Sharif Digital Repository

Two enantiomerically pure chiral dioxidomolybdenum(VI) complexes (1 and 2) of the type [MoO2L] (L = dianionic, tetradentate ONNO-ligand) were synthesized and investigated in enantioselective oxidation reactions. The solid-state structures of complex 1 and 2, determined via single-crystal X-ray diffraction analysis revealed two fundamentally different coordination geometries: a C1-symmetric cis-β isomer (Λ-1), and a C2-symmetric cis-α isomer (Δ-2). In both cases, only one of the two possible helical enantiomers (Λ- or Δ-helix) was formed. The complexes were examined as precatalysts in the epoxidation of the challenging prochiral substrate trans-stilbene, using either tert-butyl hydroperoxide... 

We study the problem of stability of chiral states, also known as problem of chirality, within the framework of a two-dimensional approximation of a symmetric double-well potential. We show how the symmetry breaking of the potential due to the molecular parity violation can stop the tunneling in a coherent way, accordingly stabilize the chiral states. Then, we use the quantum Brownian motion within a linear Lindblad-type equation to model how the intermolecular interactions make the tunneling incoherent, thus inducing a racemization by dephasing. Finally, we investigate the normal physical conditions where the dephasing racemization does not suppress the effects of the molecular parity... 

Reaction of 2-pyridinecarboxaldehyde with L-Alaninol (as a chiral amine) or 2-amino-2-methyl-1-propanol (AMP) in the presence of PdCl2 produced the new and attractive palladium(II) complexes which were synthesized by in situ method. The presence of an extra methyl group in AMP other than L-Alaninol induced the different chelating mode and, therefore, several structurally different palladium complexes obtained. Correspondingly, the chiral amine with PdCl2 produced the imine product, (Iminol (1)), and an oxazolidine compound (Imizol (1′)) as minor product. Also, the use of AMP in formation of palladium complexes led to the synthesis of imine (Ampynol (2)) and oxazolidine (Ampyzol (3))... 

Anomalies arising from nonplanar triangle diagrams of noncommutative gauge theory are studied. Local chiral gauge anomalies for both noncommutative U(1) and U(N) gauge theories with adjoint matter fields are shown to vanish. For noncommutative QED with fundamental matters, due to UV/IR mixing a finite anomaly emerges from the nonplanar contributions. It involves a generalized *-product of gauge fields  

Discrimination of chiral targets is generally achieved with chiral nanomaterials. However, the limited number of intrinsic chiral nanostructures as well as their complex synthesis procedure has led to the production of chirality-induced nanomaterials as alternatives. Chirality can be induced in nanomaterials by either chirality transfer or the formation of chiral assemblies. Using the latter approach, in this work, we have provided chiral supramolecular assemblies of CdTe quantum dots (QDs) from achiral starting materials. CTAB-QD assemblies showed chiroptical activities, and their orange emission in combination with the blue emission of carbon dots was utilized as a ratiometric chiral... 

A nonlocal continuum-based model is derived to simulate the dynamic behavior of bridged carbon nanotube-based nano-scale mass detectors. The carbon nanotube (CNT) is modeled as an elastic Euler-Bernoulli beam considering von-Kármán type geometric nonlinearity. In order to achieve better accuracy in characterization of the CNTs, the geometrical properties of an attached nano-scale particle are introduced into the model by its moment of inertia with respect to the central axis of the beam. The inter-atomic long-range interactions within the structure of the CNT are incorporated into the model using Eringen's nonlocal elastic field theory. In this model, the mass can be deposited along an... 

