Institut de Chimie de Strasbourg

CHARMM (Chemistry at HARvard Molecular Mechanics) is a highly versatile and widely used molecular simulation program. It has been developed over the last three decades with a primary focus on molecules of biological interest, including proteins, peptides, lipids, nucleic acids, carbohydrates, and small molecule ligands, as they occur in solution, crystals, and membrane environments. For the study of such systems, the program provides a large suite of computational tools that include numerous conformational and path sampling methods, free energy estimators, molecular minimization, dynamics, and analysis techniques, and model-building capabilities. The CHARMM program is applicable to problems involving a much broader class of many-particle systems. Calculations with CHARMM can be performed using a number of different energy functions and models, from mixed quantum mechanical-molecular mechanical force fields, to all-atom classical potential energy functions with explicit solvent and various boundary conditions, to implicit solvent and membrane models. The program has been ported to numerous platforms in both serial and parallel architectures. This article provides an overview of the program as it exists today with an emphasis on developments since the publication of the original CHARMM article in 1983.

The purpose of this critical review is to give a representative and comprehensive overview of the arising developments in the field of magnetic metal-organic frameworks, in particular those containing cobalt(II). We examine the diversity of magnetic exchange interactions between nearest-neighbour moment carriers, covering from dimers to oligomers and discuss their implications in infinite chains, layers and networks, having a variety of topologies. We progress to the different forms of short-range magnetic ordering, giving rise to single-molecule-magnets and single-chain-magnets, to long-range ordering of two- and three-dimensional networks (323 references).

Oxidative stress is known to play an important role in the pathogenesis of a number of diseases. In particular, it is linked to the etiology of Alzheimer's disease (AD), an age-related neurodegenerative disease and the most common cause of dementia in the elderly. Histopathological hallmarks of AD are intracellular neurofibrillary tangles and extracellular formation of senile plaques composed of the amyloid-beta peptide (Aβ) in aggregated form along with metal-ions such as copper, iron or zinc. Redox active metal ions, as for example copper, can catalyze the production of Reactive Oxygen Species (ROS) when bound to the amyloid-β (Aβ). The ROS thus produced, in particular the hydroxyl radical which is the most reactive one, may contribute to oxidative damage on both the Aβ peptide itself and on surrounding molecule (proteins, lipids, …). This review highlights the existing link between oxidative stress and AD, and the consequences towards the Aβ peptide and surrounding molecules in terms of oxidative damage. In addition, the implication of metal ions in AD, their interaction with the Aβ peptide and redox properties leading to ROS production are discussed, along with both in vitro and in vivo oxidation of the Aβ peptide, at the molecular level.

This recommendation proposes a definition for the term “halogen bond”, which designates a specific subset of the inter- and intramolecular interactions involving a halogen atom in a molecular entity.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPhotoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and EfficacyPetr Klán*†‡, Tomáš Šolomek†‡, Christian G. Bochet§, Aurélien Blanc∥, Richard Givens⊥, Marina Rubina⊥, Vladimir Popik#, Alexey Kostikov#, and Jakob Wirz∇View Author Information† Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, 625 00 Brno, Czech Republic‡ Research Centre for Toxic Compounds in the Environment, Faculty of Science, Masaryk University, Kamenice 3, 625 00 Brno, Czech Republic§ Department of Chemistry, University of Fribourg, Chemin du Musée 9, CH-1700 Fribourg, Switzerland∥ Institut de Chimie, University of Strasbourg, 4 rue Blaise Pascal, 67000 Strasbourg, France⊥ Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, 5010 Malott Hall, Lawrence, Kansas 66045, United States# Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States∇ Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland*E-mail: [email protected]. Phone: +420-54949-4856. Fax: +420-54949-2443.Cite this: Chem. Rev. 2013, 113, 1, 119–191Publication Date (Web):December 21, 2012Publication History Received29 April 2012Published online21 December 2012Published inissue 9 January 2013https://doi.org/10.1021/cr300177kCopyright © 2012 American Chemical SocietyRIGHTS & PERMISSIONSACS AuthorChoiceArticle Views77851Altmetric-Citations1248LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (17 MB) Get e-AlertscloseSUBJECTS:Alcohols,Fluorescence,Irradiation,Organic compounds,Reaction products Get e-Alerts

