Fonds Der Chemischen Industrie Research Articles

From carbon superbases to superacids

Florian Mulks studied chemistry at Heidelberg University, where he obtained his doctorate with Stephen Hashmi in 2014. He spent his postdoctoral time in a variety of chemical disciplines with Shirin Faraji (University of Groningen), Eva Hevia (University of Strathclyde and University of Bern), Mu-Hyun Baik (Institute for Basic Science and Korea Advanced Institute of Science & Technology), and Guy Bertrand (University of California, San Diego). In early 2022, he founded a research group funded by the Alexander von Humboldt Foundation and Fonds der Chemischen Industrie at RWTH Aachen University to investigate molecular carbon chemistry and steric measurements.

Terminal Imido Complexes of the Groups 9–11: Electronic Structure and Developments in the Last Decade

AbstractWe thank the Fonds der Chemischen Industrie (Liebig fellowship for D.M.), the German‐American Fulbright Commission (Fulbright‐Cottrell Award for D.M.) as well as the Bavarian Equal Opportunities Sponsorship – Realization of Equal Opportunities for Women in Research and Teaching (fellowship for A.G.) for financial support. We thank the RRZ Erlangen for computational resources.

Low-Dimensional Carbon Allotropes: Ground- and Excited-State Charge Transfer with NIR-Absorbing Heptamethine Cyanine

Summary At the focal point of our studies are mutual interactions between an anionic heptamethine cyanine and individualized single-walled carbon nanotubes (SWCNTs) or exfoliated nanographene (NG). Here, we report the distinct near-infrared absorption of the heptamethine cyanine, which assists in visualizing the electronic interactions in the ground state with ease and precision. In statistical Raman assays, we conclude from downshifted 2D- and G-modes for SWCNTs, as well as upshifted 2D- and downshifted G-modes for NG, that these electronic interactions result in stable n-doping of SWCNTs and NG. Key to this shift of charge density is the electron-donating character of the heptamethine cyanine. In the excited state, a complete but metastable transfer of charges is accompanied by a radical-ion-pair state that lives for several nanoseconds. Such a time domain has not yet been realized, for example, in NG to date.

The Role of Carbon on the Discharge Product and Cell Performance of the Sodium Superoxide (NaO2) Battery

Batteries based on the cell reaction between alkali metals and atmospheric oxygen are highly attractive energy stores due to their superior theoretical energy densities. However, despite continuous progress fundamental challenges in further developing these cell systems remain. Understanding the oxygen electrode reaction and improving cycle life while at the same time maximizing the practical energy capacity are some of the most important issues that have to be tackled. Here, we focus on the aprotic sodium-oxygen battery and the role of the carbon electrode on product formation and cell performance (cycle life and capacity)[1-2]. Two different discharge product have recently been reported in literature for the sodium-oxygen battery, one leading to either sodium peroxide or hydrated sodium peroxide and the other to sodium superoxide. [3-8] The thermodynamic driving force is quite similar for both cases and it remains unclear whether only kinetics or also nano-effects [9] determine the reaction route. One important aim of our current study therefore was to explain the discrepancy reported in literature. [1] We investigated whether the electrode material, the structure or the local current density have any influence on the product stoichiometry or the cell performance. Therefore, we tested several types of carbon materials with a broad range in properties. As important finding, we always found phase-pure NaO2 as discharge product irrespective of the type of carbon used. But at the same time, the achievable capacities range from 300 to values as high as 4000 mAh∙g(C)- 1. We further studied the impact of electrolyte composition on the cell chemistry and found significant differences depending on the type of solvent used. At last, we demonstrate that the cycle life of Na/O2 cells can be largely improved by using carbon nanotubes based electrodes yielding capacities of 231 mAh∙g(C)- 1 / 0.64 mAh∙cm- 2 for at least 140 cycles. [2] Acknowledgment: The research was supported by the BASF scientific network of electrochemistry and batteries. C.L. Bender is grateful to Fonds der chemischen Industrie (FCI) for a scholarship. Literature: [1] C.L. Bender, Adv. Energy Mater., 2014, doi: 10.1002/aenm.201301863. [2] C.L. Bender, Energy Technol., 2015, doi: 10.1002/ente.201402208 [3] Q. Sun, Electrochem. Commun., 2012, 16, 22–25. [4] W. Liu, Chem. Commun., 2013, 49,1951-1953. [5] J. Kim, Phys. Chem. Chem. Phys., 2013, 15, 3623-3629. [6] Z. Jian, J. Power Sources, 2014, 251, 466-469. [7] P. Hartmann, Nat. Mater. 2013, 12, 228-232. [8] N. Zhao, Phys. Chem. Chem. Phys., 2014, 16,15646-15652. [9] S. Kang, Nano Lett., 2014, 14, 1016- 1020.

