An Introduction to The Bibliography of Alchemy—Part I

Abstract

This article contributes to a growing body of research on the dissemination, dispersion or diffusion of scientific knowledge via pedagogical networks. By examining students’ handwritten lecture notes, I compare the eighteenth-century chemistry lectures given by William Cullen (1710–1790) at Glasgow and Edinburgh Universities with those of his one-time student George Fordyce (1736–1802), in London, at first privately and then as part of the medical education of physicians at St. Thomas's Hospital. Part I examines the broad structure of Cullen's and Fordyce's courses, comparing both course content and pedagogical approaches to ask how far knowledge flowed directly ‘downstream,’ and the extent to which it was transformed, translated or transmuted in the process of transmission. Part II (forthcoming) will approach the affinity theories of Cullen and Fordyce in greater depth, revealing the dynamics of knowledge transfer. The results shed light on the transmission of knowledge and skills between master and student, and reflect on whether Fordyce can be better described as Cullen's pedagogical progeny, or less straightforwardly as a tactical translator.     

Liesegang rings — Part I

Summary The conditions for the formation of revert type ofLiesegang rings have been studied here. Various systems of rhythmic precipitations of silver chromate are produced in a mixtures of agar and gelatin gels under different environmental conditions. Ring systems of silver, copper and other ferricyanides have also been studied in gelatin gel. The observations show that the cause of the revert systems ofLiesegang rings is the high peptizability of the precipitating matter in the media containing gel and the unreacted ions.

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Zusammenfassung Die Bedingungen der Bildung des „umgekehrten“ Types vonLiesegang-Ringen wurden untersucht. Verschiedene Systeme rhythmischer F?llung von Silberchromat wurden in einer Mischung von Agar und Gelatinegelen unter verschiedenen Umgebungsbedingungen erzeugt. Ringsysteme von Kupfer, Silber und anderen Ferricyaniden in Gelatine wurden untersucht. Die Beobachtungen zeigen, da? die Ursache für die „umgekehrten“Liesegang-Ringe in der hohen Peptisierbarkeit der Füllsubstanz im gelhaltigen Medium und den noch nicht reagierten Ionen liegt.

     

Topography and Field Effects in Secondary Ion Mass Spectrometry – Part I: Conducting Samples

Quantitative chemical characterization of surfaces with topography by secondary ion mass spectrometry (SIMS) remains a significant challenge due to the lack of systematic and validated measurement methods. In this study, we combine an experimental approach using a simple model system with computer simulation using SIMION, to understand and quantify the key factors that give rise to unwanted topographic artefacts in SIMS images of conducting samples with microscale topography. Experimental data are acquired for gold wires (diameters 33 to 125 μm) mounted onto silicon wafers. Significant loss of ion intensities and shadowing arise from the distortion of the extraction field, and the chemical analysis over the whole of the sample surface is difficult. For large primary ion incidence angles of ≥55° to the surface normal, a fraction of the primary ions are scattered from the target and impact the substrate, emitting secondary ions that may be mistaken as originating from the wire. For conducting samples, topographic field effects may be reduced by the use of a smaller extraction voltage and an extraction delay. The effects of an extraction delay on ion intensities, mass resolution and time-of-flight are studied, and its application is demonstrated on an anisotropically etched silicon sample. The use of a simple sample holder with a V-shaped groove to reduce topographic field effects for wires is also presented. Using these results, we provide clear guidance to analysts for the diagnosis and identification of topography effects in SIMS, and present key recommendations to minimize them in practical analysis.     

Hedycaryol – Central Intermediates in Sesquiterpene Biosynthesis,Part II

The known sesquiterpenes that arise biosynthetically from hedycaryol are summarised. Reasonings for the assignments of their absolute configurations are discussed. The analysis provided here suggests that reprotonations at the C1=C10 double bond of hedycaryol are directed toward C1 and generally lead to 6–6 bicyclic compounds, while reprotonations at the C4=C5 double bond occur at C4 and result in 5–7 bicyclic compounds. Read more in the Review by H. Xu and J. S. Dickschat (DOI: 10.1002/chem.202200405 ).     

