A Density Functional Theory Study of Poly (vinyl chloride) (PVC) Free Radical Polymerization

Summary: Quantum chemistry was applied to the free radical polymerization of Vinyl Chloride with the aim of elucidating the reaction kinetics and especially the formation of structural defects and low molecular weight polymer. The radical reactions were studied using the Density Functional Theory. All calculations were performed with B3LYP functionals and in particular the 6-31G(d,p) basis set was selected to evaluate the exchange and correlation energies. The computational method was first validated by predicting the rate constant of the propagation step and comparing the calculated values to experimental ones. Then intramolecular chain transfer, β-scission and branching reactions were also investigated, due to their direct connection with the production of defects in the growing chains. A comparison of the evaluated kinetic constants of such secondary reactions with other computational evaluations and experimental data was finally made.     

One- and two-photon absorption and emission properties of a Zn(II) chemosensor

This paper presents the synthesis and two photon-induced absorption (TPA) properties of a functionalized distyrylbenzene (DSB) 1 containing a tetra-azacyclododecane (cyclen) receptor for Zn(II). The influence of Zn(II) on one- and two-photon absorption characteristics of 1 has been investigated in dimethyl sulfoxide. The experiments show that the TPA action spectrum of uncomplexed 1, at 750 nm employing nanosecond-long excitation pulses, is 5 times more intense than that of the complexed form. This moderate contrast between the bound and unbound species confirms, however, the potential of this design scheme for the development of molecular structures with enhanced sensitivity and contrast to be used as Zn(II) sensors through TPA-induced fluorescence microscopy.     

Distance distributions of short polypeptides recovered by fluorescence resonance energy transfer in the 10 A domain

Fluorescence resonance energy transfer (FRET) between tryptophan (Trp) as donor and 2,3-diazabicyclo[2.2.2]oct-2-ene (Dbo) as acceptor was studied by steady-state and time-resolved fluorescence spectroscopy. The unique feature of this FRET pair is its exceptionally short F?rster radius (10 A), which allows one to recover distance distributions in very short structureless peptides. The technique was applied to Trp-(GlySer)n-Dbo-NH2 peptides with n = 0-10, for which the average probe/quencher distance ranged between 8.7 and 13.7 A experimentally (in propylene glycol, analysis according to wormlike chain model) and 8.6-10.2 A theoretically (for n = 0-6, GROMOS96 molecular dynamics simulations). The larger FRET efficiency in steady-state compared to time-resolved fluorescence experiments was attributed to a static quenching component, suggesting that a small but significant part (ca. 10%) of the conformations are already in van der Waals contact when excitation occurs.     

Synthetic polymers and biomembranes. How do they interact? Atomistic molecular dynamics simulation study of PEO in contact with a DMPC lipid bilayer

The understanding of interactions of poly(ethylene glycol) (PEG) or poly(ethylene oxide) (PEO) with biological interfaces has important technological application in industry and in medicine. In this paper, structural and dynamical properties of PEO at the dimyristoylphospatidylcholine (DMPC) bilayer/water interface have been investigated by molecular dynamics (MD) and steered molecular dynamics (SMD) simulations. The structural properties of a PEO chain in bulk water, at the water/vacuum interface, and in the presence of the membrane were compared with available experimental data. The presence of a barrier for the PEO penetration into the DMPC bilayer has been found. A qualitative estimation of the barrier provided a value equal to approximately 19 kJ/mol, that is, 7 times the value of kT at 310 K.     

ADMM for the SDP relaxation of the QAP

Semidefinite programming, SDP, relaxations have proven to be extremely strong for many hard discrete optimization problems. This is in particular true for the quadratic assignment problem, QAP, arguably one of the hardest NP-hard discrete optimization problems. There are several difficulties that arise in efficiently solving the SDP relaxation, e.g., increased dimension; inefficiency of the current primal–dual interior point solvers in terms of both time and accuracy; and difficulty and high expense in adding cutting plane constraints. We propose using the alternating direction method of multipliers ADMM in combination with facial reduction, FR, to solve the SDP relaxation. This first order approach allows for: inexpensive iterations, a method of cheaply obtaining low rank solutions; and a trivial way of exploiting the FR for adding cutting plane inequalities. In fact, we solve the doubly nonnegative, DNN, relaxation that includes both the SDP and all the nonnegativity constraints. When compared to current approaches and current best available bounds we obtain robustness, efficiency and improved bounds.     

Essential oils of Daucus carota subsp. carota of Tunisia obtained by supercritical carbon dioxide extraction

The essential oils and supercritical CO2 extracts of wild Daucus carota L. subsp. carota from two different sites in Tunisia were investigated. The main components of the essential oil of the flowering and mature umbels with seeds from Sejnane were eudesm-7(11)-en-4-ol (8.2 - 8.5%), carotol (3.5 - 5.2%), sabinene (12.0 -14.5%), a-selinene (7.4 - 8.6) and 11-alpha-(H)-himachal-4-en-1-beta-ol (12.7 - 17.4%), whereas the oils from Tunis were predominantly composed of elemicin (31.5 - 35.3%) and carotol (48.0 - 55.7%). The antimicrobial activity of the essential oils were assayed by using the broth dilution method on Escherichia coli ATCC 35218 and Staphylococcus aureus ATCC 43300, and clinical strains of Candida albicans and C. tropicalis 1011 RM. The MIC values obtained were all > 2.5% (v/v).     