Gerhard Quinkert (1927-2015).

Gerhard Quinkert (1927-2015).

P62: Sulfite oxidase catalyzes single electron transfer at molybdenum domain to reduce nitrite to NO

Molybdenum enzymes xanthine oxidase and aldehyde oxidase exhibit nitrite reductase activity. A third molybdenum enzyme, sulfite oxidase (SO), catalyzes the oxidation of sulfite to sulfate. Given the structural and functional homology of SO to plant nitrate reductase, SO was investigated as a candidate nitrite reductase. Using gas-phase NO detection and physiological concentrations of enzyme, nitrite, and sulfite, we find that SO functions as a mammalian nitrite reductase, coupling sulfite oxidation and nitrite reduction to form NO. Studies with recombinant heme and molybdenum domains of SO showed that nitrite reduction occurs at the fully reduced molybdenum IV center. Reaction rates of nitrite to NO are decreased in the presence of a functional heme domain, mediated by both direct steric and redox effects of the heme domain. Nitrite treatment of human fibroblasts activated soluble guanylate cyclase to form cGMP, which was abrogated in fibroblasts from patients with genetic deficiencies of molybdenum cofactor and SO. These data in aggregate identify SO as a new mammalian nitrite reductase that may contribute to nitrite–NO signaling. Disclosure NIH Grants R01HL098032, RO1HL096973, and PO1HL103455; the German Sciency Foundation (DFG) and the Fonds der Chemischen Industrie.

Rolf Appel (1921–2012)

Rolf Appel, Emeritus Professor at the Institute of Inorganic Chemistry of the University of Bonn, died on January 30, 2012, a few weeks before his 91st birthday. He was born in Hamburg-Harburg, finished school in 1939, and, according to his parent’s wishes, he enrolled in medicine at the University of Halle. The experimental chemistry lectures of the future Nobel Laureate Karl Ziegler fascinated him to the extent that he decided to study chemistry. After completing his Vordiplom in 1941 and disruption through military service in the navy, Rolf Appel completed his chemistry studies in Halle in early 1945 with a Diplom thesis under G. O. Schenck on the previously unknown fumaraldehyde acid. 1 1 1 The end of the war brought about significant changes to his living conditions. Along with about 3000 other scientists, he was forcefully moved on the orders of the allied forces to West Germany. In Dieburg, he and a fellow chemist founded a company for the manufacture of wood varnishes and polishing waxes. Changes in the financial situation that were brought about by the currency reform prompted him to give up his fledgling company and to start his doctoral thesis. The deciding factor in his choice of Heidelberg was his laboratory course assistant in Halle, Margot Becke-Goehring. Under her supervision, he obtained his doctoral degree in 1951 with a thesis on disulfur trioxide. His Habilitation thesis, completed in 1955, was a discourse on the technologically important reaction of sulfur trioxide with ammonia. He then took up an academic position as full professor at the University of Bonn, where he was Director of the Institute for Inorganic Chemistry from 1966 until his retirement in 1986. The first years in Bonn were dedicated to set up the institute, which subsequently developed into a research center for molecular phosphorus chemistry. At the same time, he played a decisive role in the planning of the new institute building in Endenich, to which the institute moved in 1972. Scientific activities were initially concentrated on the phosphane/carbon tetrachloride system, and led, in the presence of Brønsted acidic compounds, to the three-component reaction that bears Appel’s name. This reaction found use in the organic laboratory as a mild dehydration agent.1 Further work using hexachloroethane showed that this method could be used for the synthesis of peptides at polymer resins. The synthesis of bradykinin is no doubt a highlight of this work.2 At the end of the 1970s, Rolf Appel moved his research acitivities to organophosphorus compounds with pπ–pπ multiple bonds, and thereby contributed significantly to a renaissance of phosphorus chemistry. A large number of novel compounds with PC bonds (“phosphacarbaoligoenes”) were developed.3 Particular attention was given to the use of the C/P diagonal relationship, which afforded the phospha-Cope rearrangement as a highlight.3 Phosphorus(V) compounds with a coordination number of three should be also mentioned, such as the bis(methylene)phosphoranes or the tris(methylene)phosphate, an isosterous compound of monomeric metaphosphate.3 These studies on organophosphorus chemistry, which Appel stated was the happiest period of his scientic work, remain seminal. Given his achievements, honors had to follow, such as the IMPHOS Award (1979), the Liebig Memorial Medal of the German Chemical Society (GDCh; 1986), and being named a member of the North Rhein-Westphalian Academy of Arts and Sciences (1982). Apart from university commitments, Rolf Appel also applied himself to chemistry in general. As a member of the board of trustees of the Fonds der chemischen Industrie (FCI) he spent much time for the advancement of young scientists and the chemical research and teaching at universities. As a member of the board of the GDCh, he made great contributions to chemistry in Germany. One of Rolf Appel’s biggest passions was traveling by sea, which led him and his wife Sylvia not only to the Mediterranean coast, but also to the Arctic. His sharp wit, his benevolent advice, and his friendship remain unforgotten and will be missed. Those that had the privilege to know him well, like us, will remember him as an exceptionally gifted researcher and professor.