The total synthesis of (−)-indolactam I

The first total synthesis of (−)-indolactam I (1) is reported. An efficient synthetic route was established to furnish the natural product in 8 steps. This strategy employed a copper-catalyzed amino acid arylation, peptide coupling, and Lewis acid-mediated macrocyclization to yield 1 from readily available building blocks. In addition, the cell growth inhibition activity of the natural product was examined through assays with the K562 leukemia cell line.     

Studies on Diastereoselective Intramolecular meta-Cycloaddition ofArene to Olefin (Part I)

AprinciPalchallengeof0rganicsynthesisistheinventionofreactionsandstrategiesthatallowf0rthefacileconversionofsimPlec0mP0undsillt0comPlexmaterials,medi-cines,ormoleculesoftheoreticalinterest.WiththecaPacityt0produceuPto3newringsand6newstere0geniccentersinonestep,thearene-alkeneph0tocycloadditionreactionprovidesaremarkablyeffectivemeansofaddressingthischallenge.'-'Wehavereported"'thatintramolecularhydrogenbondeffectcouldsignificantlyincreasethedi-astereoselectivityinsuchcycloaddition.Asanextens…     

The Vanadium Redox Reactions – Electrocatalysis versus Non-Electrocatalysis

Catalytic effects of surface groups on porous carbon electrodes are claimed in literature for the redox reactions V(II)/V(III) and V(IV)/V(V). The literature is critically analysed also in relation to work of this group. A method how to overcome the problem of assessing the electrochemically active surface area on porous electrodes is presented. Applying this method, no catalytic effects for above reactions can be substantiated. It is further pointed out that the parameters electrochemical potential and temperature need to be used to assess electrocatalysis.     

Electron Ionization Mass Spectra of Organophosphorus Compounds Part I: The Mass Fragmentation Pathways of Cyclic α-Aminophosphonates Monoester Containing 1,2,4-Triazinone Moiety

Abstract

The electron impact induced fragmentation reactions of 3-(4-chlorophenyl)-3,4- dihydro-2-ethoxy-2-oxido-7-methyl-2H,6H-[1,2,4]triazino[4,3-e][1,4,5,2]thiadiazaphosphin in-6-one (1), 3,7-dimethyl-2-ethoxy-2-oxido-1,2,3,4-tetrahydro-6H-[1,2,4]triazino[4,3-b][1,2,4,5]triazaphosphinin-6-one (2), and 9-amino-3,7-dimethyl-4-ethoxy-4-oxido-2,3,4,9-tetrahydro-8H-[1,2,4]triazino[3,2-c][1,2,4,5]triazaphosphinin-8-one (3) are presented and compared. The 1,2,4-triazine rings have almost identical fragmentation routes. The 1,2,4-triazine rings are rather stable relative to the phosphorus rings. Therefore, fragmentation of the phosphorus rings is more favorable for the compounds than the stable 1,2,4-triazine rings.     

The calixarene cavity – binding site or refuge?

Consideration of the Hirshfeld surfaces for some simple inclusion complexes of p-t-butyltetrathiacalix[4]arene and a number of its metal ion derivatives indicates that a bound metal ion can significantly influence the nature of the interactions between the included molecule and the cavity. These interactions do, however, vary with the degree of deprotonation of the calixarene, the particular nature of the bound metal ion and, in some cases, with the extent of exo-cavity interactions of the included species. The possible influences of inclusion interactions on the catalytic activity of metallocalixarenes are assessed.     

