Generic division of ‘quantity’ and related terms

In the slow evolution of the International vocabulary of metrology (VIM), the first concept of ‘quantity’ has now been divided generically into ‘ordinal quantity’ and a coordinate primitive without definition and term. An analysis of the concepts by their characteristics is made, and the nature of inheritance is discussed in response to a recent communication in this journal. A completion of the initiated generic division of ‘quantity’ is suggested, and a neoterm for the sister of ‘ordinal quantity’ is offered on the basis of two proposals.     

What exactly is uncertainty?

Uncertainty is defined in VIM3 as a ‘parameter’ but that, in my view, is a mistake that detracts from the clarity of the concept. Trying to overcome the resulting difficulties while retaining ‘parameter’ has brought about progressive amendments to the definition, and an increasing list of footnotes that have failed to resolve the issue. Surely the uncertainty of a result is the density function (or mass function) that best describes the probability of possible values of the measurand.     

The third edition of ISO Guide 34: what were the drivers for the revision and what is new?

After the International Laboratory Accreditation Cooperation (ILAC) had taken in 2004, the resolution to conduct accreditation of producers of reference materials according to ISO Guide 34 ‘General requirements for the competence of reference material producers’ in combination with ISO/IEC 17025 ‘General requirements for the competence of testing and calibration laboratories’, ISO/REMCO, the ISO Committee on Reference Materials, decided in 2005 to revise ISO Guide 34 to align it closer with ISO/IEC 17025 and to clarify certain issues for accreditors and producers seeking accreditation without adding new requirements. Moreover, the publication in 2007 of ISO/IEC Guide 99 ‘International vocabulary of metrology—Basic and general concepts and associated terms (VIM)’ triggered additional adaptations of the guide.     

Douglas–Kroll–Hess Theory: a relativistic electrons-only theory for chemistry

A unitary transformation allows to separate (block-diagonalize) the Dirac Hamiltonian into two parts one part: solely describes electrons, while the other gives rise to negative-energy states, which are the so-called positronic states. The block-diagonal form of the Hamiltonian no longer accounts for the coupling of both kinds of states. The positive-energy (‘electrons-only’) part can serve as a ‘fully’ relativistic electrons-only theory, which can be understood as a rigorous basis for chemistry. Recent developments of the Douglas–Kroll–Hess (DKH) method allowed to derive a sequence of expressions, which approximate this electrons-only Hamiltonian up to arbitrary-order. While all previous work focused on the numerical stability and accuracy of these arbitrary-order DKH Hamiltonians, conceptual issues and paradoxa of the method were mostly left aside. In this work, the conceptual side of DKH theory is revisited in order to identify essential aspects of the theory to be distinguished from purely computational consideration.     

Some metrological aspects of the comparison between two ordinal measuring systems

The usage of ordinal scales (sometimes called ‘semi-quantitative’ scales) for performing measurements in the area of applied chemical metrology and quality assurance is widespread. This paper presents a method for handling actions such as calibration, measuring systems’ capabilities comparison and reproducibility evaluation as a comparison between two measuring systems (MSs) referring to a known/unknown reference standard. The strength of the agreement between these MSs is evaluated through two known versions of Cohen’s kappa statistics (the traditional one and the modified one). The effectiveness of these statistics from the metrological point of view is examined, and the preferability of the modified kappa statistics is demonstrated via an example.     

Three-way Principal Components Analysis for fluorescence spectroscopic classification of algae species

Excitation-emission matrices (EEM) from fluorescence spectroscopy may contain characteristic information about different algae species. As a result of measurements, one gets a whole stack of EEMs each of them corresponding to one species. Such a stack of matrices has to be understood as a cubic data array spanned by the dimensions ‘excitation’, ‘emission’ and ‘species’. The interpretation of higher dimensional data arrays requires efficient tools from multivariate data analysis. In this paper, it is illustrated how Three-way Principal Components Analysis as the appropriate generalization of conventional Principal Components Analysis may serve as a powerful method for classification of algae species. Received: 31 May 1996 / Revised: 1 July 1996 / Accepted: 4 Juli 1996     

Three-way Principal Components Analysis for fluorescence spectroscopic classification of algae species

Excitation-emission matrices (EEM) from fluorescence spectroscopy may contain characteristic information about different algae species. As a result of measurements, one gets a whole stack of EEMs each of them corresponding to one species. Such a stack of matrices has to be understood as a cubic data array spanned by the dimensions ‘excitation’, ‘emission’ and ‘species’. The interpretation of higher dimensional data arrays requires efficient tools from multivariate data analysis. In this paper, it is illustrated how Three-way Principal Components Analysis as the appropriate generalization of conventional Principal Components Analysis may serve as a powerful method for classification of algae species. Received: 31 May 1996 / Revised: 1 July 1996 / Accepted: 4 Juli 1996     

