维生素C的历史——从征服"海上凶神"到诺贝尔奖

This paper reviews the course of understanding vitamin C. From the "sea god" that sailors first encountered to the scurvy that caused the British Navy to suffer, understanding vitamin C is improved little by little. Until modern times, with the guidance of advanced theory and the rapid development of chemical research, human beings finally got to known vitamin C and conquered scurvy. This marks the arrival of a new era.     

Highlights of Spanish chemistry at the time of the chemical revolution of the 18th century

Summary A number of outstanding Spanish chemists and some of their major chemical contributions in the 18th century are briefly considered indicating that Spanish chemistry got a very high level at the end of the century, departing practically from nothing at the beginning of the century. The Vergara School played a very important role as the first national institution for chemistry despite of the fact that it decayed in a few years for a number of reasons. The discovery of three new elements is briefly dealt with (Pt, W, V) and the adoption of the new modern French chemistry in Spain as well as a number of critics against some of Lavoisier's theories and nomenclature posed by some Spanish chemists are considered.     

A century of progress in the sciences due to atomic weight and isotopic composition measurements

Even before the 20th century, a consistent set of internationally accepted atomic weights was an important objective of the scientific community because of the fundamental importance of these values to science, technology and trade. As the 20th century progressed, physicists, geoscientists, and metrologists collaborated with chemists to revolutionize the science of atomic weights. At the beginning of the century, atomic weights were determined from mass relationships between chemical reactants and products of known stoichiometry. They are now derived from the measured isotopic composition of elements and the atomic masses of the isotopes. Accuracy in measuring atomic weights has improved continually, leading to the revelation of small but significant variations in the isotope abundances of many elements in their normal terrestrial occurrences caused by radioactivity and a variety of physicochemical and biochemical fractionation mechanisms. This atomic-weight variability has now been recognized as providing new scientific insights into and knowledge of the history of materials. Atomic weights, except those of the monoisotopic elements, are thus no longer regarded as "constants of nature". At the beginning of the 20th century, two scales for atomic weights were in common use: that based on the atomic weight of hydrogen being 1 and that based on the atomic weight of oxygen being 16. Atomic weights are now scaled to (12)C, which has the value 12 exactly. Accurate atomic weights of silicon, silver, and argon, have enabled the values of the Avogadro, Faraday and Universal Gas constants, respectively, to be established, with consequent effects on other fundamental constants.     

分析化学的第二个春天

从研究分析化学的历史发展入手，以大量历史事实为根据，指出分析化学曾经历过两次重大变革。第一次变革(19世纪末至20世纪初)使分析化学从分析化学家的技艺发展为科学；第二次变革(20世纪70年代迄今)则使分析化学进入了分析化学家重新当家作主的、欣欣向荣的“第二个春天”。     

A STUDY ON THE RECONSTRUCTION OF THE EIGHTEENTH CENTURY MEIYU (PLUM RAINS) ACTIVITY OF LOWER CHANGJIANG(YANGTZE) REGION OF CHINA

This study presents a scheme for delimiting the meiyu period in the Lower Changjiang (Yangtze) region. This scheme was applied to the Clear and Rain Records of Nanjing, Suzhou and Hangzhou to reconstruct the 1723-1800 meiyu climate series. The beginning and ending dates, length, precipitation, and the intensity grades of meiyu were determined. The years of early, heavy, light, and empty meiyu were also given. Statistical analyses of the 18th century meiyu series indicate the existence of the quasi-periodicities of 2-3, 4-5, and 9 years. Many basic characteristics of the modern meiyu also existed in the 18th century. Some characteristics of the Northwest Pacific Subtropical High in the 18th century in typical meiyu years were inferred from the historical meiyu series.     