The IRMM – International Measurement Evaluation Programme,IMEP

 The aim of the International Measurement Evaluation Programme (IMEP) is to give an objective picture of the state-of-the-practice (SoP) of chemical measurements in field laboratories by comparing them to a reference range that contains a value that is as traceable to the SI system of measurements (in this case to the Avogadro Constant, one of the best realizations of the mole so far), as can presently be achieved, but which in any case is independent of human or political decision. Thus, a large-scale field test has been made to realize (international) comparability of these measurements by providing them with an independent scientific common basis. In the third measurement round, IMEP-3, ten trace elements, B, Ca, Cd, Cu, Fe, K, Li, Pb, Rb and Zn were measured in a synthetic and in a natural water by about 155 participating laboratories using their routine methods. The (coded) results are graphically reported and compared to certified reference values, established by IRMM and NIST, using isotope specific methods (isotope dilution mass spectrometry and neutron activation analysis), wherever possible. One of these methods (IDMS) has recently been defined as a primary method of measurement by the Consultative Committee on Amount of Substance (Comité Consultatif pour la Quantité de Matière: CCQM) in its founding meeting in April 1995 at BIPM, Paris. Results indicate a spread of more than ±50%, asymmetrically distributed around the reference range, although the declared accuracy was 5–10%. Self-assessment by participants of their analytical capabilities does not show a high correlation between a self-rating ("more experienced" or "less experienced") and actual performance. In the way they have been applied, all methods seem to produce results of approximately the same quality. There is little reduction in the spread of the measurements if the results obtained for one element in the natural water B are divided by the results obtained for the same element in the synthetic water A (which was unknowingly, a reference material). Index entries International measurement evaluation programme (IMEP).     

The interactome of CCT complex – A computational analysis

The eukaryotic chaperonin, CCT (Chaperonin Containing TCP1 or TriC-TCP-1 Ring Complex) has been subjected to physical and genetic analyses in S. cerevisiae which can be extrapolated to human CCT (hCCT), owing to its structural and functional similarities with yeast CCT (yCCT). Studies on hCCT and its interactome acquire an additional dimension, as it has been implicated in several disease conditions like neurodegeneration and cancer. We attempt to study its stress response role in general, which will be reflected in the aspects of human diseases and yeast physiology, through computational analysis of the interactome. Towards consolidating and analysing the interactome data, we prepared and compared the unique CCT-interacting protein lists for S. cerevisiae and H. sapiens, performed GO term classification and enrichment studies which provide information on the diversity in CCT interactome, in terms of protein classes in the data set. Enrichment with disease-associated proteins and pathways highlight the medical importance of CCT. Different analyses converge, suggesting the significance of WD-repeat proteins, protein kinases and cytoskeletal proteins in the interactome. The prevalence of proteasomal subunits and ribosomal proteins suggest a possible cross-talk between protein-synthesis, folding and degradation machinery. A network of chaperones and chaperonins that function in combination can also be envisaged from the CCT interactome-Hsp70 interactome analysis.     

Structural Arrangement of Fe–Sb–O Catalysts

In iron–antimony catalysts containing excess antimony oxide and consisting of a mixture of FeSbO₄ and -Sb₂O₄ phases, the structure of iron antimonate changes compared to the catalyst with an equimolar composition, which is the pure FeSbO₄ phase. In the presence of excess antimony oxide in the near-surface layer of iron antimonate, extended defects with a structure of crystallographic shift are formed. These accumulate overstoichiometric antimony. Such a structural change is associated with changes in the acid–base properties and the surface oxygen binding strength.     

The Unique Ambiphilicity of Tellurium in the [MesitylTe(I)(I2)(I3)]− Anion

A first example of an aryltellurium(II) compound with three different bonding modes to iodine featuring covalent and non-covalent bonds such as two orthogonal, ambiphilic σ-hole interactions is introduced: [MesTe(I)(I₂)(I₃)]⁻. It is a member of a series of mesityltellurenyl anions, which are formed during reactions of (MesTe)₂ with ZnI₂, phenanthroline (phen) and iodine. [Zn(phen)₃][MesTe(I)₂] ( 1 ), [Zn(phen)₃][{MesTe(I)-(I)…Te(I)Mes}{MesTeI₂}] ( 2 ) and [Zn(phen)₃][MesTe(I)(I₂)(I₃)][MesTeI₂] ( 3 ) are isolated depending on the amount of iodine used. The products contain tellurium atoms bonded to a variety of iodine species (I⁻, μ₂-I⁻, I₂ and I₃⁻) and are, thus, perfectly suitable to explore the amphiphilic behavior of tellurium(II) and its relevance for the formation of non-covalent bonds, where tellurium acts as both donor and acceptor simultaneously. The character of chalcogen and halogen bonds are evaluated by the combination of crystallographic data and computational methods.     