Intersystem crossing (ISC), formally forbidden within nonrelativistic quantum theory, is the mechanism by which a molecule changes its spin state. It plays an important role in the excited state decay dynamics of many molecular systems and not just those containing heavy elements. In the simplest case, ISC is driven by direct spin-orbit coupling between two states of different multiplicities. This coupling is usually assumed to remain unchanged by vibrational motion. It is also often presumed that spin-allowed radiationless transitions, i.e. internal conversion, and the nonadiabatic coupling that drives them, can be considered separately from ISC and spin-orbit coupling owing to the vastly different time scales upon which these processes are assumed to occur. However, these assumptions are too restrictive. Indeed, the strong mixing brought about by the simultaneous presence of nonadiabatic and spin-orbit coupling means that often the spin, electronic, and vibrational dynamics cannot be described independently. Instead of considering a simple ladder of states, as depicted in a Jablonski diagram, one must consider the more complicated spin-vibronic levels. Despite the basic ideas being outlined in the 1960s, it is only with the advent of high-level theory and femtosecond spectroscopy that the importance of the spin-vibronic mechanism for ISC in both fundamental as well as applied research fields has been revealed with significant impact across chemistry, physics, and biology. In this review article, we present the theory and fundamental principles of the spin-vibronic mechanism for ISC. This is followed by empirical rules to estimate the rate of ISC within this regime. The most recent developments in experimental techniques, theoretical methods, and models for the spin-vibronic mechanism are discussed. These concepts are subsequently illustrated with examples, including the ISC mechanisms in transition metal complexes, small organic molecules, and organic chromophores.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTMultimetallic Catalysis Based on Heterometallic Complexes and ClustersPaulin Buchwalter*, Jacky Rosé*, and Pierre Braunstein*View Author Information Laboratoire de Chimie de Coordination (UMR 7177 CNRS), Institut Le Bel - Université de Strasbourg, 4, rue Blaise Pascal F-67081, Strasbourg, France*Tel.: +33 3 68851308. E-mail: [email protected]*E-mail: [email protected]*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 1, 28–126Publication Date (Web):December 29, 2014Publication History Received14 April 2014Published online29 December 2014Published inissue 14 January 2015https://pubs.acs.org/doi/10.1021/cr500208khttps://doi.org/10.1021/cr500208kreview-articleACS PublicationsCopyright © 2014 American Chemical SocietyRequest reuse permissionsArticle Views16019Altmetric-Citations650LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Catalysts,Cluster chemistry,Hydrocarbons,Hydrogenation,Selectivity Get e-Alerts

More than 40 antimicrobial peptides and proteins (AMPs) are expressed in the oral cavity. These AMPs have been organized into 6 functional groups, 1 of which, cationic AMPs, has received extensive attention in recent years for their promise as potential antibiotics. The goal of this review is to describe recent advances in our understanding of the diverse mechanisms of action of cationic AMPs and the bacterial resistance against these peptides. The recently developed peptide GL13K is used as an example to illustrate many of the discussed concepts. Cationic AMPs typically exhibit an amphipathic conformation, which allows increased interaction with negatively charged bacterial membranes. Peptides undergo changes in conformation and aggregation state in the presence of membranes; conversely, lipid conformation and packing can adapt to the presence of peptides. As a consequence, a single peptide can act through several mechanisms depending on the peptide's structure, the peptide:lipid ratio, and the properties of the lipid membrane. Accumulating evidence shows that in addition to acting at the cell membrane, AMPs may act on the cell wall, inhibit protein folding or enzyme activity, or act intracellularly. Therefore, once a peptide has reached the cell wall, cell membrane, or its internal target, the difference in mechanism of action on gram-negative and gram-positive bacteria may be less pronounced than formerly assumed. While AMPs should not cause widespread resistance due to their preferential attack on the cell membrane, in cases where specific protein targets are involved, the possibility exists for genetic mutations and bacterial resistance. Indeed, the potential clinical use of AMPs has raised the concern that resistance to therapeutic AMPs could be associated with resistance to endogenous host-defense peptides. Current evidence suggests that this is a rare event that can be overcome by subtle structural modifications of an AMP.

The authors report the implementation of a simple one-step method for obtaining an infinite-order two-component (IOTC) relativistic Hamiltonian using matrix algebra. They apply the IOTC Hamiltonian to calculations of excitation and ionization energies as well as electric and magnetic properties of the radon atom. The results are compared to corresponding calculations using identical basis sets and based on the four-component Dirac-Coulomb Hamiltonian as well as Douglas-Kroll-Hess and zeroth-order regular approximation Hamiltonians, all implemented in the DIRAC program package, thus allowing a comprehensive comparison of relativistic Hamiltonians within the finite basis approximation.