Editorial

This special section of PES is devoted to POLYCHAR 18 - World Forum for Advanced Materials. POLYCHAR 18 took place in Siegen, Germany, from April 7th to 10th, 2010. The Conference was organized by the Institute of Macromolecular Chemistry and by the Institute of Physical Chemistry I at the University of Siegen and was held on the Campus of the university. It was sponsored by IUPAC. POLYCHAR offers a platform for sharing ideas, presenting results, meeting old and making new friends in the scientific community. Topics covered a wide areas, including synthesis, characterization, modification and application of all sorts of polymeric materials and composites, best summarized under the term ‘Advanced Materials’. More than 250 delegates from 40 different foreign countries and 5 continents participated, making made this event truly international. DAAD and IUPAC provided financial support for participation of students from underprivileged and developing countries, and DFG and Fonds der Chemischen Industrie supported the attendance of established researchers. Structure, Morphology and Properties of Polymers: characterization, testing, simulation/modeling Synthesis and Modification of Polymer Systems Polymeric Materials and Application: stimuli responsive systems, devices and processing Biorelated Polymers: bio-, medical- and sustainable approaches including recycling. The prestigious Paul J. Flory Polymer Research Prize 2010 was awarded to Prof. Andrzej Galeski from the Centre of Molecular and Macromolecular Studies of the Polish Academy of Sciences, Sienkiewicza, Poland and to Prof. Hans Wolfgang Spiess from the Max Planck Institute for Polymer Research, Mainz, Germany. Prof. Galeski was honored for his “pioneering work on strength and toughness of semicrystalline polymers, blends and filled polymer systems”, and Prof. Spiess was recognized for his “pioneering work in the field of solid-state-NMR for the analysis of structure and dynamics of polymer systems”. Both laureates received the newly coined Flory Prize Medal. The next conference in the series, POLYCHAR 19, will be held in Kathmandu, Nepal from March 20 to 24, 2011. It will be hosted by Prof. Rameshwar Adhikari.

Disulfonimide‐Catalyzed Asymmetric Vinylogous and Bisvinylogous Mukaiyama Aldol Reactions

We thank Caroline Gawlik for technical support. Furthermore, help from our analytical departments, especially the NMR, HPLC, and MS facilities is gratefully acknowledged. We thank Sanofi-Aventis, the Max-Planck-Society, the DFG (Priority Program Organocatalysis SPP1179), and the Fonds der Chemischen Industrie for funding.

