Revitalization of electro-catalysis for the formation of organic scaffolds

Organic electro-catalysis is an old successor who took his place in Faraday's pioneer work. This sector has a rich archive and is in the process of being revitalized, due to the increasing pressure of the chemical community on the ripening of green, cheap, and well-planned production methods. The control of the electrode power options makes this reaction selective. It is, therefore, an attractive alternative to the use of electrical inputs instead of toxic agents that will be harmful to the environment. The interpretation of this minor review examines a variety of electro-catalyzed reactions such as Michael's addition reaction, C-N, C-F functional reactions, and mixed reactions. Since the reactions are bestowed with sole reagent, an electron, making the methodology inherently safe and environmentally benign. This all-encompassing review of organic electro-catalysis explores the latest designs and assists those who are not adequately trained in electro-chemistry, but who can produce these different energies in a variety of biological chemicals.     

Rolf Huisgen,Eminent Chemist and Polymath (1920–2020): In His Own Words and In His Publication Metrics

As a compliment to several other publications that present and honor Rolf Huisgen's research achievements, the first part of this paper reveals the human side of this eminent chemist. From excerpts from many of his personal and professional writings, Huisgen's personality and philosophies of life are revealed. Also revealed is Huisgen functioning as a historian of chemistry. The second part of this paper examines the scientometrics of Huisgen's publication history. In the late 1950s and early 1960s, Huisgen's career experienced a major transition in terms of publication metrics and the influence these papers had on the organic chemistry community. This was the result of his research into 1,3‐dipolar cycloadditions. Citations to his scientific contributions are well spread over many of his papers, demonstrating his constant work and the building up of a research topic, which continued after his official retirement in 1988. In fact, 17 % of his more than 600 publications appeared after 1988. The majority of Huisgen's papers were co‐authored with his many graduate and postdoctoral students. Consistent with the trend of that era, Huisgen was the sole author of most of his Review articles, and not just those of his many plenary lectures, and it is those Review articles that proved to be his most cited publications. This demonstrates the power and influence of Review articles—secondary sources, in the vocabulary of historians and sociologists of science. In those Review articles, Huisgen principally described the state of the art of 1,3‐dipolar cycloadditions—his golden offspring.     

Rolf Huisgen,Eminent Chemist and Polymath (1920–2020): In His Own Words and In His Publication Metrics

As a compliment to several other publications that present and honor Rolf Huisgen's research achievements, the first part of this paper reveals the human side of this eminent chemist. From excerpts from many of his personal and professional writings, Huisgen's personality and philosophies of life are revealed. Also revealed is Huisgen functioning as a historian of chemistry. The second part of this paper examines the scientometrics of Huisgen's publication history. In the late 1950s and early 1960s, Huisgen's career experienced a major transition in terms of publication metrics and the influence these papers had on the organic chemistry community. This was the result of his research into 1,3-dipolar cycloadditions. Citations to his scientific contributions are well spread over many of his papers, demonstrating his constant work and the building up of a research topic, which continued after his official retirement in 1988. In fact, 17 % of his more than 600 publications appeared after 1988. The majority of Huisgen's papers were co-authored with his many graduate and postdoctoral students. Consistent with the trend of that era, Huisgen was the sole author of most of his Review articles, and not just those of his many plenary lectures, and it is those Review articles that proved to be his most cited publications. This demonstrates the power and influence of Review articles—secondary sources, in the vocabulary of historians and sociologists of science. In those Review articles, Huisgen principally described the state of the art of 1,3-dipolar cycloadditions—his golden offspring.     