Recent years have seen the rapid development of a new field of palladium catalysis in organic synthesis. This chemistry takes place outside the usually encountered Pd(0)/Pd(II) cycles. It is characterized by the presence of strong oxidants, which prevent further palladium(II)-promoted reactions at a given point of the catalytic cycle by selective metal oxidation. The resulting higher-oxidation-state palladium complexes have been used to develop a series of new synthetic transformations that cannnot be realized within conventional palladium catalysis. This type of catalysis by palladium in a higher oxidation state is of significant synthetic potential.

Weak attractive interactions between closed shell metal ions have been increasingly studied in the last few years and are generally designated as metallophilic interactions. They are best evidenced in the solid state where structural data obtained by X-ray diffraction provide precise information about the distance between the metals involved. The strength of such metal-metal interactions has been compared to that of hydrogen bonding (ca. 7-11 kcal mol(-1)) and is clearly sufficient to bring about novel bonding and structural features and confer interesting physical properties such as luminescence, polychromism, magnetism or one-dimensional electrical conductivity. The Cu(I)-Cu(I), Ag(I)-Ag(I) and Au(I)-Au(I) interactions have been increasingly observed and the latter have certainly been the most studied. Early qualitative analyses of the aurophilic attraction focused on Au-Au bonding originating from 6s, 6p and 5d orbital mixing. Numerous theoretical studies on metallophilic interactions continue to be carried out at various levels of sophistication which take into account relativistic and correlation effects to describe these van der Waals-type interactions. In this critical review, we would like to focus on the synthesis and structures of heterometallic clusters of the transition metals in which intra- rather than intermolecular d(10)-d(10) interactions are at work, in order to limit the role of packing effects. We wish to provide the reader with a comparative overview of the metal core structures resulting from or favoring metallophilic interactions but do not intend to provide a comprehensive coverage of the literature. We will first examine heterometallic clusters displaying homometallic and then heterometallic d(10)-d(10) interactions. Although the focus of this review is on d(10)-d(10) interactions involving metals from the group 11, we shall also briefly examine for comparison some complexes displaying intramolecular d(10)-d(10) interactions involving metals from other groups (188 references).

Abstract Ultrathin metal–organic framework (MOF) nanosheets (NSs) offer potential for many applications, but the synthetic strategies are largely limited to top‐down, low‐yield exfoliation methods. Herein, Ni–M–MOF (M=Fe, Al, Co, Mn, Zn, and Cd) NSs are reported with a thickness of only several atomic layers, prepared by a large‐scale, bottom‐up solvothermal method. The solvent mixture of N , N ‐dimethylacetamide and water plays key role in controlling the formation of these two‐dimensional MOF NSs. The MOF NSs can be directly used as efficient electrocatalysts for the oxygen evolution reaction, in which the Ni–Fe–MOF NSs deliver a current density of 10 mA cm −2 at a low overpotential of 221 mV with a small Tafel slope of 56.0 mV dec −1 , and exhibit excellent stability for at least 20 h without obvious activity decay. Density functional theory calculations on the energy barriers for OER occurring at different metal sites confirm that Fe is the active site for OER at Ni–Fe–MOF NSs.

Abstract Metal–organic frameworks (MOFs), which consist of central metal nodes and organic linkers, constitute a fast growing class of crystalline porous materials with excellent application potential. Herein, a series of Mn‐based multimetallic MOF (bimetallic and trimetallic MIL‐100) nano‐octahedra are prepared by a facile one‐pot synthetic strategy. The types and proportions of the incorporated elements can be tuned while retaining the original topological structure. The introduction of other metal ions is verified at the atomic level by combining X‐ray absorption fine structure experiments and theoretical calculations. Furthermore, these multimetallic Mn‐based MIL‐100 nano‐octahedra are utilized as sulfur hosts to prepare cathodes for Li–S batteries. The MnNi‐MIL‐100@S cathode exhibits the best Li–S battery performance among all reported MIL‐100@S composite cathode materials, with a reversible capacity of ≈708.8 mAh g −1 after 200 cycles. The synthetic strategy described herein is utilized to incorporate metal ions into the MOF architecture, of which the parent monometallic MOF nano‐octahedra cannot be prepared directly, thus rationally generating novel multimetallic MOFs. Importantly, the strategy also allows for the general synthesis and study of various micro‐/nanoscale MOFs in the energy storage field.