Sweets for Catalysis – Facile Optimisation of Carbohydrate‐Based Bis(oxazoline) Ligands (Eur. J. Org. Chem. 7/2009)

AbstractThe cover picture shows various uses for carbohydrates in nature: Chitin in the exoskeleton of crustaceans (lower left corner), cellulose in plants (upper right corner) and as the energy‐storage compound sucrose in plants, which ultimately makes its way into sweets such as candy canes. In the laboratory, carbohydrates can be transformed into interesting and versatile tools for stereoselective synthesis such as chiral ligands for asymmetric catalysis. The article by M. M. K. Boysen on p. 997 ff describes carbohydrate‐based bis(oxazoline) ligands. These sweets for catalysis were successfully fine‐tuned for asymmetric cyclopropanation reactions by the introduction of O‐substituents with varying steric and electronic properties. The authors thank Anja Glinschert for her help with the cover design. Financial support of the German Research Foundation, VolkswagenFoundation and Fonds der Chemischen Industrie is gratefully acknowledged.

Graphical Abstract: Eur. J. Org. Chem. 7/2009

AbstractThe cover picture shows various uses for carbohydrates in nature: Chitin in the exoskeleton of crustaceans (lower left corner), cellulose in plants (upper right corner) and as the energy‐storage compound sucrose in plants, which ultimately makes its way into sweets such as candy canes. In the laboratory, carbohydrates can be transformed into interesting and versatile tools for stereoselective synthesis such as chiral ligands for asymmetric catalysis. The article by M. M. K. Boysen on p. 997 ff describes carbohydrate‐based bis(oxazoline) ligands. These sweets for catalysis were successfully fine‐tuned for asymmetric cyclopropanation reactions by the introduction of O‐substituents with varying steric and electronic properties. The authors thank Anja Glinschert for her help with the cover design. Financial support of the German Research Foundation, VolkswagenFoundation and Fonds der Chemischen Industrie is gratefully acknowledged.

A Grp on the Hsp90 Mechanism

In a recent issue of Molecular Cell, Dollins et al. (2007) present the crystal structure of Grp94, which highlights the similarity between Grp94 and Hsp90 and provides insight into the resting state of Grp94 and potentially other Hsp90 family members.

Rubber Stamp-type Decisions for Funding of Academic Research: Paradigms and Conflicts of Interest

In review of Guardians of Science: Fairness and Reliability of Peer Review (Daniel, 1993), it was suggested that some of the peer review decisions discussed in the book might be of a type of rubber stamp approval... (Moran, 1995, p. 92). decisions in question related articles published in honor of Prof. Jan Thesing. Some of these articles were funded by Deutsche Forschungsgemeinshaft (DFG), Fonds der Chemischen Industrie (FCI), and the chemical company, Merck. Thesing's career included high positions at DFG, FCI, Merck, and on the editorial board of Angewandte Chemie (the chemical journal in which these articles in honor of Thesing were published).The rubber stamp aspect of peer review decisions in this case is based on overlapping, interlocking industrial-governmental-academic complex... (Moran, 1995, p. 91), in which prestigious professors, experts in their field, have key positions in funding agencies, professional and learned societies, industrial companies, and editorial leadership at prestigious academic journals. It would appear that situations such as these would lead type of rubber stamp peer review decision process (both for approvals and rejections) regarding funding of research as well as publications of research results.In fact, very strong recent trends in academia toward university-industrial partnerships (and various types of collaboration that result in financial gain for the university) increase the possibility and likelihood for rubber stamp-type funding decisions. Much has been written on the subject, often referred as academic capitalism. One of the most penetrating studies in this field is the book by Sheldon Krimsky (2003), Science in the Private Interest: Has the Lure of Profits Corrupted Biomedical Research? word corrupted in the subtitle indicates that issues relating information ethics are directly involved, including clash between the traditional academic ethic of search for the truth and the primary business motive of financial gain. Such clash involves questions of bias, conflicts of interest, etc.Paradigms and Academic ControversiesIn general, much research funding is awarded and distributed for studies that conform paradigms of specific academic disciplines. In academic controversies, grant applications for research and studies that contest the reigning tend get rubber stamp rejection. notion of paradigm can extend specific agenda, or position in research (so-called advocacy research.) Along this line, the John Templeton Foundation recently gave very large sum the Gruter Institute For Law and Behavioral Research, as grant to develop that will investigate the role of values in free economic system (Gruter Institute, 2005, p. 1). Most likely, proposal study The Virtues of Marxism and the Evils of Capitalism would receive rubber stamp rejection from Gruter.Also within the realm of paradigms is what Broad and Wade (1982) describe as old-boy in which, for example, at the National Science Foundation, program managers rely on trusted friends in the academic community.... These friends recommend their friends as reviewers, resulting in a monopoly game of grantsmanship (pp. 100-101). In such network, members are drawn from the same elite groups and institutions that end up receiving the of the grants (p. 100). In this and similar settings, the terms monopoly, and bulk of, would go hand in hand with rubber stamp grant approval.In Hans Ruesch's (1992) Naked Empress: Or the Great Medical Fraud, chapter subtitle is Stop Funding Dissenters. Ruesch describes how Irving Bross received no National Cancer Institute (NCI) funding after Bross released findings that were critical of some of NCI's policies and operations. (pp. 76-77). And Ruesch states that an NCI official, Gio Gori, was fired after he contested some aspects of the cancer research (p. …