New Routes for Thermal Analysis and Calorimetry As Applied to Polymeric Systems

Over the last few decades there has been a strong decrease in the number of Thermal Analysis and Calorimetry (TA and C) ‘practitioners’ - scientists who know the in sand outs of TA and C and its (im)possibilities and are capable of initiating new developments. By contrast, an increasing number of TA and C ‘users’ are scarcely able to acquire in-depth knowledge of TA and C. It is therefore of great importance that national TA and C societies create the infrastructure for dedicated education. In addition, the feasibility of setting up one or more expertise centers per country, where ‘practitioners’ can do research,carry out contract research and give advice to users, needs to be investigated. Equally important, the TA and C community needs to address a number of challenges in the coming decade with the aim of controlling the ‘knowledge cycle’ in the field of polymers: to translate non-optimal properties into improved processing conditions or even a more suitable macromolecular architecture, in order to reduce the lead times for the development and optimization of materials. Although Thermal Analysis and Calorimetry can generally be considered to be ‘mature’, in specific subareas a large number of new developments take place. A few examples of these developments and of state-of-the-art TA and C are given:quantitative heat capacity measurements by means of DSC; (very) high pressure DSC;real-time morphological analysis and temperature-modulated X-ray analysis. In addition, anew form of TA and C is discussed: High Performance DSC (HPer DSC), which is also a high rate DSC and a high throughput DSC. This revised version was published online in July 2006 with corrections to the Cover Date.     

Electron transfer dynamics

This paper surveys the current ‘state-of-art’ of the theoretical understanding of electron transfer dynamics in donor-acceptor systems, which provide the conceptual and technical basis for solar energy conversion via optical and optoelectronic molecular devices and for the primary charge separation in photo-synthesis.     

Biophysical,spectroscopic vis-à-vis biochemical investigation on DNA–metalloprotein interaction: a model study involving cobalt(II)-glutathione complex

Abstract  The interaction of cobalt(II)-glutathione (CoGSH) with deoxyribonucleic acid (DNA) has been studied by UV–vis, fluorescence, circular dichroism (CD), thin-film infrared (IR), and viscometric techniques. From the UV-spectroscopic method, binding constant (K _b) was determined and was found to be 2.3 × 10⁶ M⁻¹. In fluorimetric analysis, the quenching of fluorescence intensity of DNA bound to ethidium bromide (EB) was investigated. The Stern–Volmer quenching constant (K _sv) was also estimated from this study and was found to be 2.8 × 10⁶ M⁻¹at 37 °C. The solution CD spectra of DNA and DNA–CoGSH indicate that in each case, DNA exists in the ‘B’ conformation and suggested an intercalative binding mode. Thin-film IR data also reveal that DNA attains the ‘B’ family of conformations after interaction with CoGSH complex. The increase in DNA viscosity in the presence of CoGSH complexes is attributed to the lengthening of DNA helix due to intercalation. Graphical Abstract  The spectrophotometric, CD, thin film IR, viscometric and fluorimetric studies on the interaction of CoGSH with DNA indicated an intercalative binding mode with the retention of ‘B’ conformation of DNA.      

Are kinetic parameters of non-isothermal thermogravimetric degradation of polymers unequivocal?

Due to the complex character of the thermal degradation of polymers as a solid-gas chain reaction, an unequivocal kinetic characteirzation is possible only for stationary states of both radical concentration and reaction mechanism. These conditions are hardly realizable in non-isothermal thermogravimetry. Additional the weight losses are depedent on the volatility of the reaction products. That is not always certain in polymer degradation. As a consequence the deduced ‘kinetic parameters’ are not unequivocal. They are conversion and heating rate dependent and may be influenced by sample shape and size. Thus the ‘kinetic parameters’ are in fact from the point of view of mathematics the fitting parameters of a ‘rate equation’ like relation, specific for the used reaction conditions only. From the point of view of chemical kinetics they are neither attributable to a determined reaction mechanism nor can they be used for predictions. Dedicated to the 70^th Anniversary of Dr. Jo Flynn     

The mole: definition versus practical use

Most base units in the SI relate to specific sensoric qualities our body is able to observe: space, heat, brightness, etc. The base unit ‘mole’ incorporates intellectual insight: the atomistic perception of the world. This perception is a quintessence of over 300 years of scientific research. The quintessence, from Dalton’s ‘The sceptical chymist’ to Perrin’s Nobel Prize in 1926 and Pauling’s ‘Nature of the Chemical Bond’ in 1939, results in the conclusion that the base unit of the SI quantity ‘amount of substance’ is not the mole but the dimensionless entity.     

