Molecular modelling of dendrimers for nanoscale applications

Dendrimers are well defined, highly branched macromolecules that radiate from a central core and are synthesized through a stepwise, repetitive reaction sequence that guarantees complete shells for each generation, leading to polymers that are monodisperse. The synthetic procedures developed for dendrimer preparation permit nearly complete control over the critical molecular design parameters, such as size, shape, surface/interior chemistry, flexibility, and topology. Recent results suggest that dendritic polymers may provide the key to developing a reliable and economical fabrication and manufacturing route to functional nanoscale materials that would have unique properties (electronic, optical, opto-electronic, magnetic, chemical, or biological). In turn, these could be used in designing new nanoscale devices. In this paper, we determine the 3D molecular structure of various dendrimers with continuous configurational Boltzmann biased direct Monte Carlo method and study their energetic and structural properties using molecular dynamics after annealing these molecular representations

Preparation, Structure, and Reactivity of Nonstabilized Organoiron Compounds. Implications for Iron-Catalyzed Cross Coupling Reactions

A series of unprecedented organoiron complexes of the formal oxidation states −2, 0, +1, +2, and +3 is presented, which are largely devoid of stabilizing ligands and, in part, also electronically unsaturated (14-, 16-, 17- and 18-electron counts). Specifically, it is shown that nucleophiles unable to undergo β-hydride elimination, such as MeLi, PhLi, or PhMgBr, rapidly reduce Fe(3+) to Fe(2+) and then exhaustively alkylate the metal center. The resulting homoleptic organoferrate complexes [(Me4Fe)(MeLi)][Li(OEt2)]2 (3) and [Ph4Fe][Li(Et2O)2][Li(1,4-dioxane)] (5) could be characterized by X-ray crystal structure analysis. However, these exceptionally sensitive compounds turned out to be only moderately nucleophilic, transferring their organic ligands to activated electrophiles only, while being unable to alkylate (hetero)aryl halides unless they are very electron deficient. In striking contrast, Grignard reagents bearing alkyl residues amenable to β-hydride elimination reduce FeXn (n = 2, 3) to clusters of the formal composition [Fe(MgX)2]n. The behavior of these intermetallic species can be emulated by structurally well-defined lithium ferrate complexes of the type [Fe(C2H4)4][Li(tmeda)]2 (8), [Fe(cod)2][Li(dme)]2 (9), [CpFe(C2H4)2][Li(tmeda)] (7), [CpFe(cod)][Li(dme)] (11), or [Cp*Fe(C2H4)2][Li(tmeda)] (14). Such electron-rich complexes, which are distinguished by short intermetallic Fe−Li bonds, were shown to react with aryl chlorides and allyl halides; the structures and reactivity patterns of the resulting organoiron compounds provide first insights into the elementary steps of low valent iron-catalyzed cross coupling reactions of aryl, alkyl, allyl, benzyl, and propargyl halides with organomagnesium reagents. However, the acquired data suggest that such C−C bond formations can occur, a priori, along different catalytic cycles shuttling between metal centers of the formal oxidation states Fe(+1)/Fe(+3), Fe(0)/Fe(+2), and Fe(−2)/Fe(0). Since these different manifolds are likely interconnected, an unambiguous decision as to which redox cycle dominates in solution remains difficult, even though iron complexes of the lowest accessible formal oxidation states promote the reactions most effectively

Domestic heating behaviour and room temperatures: Empirical evidence from Scottish homes

In this paper, we describe patterns of residential heating based on data from 255 homes in and around Edinburgh, Scotland, UK, spanning August 2016 to June 2018. We describe: (i) the room temperatures achieved, (ii) the diurnal durations of heating use, and (iii) common diurnal patterns of heating behaviour. We investigate how these factors vary between weekdays and weekends, over the course of the year, by external temperature, and by room type. We compare these empirical findings with the simplifying assumptions about heating patterns found in the UK’s Standard Assessment Procedure (SAP), a widely-used building energy performance model. There are areas of concurrence and others of substantial difference with these model assumptions. Indoor achieved temperatures are substantially lower than SAP assumptions. The duration and timings of heating use vary substantially between homes and along lines of season and outdoor temperature, whereas the SAP model assumes no such variation. Little variation is found along the lines of weekday vs. weekend, whereas the SAP model assumes differences, or between living space and other rooms, consistent with the SAP. The results are relevant for those interested in how SAP assumptions regarding household heating behaviours and achieved indoor temperatures concur with empirical data

Gas-Phase Lubrication of ta-C by Glycerol and Hydrogen Peroxide. Experimental and Computer Modeling

