and ethyl acetate yield no hint of a crossover region between d...

In this bibliography-based review-paper, the general considerations of light scattering in dense media are followed by a presentation of the theory of Brillouin scattering from bulk polymers (Section II). A discussion of the necessary apparatus is given in Section III. A review of scattered intensity studies in polymers follows in Section IV. A sur...

Polarized Rayleigh scattering is studied near the glass-rubber relaxation in atactic polystyrene using photon correlation spectroscopy. Average relaxation times determined from the data agree well with previous results obtained using depolarized Rayleigh scattering. The light scattering results follow the same trend observed by dielectric and mecha...

Brillouin scattering measures the velocity and attenuation of hypersonic thermal acoustic phonons using light scattering. This technique has been applied now to many problems in polymer science. This chapter describes the theory and experimental procedures used in Brillouin scattering. Many examples are presented of the types of information that ca...

The cooperative diffusion coefficient Dc for concentration fluctuations is studied as a function of polymer concentration during the thermal polymerization of styrene using photon correlation spectroscopy. Measurements were carried out from the semidilute region to approximately 90% polymer. From 2-10%, polymer Dc rose linearly with concentration....

The depolarized Rayleigh spectrum of polymerizing styrene is studied as a function of time near the end of the reaction. The average relaxation time changes over five orders of magnitude as the reaction proceeds to its end point. The relaxation function observed for the anisotropy fluctuations is not a single exponential. The same form used to fit...