The emergence of N-heterocyclic carbenes as ligands across the Periodic Table had an impact on various aspects of the coordination, organometallic, and catalytic chemistry of the 3d metals, including Cu, Ni, and Co, both from the fundamental viewpoint but also in applications, including catalysis, photophysics, bioorganometallic chemistry, materials, etc. In this review, the emergence, development, and state of the art in these three areas are described in detail.

We present the syntheses, structural characterization, gas sorption, I2 uptake, and magnetic properties of a double-walled porous metal-organic framework, [Co(II)3(lac)2(pybz)2]·3DMF (1·3DMF, purple, where pybz = 4-pyridyl benzoate, lac = d- and l-lactate) and of its post-synthetic modified (PSM) congeners, [Co(II)3(lac)2(pybz)2]·xGuest (xGuest = 6MeOH, purple; 4.5EtOH, purple; 3PrOH, purple; 2C6H6, purple; 2.7I2, black), [Co(II)3(lac)2(pybz)2] (1, purple), [Co(II)3(pybz)2(lac)2(H2O)2]·7H2O (1a·7H2O, green), and [Co(III)Co(II)2(pybz)2(lac)2(H2O)2]I·2H2O·1.5DMSO (1b·I(-)·2H2O·1.5DMSO, yellow, DMSO = dimethyl sulfoxide). Crystallography shows that the framework is not altered by the replacement of DMF by different solvents or by the removal of the solvent molecules during the single-crystal to single-crystal (SC-SC) transformations, while upon exchange with H2O or partial oxidation by molecular iodine, the crystallinity is affected. 1 absorbs N2, H2, CH4, CH3OH, C2H5OH, PrOH, C6H6, and I2, but once it is in contact with H2O the absorption efficiency is drastically reduced. Upon PSM, the magnetism is transformed from a canted antiferromagnet (1·3DMF and 1·xGuest) to single-chain magnet (1), to a ferrimagnet (1a·7H2O), and to a ferromagnet (1b·I(-)·2H2O·1.5DMSO). Raman spectroscopy suggests the color change (purple to green 1a·7H2O or yellow 1b·I(-)·2H2O·1.5DMSO) is associated with a change of geometry from a strained octahedron due to the very acute chelating angle (∼60°) of the lactate of a cobalt center to a regular octahedron with a monodentate carboxylate and one H2O. The magnetic transformation is explained by the different interchain exchanges (J'), antiferromagnetic for 1·3DMF and 1·xSolvent (J' < 0), SCM for 1 (J' verge to 0), and ferromagnetic for 1a·7H2O (J' > 0), between homometal topological ferrimagnetic chains (two octahedral and one tetrahedral Co(II) ions) connected by the double walls of pybz at 13.3 Å (shortest Co···Co). For 1b·I(-)·2H2O·1.5DMSO the moment of the tetrahedral site is turned off, thus stabilizing a ferromagnetic state (J' > 0). The present stabilization of four magnetic ground states is unique in the field of metal-organic frameworks as well as the electrical conductivity of 1·2.7I2.

