Sense and nonsense of quality assurance in an R&D environment

Quality has always been one of the key issues in laboratories in general and formal quality assurance (QA) in testing laboratories has gained popularity over the last decade. However, the implementation QA in research and development (R&;D) laboratories is still the domain of a few pioneers. We can even ask whether a QA system in research makes sense at all and if such a system really provides any added value? Difficulties with respect to the implementation of such a system are mainly associated with the nature of the research process itself. However, it is obvious that QA offers clear advantages in R&;D, if some critical success factors have been taken into account. An important issue is the selection of a good QA standard for R&;D. This is certainly not an easy task, since there are no specific standards. Fortunately, some useful international guides have been published recently.     

Implementing quality assurance in an R&D environment at the Belgian Nuclear Research Centre – SCK·CEN

If we agree that quality assurance (QA) in R&;D indeed provides added value, just how do we show the public that such a QA system is operating well? At the Belgian Nuclear Research Centre (SCKÖbullet CEN), where a QA system has been implemented by various laboratories in accordance with the EN 45001 standard within the general framework of ISO 9001 at the institutional level, several laboratories have already been accredited. At the request of one of our customers the Belgian Agency for Radioactive Waste Management (NIRAS/ONDRAF), we implemented a quality system for research projects related to the characterization, treatment and processing of radioactive wastes in view of disposal. We obtained accreditation for this research in 1999. In this paper, we discuss the implementation of our QS and important issues related to the overall management of the QA system, broken down into three parts: organizational, technical and project-specific quality elements such as the QA plan and internal communication.     

CFC phase-out: have we met the challenge?

In 1974 Nobel prize winners Rowland and Molina proposed that chlorofluorocarbons (CFCs) were stable enough to reach the stratosphere, where, under intense solar radiation they released Cl atoms that could destroy stratospheric ozone protecting the earth’s surface from UV rays. The CFC industry funded both scientific studies to test the Rowland and Molina hypothesis and programmes to identify potential replacements, from which the HFCs emerged as likely candidates. After 5 years it was concluded, on the best scientific evidence available, that stratospheric ozone was being depleted at ∼3% per decade, but sufficient time was available for an orderly phase-out. Although the USA and a few other countries stopped the use of CFCs in aerosols little further work was done until 1985 when the CFC debate was renewed following the discovery of stratospheric ozone depletion over the Antarctic during its spring. Manufacturers restarted their R&D programmes; governments negotiated the Montreal Protocol in 1987 agreeing the partial phase-out of the CFCs. As a result of subsequent amendments CFCs have now been phased-out in the developed world and HCFCs will follow over the next two decades. This paper reviews what has been achieved and what remains to be done. Has the world-wide effort been successful in protecting the ozone layer? Have “acceptable” alternatives been found for the CFCs/HCFCs in their various applications?     

Book Reviews

Ion-Selective Electrodes in Analytical Chemistry, VOL. 2, H. Freiser (ed.), Plenum Press, New York, 1980.

Pesticide Analytical Methodology by John Harvey, Jr. (E. I. Du Pont de Nemours and Company) and Gunter Zweig (U.S. Environmental Protection Agency), ACS Symposium Series 136, 406 pages (including 177 figures, 54 tables and an index of 18 pages), linen, format 235 × 160mm, ISBN 0-8412-0581-7, American Chemical Society, 1155 Sixteenth Street, N.W. Washington, D.C. 20036, 1980, US38.00.

Particulates in Water, Characterization, Fate, Effects, and Removal by Michael C. Kavanaugh (James M. Montgomery, Consulting Engineers, Inc., Pasadena) and James O. Leckie (Stanford University, Stanford) ACS Advances in Chemistry Series 189, 401 pages (including 145 figures, 56 tables and an index of 11 pages), linen, format 235 × 160mm, ISBN 0-8412-0499-3, American Chemical Society, 1155 Sixteenth Street, N.W. Washington, D.C. 20036, 1980, USS59.50.

Pesticide Manufacturing and Toxic Materials Control Encyclopedia Editor, M. Sittig; 810 pages, $96; 1980, Noyes Data Corporation, Park Ridge, N.J., U.S.A. ISBN 0-8155-0814-X. Reviewed by A. de Kok, Section of Environmental Chemistry, Free University, Amsterdam, The Netherlands.

Dictionary of Chemical Terminology (In Five Languages–English, German, French, Polish and Russian. Edited by D. Kryt, Warsaw, Poland). Elsevier Scientific Publishing Company, Amsterdam and New York. 1980, 612 pages, Price: US $95.00/Dfl. 195.00 ISSBN 0-444-99788-1.     

