Analysis of pellets found in the north area of the Asiago plateau (Vicenza, Italy), a locality of the 1914-1918 World War

Pellets of unknown material contained in an aluminium cylinder were found in the north area of the Asiago plateau (Vicenza), a locality of the First World War (1914-1918). Elemental analysis, infrared, chromatography and NMR experiments indicate that the main product is pentaerythritol tetranitrate (PETN). This substance was probably an igniting primer used by Austro-Hungarian (A.U.) military engineering. Hypothesis of medical use of the pellets can be disregarded while it seems improbable the use of this explosive by German Army during the Second War World.     

History of Synthetic Rubber

Synthetic rubber undoubtedly represents the earliest development of the synthesis of macromolecules. It dates back to the historic discovery by Greville Williams in 1860 that isoprene is the “mother substance” of natural rubber. Attempts to convert isoprene, and later other 1,3-dienes, to a synthetic rubber began shortly thereafter, although the first commercial production of such a material did not take place until a half century later. The period between World War I and II witnessed the first development of a true synthetic substitute for natural rubber, i.e., sodium-polymerized butadiene, which was produced in Germany as Buna rubber and in the USSR as SK rubber. However, during the 1930s, Germany developed the emulsion copolymerization of butadiene-styrene (Buna S), whereas sodium polybutadiene continued as the principal general purpose synthetic rubber in the Soviet Union. The United States which, up till then, had only developed special-purpose synthetic rubbers like neoprene, entered the synthetic rubber age during the emergency of World War II when natural rubber supplies were cut off, and developed a giant industry based on Buna S technology virtually overnight.

Among the synthetic polymers in use today, synthetic rubber is unique in that it was developed not as an interesting new material but to fill a dire need of the modern world. As a matter of fact, here in the United States, it arose solely out of the emergency of World War II.

The reason for this unique position of synthetic rubber is, of course, the unique property of rubber, the only substance which exhibits long-range elasticity, and which therefore fills a special need in modern technology. Natural rubber was discovered in the New World as early as Columbus's voyages, but its use in technology did not really take place until after the Industrial Revolution, i.e., with the start of the 19th century. However, it was not until the latter part of the last century that the first attempts were made to synthesize rubber from simple chemical compounds.     

Ein synthetisches Kaffeearoma

Initiated by the experiences of World War I Hermann Staudinger tried to create a synthetic coffee flavor and asked his assistant Tadeusz Reichstein first with the isolation and analysis of the natural flavor followed by the development of a synthetic substitute. Reichstein worked from 1922 until 1932 to solve this task which proved to be very intricate. Since 1928 he worked closely together with Max Kerschbaum from “Haarman and Reimer”, then the leading company for artificial flavors. They finished their research without being able to create with their “Coffarom” a real substitute for the natural coffee flavor. Nevertheless this project is of significant interest for the history of chemistry because of the highly sophisticated microchemical methods applied as well as it is interesting as an early example of the cooperation between university‐based scientific research and industry‐sponsored applied chemistry. When Max Morgenthaler, working for the Nestlé company developed his “Nescafé”, the ascent of this firm to the biggest food producing conglomerate in the world began.     

Polyvinylpyrrolidon. Ein Tausendsassa in der Chemie

Exactly 70 years ago, PVP was invented by Prof. Dr. Walter Reppe at BASF and registered as a patent. Polyvinylpyrrolidone was initially used as a blood plasma substitute in the Second World War. Afterwards, little by little, it started being utilized in a multiplicity of sectors: pharmaceutical, cosmetic and detergent industries. PVP is now being used in more than one hundred different technical applications such as membranes, glue sticks, hot‐melt adhesives, hydrogels and for crop protection. Due to its versatile features such as water solubility, film and complex formation, adhesive and bonding power as well as due to its toxicological harmlessness, PVP is one of the most interesting technical specialty polymers in the field of chemistry.     

Different synthetic routes to obtain hydrophilic matrices

The aim of this study was to examine two different synthetic routes for obtaining new hydrophilic matrices either by the modification of a synthetic matrix or by the copolymerization of hydrophilic monomers. First, the acrylic acid‐ethylene glycol dimethacrylate (AAc‐EGDMA) matrix, obtained from suspension with cyclohexane as the diluent at 70 °C after 2 h of reaction, was used as a base to be modified with TRIS(hydroxymethyl)aminomethane (TRIS). Experimental variables affecting the carbodiimide‐mediated amide‐bond development (i.e., the type of carbodiimide, reaction time, pH, and concentration of the matrix in the reaction medium) on the synthetic AAc‐EGDMA matrix with TRIS were studied. Second, the N‐acryloyl‐TRIS(hydroxymethyl)aminomethane‐ethylene glycol dimethacrylate (NAT‐EGDMA) matrix was obtained under the same experimental conditions as reported for AAc‐EGDMA. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 489–497, 2000     

