Browsing by Subject "Chirality"
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Item Open Access Chiral ceramic nanoparticles and peptide catalysis(American Chemical Society, 2017) Jiang S.; Chekini, M.; Qu, Z.-B.; Wang Y.; Yeltik A.; Liu, Y.; Kotlyar, A.; Zhang, T.; Li, B.; Demir, Hilmi Volkan; Kotov, N. A.The chirality of nanoparticles (NPs) and their assemblies has been investigated predominantly for noble metals and II-VI semiconductors. However, ceramic NPs represent the majority of nanoscale materials in nature. The robustness and other innate properties of ceramics offer technological opportunities in catalysis, biomedical sciences, and optics. Here we report the preparation of chiral ceramic NPs, as represented by tungsten oxide hydrate, WO3-x·H2O, dispersed in ethanol. The chirality of the metal oxide core, with an average size of ca. 1.6 nm, is imparted by proline (Pro) and aspartic acid (Asp) ligands via bio-to-nano chirality transfer. The amino acids are attached to the NP surface through C-O-W linkages formed from dissociated carboxyl groups and through amino groups weakly coordinated to the NP surface. Surprisingly, the dominant circular dichroism bands for NPs coated by Pro and Asp are different despite the similarity in the geometry of the NPs; they are positioned at 400-700 nm and 500-1100 nm for Pro- and Asp-modified NPs, respectively. The differences in the spectral positions of the main chiroptical band for the two types of NPs are associated with the molecular binding of the two amino acids to the NP surface; Asp has one additional C-O-W linkage compared to Pro, resulting in stronger distortion of the inorganic crystal lattice and greater intensity of CD bands associated with the chirality of the inorganic core. The chirality of WO3-x·H2O atomic structure is confirmed by atomistic molecular dynamics simulations. The proximity of the amino acids to the mineral surface is associated with the catalytic abilities of WO3-x·H2O NPs. We found that NPs facilitate formation of peptide bonds, leading to Asp-Asp and Asp-Pro dipeptides. The chiroptical activity, chemical reactivity, and biocompatibility of tungsten oxide create a unique combination of properties relevant to chiral optics, chemical technologies, and biomedicine.Item Open Access Chiral metamaterials: From negative index to asymmetric transmission(IEEE, 2013) Mutlu, Mehmet; Li, Zhaofeng; Özbay, EkmelChiral metamaterials are attractive for their intriguing properties such as negative refractive index, optical activity and circular dichroism, and asymmetric transmission. In this paper, we review the research we have conducted for the purpose of investigating these exciting properties. © 2013 EurAAP.Item Open Access Functionalized carbon nanotubes and device applications(IOP, 2004) Çıracı, Salim; Dağ, Sefa; Yıldırım, T.; Gülseren, Oğuz; Senger, Ramazan TuğrulCarbon nanotubes, in which the two-dimensional hexagonal lattice of graphene is transformed into a quasi-one-dimensional lattice by conserving the local bond arrangement, provide several structural parameters for engineering novel physical properties suitable for ultimate miniaturization. Recent interest in nanoscience and nanotechnology has driven a tremendous research activity in carbon nanotubes, which has dealt with a variety of problems and produced a number of new results. Most of the effort has gone into revealing various physical properties of nanotubes and functionalizing them in different ways. This paper covers a narrow region in this enormous research field and reviews only a limited number of recent studies which fit within its scope. First, we examine selected physical properties of bare carbon nanotubes, and then study how the mechanical and electronic properties of different tubes can be modified by radial strain, structural defects and adsorption of foreign atoms and molecules. Magnetization of carbon nanotubes by foreign atom adsorption has been of particular interest. Finally, we discuss specific device models as well as fabricated devices which exploit various properties of carbon nanotubes.Item Open Access Landau quantization of two-dimensional heavy holes, energy spectrum of magnetoexcitons and Auger-recombination lines(2013) Podlesny I.V.; Moskalenko, S.A.; Hakioǧlu, T.; Kiselyov, A.A.; Gherciu L.The Landau quantization of the two-dimensional (2D) heavy holes, its influence on the energy spectrum of 2D magnetoexcitons, as well as their optical orientation are studied. The Hamiltonian of the heavy holes is written in two-band model taking into account the Rashba spin-orbit coupling (RSOC) with two spin projections, but with nonparabolic dispersion law and third-order chirality terms. The most Landau levels, except three with m=0,1,2, are characterized by two quantum numbers m-3 and m for m≥3 for two spin projections correspondingly. The difference between them is determined by the third-order chirality. Four lowest Landau levels (LLLs) for heavy holes were combined with two LLLs for conduction electron, which were taken the same as they were deduced by Rashba in his theory of spin-orbit coupling (SOC) based on the initial parabolic dispersion law and first-order chirality terms. As a result of these combinations eight 2D magnetoexciton states