Controversy and complementarity in mechanistic organic chemistry. The transition state and structural theories reexamined

It is proposed that molecular phenomena may only be described within the framework of the Complementarity Principle (‘CP’), and that scientific controversy may originate in the essential incompatibility of complementary representations. Complementarity based on the temporal Uncertainty Principle leads to new insights into transition state theory, microscopic reversibility and the Curtin-Hammett Principle. An empirical application of the ‘CP’ to the structural theory leads to a revision of present concepts of ‘reaction dynamics’, with the Principle of Least Nuclear Motion (‘PLNM’) emerging as a general alternative to electronic theories of reactivity. In fact, it is argued that the ‘PLNM’ is a better basis for the Woodward-Hoffmann rules than is orbital symmetry. A more flexible approach to organic reaction mechanisms is thus indicated. Also, as the basis of the structural theory is fundamentally uncertain, and the present theory of X-ray diffraction apparently incompatible with the ‘UP’, a reinterpretation of the Bragg equation has been attempted.     

Structure of Composite Films Containing Polyaniline Studied by DSC

A structural study of conductive composite films consisting of ethylene-co-vinylacetate (EVA) copolymer, polyaniline (PANI) and dodecylbenzenesulfonic acid (DBSA), a part of which being complexed with PANI, was performed by using differential scanning calorimetry (DSC) and presented for the first time. An additional crystalline phase is formed during the film formation by thickening EVA chain-folded lamellae with participation of‘free’ DBSA molecules at lower net PANI content (up to 5 mass%) and of both ‘free’ and complexed DBSA molecules (up to 7.5 mass%). At higher PANI content PANI-DBSA complex starts to form its own crystals and at 17.5 mass% of PANI mixed crystals of EVA with ‘free’ DBSA alkyl chains are preferably formed. It is also found that the Fox' equation correlating the glass transition temperature of a miscible blend system with its composition can be actually used in estimating the miscibility of EVA/PANI blends no matter the presence of DBSA. This revised version was published online in August 2006 with corrections to the Cover Date.     

Explanation and theory formation in quantum chemistry

In this paper I expand Eric Scerri’s notion of Popper’s naturalised approach to reduction in chemistry and investigate what its consequences might be. I will argue that Popper’s naturalised approach to reduction has a number of interesting consequences when applied to the reduction of chemistry to physics. One of them is that it prompts us to look at a ‘bootstrap’ approach to quantum chemistry, which is based on specific quantum theoretical theorems and practical considerations that turn quantum ‘theory’ into quantum ‘chemistry’ proper. This approach allows us to investigate some of the principles that drive theory formation in quantum chemistry. These ‘enabling theorems’ place certain limits on the explanatory latitude enjoyed by quantum chemists, and form a first step into establishing the relationship between chemistry and physics in more detail.     

Prompt gamma activation analysis and time of flight neutron diffraction on ‘black boxes’ in the ‘Ancient Charm’ project

The aim of the ‘Ancient Charm’ project is combining neutron tomography, prompt gamma activation analysis, time of flight neutron diffraction and neutron resonance transmission to generate elemental, and phase compositions of complex museum objects in 3D. To develop a protocol for such investigations, complex test samples were constructed and then analyzed by each method. The ‘black boxes’ are sealed iron and aluminum walled cubes, containing 2D or 3D arrangements of materials relevant for the compositions of archaeological samples. The experimental results obtained from bulk PGAA at BNC and TOF-ND at ISIS on two selected boxes are reported.     

The chemical ‘Knight’s Move’ relationship: what is its significance?

Similarities in properties among pairs of metallic elements and their compounds in the lower-right quadrant of the Periodic Table have been named the ‘Knight’s Move’ relationship. Here, we have undertaken a systematic study of the only two ‘double-pairs’ of ‘Knight’s Move’ elements within this region: copper-indium/indium-bismuth and zinc-tin/tin-polonium, focussing on: metal melting points; formulas and properties of compounds; and melting points of halides and chalcogenides. On the basis of these comparisons, we conclude that the systematic evidence for ‘Knight’s Move’ relationships derives from similarities in formulas and properties of matching pairs of compounds in the same oxidation state. Physical properties, such as melting points, do not provide consistent patterns and trends and hence should not be considered as a common characteristic of this relationship.     

From phlogiston to caloric: chemical ontologies

The ‘triumph of the anti-phlogistians’ is a familiar story to the historians and philosophers of science who characterize the Chemical Revolution as a broad conceptual shift. The apparent “incommensurability” of the paradigms across the revolutionary divide has caused much anxiety. Chemists could identify phlogiston and oxygen, however, only with different sets of instrumental practices, theoretical schemes, and philosophical commitments. In addition, the substantive counterpart to phlogiston in the new chemistry was not oxygen, but caloric. By focusing on the changing visions of chemical body across the revolutionary divide with a more sensitive probe into the historical actors’ material manipulations and linguistic usage, we can historicize their laboratory realities and philosophical agenda. An archeology of chemical bodies that configures the fragile stability of the material worlds chemists created in succession promises a philosophical horizon that would recognize our hybrid (natural–artificial) environment as an evolving investigative object of science.