Berthelot’s Pathway from Synthesis to Thermochemistry

Why did Marcellin Berthelot turn away from his successful research in organic synthesis around 1864 to devote himself to the difficult and uncertain path of thermochemistry? Jean Jacques and others have argued that Berthelot’s shift can be seen as a result of his flawed understanding of the emerging atomistically based theories of structural chemistry; a sense that he was being left behind by this field, it is maintained, led him to try something different. In contrast, I will argue that thermochemistry was a logical progression of Berthelot’s overarching desire to predict chemical action, a great challenge in the middle of the nineteenth century. Berthelot hoped and expected that synthesis and chemical industry would transform the conditions of our existence. He asked such questions as: What substances can we expect to create? From which reagents? And most important: how can we tell in advance whether a particular chemical reaction will occur?     

Coordinating California’s efforts to promote waste to alcohol production

Alcohol fuels produced from biomass can improve air quality, enhance energy security, create employment opportunities, and reduce waste disposal problems. Opportunities in California exist to produce alcohols from waste streams from various sectors of the economy. Government agencies have promoted waste-to-alcohol activities, but efforts have been inconsistent and intermittent. Often these efforts have been hindered by contradictory but mandate-driven policies. A prudent approach to coordinate statewide efforts includes the development of an integrated statewide policy to examine barriers that impede private sector business efforts to produce alcohols from biomass. A multi-agency task force to promote research, development, commercialization, and marketing efforts for biomass-produced alcohols is desirable. The views and opinions contained in this document do not necessarily reflect those of the California Energy Commission, its staff, management, or the State of California.     

Mayer’s orthogonalization: relation to the Gram-Schmidt and Löwdin’s symmetrical scheme

A method introduced by Mayer (Theor Chem Acc 104:163, 2000) for generating an orthogonal set of basis vectors, perpendicular to an arbitrary start vector, is examined. The procedure provides the complementary vectors in closed form, expressed with the components of the start vector. Mayer’s method belongs to the family of orthogonalization schemes, which keep an arbitrary vector intact without introducing any non-physical sequence-dependence. It is shown that Mayer’s orthogonalization is recovered by performing a two-step combination of the Gram-Schmidt and Löwdin’s symmetrical orthogonalization. Processor time requirement of constructing Mayer’s orthonormal set is proportional to ～N ², in contrast to the rough ～N ³ CPU requirement of performing either a full Gram-Schmidt or Löwdin’s symmetrical orthogonalization. Utility of Mayer’s orthogonalization is demonstrated on an electronic structure application using perturbation theory to improve multiconfigurational wavefunctions.     

Alternatives to Bazley’s special choice for eigenvalue lower bounds

Bazley’s special choice operator is a lesser operator to a positive perturbation of a self-adjoint semi-bounded operator that possesses an exactly soluble base eigenvalue problem. It allows the construction of an exactly soluble intermediate problem that gives eigenvalues not less than the base problem and not greater than the perturbed problem so that lower bounds to the eigenvalues of the perturbed operator are produced. This paper considers alternate derivations of Bazley’s special choice which lead to two alternate methods to determine eigenvalue lower bounds. One is simpler, but gives poorer bounds; the other is more difficult, but sometimes yields superior bounds. Lower bounds to the particle in a box model with a linear perturbation and lower bounds to the helium atom are calculated using the two methods introduced and are compared to those given with Bazley’s special choice.      

N. S. Kurnakov’s contribution to coordination chemistry

N.S. Kurnakov’s most important works in coordination chemistry are overviewed. Special attention is given to Kurnakov’s dissertation “On Complex Metal Bases,” to his understanding of the structure of coordination compounds, to the mutual effects of ligands, and to the key ideas in coordination chemistry developed by Chugaev and Chernyaev’s school. Kurnakov’s role in the foundation of the Soviet platinum industry is pointed out.     

New approach to Tian’s equation applied to heat conduction and liquid injection calorimeters

In the calorimeters used for the determination of thermodynamical properties of liquid environments, the mixture takes place when injecting liquid in the mixture zone, this injection incorporates an additional calorific power that is a function of the volumetric heat capacity of the injected liquid and the injection flow. In this article, it is rewritten Tian??s equation including this additional power to relate correctly the experimental output to the mixture enthalpy. It is applied Tian??s equation, once it has been corrected, to two types of calorimeters: flow-microcalorimeters and isothermal titration calorimeters. In this second case, it has been taken into account the classical operating mode (titration) and the continuous liquid injection mode. Tian??s equation, completed with all the energetic terms additional to the mixture process, is of great interest for the scientific and academic community because it allows to explain, in a simple and effective way, the operation of these instruments.     

Metabolomic approach to Alzheimer’s disease diagnosis based on mass spectrometry

Alzheimer??s disease is the most common neurodegenerative disease, but there is still no cure and early diagnosis remains very difficult. For this reason, the discovery of new biomarkers is of great importance. The application of metabolomics is emerging in this field, based on the use of mass spectrometry as a technique of analysis. In this work, blood serum samples (from Alzheimer??s disease patients and healthy controls) were analysed by mass spectrometry in order to search for potential metabolomic biomarkers. The application of multivariate statistical tools (PLS-DA) enabled us to discriminate between groups. In addition, some phosphatidylcholine compounds were identified as markers of the disease.     

