58 research outputs found
Influence of Metal, Ligand and Solvent on Supramolecular Polymerizations with Transition-Metal Compounds: A Theoretical Study
The nature of intermolecular interactions governing supramolecular polymerizations is very important to control their cooperativity. In order to address this problem, supramolecular columns made of Pt(II) and Pd(II) complexes of oligo(phenyleneethynylene)-based pyridine (OPE) and tetrazolyl-pyridine ligands (TEP) were investigated through the dispersion-corrected PM6 method. Aromatic, CH-π, M-Cl and metallophilic interactions helped stabilize the supramolecules studied, and their geometries and associated cooperativities were in excellent agreement with experimental data. The OPE ligand and/or the presence of Pt(II) have led to stronger metallophilic interactions and also to cooperative supramolecular polymerizations, which clearly suggests that metallophilic interactions are a key factor to control cooperativity. The results indicate that sequential monomer addition is in general less spontaneous than the combination of two larger pre-formed stacks. The present theoretical investigations contribute to the further understanding of the relation between the thermodynamics of supramolecular polymerizations and the nature of different synthons
Secure Sharing of PHR Data Using Re-Encryption: SESPHR
We propose a technique called SeSPHR for secure sharing of the PHRs in the cloud. The SeSPHR plan guarantees tolerant driven control on the PHRs and jelly the classification of the PHRs. The patients store the scrambled PHRs on the un-confided in cloud servers and specifically award access to various kinds of clients on various segments of the PHRs. A semi-believed intermediary called Setup and Re-encryption Server (SRS) is acquainted with set up people in general/private key sets and to create the re-encryption keys. In addition, the strategy is secure against insider dangers and furthermore implements a forward and in reverse access control. Moreover, we officially examine and confirm the working of SeSPHR strategy through the High Level Petri Nets (HLPN)
Supramolecular Polymerization: A Coarse Grained Molecular Dynamics Study
A coarse-grained
(CG) force field to model the self-assembly of
benzene-1,3,5-tricarboxamide (BTA) class of compounds in nonpolar
solvents has been developed. The model includes an intrinsic point
dipole embedded on one of the CG beads so as to impart a macrodipole
moment to the oligomer, one of its characteristic feature. Chemical
specificity has been preserved by benchmarking against results, including
dimerization and solvation free energies, obtained from an all-atom
representation. Starting from a well-dispersed configuration in <i>n</i>-nonane, BTA molecules self-assemble to form one-dimensional
stacks. Free energy (FE) changes for the various manner in which short
oligomers can exchange between the assembled and the dispersed states
have been calculated. These calculations show BTA to self-assemble
via a downhill cooperative mechanism with a nucleus size of three
Adducts of N-Heterocyclic Drugs, Niacin, Allopurinol, and Amiloride, with 2,4-Pyridinedicarboxylic Acid Coformer
A co-crystallization of three drug molecules, niacin (3-pyridine-carboxylic acid = NIA), allopurinol (pyrazolo(3,4-d)pyrimidin-4-one = ALP), and amiloride (3,5-diamino-6-chloro-pyrazine-2-carbonyl)-guanidine = AMI), with the same coformer, 2,4-pyridinedicarboxylic acid (PDA), resulted in three new crystalline products, (NIA)(PDA) (1), (ALP)2(PDA)·1.5H2O (2), and (AMI)2(PDA)2(H2O)2 (3). The formation of new phases was confirmed by IR spectra and X-ray single-crystal and powder diffraction analysis. The proton transfer resulted in the zwitterionic co-crystal 1. In co-crystal 2, neutral ALP molecules existed in the oxo-tautomeric form. Compound 3 crystallizes as the salt with the guanidinium cationic part as in the started amiloride hydrochloride hydrate, and the PDA coformer as the zwitterionic pyridinium dicarboxylate anion. Thus, the diversity of the PDA coformer ionization states included the neutral, zwitterion, and zwitterion anionic forms. All compounds were layered structures where the heterocyclic molecules were linked in the H-bonded corrugated layers stabilized by the diverse conventional and charge-assisted hydrogen bonds with π-π stacking interactions between the layers supported by the mediated water molecules in 2 and 3. © 2017 American Chemical Society
Solvent clathrate driven dynamic stereomutation of a supramolecular polymer with molecular pockets