Nehemiah Grew (1641–1712) and the Saline Chymistry of Plants

Abstract

In a series of lectures appended to his magisterial Anatomy of Plants (1682), Nehemiah Grew (1641–1712) explained the results of his own research into the saline chemistry of plants, following an established tradition in early modern chemistry. Members of the Royal Society such as Daniel Coxe were heavily involved in researching salt chemistry in the latter part of the seventeenth century, analysing the role of salts in spa waters, physiology, and as a fundamental element in iatrochemistry. Such researches of Royal Society members were often based upon the chemistry of Johann Van Helmont (1577–1634). As this paper will demonstrate, Grew's work drew from his microscopic research to elaborate and question some of Coxe's and hence Van Helmont's ideas about the principles of matter. Grew also used the results of his chemical research to draw conclusions about plant structure and colour, and applied his results to other areas in natural history such as meteorology, illustrating that chemistry was the basic analytical tool for seventeenth-century investigators of anatomy and natural history.     

Michael Combrune,Peter Shaw and Commercial Chemistry: the Boerhaavian Chemical Origins of Brewing Thermometry

Abstract

Recent work by David P. Miller indicates how the chemical activity of a much-studied figure, James Watt, has been obscured by the retrospective assigning of heat studies in general to physics. This paper applies a similar analysis to the work of Michael Combrune, a philosophically inclined brewer of the mid-eighteenth century; remembered chiefly within the brewing profession as a pioneering thermometrist, Combrune understood the thermometer as the central diagnostic tool in a chemically derived system of management that is now largely forgotten. In the course of retrieving this scheme, I display its origins in the chemistry of Herman Boerhaave as mediated by his unauthorised translator Peter Shaw, Combrune's intellectual patron, whose association with the gentlemanly representatives of artisanal trades derived from his concern to establish "commercial chemistry." I next demonstrate Combrune's considerable conceptual independence and forcefully reductive quantitative agenda, and finally outline three reasons why later practitioners abandoned his scheme: the displacement of its supporting authorities, the affording of independence to users, and the acceptance of its practical outcomes as simple givens — all circumstances that might befall a "mainstream" as easily as a "marginal" theory.     

Ca-Oxalate films and microbiological investigations of the influence of ancient pigments on the growth of lichens

Simultaneous thermogravimetry and thermomicroscopy were performed on Ca-oxalates which play an important role in the appearance of oxalate films connected with lichens superficially growing on human artefacts. Ca-oxalate exists in two well-described modifications: as the more stable monoclinic monohydrate whewellite and the less stable tetragonal dihydrate weddelite. Weddelite serves for lichens as a water absorbing and accumulating substrate which transforms to whewellite when humidity drops. To follow these morphological changes optically and the water loss gravimetrically at the same time, a combination of thermomicroscopy and thermogravimétric analysis was constructed, The reflection light microscope was connected to a video camera and computer so that the morphological changes and the thermogravimetric curves could be shown simultaneously on the screen as function of time and temperature.Lichens — double organisms composed of algae and fungi — form surface layers not only on natural organic and inorganic material but also on human artefacts. In calcareous artefacts such as the famous Chinese terracotta soldiers or Egyptian epigraphs they lead to a destruction of the surface by forming Ca-oxalate layers and thus to a deterioration of the historian work of art. But in places where the surface is covered by some blue colours (Egyptian and Chinese Blue, Chinese Purple) the growth of lichens is inhibited and the artefacts are well preserved. The copper ion contained in the pigments is responsible for this effect since copper is a strong poison for microorganism.As lichens exhibit an extremely slow growth under natural and laboratory conditions the two lichen components: algae and fungi were investigated separately. The three mentioned ancient pigments have very low solubility products and thus do not act on the quickly growing fungi. But under special experimental conditions Egyptian Blue formed clear halos on the growth plates of the algaeChlorella minutissima andTrebouxia glomerata. These halos were compared with those of the easily soluble copper sulphate as a standard.We are deeply indebted to Mrs. R. Daum for skilled assistance in handling the microbial strains and to Prof. Dr. G. Marx and Dr. H. Bischoff for the determination of the solubility products.     