Simulation of droplet heating and desolvation in an inductively coupled plasma — Part I

The total desolvation rate of sample droplets in an argon inductively coupled plasma (Ar ICP) is investigated through the development of a two-phase continuum flow computer model. The desolvation model is supplemented by equations used to determine the trajectories of particles through the plasma. The model is used to calculate the behavior of aerosol droplets from a direct injection high efficiency nebulizer (DIHEN), a micronebulizer used to inject microliter quantities of samples that are toxic, expensive, or of limited volume. We use the combination of desolvation and transport models to present the first predicted spatial distribution of droplet concentrations and evaporation rates in an ICP flow. These data are compared with the behavior of a DIHEN spray in an environment with no net argon gas flow to determine the importance of gas flow rates to overall droplet concentration profiles in the ICP. In addition, two separate techniques (Stokes’ equation and the direct simulation Monte Carlo treatment) for determining droplet trajectories are contrasted.     

Fire retardant systems based on melamine hydrobromide: Part I—Fire retardant behaviour

The fire retardant characteristics of additives based on mixtures of melamine hydrobromide-free radical initiator-basic bismuth carbonate (or antimony trioxide) are discussed on the basis of the dependence of oxygen index on composition in the case of polypropylene.It is shown that the free radical initiator enhances the effectiveness of the fire retardant action of melamine hydrobromide. A further significant decrease of flammability, as measured by oxygen index, is induced by addition of the metal compound. Thus, polypropylene can be fire retarded with very small amounts of additive (<2%) without excessive formation of smoke which is typical of the most common halogenated additives. This seems to be due to a smoke suppressant activity of the melamine structure.These additives act by a condensed phase mechanism which seems not to be limited to induction of extensive dripping of the polymer on burning.     

Tutorial review on validation of liquid chromatography–mass spectrometry methods: Part I

This is the part I of a tutorial review intending to give an overview of the state of the art of method validation in liquid chromatography mass spectrometry (LC–MS) and discuss specific issues that arise with MS (and MS/MS) detection in LC (as opposed to the “conventional” detectors). The Part I briefly introduces the principles of operation of LC–MS (emphasizing the aspects important from the validation point of view, in particular the ionization process and ionization suppression/enhancement); reviews the main validation guideline documents and discusses in detail the following performance parameters: selectivity/specificity/identity, ruggedness/robustness, limit of detection, limit of quantification, decision limit and detection capability. With every method performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to determine it, specifically in the case of LC–MS methods.     

Synthetic Routes to α-Aminoacids Derivatives. Part I. Carbomethoxylation of Metalated N-Nitrosoamines

N-nitrosoamines are well known to undergo α-metalation when treated with appropriate strong bases^1,2.     

The solvent extraction behavior of rhenium—I: The nitric acid-tributyl phosphate system

The distribution of heptavalent rhenium between aqueous nitric acid and solutions of tributyl phosphate (TBP) in n-dodecane (NDD) has been investigated as a function of acid, nitrate, and extractant concentrations at 25, 40, and 60°C. The distribution coefficient was found to increase with increasing hydrogen ion activity (up to a maximum at 0.8 M HNO₃), increasing TBP concentration, and decreasing temperature; addition of a neutral nitrate salt (NaNO₃) had no effect. The extraction was found to proceed according to the reaction 3TBP + H⁺ + ReO₄⁻⇄[HReO₄ · 3TBP]_org at 25°C. A discussion of possible extraction mechanisms is presented, along with values for ΔG, ΔH, ΔS, and the equilibrium constant for the reaction. These results are compared and contrasted with those obtained for the analogous pertechnetate system.