Fritz Haber und Clara Immerwahr. Lernen aus der Geschichte

This contribution about Fritz Haber (1868–1934) and his wife Clara Immerwahr (1870–1915) shows us not only the changeful life of these two personalities which began their life full of hope and finished it then in tragedy. Their time is embedded into the history about the break‐up and then come‐down by the First World War of the first period of the German Empire, and also points out exemplarily science and industry of this time.     

Direct electrochemistry of hemoglobin immobilized on CdS:Mn nanoparticles

The First International Congress of Applied Chemistry was organised by the Association of Belgian Chemists in 1894, the eighth and last was held in Washington and New York in 1912. These congresses, unlike the early congresses on pure chemistry, were very successful and held with the highest patronage in the host countries. The ninth planned for St. Petersburg in 1915 was not held due to the intervention of the First World War. The initiative passed to IUPAC but due to political and financial restraints the International Congresses of Pure and Applied Chemistry did not commence till 1934.     

Die Firma Leopold Cassella & Co.

Leopold Cassella & Co. originated in the Frankfurt ghetto as a trading company for natural dyestuffs, and developped into a worldwide acting enterprise by the joint activities of the Cassella‐Gans‐Weinberg families. After the invention of the first synthetic dyes the owner families 1870 founded a chemical and dyestuff factory. Clever exploration and exploitation of the chemistry of naphthaline and its derivatives made the works into the largest and most profitable azo‐dyestuff‐company of the world about 1900. Leopold Cassella & Co. offered their products worldwide thru a network of fully and partly owned, cooperating companies. In 1925 the company joined IG‐Farbenindustrie AG, but remained an own entity, until the Nazi‐government – which brought distress and death to many members of the ownerfamilies – 1938 ordered the full integration (arization) into IG‐Farbenindustrie AG. After the demolition of IG‐Farbenindustrie AG following the end of World War II, Cassella 1952 evolved as an independent dyestuff AG, the majority of which 1970 was bought by Hoechst AG. 1995 Cassella was fully integrated into Hoechst AG, which dissolved itself shortly thereafter. Following a short term with Clariant of Switzerland, the Fechenheim works were sold to private investors, who founded AllessaChemie GmbH, which will celebrate their 10th anniversary on July 1, 2011.     

Facile Synthesis of 3,6‐Diaminopyridazine

An efficient two‐step synthesis of 3,6‐diaminopyridazine from 3,6‐dichloropyridazine is reported. In this synthetic procedure, 4‐methoxybenzylamine was used as a nitrogen source to substitute the chloro groups of 3,6‐dichloropyridazine to form N,N′‐bis‐(4‐methoxybenzyl)‐pyridazine‐3,6‐diamine. The 4‐methoxybenzyl groups were then removed by treatment with hydrochloric acid to provide the target 3,6‐diaminopyridazine with an overall yield of 78%.     

Regulation of Black Pepper Inflorescence Quantity by Shading at Different Growth Stages

Black pepper is a perennial plant that can bloom throughout the year. It is generally expected that pepper inflorescence quantity could be minimized at the nonfull‐bloom stage. The objective of this study was to find an appropriate shading measure that could inhibit blooming at other growing stages except the full‐bloom stage and did not cause any reduction in pepper yield and quality. In this study, pepper trees were shaded up to 15%, 30%, 60% and 75%, respectively, and the inflorescence quantity, photosynthetic characteristics, pepper yield and quality traits were investigated at every growing stage. The results showed that the effect of shading on pepper yield decreased as time progressed. Shading treatment did not alter the composition of piperine and volatile oil, but reduced the moisture content. Based on the correlation between photosynthetic parameter and inflorescence number, the appropriate shading intensities for regulating inflorescence quantity at different phenological stages were determined. Moreover, it was found that the regulation of inflorescence quantity could be achieved by controlling leaf temperature during recovery to filling period. This research outcome also will give us some guidelines to develop other management strategies that control leaf temperature and regulate inflorescence quantity to consequently improve pepper yield.     