Medicines,Monopolies and Mortars: the Chemical Laboratory and Pharmaceutical Trade at the Society of Apothecaries in the Eighteenth Century

Abstract

In 1672, a laboratory was founded by the Society of Apothecaries at its premises in Blackfriars, London, to manufacture chemical medicines. By exploring the society's motivations for constructing a laboratory and its development during the eighteenth century, this paper examines the roles that chemistry played within the activities of the institution. While the chemistry's primary utility was in drug manufacturing for the society's pharmaceutical trade, through its laboratory, the society used chemistry to develop its corporate and educational aims, thus helping to secure its institutional authority in London's medical marketplace.     

A Previously Unknown Path to Corpuscularism in the Seventeenth Century: Santorio’s Marginalia to the Commentaria in Primam Fen Primi Libri Canonis Avicennae (1625)

This paper presents some of Santorio's marginalia to his Commentaria in primam fen primi libri Canonis Avicennae (Venice, 1625), which I identified in the Sloane Collection of the British Library in 2016, as well as the evidence for their authorship. The name of the Venetian physician Santorio Santori (1561–1636) is linked with the introduction of quantification in medicine and with the invention of precision instruments that, displayed for the first time in this work, laid down the foundations for what we today understand as evidence-based medicine. But Santorio's monumentale opus also contains evidence of many quantified experiments and displays his ideas on mixtures, structure of matter and corpuscles, which are in many cases clarified and completed by the new marginalia. These ideas testify to an early interest in chemistry within the Medical School of Padua which predates both Galileo and Sennert and which has hitherto been unknown.     

物理化学家——梁敬魁

梁敬魁院士于2019年1月19日因病去世。他一系列有关相图的研究工作被认为是我国相图工作中卓有成效的高水平工作,具有很好的理论和实用价值,因此他的科研成果令人瞩目。本文就梁敬魁的生平、求学经历及其对物理化学的贡献进行了论述。     

Research strategies in click chemistry: Measuring its cognitive contents and knowledge flow

The issue about how outstanding scientists obtained innovative findings has drawn the interest of researchers in science, policy and scientometrics. Here, we attempt to address this question by using computational methods to measure the cognitive content and concepts of K. Barry Sharpless’ research and estimate the knowledge flow of his click chemistry to other fields. First, we traced Sharpless' conceptual journey over time through topic modeling approach, mapping and clustering of the epistemic network from distant reading his publications. We find that connectivity and functions, the core features of click chemistry, are embodied in his constant search for simplicity. What makes simplicity possible is his continuous work with collaborators on reactivity and reaction mechanisms. Moreover, citation and link analysis show that click chemistry had a much richer impact on other research fields than what is generally acknowledged, and drew solutions to significant and practical questions back to chemistry from biology. Together with these findings, we propose that the click chemistry philosophy follows the way that values nature's principle. Chemistry has a clear-cut epistemic domain in modeling Nature. Thus, click chemistry as a concept on doing science beyond a connective technology goes across the boundaries between disciplines and impacts many other fields.     

Emil Wohlwill's “Entdeckung des Isomorphismus”: A Nineteenth-Century “Material Biography” of Crystallography

Abstract

Eilhard Mitscherlich's experimental work on isomorphism in the crystallisation of many inorganic compounds was regarded by Emil Wohlwill (1835–1912) as a milestone in the history of the atomic–molecular theory. Despite his positivist account, Wohlwill's 1866 survey was primarily concerned with the material conditions that shaped Mitscherlich's theoretical assumptions on iso- and polymorphic crystallisation, narrowing the range of possible alternative models. Following an account of Wohlwill's exposition, and a discussion of his historiographic views, the paper shows how, from a historico-epistemological perspective, technical improvements in crystallography (an emerging branch of early-nineteenth-century mineralogy) were deeply entangled with a new interest in crystal formation as a cutting-edge research field of inorganic chemistry. This had fundamental implications for the development of atomic and molecular theory.     