A role of the 9-aminoacridines and their conjugates in a life science

The 9-aminoacridines play an important role in medicine. They were applied first in a treatment of protozoal infections in the beginning of the last century. Recently, it has been shown that the 9-aminoacridines are successful candidates for treatment of cancer, viral and prion diseases. Their conjugation with biomolecules such as peptides and proteins may modulate their activity, bioavailability and applicability. This review deals with the synthesis of 9-aminoacridine, its conjugation with variety of molecules and utilization of such conjugates in several fields of science.     

Methodologies for the synthesis of pentacene and its derivatives

In recent years, due to its high hole-mobility, high on/off current ratio and low threshold voltage, pentacene and its derivatives have found increasing application in the fabrication of light-emitting diodes, field-effect transistors and photovoltaic cells. It has also emerged as an alternative to silicon due to its similar performance to inorganic semiconductors. Pentacene cannot be isolated from the petroleum fractions like other acenes such as anthracene or tetracene, and therefore it needs to be chemically synthesized. The first successful synthesis of pentacene was reported in early 19th century where pentacene was obtained via dehydrogenation of 6,14-dihydropentacene. Since then a number of methods have been reported for the synthesis of pentacene. This review describes various strategies used for the synthesis of pentacene and its derivatives reported since 2005.     

Sir Robert Robinson's “Anthocyanin Period”: 1922–1934 — A Case Study of an Early Twentieth-Century Natural Products Synthesis

Abstract

Sir Robert Robinson was one of the leading synthetic organic chemists of the twentieth century. His work in both theoretical chemistry and natural product synthesis was pioneering and led to his being awarded the Nobel Prize in chemistry in 1947. His specific accomplishments in terms of chemical structures synthesised and the introduction of new theoretical propositions represented major accomplishments in chemistry in the first half of the twentieth century. As he was one of the leading figures in the emerging field of natural product synthesis, it is a valuable exercise to examine his publication pattern as it pertained to a natural products synthesis project. This pattern manifested itself in the publication of a series of papers over several years, each focused on a specific family of natural products, with the publications first concentrating on simple precursor structures, but quickly moving on to full synthetic procedures for the targeted natural products. This was followed by an exhaustive study of the particular family of compounds. This paper reports one of Robinson's synthetic programmes, namely the synthesis of anthocyanins, which was carried out from 1922 to 1934 and resulted in the publication of forty-seven papers, including one on the first artificial synthesis of a flower pigment. This approach, as outlined in Robinson's publications, to tackling a complex synthetic challenge provides insight into the methodology of one of the leading natural product chemists of the first half of the twentieth century.     

Theory versus Practice in the Twentieth-Century Search for the Ideal Anaesthetic Gas

At the beginning of the twentieth century, an anaesthetist could choose between nitrous oxide, chloroform, and ether (diethyl ether) for the induction of painrelieving unconsciousness. By the end of century, the choice was between a small number of fluorinated aliphatic ethers such as Enflurane, Desflurane, and Sevoflurane, and (in some jurisdictions) the rare gas, xenon. Between these endpoints researchers had identified a surprisingly broad range of hydrocarbons, noble gases, organohalogens, and aliphatic ethers that possessed anaesthetic properties. None was entirely satisfactory, but clinicians at various times and in various places employed substances in each of these categories. Behind the search for new anaesthetic gases was a theory of action (Meyer- Overton theory) that was known to be inadequate, but as no alternative was strong enough to displace it the search continued on purely empirical grounds, while lip-service was paid to the theory. By the time a theory couched in more modern terms was proposed, a suite of modern anaesthetic gases was in place, and there have been no attempts to use that theory to drive a new search.     