Preparation of Porous Three‐Dimensional Quaternary Thioantimonates(III) ACuSb2S4 (A=Rb,Cs) through a Surfactant‐Thermal Method

Two novel porous three‐dimensional (3D) quaternary thioantimonates(III) ACuSb₂S₄ (A=Rb, Cs) were successfully synthesized by employing the neutral surfactant PEG‐400 (PEG=polyethyleneglycol) as reaction media, these are significantly different from the known quaternary A?Cu?Sb?S thioantimonates(III) with two‐dimensional (2D) crystal structures. This is the first time that crystalline quaternary chalcogenides have been prepared in surfactant media. Both experimental and theoretical studies confirm they are semiconductors with narrow band gaps. Our results demonstrated that the surfactant‐thermal strategy could offer a new opportunity to explore novel chalcogenides with diverse crystal structures and interesting physicochemical properties.     

Molecular core-valence correlation effects involving the post-d elements Ga-Rn: benchmarks and new pseudopotential-based correlation consistent basis sets

Correlation consistent basis sets that are suitable for the correlation of the outer-core (n-1)spd electrons of the post-d elements Ga-Rn have been developed. These new sets, denoted by cc-pwCVXZ-PP (X=D,T,Q,5), are based on the previously reported cc-pVXZ-PP sets that were built in conjunction with accurate small-core relativistic pseudopotentials (PPs) and designed only for valence nsp correlation. These new basis sets have been utilized in benchmark coupled cluster calculations of the core-valence correlation effects on the dissociation energies and spectroscopic properties of several small molecules. As expected, the most important contribution is the correlation of the (n-1)d electrons. For example, in the case of the group 13 homonuclear diatomics (Ga(2),In(2),Tl(2)), this leads to a dissociation energy increase compared to a valence-only treatment from 1.5 to 3.2 kcal/mol, bond length shortenings from -0.076 to -0.125 A?, and harmonic frequency increases of 7-8?cm(-1). Even in the group 15 cases (As(2),Sb(2),Bi(2)), the analogous effects of (n-1)d electron correlation are certainly not insignificant, the largest values being +4.4?kcal/mol, -0.049 A?, and +9.6?cm(-1) for the effects on D(e), r(e), and ω(e), respectively. In general, the effects increase in magnitude down a group from 4p to 6p. Correlation of the outer-core (n-1)p electrons is about an order of magnitude less important than (n-1)d but larger than that of the (n-1)s. The effect of additional tight functions for Hartree-Fock and valence sp correlation was found to be surprisingly large, especially for the post-4d and post-5d elements. The pseudopotential results for the molecules containing post-3d elements are also compared to the analogous all-electron calculations employing the Douglas-Kroll-Hess Hamiltonian. The errors attributed to the PP approximation are found to be very small.     

Darkness at noon: sunscreens and vitamin D3

We are assured by responsible scientific and governmental organizations that sunscreens should be routinely worn to reduce skin cancer risk. We are also advised that wearing sunscreens will not hinder our ability to produce sufficient previtamin D3 (preD3) from casual sunlight exposure. We report the examination of a series of 166 solar spectra, obtained on different days throughout a year, evaluated for erythemic and preD3 effectiveness and the relative effects of recommended Sun protection factor (SPF) 15 sunscreen. The results show that the sunscreen is much more effective in blocking the formation of preD3, than its labeled SPF for preventing sunburn. In fact with sunscreen applied only miniscule amounts of preD3 are predicted to be made outdoors even with extensive exposure. This raises important questions regarding the safest way to use sunlight exposure to promote healthy vitamin D3 levels and suggests the need to modify the public safety "Safe Sun" messages.     

Selecting parameters and limits for equipment operational qualification

While operational qualification (OQ) is a well-established term within equipment qualification, users of equipment often become unsure when it comes to implementation. The biggest problem is how to select procedures and acceptance criteria. Should these be the vendor's specifications or should the users define their own limits, and, if so, how? Should all instruments of the same type have the same values or should these be optimized for each individual instrument? This article will provide an overall strategy and specific examples for HPLC on how to select procedures and acceptance limits that are based on efficient use of resources, on practicality and on the intended use of the equipment.     

Cu‐Catalyzed Intramolecular Amidation of Unactivated C(sp3)−H Bonds To Synthesize N‐Substituted Indolines

A copper‐catalyzed intramolecular amidation of unactivated C(sp³)?H bonds to construct indoline derivatives has been developed. Such an amidation proceeded well at primary C?H bonds preferred to secondary C?H bonds. The transformation owned a broad substrate scope. The corresponding indolines were obtained in good to excellent yields. N‐Formal and other carbonyl groups were suitable and were easily deprotected and transformed into methyl or long‐chained alkyl groups. Preliminary mechanistic studies suggested a radical pathway.     