Alexander Crum Brown and his Doctoral Thesis of 1861

Abstract

Organic chemistry began at the universities in the Habsburg Empire about 1840, when Josef Redtenbacher, a post-graduate student of Liebig in Giessen, established the first organic laboratory at Charles University, Prague. Following Liebig's teaching methods, he required laboratory work from his students. Redtenbacher's students then headed the new chemistry departments, which were established after the revolution of 1848. Several of Redtenbacher's students had also been trained as botanists and they focussed their research on phytochemical questions. Austrian chemists also contributed to theoretical organic chemistry. In 1853 Rochleder published a paper in which the quadrivalence of carbon was assumed. A more important contribution was made by Josef Loschmidt in 1861, when he published the graphical formulae of several hundred compounds. In contrast to the ideas of Gerhardt and Kekulé, Loschmidt assumed that the constitution of a compound can be deducted from its reactions. Loschmidt's work attracted little interest abroad and was only rediscovered many years later by Richard Anschütz.     

Nondestructive analysis of ancient Egyptian funerary relics by Raman spectroscopic techniques

The non-destructive Raman spectroscopic analysis of a range of ancient Egyptian funerary artefacts has been undertaken with a view to establish the identification of the pigment composition and nature of the interaction with the substrate. The specimens date from the New Kingdom to the Graeco-Roman period, ca. 3900-1800 years b.p. In this study a comparison has also been effected between the near-infrared and red excitation wavelengths for the characterisation of these materials. A particular problem for Raman analysis of these artefacts was found in the application of resin or organic compounds to the surface or substrata, as colourants or to aid adhesion of the pigments, and degradation of the resins with burial environment and exposure has resulted in large fluorescent backgrounds. Nevertheless, useful information has been obtained which assists in the interpretation of the construction of some of the artefacts.     

Alfred Werner: Overlooked Genius of the Periodic System

2019, which was proclaimed by the United Nations as the International Year of the Periodic Table, sees one hundred years since Alfred Werner, the first Swiss to receive a Nobel Prize in chemistry, passed away. The undoubted father of coordination chemistry, he is also well-known for influencing many other fields of chemistry, including organic, inorganic, organometallic, bioinorganic, and stereochemistry. However, one of his more rare and unique contributions to chemistry, his 1905 version of the periodic system, to this day remains overlooked. The simple and elegant idea which he used to construct his periodic table has not been communicated to the English-speaking world, because Alfred Werner published his only original paper on the periodic table in German. Werner's simple mathematical approach lead to overwhelming success with anticipating the future f-block. He managed to predict almost perfectly the number of lanthanides, which was hotly debated at that time. Werner's genius vision was considerably ahead of its time. It was not until the 1940s and the discovery of actinide series when the idea of representing the elements as a 32-column periodic table finally became justified.     

P.‐O. Löwdin and the International Journal of Quantum Chemistry: A kaleidoscopic agenda for quantum chemistry

This is a article about P.‐O. Löwdin's life, his work in shaping quantum chemistry into a mature discipline at the intersection of mathematics, physics, chemistry, and biology, and his founding of the International Journal of Quantum Chemistry in 1967. Unavoidably, it is, also, a article reflecting our views about the history of quantum chemistry. We attempt to convey the complexities in the becoming of a subdiscipline, like quantum chemistry, where a variety of factors will have to be taken into consideration for a comprehensive understanding of its historical developments: the relations of chemists to the Heisenberg‐Schrödinger formulation of quantum mechanics after 1926, the institutional dynamics centered around the establishment of new courses and chairs, the research agendas and the vying for dominance within the community of quantum chemists, the methodological, and philosophical issues that have never left the quantum chemists indifferent, and, of course, the dramatic role of the computer in transforming the culture for actually practicing quantum chemistry. Furthermore, attracted by American history, culture, and ways of life, Löwdin suggested in the late 1970s that the post‐WWII character of quantum chemistry was dependent on its ability to hub a “scientific melting pot,” much like the United States of America which he viewed as a fusion of people from diverse provenances and cultures. In this article, we attempt to investigate another metaphor, that of the “kaleidoscope.” Löwdin believed that quantum chemistry's strength arose from its ability to nurture a multiplicity of heterogeneous cultural elements/subcultures and practices, interacting with each other, exchanging perspectives and modes of action, which circulated in an increasingly extended network of actors and institutional frameworks. © 2013 Wiley Periodicals, Inc.     