New water-soluble platinum(II) phenanthroline complexes tested as cisplatin analogues: First-time comparison of cytotoxic activity between analogous four- and five-coordinate species

Four- and five-coordinate platinum(II) complexes, cis-[PtCl2(A2)] (1) and [PtCl2(A2)(eta2-ethylene)] (2) {A2 = 4,7-diphenyl-1,10-phenanthroline disulfonic acid disodium salt, BPS (mixture of isomers) (a); 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline disulfonic acid disodium salt, BCS (mixture of isomers) (b)} have been synthesized and characterized by 1H, 13C, and 195Pt NMR spectroscopy. The stability and high water solubility of complexes 1a, 1b and 2b, due to the presence of the polar SO3- groups on the ligands skeleton, allowed to test their in vitro cytotoxicity on HeLa tumour cells in a wide range of drug concentration. At low and medium incubation doses (<200 microM) 1a, 1b and 2b all showed similar in vitro cytotoxicity, negligible or much lower with respect to cisplatin. At doses higher than 200 microM their activity increased and 1b, the most active among the new complexes, exhibited a cytotoxicity comparable, although still lower, with respect to cisplatin. GFAAS Platinum analytical data showed that the tested compounds 1a, 1b and 2b, although carrying sulfonate charged groups, may undergo cellular uptake, which, in the case of 1b and 2b, is even higher with respect to cisplatin. Furthermore, in the case of 1b and 2b it has been possible to compare, for the first time, the cytotoxic activity for square-planar four-coordinate and trigonal-bipyramidal five-coordinate platinum(II) complexes having the same carrier ligand. The tendency of the five-coordinate species 2b to give at longer incubation time similar cytotoxicity with respect to the square-planar compound 1b suggests a possible use of the trigonal-bipyramidal five-coordinate complexes as prodrugs.     

Ferroelectricity of pyridinium perchlorate, a molecular level point of view

The behavior of ferroelectric and thermodynamic parameters of pyridinium perchlorate (PyClO(4)) was simulated based on experimental NMR data and properties of the individual constituting ions. Dynamic (2)H NMR spectroscopy was used to investigate the order-disorder character of ferroelectricity in PyClO(4). Quadrupole echo and inversion recovery experiments were performed in the range from 140 to 300 K. The spectra can be simulated by a rotational jump motion of the pyridinium cations about their pseudo-C(6) axis. This confirms that the ferroelectricity of this compound below a first-order phase transition at 248 K is primarily due to the ordering of cations along a ferroelectric axis. In an intermediate phase between 248 and 233 K, the cation-anion sublattice displacement mechanism also gives a small positive contribution to ferroelectricity. In the family of the ferroelectric pyridinium salts, the paraelectric-ferroelectric phase transition temperature increases with the size and polarizability of the constituting anions, suggesting that the main interaction for ferroelectric ordering occurs via an indirect superexchange mechanism, whereas in compounds with small anions of low polarizability the direct dipole-dipole interaction dominates and leads to antiferroelectric order.     

Ubiquitin Associates with the N‐Terminal Domain of Nerve Growth Factor: The Role of Copper(II) Ions

Many biochemical pathways involving nerve growth factor (NGF), a neurotrophin with copper(II) binding abilities, are regulated by the ubiquitin (Ub) proteasome system. However, whether NGF binds Ub and the role played by copper(II) ions in modulating their interactions have not yet been investigated. Herein NMR spectroscopy, circular dichroism, ESI‐MS, and titration calorimetry are employed to characterize the interactions of NGF with Ub. NGF_1–14, which is a short model peptide encompassing the first 14 N‐terminal residues of NGF, binds the copper‐binding regions of Ub (K_D=8.6 10^?5 m ). Moreover, the peptide undergoes a random coil–polyproline type II helix structural conversion upon binding to Ub. Notably, copper(II) ions inhibit NGF_1–14/Ub interactions. Further experiments performed with the full‐length NGF confirmed the existence of a copper(II)‐dependent association between Ub and NGF and indicated that the N‐terminal domain of NGF was a valuable paradigm that recapitulated many traits of the full‐length protein.     

Two natural products from the algae Laurencia scoparia

The structures and absolute stereochemistries of two chamigrene-type metabolites (spiro­[5.5]­un­decane derivatives) isolated from the red algae Laurencia scoparia are described. One, a non-sesquiterpene named ma?lione (8-bromo-9-hydroxy-7,7-di­methyl-11-methyl­ene­spiro­[5.5]­undec-1-en-3-one), C₁₄H₁₉BrO₂, was detected previously in Laurencia cartilaginea, while the other, the sesquiterpene isorigidol (8-bromo-3,7,7-tri­methyl-11-methyl­ene­spiro­[5.5]-undec-1-ene-3,9-diol), C₁₅H₂₃BrO₂, is a new isomer of rigidol, first isolated from Laurencia rigida. The A rings of these spiro­cyclic compounds show the same carbon skeleton. However, the relative stereochemistry of the 8-Br and 9-OH substituents is different. While ma?lione displays the usual syn (or cis) relative stereochemistry of the bromo­hydroxy vicinal group, isorigidol shows an anti (or trans) arrangement. The 8-Br and 9-OH groups are both in equatorial positions in isorigidol, while the 9-OH group is axial in ma?lione, as in most chamigrenes. The absolute configurations of the chiral centers were determined as 6S, 8S and 9R in ma?lione, and 3R, 6S, 8S and 9S in isorigidol.