Control over the helical organization of synthetic supramolecular systems is intensively pursued to manifest chirality in a wide range of applications ranging from electron spin filters to artificial enzymes. Typically, switching the helicity of supramolecular assemblies involves external stimuli or kinetic traps. However, efforts to achieve helix reversal under thermodynamic control and to understand the phenomena at a molecular level are scarce. Here we present a unique example of helix reversal (stereomutation) under thermodynamic control in the self-assembly of a coronene bisimide that has a 3, 5- dialkoxy substitution on the imide phenyl groups (CBI-35CH), leading to "molecular pockets" in the assembly. The stereomutation was observed only if the CBI monomer possesses molecular pockets. Detailed chiroptical studies performed in alkane solvents with different molecular structures reveal that solvent molecules intercalate or form clathrates within the molecular pockets of CBI-35CH at low temperature (263 K), thereby triggering the stereomutation. The interplay among the helical assembly, molecular pockets, and solvent molecules is further unraveled by explicit solvent molecular dynamics simulations. Our results demonstrate how the molecular design of selfassembling building blocks can orchestrate the organization of surrounding solvent molecules, which in turn dictates the helical organization of the resulting supramolecular assembly
Sulfuric acid and Amberlyst-H\u3csup\u3e+\u3c/sup\u3e catalyzed condensation reactions of renewable keto acids with paraformaldehyde: Synthesis of a new dispiro bis-lactone ring system 2,9,13-trioxadispiro[4.1.4.3]tetradecane-3,6,10-trione
The sulfuric acid and Amberlyst-H+ catalyzed condensation reactions of renewable feedstock levulinic acid with paraformaldehyde under neat conditions at 80 °C gives 2,9,11,14-tetraoxadispiro[4.1.5.3]pentadecane-3,6-dione in 91-93% yield, in which the structure was confirmed by single crystal X-ray crystallography. A similar condensation reaction between 4-ketopimelic acid and paraformaldehyde at 80 °C gives 2,9,13-trioxadispiro[4.1.4.3]tetradecane-3,6,10-trione. This new dispiro bis-lactone was found to composed of a 1.6 : 1 mixture of isomers with planes of symmetry bisecting the tetrahydro-2H-pyran-4-one rings through the carbonyl groups
Development of New Transferable Coarse-Grained Models of Hydrocarbons
We
have utilized an approach that integrates molecular dynamics
(MD) simulations with particle swarm optimization (PSO) to accelerate
the development of coarse-grained (CG) models of hydrocarbons. Specifically,
we have developed new transferable CG beads, which can be used to
model the hydrocarbons (C5 to C17) and reproduce their experimental
properties with good accuracy. First, the PSO method was used to develop
the CG beads of the decane model represented with a 2:1 (2-2-2-2-2)
mapping scheme. This was followed by the development of the nonane
model described with hybrid 2-2-3-2 and 3:1 (3-3-3) mapping schemes.
The force-field parameters for these three CG models were optimized
to reproduce four experimentally observed properties including density,
enthalpy of vaporization, surface tension, and self-diffusion coefficient
at 300 K. The CG MD simulations conducted with these new CG models
of decane and nonane, at different timesteps, for various system sizes,
and at a range of different temperatures, were able to predict their
density, enthalpy of vaporization, surface tension, self-diffusion
coefficient, expansibility, and isothermal compressibility with good
accuracy. Moreover, a comparison of structural features obtained from
the CG MD simulations and the CG beads of mapped all-atom trajectories
of decane and nonane showed very good agreement. To test the chemical
transferability of these models, we have constructed the models for
hydrocarbons ranging from pentane to heptadecane, by using different
combinations of the CG beads of decane and nonane. The properties
of pentane to heptadecane predicted by these new CG models showed
excellent agreement with the experimental data
Supramolecular Polymerization of <i>N</i>,<i>N</i>′,<i>N</i>″,<i>N</i>‴-<i>tetra</i>-(Tetradecyl)-1,3,6,8-pyrenetetracarboxamide: A Computational Study
The role of molecular
dipole orientations and intermolecular interactions
in a derivative of pyrene on its supramolecular self-assembly in solution
has been investigated using quantum chemical and force field based
computational approaches. Five possible dipole configurations of the
molecule have been examined, among which the one in which adjacent
dipole vectors are antiparallel to each other is determined to be
the ground state, on electrostatic grounds. Self-assembly of this
molecule under realistic conditions has been studied using MD simulations.
Dipolar relaxation in its liquid crystalline (LC) phase has been investigated
and contrasted against that in the well-established benzene-1,3,5-tricarboxamide
(BTA) family. The dihedral barrier related to the amide dipole flip
is larger in the pyrene system than in BTA which explains the differences
in their dipolar relaxation behaviors. The mechanism underlying polarization
switching upon the application of an external electric field in the
LC phase is investigated. Unlike in BTA, this switching is not associated
with a reversal of the helical sense of the hydrogen bonded chains,
due to differences in molecular symmetry. The observations enable
general conclusions on the relationship between electric field induced
chiral enhancement and symmetry to be drawn
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