从零维到三维的金范式: 金单质概念的新发展

含有零维金纳米球的胶体金,在古埃及就已经被用于制造彩色玻璃,但直到20世纪,人们才对其进行系统的研究。20世纪下半叶,一维金纳米棒的合成及其奇异的光学性质引起了科学家对金纳米颗粒的关注。随后,二维金纳米片、三维金纳米哑铃等金纳米颗粒的相继出现,丰富和发展了金单质的概念。几种新的金单质的发现,构建了从零维到三维的金范式,从而启发人们对“金单质”及其应用进行更加深入的探究。     

On the Transition from Tin-Rich to Antimony-Rich European White Soda-Glass Trade Beads for the Senecas of Northeastern North America

It has been shown that several modifications occurred, over the span of the 17th to 19th centuries, in the agents used to opacify European-made white soda-glass beads that were transmitted as trade goods to northeastern North America. Tin was used at the beginning of the 17th century, followed by Sb later in the century, and then by As during the 18th and 19th centuries. In an attempt to define more closely the transition from Sn-rich to Sb-rich white beads, we analyzed 198 white glass beads from a number of archaeological sites in western New York State. Chemical analysis shows that the arrival of Sb-white soda-glass trade beads began in this region during the period from approximately A.D. 1625–1640, and that they had completely replaced Sn-white beads by A.D. 1675. Specific bead chemistries link a number of the archaeological sites.     

The Betti base: the awakening of a sleeping beauty

The multicomponent reaction between 2-naphthol, aryl aldehydes and ammonia or amines yields aminobenzylnaphthols in a process known as the Betti reaction, which was first uncovered at the beginning of the 20th century. The aminobenzylnaphthols could be easily resolved into their enantiomers. After a long silence, the results of our research a decade ago on this useful reaction and on the chiral materials produced has stimulated further work in a number of other laboratories. As a result, novel applications of the Betti reaction to produce new chiral aminobenzylnaphthols were reported together with the evaluation of these chiral bases in asymmetric synthesis. Herein, we present a selection of the relevant studies on this topic.     

干水：从概念提出到实际应用

通过对干水的发展史考证可知，20世纪中期，科学家研制出一种由二氧化硅颗粒包裹着水滴的干性粉末并将其命名为“干水（Dry Water）”，但在很长的一段时间内并没有引起人们的关注。至21世纪初，关于干水形成机理和制备技术的一系列研究相继展开。随后，干水巨大的潜在应用价值备受人们关注，其在化妆品、水合物储气、催化剂、灭火剂等众多领域的应用得到了一定程度的开发。干水相关技术的发展会使化学物质的利用方式不断创新。干水的相关知识和发展史改变了人们对水的认识，并会成为化学教科书和百科全书的重要内容。     

Determination of phase compositions in ceramics from Gobi desert using complementary diffraction techniques

The city Khara Khoto is located in the Gobi desert in Inner Mongolia. This city was deserted in the late 14th century and rediscovered in the beginning of the 20th century. In the present study, ceramic sherds typical for the Khara Khoto area have been analysed using neutrons, laboratory X-ray diffraction, synchrotron radiation X-ray diffraction as well as optical microscopy as complementary probes in extracting information on the mineral phase compositions as well as on the firing conditions during the pottery production. The data evaluation was performed with the standard diffraction analysis package GSAS and the new developed program AmPhOrAe. The dominating phase is mullite (~60 %) compared to a variable mixture of SiO₂ quartz and cristobalite phases (~35 %) and feldspar as a minority phase. Refiring experiments on one of the sherds allow estimating the firing temperatures of the ceramics within the region of 1,150 and 1,250 °C.     

The temperature-dependent optical activity of quartz: from Le Châtelier to chirality measures

Quartz, the most abundant mineral in Earth’s crust, is a chiral crystal. It was the first material for which the phenomenon of the optical rotation was observed. In the late 19th century/beginning of the 20th, several researchers, the most famous of which is Le Châtelier, investigated how this optical rotation changes with temperature. By employing a modern analytical/computational tool for evaluating the degree of chirality on a continuous scale, we were able to show a remarkable agreement between the original optical rotation/temperature curve, and the chirality/temperature curve. We thus provide a direct interpretation of the early observations, as reflected in the dependence of the optical rotation of the degree of chirality, linking these two properties quantitatively.     