Summary The results obtained by the author in the study of clay‐minerals diagenesis are compared critically with the principal publications in this field, giving a general picture of the transformation of sheet silicates. Kaolinite minerals are related to the surficial zones of the earth's crust where they are formed. They are characterized by the hexacoordination of aluminium. They furnish paleogeographic indications in ancient sediments. During diagenesis they are very sensitive to the geochemical environment, stable in acid conditions, unstable in alkaline conditions. However, the increase in temperature by burial causes their destruction sooner or later. In the transitional zone to metamorphism (anchizone), kaolinite is not present. Only dickite and nacrite can be observed, provided that the environment is acid. Montmorillonites are hydrated minerals. The rise in temperature and above all in pressure during burial expels water from the interlayers. Concentrated interstitial solutions of diagenesis provide cations which replace molecules of water between the layers. It is an irreversible reaction which produces 14‐Å minerals (chlorites) or 10‐Å minerals (illites), passing generally through mixed‐layer structures. The lack of montmorillonite is normal in formations which have undergone a marked burial. Mixed‐layers are intermediate stages which occur during degradation by weathering and during aggradation by deep diagenesis. This aggradation is the result of an incorporation of certain cations taken up from interstitial solutions, and of a rearrangement within the lattice. There are two major pathways: a potassium and sodium pathway, which produces the illites, then the micas, passing possibly by regular mixed‐layering of the allevardite‐rectorite type; and a magnesium pathway, which produces the chlorites, passing possibly by a regular mixed‐layering of the corrensite type. These mixed‐layers can remain stable until the border of meta‐morphism (anchizone). Micaceous clay minerals or illites form a very heterogenous group in the sediments which have been hardly diagenetized. Particles of diverse origin are found. They become more regular during burial. In deep diagenesis and the anchizone, crystallo‐graphic parameters of the illite are sufficiently well defined to serve as a scale of recrystallization, a zoneographic index. The morphology of the particles changes. Polymorphic types 1Md and 1M are replaced by the 2M‐type. The sharpness of the 10‐Å peak, conventionally called “crystallinity”, is an interesting quantitative criterium, together with the intensity ratio of the 5‐Å and 10‐Å peaks, which is related to the chemical composition of the octahedral layer. Micas in low‐grade metamorphism, called sericites by petrographers, replace the illites discussed above. They are different from the true micas by a weaker layer charge, less than 0.9 by half‐cell. They often contain sodium (paragonitic muscovites and paragonites). The octahedral charge (zero for the muscovite) is generally high, due to the replacement of Al by Fe 2+ and Mg (phengites). These transformations should not obscure the fact that metamorphism is also accompanied by crystalline growth and massive neoformation. Chlorites are the least well‐known clay minerals in diagenesis. Detrital particles can be aggraded to chlorite during early diagenesis by passing through the mixed‐layer stage of corrensite. A massive growth of chlorite is observed in late diagenesis and the anchizone. Illite and chlorite slates give place to sericite and chlorite schists. At present, general data are not available on the crystal chemistry of chlorites in the anchizone and the greenschist facies. The stages in the diagenetic evolution of clay minerals are too little understood to be able to give them precise limits. However, the following provisional scheme can be proposed: ( 1 ) Early diagenesis (= “diagenesis” of Russian authors; = the “shallow‐burial stage” of M üller , 1967a). In this stage all the clay minerals are stable; some undergo aggradation by adsorption of Mg, K and Na (various mixed‐layers); some are neoformed (montmorillonites). ( 2 ) Middle diagenesis (= “early catagenesis or epigenesis” of Russian authors; the “deep‐burial stage” of M üller , 1967a, includes this stage and all the following until metamorphism). In this stage the sediment becomes compact. It has lost at least 50% of its connate water. Porosity is high and circulation still plays an essential part. Some detrital minerals, such as biotite, are unstable. All the clay minerals are still stable, but many types of replacement take place, due to interstitial circulation. Dickitization of kaolinite and illitization of montmorillonite can already be observed. ( 3 ) Deep or late diagenesis (= “late catagenesis or epigenesis” of Russian authors). In this stage the temperature is greater than 100 °C, pressure increases and porosity becomes very weak. Montmorillonites and irregular mixed‐layers disappear. Kaolinite recrystallizes as dickite in acid environment. These changes are irreversible. ( 4 ) Anchizone (= “metagenesis” of Russian authors; = “zone anchimétamorphique” of K ubler , 1964). This is the transitional zone to metamorphism. It agrees with temperatures around 200 °C. Illite and chlorite are almost the only sheet silicates. However, dickite can be observed as well as pyrophyllite generally associated with allevardite. The crystallographic parameters of illite define the limit of the following zone, the metamorphic epizone or greenschist facies. The crystallochemical processes that take place during the diagenetic evolution of clay minerals are schematically the following: ( 1 ) Gradual tetracoordination of aluminium. ( 2 ) Filling of octahedral sites either by interlayer cations, either by cations derived from outside the lattice, without the distinction dioctahedral‐trioctahedral becoming very clear. ( 3 ) Interlayer exchange between crystal lattice and interstitial solution. Gradual closing of the layers by alkaline cations or octahedral brucite‐like sheets. ( 4 ) Massive crystalline growth in the anchizone and the epizone. These processes are roughly symmetrical with those which occur during weathering. This review is a summary of the conclusions drawn in a Docteur‐ès‐Sciences thesis (G. D unoyer de S egonzac , 1969: Les Minéraux argileux dans la Diagenèse. Passage au Métamorphisme , 339 p., 45 tables, 110 illus.) to be published as part of the series Mémoires du Service de la Carte Géologique d'Alsace et de Lorraine . Most of the evidence on which these conclusions have been based is not cited directly in this article, but can be found in the thesis mentioned above, to which the reader is referred.