分析测试中心面临的挑战

在总结中国科学院所属的分析测试中心的工作任务和所起的作用之后，对分析测试中心的发展趋势做了评述；分析了中科院所属分析测试中心在目前处于困境的根源，对中心今后的工作方向和如何能走出困境，更好地为科研和生产服务提出了建议和看法     

3D printing for aqueous and non-aqueous redox flow batteries

Additive manufacturing technologies, generally grouped under the name of 3D printing, are experiencing an explosion of interest during the last few years. The possibility of fast prototyping enabled by 3D printing has been recognized as a crucial booster for device fabrication and general scientific advancements. In this review, attention is focused on the latest developments in the field of redox flow batteries which are, similar to other energy related devices, characterized by the recent adoption of 3D printing methods for the fabrication of key components. Whether simply to investigate flow phenomena, test new designs or fabricate final-product components with custom features, the use of 3D printing can critically drive this field of research towards better performing energy-storage systems. The latest and most representative examples of redox flow battery studies will be discussed, categorized in relation to the electrolyte used and whether the devices are employed in aqueous or non-aqueous applications.     

Copper‐Catalyzed Oxidative Reaction of β‐Keto Sulfones with Alcohols via C−S Bond Cleavage: Reaction Development and Mechanism Study

A Cu‐catalyzed cascade oxidative radical process of β‐keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β‐keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C?S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four‐coordinated Cu^II intermediate, O?O bond homolysis induced C?S bond cleavage and Cu‐catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C?S bond cleavage and transformations.     

Crystalline Red Phosphorus Nanoribbons: Large‐Scale Synthesis and Electrochemical Nitrogen Fixation

Two dimensional (2D) nanoribbons constitute an emerging nanoarchitecture for advanced microelectronics and energy conversion due to the stronger size confinement effects compared to traditional nanosheets. Triclinic crystalline red phosphorus (cRP) composed by a layered structure is a promising 2D phosphorus allotrope and the tube‐like substructure is beneficial to the construction of nanoribbons. In this work, few‐layer cRP nanoribbons are synthesized and the effectiveness in the electrochemical nitrogen reduction reaction (NRR) is investigated. An iodine‐assisted chemical vapor transport (CVT) method is developed to synthesize circa 10 g of bulk cRP lumps with a yield of over 99 %. With the aid of probe ultrasonic treatment, high‐quality cRP microcrystals are exfoliated into few‐layer nanoribbons (cRP NRs) with large aspect ratios. As non‐metallic materials, cRP NRs are suitable for the electrochemical nitrogen reduction reaction. The ammonia yield is 15.4 μg h^?1 mg_cat.^?1 at ?0.4 V vs. reversible hydrogen electrode in a neutral electrolyte under ambient conditions and the Faradaic efficiency is 9.4 % at ?0.2 V. Not only is cRP a promising catalyst, but also the novel strategy expands the application of phosphorus‐based 2D structures beyond that of traditional nanosheets.     

大科学装置同步辐射光源在生命分析化学中的应用

大科学装置的建设和水平是一个国家科技发展程度的标志. 同步辐射装置是一种先进的多学科交叉的高端大科学研究设施, 作为独特的宽光谱高亮度光源, 同步辐射光源提供了其他光源所无法比拟的优势. 我国迄今已建成的最大的大科学装置—— 上海光源的建立和应用是新中国成立60年来的重大成就之一, 标志着我国在建设国际先进水平的大型科学实验装置方面具备了高水平的技术和集成与创新的能力, 已进入国际先进行列. 本文侧重介绍同步辐射光源在生命分析化学领域中的巨大作用, 并以上海光源为例介绍同步辐射光源装置的发展和应用状况, 旨在唤起和推动我国分析化学家的高度重视, 并充分利用我国这一先进的大型科学装置, 将生命分析化学的研究推进到一个崭新的、更高的层次.     

大型科学仪器专业技术培训促进使用效益提升的思考

大型科学仪器是科学研究和培养技术人才的重要基础,专业技术培训是促进大型科学仪器使用效益提升的重要方式.为进一步提升培训效果,应加强基本功培训、同行技术交流培训以及技术创新高级培训.     