Computer‐Assisted Synthetic Planning: The End of the Beginning

Exactly half a century has passed since the launch of the first documented research project (1965 Dendral) on computer‐assisted organic synthesis. Many more programs were created in the 1970s and 1980s but the enthusiasm of these pioneering days had largely dissipated by the 2000s, and the challenge of teaching the computer how to plan organic syntheses earned itself the reputation of a “mission impossible”. This is quite curious given that, in the meantime, computers have “learned” many other skills that had been considered exclusive domains of human intellect and creativity—for example, machines can nowadays play chess better than human world champions and they can compose classical music pleasant to the human ear. Although there have been no similar feats in organic synthesis, this Review argues that to concede defeat would be premature. Indeed, bringing together the combination of modern computational power and algorithms from graph/network theory, chemical rules (with full stereo‐ and regiochemistry) coded in appropriate formats, and the elements of quantum mechanics, the machine can finally be “taught” how to plan syntheses of non‐trivial organic molecules in a matter of seconds to minutes. The Review begins with an overview of some basic theoretical concepts essential for the big‐data analysis of chemical syntheses. It progresses to the problem of optimizing pathways involving known reactions. It culminates with discussion of algorithms that allow for a completely de novo and fully automated design of syntheses leading to relatively complex targets, including those that have not been made before. Of course, there are still things to be improved, but computers are finally becoming relevant and helpful to the practice of organic‐synthetic planning. Paraphrasing Churchill's famous words after the Allies’ first major victory over the Axis forces in Africa, it is not the end, it is not even the beginning of the end, but it is the end of the beginning for the computer‐assisted synthesis planning. The machine is here to stay.     

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.     

Ynamides: Versatile Tools in Organic Synthesis

Ynamides display an exceptionally fine balance between stability and reactivity. They also offer unique and multiple opportunities for the inclusion of nitrogen‐based functionalities into organic molecules, and are emerging as especially useful and versatile building blocks for organic synthesis. Recent breakthroughs in the preparation of these substrates have revitalized interest in nitrogen‐substituted alkynes, and the beginning of the 21st century has witnessed an ever‐increasing number of publications reporting the development of new reactions or synthetic sequences starting from ynamides. This Review highlights major developments in this area.     

PXRF, μ-XRF, vacuum μ-XRF, and EPMA analysis of Email Champlevé objects present in Belgian museums

The enamel of 20 Email Champlevé objects dating between the 12th and 19th centuries was investigated by means of microscopic and portable X-ray fluorescence analysis (μ-XRF and PXRF). Seven of these objects were microsampled and the fragments were analyzed with electron probe microanalysis (EPMA) and vacuum μ-XRF to obtain quantitative data about the composition of the glass used to produce these enameled objects. As a result of the evolution of the raw materials employed to produce the base glass, three different compositional groups could be discriminated. The first group consisted of soda-lime-silica glass with a sodium source of mineral origin (with low K content) that was opacified by addition of calcium antimonate crystals. This type of glass was only used in objects made in the 12th century. Email Champlevé objects from the beginning of the 13th century onward were enameled with soda-lime-silica glass with a sodium source of vegetal origin. This type of glass, which has a higher potassium content, was opacified with SnO2 crystals. The glass used for 19th century Email Champlevé artifacts was produced with synthetic and purified components resulting in a different chemical composition compared to the other groups. Although the four analytical techniques employed in this study have their own specific characteristics, they were all found to be suitable for classifying the objects into the different chronological categories.     

氢元素概念发展史与化学思想的演进

18世纪,发现氢气的卡文迪什认为该气体是水与燃素的化合物;但发现水的组成的拉瓦锡认为氢气是一种元素物质.到19世纪,原子分子论形成后,氢气被认为是由双原子分子构成的单质.20世纪30年代,氢同位素的发现使人们对氢元素概念有了新认识,并逐渐形成现代氢元素概念.氢元素概念的发展史不仅是元素概念的发展史,也是科学思想的演进史...