Abstract We report the synthesis and physical study of a series of 1,1‐dicyano‐4‐[4‐(diethylamino)phenyl]buta‐1,3‐dienes in which the number and position of additional CN substituents along the 1,1‐dicyanobuta‐1,3‐dienyl fragment is systematically varied. While X‐ray analysis provided unambiguous information about molecular geometries in the crystal, UV/Vis and electrochemical measurements, by cyclic voltammetry (CV) and rotating disk voltammetry (RDV), revealed that introduction of additional cyano groups in the C2‐ and C4‐positions most affected the optical properties of these molecules in solution, in terms of intramolecular charge‐transfer absorption energy and intensity. A comparison with structurally related chromophores indicates that the shift of the anilino donor from position 2/3 to 4 along the butadiene scaffold results in a remarkable bathochromic shift of the ICT absorption maxima, mainly due to the higher planarity in the present series. These findings are further corroborated by density functional theory calculations. Preliminary nonlinear optical (NLO) measurements confirm the promise of the new push‐pull chromophores as third‐order nonlinear‐optical molecular materials.

Readily available biphenyl derivatives containing an alkyne unit at one of their ortho positions are converted into substituted phenanthrenes upon exposure to catalytic amounts of either PtCl(2), AuCl(3), GaCl(3), or InCl(3) in toluene. This 6-endo-dig cyclization likely proceeds through initial pi-coordination of the alkyne unit followed by interception of the resulting eta(2)-metal complex by the adjacent arene ring. The reaction is inherently modular, allowing for substantial structural variations and for the incorporation of substituents at any site of the phenanthrene product except C-9. Moreover, the reaction is readily applied to the heterocyclic series as exemplified by the preparation of benzoindoles, naphthothiophenes as well as bridgehead nitrogen heterocycles.

Metal-organic frameworks (MOFs) with controllable shapes and sizes show a great potential in Li-S batteries. However, neither the relationship between shape and specific capacity nor the influence of MOF particle size on cyclic stability have been fully established yet. Herein, MIL-96-Al with various shapes, forming hexagonal platelet crystals (HPC), hexagonal bipyramidal crystals (HBC), and hexagonal prismatic bipyramidal crystals (HPBC) are successfully prepared via cosolvent methods. Density functional theory (DFT) calculations demonstrate that the HBC shape with highly exposed (101) planes can effectively adsorb lithium polysulfides (LPS) during the charge/discharge process. By changing the relative proportion of the cosolvents, HBC samples with different particle sizes are prepared. When these MIL-96-Al crystals are used as sulfur host materials, it is found that those with a smaller size of the HBC shape deliver higher initial capacity. These investigations establish that different crystal planes have different adsorption abilities for LPS, and that the MOF particle size should be considered for a suitable sulfur host. More broadly, this work provides a strategy for designing sulfur hosts in Li-S batteries.

It has recently been demonstrated that dopamine solutions put in contact with a variety of solid substrates allow the production of thin coatings probably made of melanin (Science 2007, 318, 426). In this article, we show that the thickness of these coatings can be controlled to allow a growth regime that is proportional to the reaction time if fresh dopamine is regularly provided. We propose that the growth is initiated by the adsorption of a radical compound. When dopamine polymerization or aggregation has reached a steady state in solution, the produced species do not adhere anymore to the substrate, emphasizing the role played by unoxidized dopamine. X-ray photoelectron spectroscopy showed that the thickness of the deposit increases linearly with the number of immersion steps, but the thickness measured in ultravacuum is about 4 times smaller than the thickness measured by ellipsometry in conditions of ambient humidity. This suggests that the drying of the deposit has a considerable influence on its properties. The Si2p signal characteristic of the silicon substrate decreases progressively when the number of deposition steps increases but does vanish even after 32 deposition steps. This observation will be discussed with respect to the formation of a continuous film. Cyclic voltammetry experiments showed that a deposit impermeable to ferrocyanide is obtained after the immersion in nine freshly prepared dopamine solutions, demonstrating the formation of a film. The atomic composition of the film determined by X-ray photoelectron spectroscopy is compatible with that of melanin. Finally, we show that the deposit can be quantitatively removed from the substrate when put in a strongly alkaline solution.