In this study, we apply the monitoring master equation describing decoherence of internal states to an optically active molecule prepared in a coherent superposition of nondegenerate internal states interacting with thermal photons at low temperatures. We use vibrational Raman scattering theory up to the first chiral-sensitive contribution, i.e., the mixed electric-magnetic interaction, to obtain scattering amplitudes in terms of molecular polarizability tensors. The resulting density matrix is used to obtain elastic decoherence rates  

The first asymmetric synthesis of α,β-disubstituted γ-phosphono sulfonates is reported. The key step is the Michael addition of a lithiated enantiopure sulfonate bearing an inexpensive chiral sugar auxiliary to α,β-unsaturated phosphonates in good diastereoselectivities. After chromatographic purification, the cleavage of the chiral sugar auxiliary proceeds without any epimerization or racemization to form the corresponding isopropyl sulfonate in very good overall yield (75%) and excellent diastereomeric and enantiomeric excess (de, ee ≥ 95%). © 2009 Elsevier Ltd. All rights reserved  

When the interface of a superconductor (SC) with a Weyl semimetal (WSM) supports Fermi arcs, the chirality blockade eliminates the induction of superconductivity into the bulk of time-reversal symmetry (TRS) breaking WSM. This leaves the Fermi arc states as the only low-energy degrees of freedom in the proximity problem. Therefore the SC|WSM system will be a platform to probe transport properties which involve only the Fermi arcs. With a boundary condition that flips the spin at the boundary, we find a Z2 protected Bogoliubov Fermi contour (BFC) around which the Bogoliubov quasiparticles disperse linearly. The resulting BFC and excitations around it leave a distinct T2 temperature dependence... 

The asymmetric transmission (AT) has attracted wide attention due to its novel applications. In this paper, we propose and investigate a tunable polarization-dependent intrinsically chiral graphene metasurface composed of split ring arrays in terahertz (THz) region. The resonance frequency of the structure is sensitive to the graphene chemical potential. Circular conversion dichroism (CCD) of the proposed structure is tunable and is reached to 0.36. Our work paths a new approach to propose some other compact and on-chip polarization-dependent structures in THz region. Furthermore, our proposed structure could be a useful segment in polarization-dependent systems. © 2019 Elsevier B.V  

Chiral discrimination has always been a hot topic in chemical, food and pharmaceutical industries, especially when dealing with chiral drugs. Enantiomeric recognition not only leads to better understanding of the mechanism of molecular recognition in biological systems, but may further assist in developing useful molecular devices in biochemical and pharmaceutical studies. By emerging nanotechnology and exploiting nanomaterials in sensing applications, a great deal of attention has been given to the design of optical nanoprobes that are able to discriminate enantiomers of chiral analytes. This review explains how engineering nanoparticles (NPs) with desired physicochemical properties allows... 

A series of bifunctional Cu-ZnO-ZrO2/H-Y catalysts of different compositions were prepared by coprecipitating sedimentation method and were characterized by surface area and XRD analyses. The catalytic performance in synthesis of tetrahydrofuran was evaluated and optimized in a three-phase slurry batch reactor. The experimental results showed that the appropriate ratio of Cu/ZnO in the hydrogenation catalyst was 50/45, for which the conversion of maleic anhydride (MA) and selectivity of tetrahydrofuran (THF) reached 100% and 46%, respectively, at 50 bar and 493 K after 6 h of operation. Also, according to these results, it was demonstrated that the incorporation of zirconium oxide in the... 

Benzopyrans, or chromenes, are widespread in nature and are considered to be a privileged scaffold in medicinal chemistry. Herein, we report the first organocatalyzed asymmetric synthesis of chiral benzopyrans. The benzopyran unit is constructed through a domino reaction involving an oxa-Michael attack of salicylic aldehyde derivatives onto α,β-unsaturated aldehydes, activated through iminium-ion formation with the organocatalyst, followed by an intramolecular aldol reaction and subsequent elimination of water. This overall reaction sequence provides benzopyrans with aromatic C-2 substituents in up to 60% yield and 60% enantioselectivity, while C-2 aliphatic analogues can be obtained in 90%... 

We explore the interplay between tunneling process and chiral interactions in the discrimination of chiral states for an ensemble of molecules in a biological environment. Each molecule is described by an asymmetric double-well potential and the environment is modeled as a bath of harmonic oscillators. We carefully analyze different time-scales appearing in the resulting master equation at both weak- and strong-coupling limits. The corresponding results are accompanied by a set of coupled differential equations characterizing optical activity of the molecules. We show that, at the weak-coupling limit, chiral interactions prohibit the coherent racemization induced by decoherence effects and...