AFM nanoindentation to determine Young’s modulus for different EPDM elastomers

AFM nanoindentation was investigated as a method for determining the micromechanical properties of polymer materials. It is generally accepted that the shape of the tip of the cantilever undergoes a change in a standard AFM setup. The shape defines the projected contact area, so it is a parameter directly proportional to the elastic modulus; any change in the shape thus affects the accuracy of the results. The method suggested in this paper relies on the introduction of an experimentally determined tip-area function. Values for Young’s modulus were calculated for EPDM samples with different degrees of cure and crystallinity. The degree of crystallinity has a greater impact on the mechanical properties of the material than the degree of cure. Depending on the amplitude of the indentation, the E-moduli determined by AFM are systematically higher. When studying different regions of polymer materials, the values of the E-modulus determined by AFM become identical to those measured by means of DMA on extrapolation of the modulus at zero indentation.     

Honda’s thermobalance

Kotaro Honda (2/23/1870–2/12/1954) graduated from the Department of Physics, Tokyo Imperial University in 1897. Between 1907 and 1911, he stayed in Europe, and spent the majority of his time at Göttingen University to study physical metallurgy under Professor Gustav Tammann. In 1911, he returned to Japan and was nominated professor of physics at Tohoku Imperial University, Sendai. An university-affiliated institute for research on iron and steel was established on a permanent basis in 1919, and the institute developed to the Research Institute for Iron, Steel, and Other Metals (RIISOM, KINKEN in Japanese) in 1922. Professor Honda served as the Director of the Institute until 1933. The RIISOM was reorganized as a national collaborative research institute named Institute for Materials Research in 2001. Professor Honda and his colleagues achieved distinguished research works of physical metallurgy, in which thermoanalytical techniques such as differential thermal analysis (DTA), thermodilatometry and thermomagnetometry were utilized effectively. Professor Honda also played an important role in the field of thermogravimetry (TG) by means of the first development of the thermobalance. In the present paper, Honda’s original thermobalance, various modifications carried out by his school, the commercialized Honda’s thermobalance and other related matters are briefly summarized.     

Editor’s note

Journal of Solid State Electrochemistry -     

Catalytic Access to Functionalized Allylic gem-Difluorides via Fluorinative Meyer–Schuster-Like Rearrangement

An unprecedented approach for efficient synthesis of functionalized allylic gem-difluorides via catalytic fluorinative Meyer–Schuster-like rearrangement is disclosed. This transformation proceeded with readily accessible propargylic fluorides, and low-cost B–F reagents and electrophilic reagents by sulfide catalysis. A series of iodinated, brominated, and trifluoromethylthiolated allylic gem-difluorides that were difficult to access by other methods were facilely produced with a wide range of functional groups. Importantly, the obtained iodinated products could be incorporated into different drugs and natural products, and could be expediently converted into many other valuable gem-difluoroalkyl molecules as well. Mechanistic studies revealed that this reaction went through a regioselective fluorination of alkynes followed by a formal 1,3-fluorine migration under the assistance of the B–F reagents to give the desired products.     

A New Pathway to Synthesize Cyclomercurated Ferrocenylimines Containing Heterocyclic Ring

The cyclomercurated ferrocenylimines containing heterocyclic ring were prepared by the condensation of cyclomercuration of acylferrocene with the appropriate heterocyclic amine.This procedure provides an efficient method for the synthesis of cyclomerucurated ferrocenylimines containing heterocyclic ring which are difficultly synthesized by the conventional method.The reaction mechanism is proposed.     

Analytical solution to transient inverse heat conduction problem using Green’s function

Journal of Thermal Analysis and Calorimetry - A transient inverse heat conduction problem concerning jet impingement heat transfer has been solved analytically in this paper. Experimentally...     

Today’s and tomorrow’s bio-based bulk chemicals from white biotechnology

Little information is yet available on the economic viability of the production of bio-based bulk chemicals and intermediates from white biotechnology (WB). This paper details a methodology to systematically evaluate the techno-economic prospects of present and future production routes of bio-based bulk chemicals produced with WB. Current and future technology routes are evaluated for 15 products assuming prices of fermentable sugar between 70 euro/t and 400 euro/t and crude oil prices of US $25/barrel and US $50/barrel. The results are compared to current technology routes of petrochemical equivalents. For current state-of-the-art WB processes and a crude oil price of US $25/barrel, WB-based ethanol, 1,3-propanediol, polytrimethylene terephthalate and succinic acid are economically viable. Only three WB products are economically not viable for future technology: acetic acid, ethylene and PLA. Future-technology ethylene and PLA become economically viable for a higher crude oil price (US $50/barrel). Production costs plus profits of WB products decrease by 20-50% when changing from current to future technology for a crude oil price of US $25 per barrel and across all sugar prices. Technological progress in WB can thus contribute significantly to improved economic viability of WB products. A large-scale introduction of WB-based production of economically viable bulk chemicals would therefore be desirable if the environmental impacts are smaller than those of current petrochemical production routes.