Determination of alachlor residues in pepper and pepper leaf using gas chromatography and confirmed via mass spectrometry with matrix protection

Alachlor residues were determined in pepper and pepper leaf, after 49 days of manufacturer‐recommended single‐ and double‐dose application to the soil and plant. The samples were extracted with acetonitrile, partitioned with n‐hexane, and purified through solid‐phase extraction, and finally detected with a gas chromatography–microelectron capture detector. The linearity of the analytical response across the studied range of concentrations (0.05–4.0 µg/mL) was excellent, obtaining coefficients of determination (r²) of 0.999. Recovery studies were carried out on spiked pepper and pepper leaf samples, at two concentrations levels (0.2 and 1.0 mg/kg), with three replicates performed at each level. Mean recoveries of 73.1–109.0% with relative standard deviations of 1.3–2.3% were obtained. The method was successfully applied to field samples, and alachlor residue was found in pepper (0.02 mg/kg) and pepper leaf (0.03 mg/kg), at levels lower than the maximum residue limits (0.2 mg/kg) set by the Korea Food and Drug Administration. The field‐detected residues were further confirmed with gas chromatography–mass spectrometry with the help of pepper leaf matrix protection. Copyright © 2013 John Wiley & Sons, Ltd.     

Radiation Processing: Current Status and Future Possibilities

Radiation processing developed following the Second World War and employs gamma- or electron-irradiation to process polymers, cure alkene-based inks and coatings, sterilize medical supplies, irradiate food, and manage wastes. The current status of these applications is described with the probable direction of future developments.     

2‐Methoxy‐4‐methylsulfinylbenzyl: A Backbone Amide Safety‐Catch Protecting Group for the Synthesis and Purification of Difficult Peptide Sequences

The use of 2‐methoxy‐4‐methylsulfinylbenzyl (Mmsb) as a new backbone amide‐protecting group that acts as a safety‐catch structure is proposed. Mmsb, which is stable during the elongation of the sequence and trifluoroacetic acid‐mediated cleavage from the resin, improves the synthetic process as well as the properties of the quasi‐unprotected peptide. Mmsb offers the possibility of purifying and characterizing complex peptide sequences, and renders the target peptide after NH₄I/TFA treatment and subsequent ether precipitation to remove the cleaved Mmsb moiety. First, the “difficult peptide” sequence H‐(Ala)₁₀‐NH₂ was selected as a model to optimize the new protecting group strategy. Second, the complex, bioactive Ac‐(RADA)₄‐NH₂ sequence was chosen to validate this methodology. The improvements in solid‐phase peptide synthesis combined with the enhanced solubility of the quasi‐unprotected peptides, as compared with standard sequences, made it possible to obtain purified Ac‐(RADA)₄‐NH₂. To extend the scope of the approach, the challenging Aβ(1‐42) peptide was synthesized and purified in a similar manner. The proposed Mmsb strategy opens up the possibility of synthesizing other challenging small proteins.     

World War I, international participation and reorganisation of the Japanese chemical community

What kind of "war" did Japanese chemists fight during World War I, and what impact did their experiences have on Japanese chemistry in its aftermath? By focusing on the role of Jōji Sakurai (1858-1939), this paper attempts to answer these questions by looking at the drastic changes in the international relationships of the Japanese chemical community caused by the war. It examines how the Japanese National Research Council was established in 1920 as part of the International Research Council, a product of the reconfiguration of international scientific powers triggered by World War I. This paper argues that Sakurai advocated the establishment of the National Research Council after the American model of wartime mobilisation of science, coordinated fractured Japanese chemical communities for international functions, and facilitated Japan's participation and increased influence in international scientific associations such as the International Union of Pure and Applied Chemistry, established in 1919.     

Open‐tubular capillary electrochromatographic application of a sol‐gel matrix with chilli peppers,garlic, or synthetic additives

This article describes a possible combination of two promising fields of analytical chemistry—the preparation of sol‐gel matrices with varying additives and their application in capillary electrochromatography. The inner surfaces of capillaries were coated with the sol‐gel solution containing either pure synthetic chemical additive—alliin or capsaicin—or an extract of their natural sources—garlic and chilli pepper, respectively. The modified capillaries were tested for interaction with two neurotransmitters, oligopeptides and nucleotides under conditions of open‐tubular capillary electrochromatography. Because both of the natural extracts also contain vitamin C and saccharose, the capillaries with sol‐gel modifiers containing each of these substances were also tested. The obtained results from the perspective of changes in the electrochromatograms and the effective mobilities of analytes are discussed with respect to mild conditions both in the preparation process of the sol‐gel matrix and during the separations.     