were formed. Their energy spectrum and the selection rules for the quantum transitions from the ground state of the crystal to exciton states were determined. On this base such optical orientation effects as spin polarization and magnetoexciton alignment are discussed. The continuous transformation of the shake-up (SU) into the shake-down (SD) recombination lines is explained on the base of nonmonotonous dependence of the heavy hole Landau quantization levels as a function of applied magnetic field. © 2013 Elsevier B.V. All rights reserved.Item Open Access Multiband one-way polarization conversion in complementary split-ring resonator based structures by combining chirality and tunneling(OSA - The Optical Society, 2015) Serebryannikov, A. E.; Beruete, M.; Mutlu, M.; Özbay, EkmelMultiband one-way polarization conversion and strong asymmetry in transmission inspired by it are demonstrated in ultrathin sandwiched structures that comprise two twisted aperture-type arrays of complementary split-ring resonators (CSRRs), metallic mesh, and dielectric layers. The basic features of the resulting mechanism originate from the common effect of chirality and tunneling. The emphasis is put on the (nearly) perfect polarization conversion of linear incident polarization into the orthogonal one and related diodelike asymmetric transmission within multiple narrow bands. Desired polarization conversion can be obtained at several resonances for one of the two opposite incidence directions, whereas transmission is fully blocked for the other one. The resonances, at which the (nearly) perfect conversion takes place, are expected to be inherited from similar structures with parallel, i.e., not rotated CSRR arrays that do not enable chirality and, thus, polarization conversion. It is found that the basic transmission and polarization conversion features and, thus, the dominant physics are rather general, enabling efficient engineering of such structures. The lowest-frequency resonance can be obtained in structures made of conventional materials with total thickness less than λ?/ 50 and up to ten such resonances can correspond to thickness less than λ ?/ 20 . ©2015 Optical Society of America.Item Open Access Supramolecular chirality in self-assembled peptide amphiphile nanostructures(Royal Society of Chemistry, 2015) Garifullin, R.; Güler, Mustafa O.Induced supramolecular chirality was investigated in the self-assembled peptide amphiphile (PA) nanosystems. Having shown that peptide chirality can be transferred to the covalently-attached achiral pyrene moiety upon PA self-assembly, the chiral information is transferred to molecular pyrene via weak noncovalent interactions. In the first design of a supramolecular chiral system, the chromophore was covalently attached to a peptide sequence (VVAGH) via an ε-aminohexanoic acid spacer. Covalent attachment yielded a PA molecule self-assembling into nanofibers. In the second design, the chromophore was encapsulated within the hydrophobic core of self-assembled nanofibers of another PA consisting of the same peptide sequence attached to lauric acid. We observed that supramolecular chirality was induced in the chromophore by PA assembly into chiral nanostructures, whether it was covalently attached, or noncovalently bound.Item Open Access Supramolecular peptide nanofiber morphology affects mechanotransduction of stem cells(American Chemical Society, 2017-08) Arslan, Elif; Koc,, Meryem Hatip; Uysal, Ozge; Dikecoglu, Begum; Topal, Ahmet E.; Garifullin, Ruslan; Ozkan, Alper D.; Dana, A.; Hermida-Merino, D.; Castelletto, V.; Edwards-Gayle, C.; Baday, S.; Hamley, I.; Tekinay, Ayse B.; Güler, Mustafa O.Chirality and morphology are essential factors for protein function and interactions with other biomacromolecules. Extracellular matrix (ECM) proteins are also similar to other proteins in this sense; however, the complexity of the natural ECM makes it difficult to study these factors at the cellular level. The synthetic peptide nanomaterials harbor great promise in mimicking specific ECM molecules as model systems. In this work, we demonstrate that mechanosensory responses of stem cells are directly regulated by the chirality and morphology of ECM-mimetic peptide nanofibers with strictly controlled characteristics. Structural signals presented on l-amino acid containing cylindrical nanofibers (l-VV) favored the formation of integrin β1-based focal adhesion complexes, which increased the osteogenic potential of stem cells through the activation of nuclear YAP. On the other hand, twisted ribbon-like nanofibers (l-FF and d-FF) guided the cells into round shapes and decreased the formation of focal adhesion complexes, which resulted in the confinement of YAP proteins in the cytosol and a corresponding decrease in osteogenic potential. Interestingly, the d-form of twisted-ribbon like nanofibers (d-FF) increased the chondrogenic potential of stem cells more than their l-form (l-FF). Our results provide new insights into the importance and relevance of morphology and chirality of nanomaterials in their interactions with cells and reveal that precise control over the chemical and physical properties of nanostructures can affect stem cell fate even without the incorporation of specific epitopes.