Tetrahedrally coordinated hydrogen-free amorphous diamond-like carbon coating (denoted as ta-C) presents ultralow friction under boundary lubrication conditions at 80 °C in presence of OH-containing molecules. To understand the mechanism of ultralow friction, we performed gas-phase lubrication experiments followed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses and this using two simple molecules: deuterated glycerol and hydrogen peroxide. The experiments were complemented by computer simulations using the ReaxFF reactive force field. These simulations suggest a ta-C surface rich in sp^2 carbon with some reactive sp^1 carbon atoms, in agreement with previous energy filtered transmission electron microscopy (EFTEM) results. Sliding simulations show that the carbon surface atoms react with glycerol and hydrogen peroxide to form OH-termination. Moreover, the hydroxylation is then followed by the chemical dissociation of some of the glycerol molecules leading to the formation of water. This is in agreement with the secondary ion mass spectrometry (SIMS) analyses and mass spectrometer results obtained with gas-phase lubrication experiments with the same molecules. Both experimental and computer simulations strongly suggest that the hydroxylation of the carbon surface is at the origin of ultralow friction together with the formation of water-rich film in the sliding interface

Force Dynamics in Weakly Vibrated Granular Packings

The oscillatory force F_b^ac on the bottom of a rigid, vertically vibrated, grain filled column, reveals rich granular dynamics, even when the peak acceleration of the vibrations is signicantly less than the gravitational acceleration at the earth's surface. For loose packings or high frequencies, F_b^ac 's dynamics are dominated by grain motion. For moderate driving conditions in more compact samples, grain motion is virtually absent, but F_b^ac nevertheless exhibits strongly nonlinear and hysteretic behavior, evidencing a granular regime dominated by nontrivial force-network dynamics.Comment: 4 pages, 5 figure

Superlubricity mechanism of diamond-like carbon with glycerol. Coupling of experimental and simulation studies

We report a unique tribological system that produces superlubricity under boundary lubrication conditions with extremely little wear. This system is a thin coating of hydrogen-free amorphous Diamond-Like-Carbon (denoted as ta-C) at 353 K in a ta-C/ta-C friction pair lubricated with pure glycerol. To understand the mechanism of friction vanishing we performed ToF-SIMS experiments using deuterated glycerol and 13C glycerol. This was complemented by first-principles-based computer simulations using the ReaxFF reactive force field to create an atomistic model of ta-C. These simulations show that DLC with the experimental density of 3.24 g/cc leads to an atomistic structure consisting of a 3D percolating network of tetrahedral (sp3) carbons accounting for 71.5% of the total, in excellent agreement with the 70% deduced from our Auger spectroscopy and XANES experiments. The simulations show that the remaining carbons (with sp2 and sp1 character) attach in short chains of length 1 to 7. In sliding simulations including glycerol molecules, the surface atoms react readily to form a very smooth carbon surface containing OH-terminated groups. This agrees with our SIMS experiments. The simulations find that the OH atoms are mostly bound to surface sp1 atoms leading to very flexible elastic response to sliding. Both simulations and experiments suggest that the origin of the superlubricity arises from the formation of this OH-terminated surface

Polynomials for Torus Links from Chern-Simons Gauge Theories

Invariant polynomials for torus links are obtained in the framework of the Chern-Simons topological gauge theory. The polynomials are computed as vacuum expectation values on the three-sphere of Wilson line operators representing the Verlinde algebra of the corresponding rational conformal field theory. In the case of the $SU(2)$ gauge theory our results provide explicit expressions for the Jones polynomial as well as for the polynomials associated to the $N$-state ($N>2$) vertex models (Akutsu-Wadati polynomials). By means of the Chern-Simons coset construction, the minimal unitary models are analyzed, showing that the corresponding link invariants factorize into two $SU(2)$ polynomials. A method to obtain skein rules from the Chern-Simons knot operators is developed. This procedure yields the eigenvalues of the braiding matrix of the corresponding conformal field theory.Comment: 50 page

Past Choices/Present Landscapes: The Impact of Urban Renewal on the Twin Cities.

Urban renewal was designed to clean up and rebuild our deteriorating American cities. In the 1950s clearance and new construction were emphasized. In the 1960s attention turned to rehabilitation. By 1989 the program was mostly forgotten, but it left an indelible mark on the landscapes of the cities. Martin and Goddard trace the history of urban renewal in Minneapolis and St. Paul, looking at both downtown and neighborhood projects. They document the social and political processes that guided local renewal decisions, demonstrating that urban renewal in the Twin Cities was substantially different from elsewhere