First separation of four aromatic acids and two analogues with similar structures and polarities from Clematis akebioides by high‐speed counter‐current chromatography

In this paper, we report an efficient method by high‐speed counter‐current chromatography for the first separation of four aromatic acids and two analogs with similar structures and polarities from Clematis akebioides. First, the ethyl acetate extract was treated by silica gel column chromatography to enrich the target compounds. And then the fraction with target compounds were purified by high‐speed counter‐counter chromatography using a two‐phase solvent system consisting of chloroform/acetonitrile/water (10:6:4, v/v). The results showed high‐speed counter‐current chromatography could be a powerful technology for the separation of compounds with similar structures and polarities. Besides, it was found acetonitrile could be a good methanol substitute when a chloroform/methanol/water system could not provide a good separation factor. This study provides a reference for the separation of compounds from Clematis akebioides.     

A convenient synthesis of 2‐alkoxy‐2‐oxo‐1,4,2‐oxazaphosphinanes

A study on the synthesis of the novel cyclic α‐aminophosphonates and 2‐alkoxy‐2‐oxo‐1,4,2‐oxazaphosphinanes 4a‐r has been carried out. The title compounds were obtained in good yields by one‐pot procedure using o‐aminophenol, alkyl dichlorophosphinite, and ketones or benzaldehyde. One of their geometric stereoisomers was isolated and characterized. Configurations of 4k and one isomer of 4r have been established by X‐ray diffraction analysis. The synthetic methods provide an easy access to the organophosphorus heterocycles with the ring system mentioned above. The abnormal chemical shifts of alkyl‐substitute protons in ¹H NMR spectra were given reasonable explanation. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:65–69, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20258     

Anecdotal History of Styrene and Polystyrene

A formal history of styrene and polystyrene from 1839 through 1952 appears in the Styrene monograph edited by Boundy and writer but now out of print. Updating of the story by several teams of Dow writers appeared in the Kirk-Othmer Encyclopedia, the Encyclopedia of Polymer Science and Technology, and the SPE Award address of Amos. We propose a more personalized history written from the perspective of one whose 40-year professional career was involved in scientific and technological aspects of the subject. We view this history as a complex interplay of science, technology, industrial activity, management decisions, legal and patent activities, people, and the vagaries of World War II. Germany had an early industrial lead prior to 1941 with a monomer process and mass polymerization techniques. Original work on styrene-butadiene elastomers was another first. Germany also had a scientific lead as academic scientists such as Staudinger, Kern, Schulz, Jenckel, and Ueberreiter became involved in the chemistry and physics of styrene and polystyrene (PS). Mark was first in industry and then in the university. Several United States companies were active with styrene and PS, also prior to 1941. Involvement of the United States in World War II lead to a government decision to produce SBR. This catapulted styrene into a major synthetic chemical. The lead passed from Germany to the United States, especially with the large excess capacity for monomer after 1945. Management decisions encouraged diverse large-scale polymer uses for styrene, aided by the low price for the monomer. Through a bizarre series of events (war, people, and legal action), proprietary industrial knowledge in both Germany and the United States had diffused into the domain of public knowledge. Styrene and PS now face the problems of any petrochemical product.     

Letter to the Editor Industrial Mixed Acid Nitration

Abstract

Biochemistry — including molecular biology — constituted a major part of Dutch chemical research over the period from 1940 to 1980. However, the Netherlands did not occupy a strong position in that field of research after the Second World War. The present paper seeks to explain the successful development of biochemistry in the Netherlands into an independent discipline of international standing. Formulating the goal of biochemistry as “science for its own sake” played an important role in this development. Post-doctoral positions, senior fellowships and editorships of journals were crucial for biochemistry in the Netherlands in building a network of international contacts that could keep researchers informed about current developments. Westenbrink and Slater were key participants in the development of these networks. These two scientists developed international contacts via fellowships and as editors of major biochemical journals. It was through these forms of communication that the hitherto peripheral Dutch biochemical research community gained a more central position.     

Synthesis of Cytostatic Tetradecacyclic Pyrazines and a Novel Reduction‐Oxidation Sequence for Spiroketal Opening in Sapogenins

Aiming towards spiroketal‐modified artificial cephalostatin molecules, two orthogonal approaches were investigated. First, the introduction of 17‐O‐functionality into hecogenin derivatives with a closed spiroketal moiety was accomplished by different remote‐oxidation procedures. These allowed the synthesis of tetradecacyclic artificial cephalostatin molecules with improved tumor‐inhibiting properties. Second, a novel reduction‐oxidation pathway for spiroketal opening in sapogenins was discovered, which should provide the basis for a broad access towards spiroketal‐modified building blocks for cephalostatins.