Early Industrial Roots of Green Chemistry and the history of the BHC Ibuprofen process invention and its Quality connection

Conventional wisdom and many published histories of “Green Chemistry” describe its start as being a result of governmental and/or regulatory actions at the US Environmental Protection Agency (“EPA”) during the early 1990’s. But there were many Real World industrial examples of environmentally friendly commercial processes in the oil and commodity chemicals industries for decades prior to the 1990s. Some early examples of commercial “Green Chemistry” are briefly described in this article. The Boots/Hoechst Celanese (“BHC”) Ibuprofen process was one of the earliest multiple-award-winning examples of industrial “Green Chemistry” in the fine chemical/pharmaceutical industry. The author, who conceived the BHC Ibuprofen synthetic strategy in 1984, reveals and documents that the BHC Ibuprofen process was not primarily a result of governmental or regulatory mandates, or environmentalist or political motivations. The BHC ibuprofen process, and probably many other early industrial “green” inventions, evolved from, and their development and commercialization motivated and guided by, a long prior industrial culture of both scientific and technical evolution. The invention and commercialization of these early industrial commercialized processes, and the BHC Ibuprofen process were also guided by both competitive and economic market needs, personal human motivations, and a low waste culture of “Quality” and “Continuous Improvement” that the commodity chemical industry internally promoted in the 1980’s. The author comments on some perceptions of the status of Green Chemistry now, and directions it should consider going in the future. The author recommends that young Green Chemists and/or Green Engineers reconsider “Quality” approaches in order to genuinely lead Society toward a Greener future.     

Phosphorus within planetary boundaries

ABSTRACT

In this paper the screening calculations of the removal time of phosphorus from water bodies of federal districts of Russia are presented. Calculations are made using the matrix algebra based approach and are applied as a tool for the estimation of the fate of phosphates in different environmental media (water, air, soil, biota, etc.). The results show that the use of phosphate fertilizers is sometimes quite high in the most vulnerable federal districts. It means that the application of fertilizers in order to increase the yield of agriproducts should be accompanied by detailed assessment of the risks of eutrophication. Calculations have shown high vulnerability in the district of the Lake Baika.     

Reversal of Solvatochromism: A New Strategy to Construct Activatable Two-photon Fluorescent Probes for Sensing

Two-photon (TP) imaging with a donor-acceptor (D?A) type fluorophore is an emerging tool for bioimaging and sensing. However, current TP probes suffer from serious solvatochromic quenching in aqueous solution due to their strong intramolecular charge transfer (ICT) in excited states. In this work, based on solvatochromism reversal, we report a novel strategy to develop TP probes for bioimaging. Specifically, compared with the normal two-photon probes that showed a fluorescence off with ICT suppressed, the novel probes exhibited strong fluorescence in the aqueous solution when their ICT was inhibited. This strategy not only provides a new way for the design of high-performance TP probes, but also expands the biological analysis toolbox for use in living systems.     

Mechanistic Study on the Cleavage and Reorganization of C(sp3)?H and CN Bonds in Carbodiimides: Synthesis of 1,2‐Dihydrothiopyrimidines and 2,3‐Dihydropyrimidinthiones through Four‐Component Coupling

This study sheds light on the cleavage and reorganization of C(sp³)? H and C?N bonds of carbodiimides in a three‐component reaction of terminal alkynes, sulfur, and carbodiimides by a combination of methods including 1) isolation and X‐ray analysis of six‐membered‐ring lithium species 2‐S , 2) trapping of the oxygen‐analogues ( B‐O and D‐O ) of both four‐membered‐ring intermediate B‐S and ring‐opening intermediate D‐S , 3) deuterium labeling studies, and 4) theoretical studies. These results show that 1) the reaction rate‐determining step is [2+2] cycloaddition, 2) the C?N bond cleavage takes place before C(sp³)? H bond cleavage, 3) the hydrogen attached to C6 in 2‐S originates from the carbodiimide, and 4) three types of new aza‐heterocycles, such as 1,2‐dihydrothiopyrimidines, N‐acyl 2,3‐dihydropyrimidinthiones, and 1,2‐dihydropyrimidinamino acids are constructed efficiently based on 2‐S . All results strongly support the idea that the reaction proceeds through [2+2] cycloaddition/4π electrocyclic ring‐opening/1,5‐H shift/6π electrocyclic ring‐closing as key steps. The research strategy on the synthesis, isolation, and reactivity investigation of important intermediates in metal‐mediated reactions not only helps achieve an in‐depth understanding of reaction mechanisms but also leads to the discovery of new synthetically useful reactions based on the important intermediates.     

The Role of Guest Molecules in the Self-assembly of Metal—ligand Clusters

Abstract

Understanding the self-assembly of nanoscale metal—ligand clusters is an important research area in supramolecular chemistry, especially, if one wishes to develop a truly predictive design strategy for synthesizing these nanoscale clusters. As the building blocks for forming these clusters have become larger and more complex, spacious clusters have been synthesized which often contain large cavities. These assemblies can house guest molecules which play a previously uncharacterized role in the self-assembly processes. We seek to analyze this role: do these guest molecules act as templates? Are the guest molecules necessary for cluster formation? Does the guest drive cluster assemble by forming a stable host—guest complex with the cluster? Must a truly rational design strategy for forming metal—ligand clusters incorporate the use of templates? The role of guest molecules in the self-assembly of nanoscale coordination clusters is reviewed in this article.