Chemistry and dynamics in the thought of G.W. Leibniz I

Chemistry and dynamics are closely related in G.W. Leibniz's thinking, from the corpuscularism of his youth to the theory of conspiracy movements that he proposes in his later years. Despite the importance of chemistry and chemical thought in Leibniz's philosophy, interpreters have not paid enough attention to this subject, especially in the recent decades. This work aims to contribute to filling this gap in Leibnizian studies. In this first part of the work I will expose the theory of matter that the young Leibniz conceives under the influence of chemical corpuscularism. Leibniz uses R. Boyle's interpretation of the Aristotelian idea of form in order to give an explanation of the unity and cohesion of bodies. As opposed to the Cartesians, Leibniz puts forth the idea of a dependence between the variables of extension, movement and figure, without losing analytical clarity and with the aim of extending the explanatory power of physics to natural phenomena difficult to approach by Cartesian mechanics.

     

From Candles to Cabinets: “Familiar Chemistry” in Early Victorian Britain

Abstract

“Familiar chemistry” flourished in early Victorian Britain. This set of texts an practices advocated drawing scientific lessons from the habitual activities of daily life, in which the hidden chemical contents of common objects and quotidian processes were revealed. Through sensory interactions in the family environment — enlightening conversation and hands-on explorations — a wide range of phenomena could be introduced to childish bodies and minds. A close reading of texts such as Albert J. Bernays' Household Chemistry (1852), alongside a consideration of everyday artefacts, as well as novel specialist objects such as Robert Best Ede's “Youth's Laboratory” (ca. 1837–1845), allows a discussion of this educational style, and an introduction of this new analytic category. In particular, I argue, familiar chemistry succeeded by reworking the popular literary genre of the familiar introduction with an emphasis on embodied interactions with emphatically real things, and gave a central role to the familial domestic context. From candles to cabinets, and beyond, in this article I will demonstrate that familiar chemistry provides a new perspective on scientific education and participation in the nineteenth century.     

Alchemy,Prophecy, and Politics in Eighteenth-Century Iberia: Anselmo Castelo Branco's Critique of Benito Feijoo

The Benedictine monk Benito Jerónimo Feijoo (1676–1764) is now considered one of the major figures of the Spanish and Iberian Enlightenment. However his work, both in Spain and in Portugal, was far from being universally acclaimed. His critical approach to the subject of alchemy in his essay “Piedra Filosofal,” published in the third volume of his magisterial Teatro Crítico Universal (1726–1739), sparked an unexpected response from the Portuguese alchemist Anselmo Castelo Branco, who sought to refute Feijoo's claims in his own work, the Ennoea. This paper presents an outline of this exchange and its position within Iberian Enlightenment circles. It further argues that Castelo Branco's defence of alchemy was informed by his political and prophetic views, in particular his adherence to the Portuguese messianic doctrine of Sebastianism.     

Linking chemistry with physics: arguments and counterarguments

The many-faced relationship between chemistry and physics is one of the most discussed topics in the philosophy of chemistry. In his recent book Reducing Chemistry to Physics. Limits, Models, Consequences, Hinne Hettema (Reducing chemistry to physics. Limits, models, consequences, Rijksuniversiteit Groningen, Groningen, 2012) conceives this relationship as a reduction link, and devotes his work to defend this position on the basis of a “naturalized” concept of reduction. In the present paper I critically review three kinds of issues stemming from Hettema’s argumentation: philosophical, scientific and methodological.