Low‐Valent Titanium−Pentafulvene Complexes − Formation of Dinuclear Titanium−Nitrogen Complexes (Eur. J. Inorg. Chem. 6/2005)

The cover picture shows a high-yield, one-step synthesis of end-on bridged dinuclear titanium−dinitrogen complexes using Cp*TiCl3, N2 and pentafulvenes under reductive conditions. The Cp* as well as the fulvene ligands are arranged in a stereoregular manner along the Ti−N≡N−Ti axis, both in the solid state as well as in solution, as proved by extensive NMR measurements. Details are discussed in the article by R. Beckhaus et al. on p. 1003 ff. In a similar way a nitrogen-free, low-coordinated titanium complex is obtained by using sterically demanding benzofulvenes. We thank the Fonds der Chemischen Industrie for a kindly granted scholarship (A. S.).

Synthesis, Molecular Structure, and Reactivity of Iridium(I) and Iridium(III) Complexes Formed by Coordination and C−H Activation of the Substituted Arenes C6H5CH2CH2PiPr2and C6H5OCH2CH2PtBu2

The generous financial support by MCYT (BQU2000-1170), the Deutsche Forschungsgemeinschaft, and the Fonds der Chemischen Industrie (Ph.D. grant to G.C.) is gratefully acknowledged. This research was supported through a European Community Marie Curie fellowship (to G.C., HTMP-CT-2000-00200).

Use of enzymes deactivated by site-directed mutagenesis for the preparation of enantioselective membranes.

Use of enzymes deactivated by site-directed mutagenesis for the preparation of enantioselective membranes.

Stereoselective synthesis of beta-D-mannopyranosides with reactive mannopyranosyl donors possessing a neighboring electron-withdrawing group.

Stereoselective synthesis of beta-D-mannopyranosides with reactive mannopyranosyl donors possessing a neighboring electron-withdrawing group.

ULTRA loaded resins based on the cross-linking of linear poly(ethylene imine). Improving the atom economy of polymer-supported chemistry.

ULTRA loaded resins based on the cross-linking of linear poly(ethylene imine). Improving the atom economy of polymer-supported chemistry.

1,2,3,5-Tetrahydro-1,2,3-methenopentalene, a valence isomer of isoindene: synthesis and Diels-Alder reactions.

A strong pyramidalization of the double bond in the Diels–Alder adducts 3, as suggested by quantum-chemical calculations and NMR spectroscopic data, is probably the reason why these very reactive compounds are observable at best at low temperatures. The title compound 2, required for preparation of 3, was prepared in five steps from benzvalene 1.

Cyanoethynylethenes: A Class of Powerful Electron Acceptors for Molecular Scaffolding We thank the ETH Research Council and the Fonds der Chemischen Industrie for their support of this work. Robin Gist is acknowledged for the supply of starting materials.

Ausgedehnte π-Elektronenacceptoren wie 1 wurden durch die Aneinanderreihung von neuartigen Cyanoethinylethenen hergestellt. Elektrochemische Analysen zeigen, dass die Acceptorstärke von der Länge der π-Elektronenkonjugation abhängt und eine lineare Korrelation zwischen der Elektronenaffinität (B3LYP, 3-21G) und dem ersten Reduktionspotential besteht.