Novel organic LED structures based on a highly conductive polymeric photonic crystal electrode

NASA Astrophysics Data System (ADS)

Petti, Lucia; Rippa, Massimo; Capasso, Rossella; Nenna, Giuseppe; De Girolamo Del Mauro, Anna; Grazia Maglione, Maria; Minarini, Carla

2013-08-01

In this work we demonstrate the possibility to realize a novel unconventional ITO-free organic light emitting diode (OLED) utilizing a photonic polymeric electrode. Combining electron beam lithography and a plasma etching process to partially structure the highly conductive poly(3,4 ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) it is possible to realize an embedded photonic crystal (PC) structure. The realized PC-anode drastically reduces the light trapped in the OLED, demonstrating the possibility to eliminate further process stages and making it easier to use this technology even on rollable and flexible substrates.

Enhanced fluorescence from CdSe/ZnS quantum dot nanophosphors embedded in a one-dimensional photonic crystal backbone structure.

PubMed

Min, Kyungtaek; Choi, Serok; Choi, Yunkyoung; Jeon, Heonsu

2014-11-06

A nano-engineered phosphor structure that produces enhanced fluorescence is reported. Two kinds of polymer materials with different refractive indices are spin-coated alternately to realize a one-dimensional (1D) photonic crystal (PC) phosphor platform, in which CdSe/ZnS core-shell quantum dots (QDs) were embedded as a fluorescence agent. The 1D PC phosphor structure is designed to match the pump photon energy with one of the photonic band-edges (PBEs), where the photon group velocity becomes zero, and thus the interaction between pump photons and fluorescent centres strengthened. A reference phosphor structure is also designed and fabricated; however, it has no PBE and exhibited bulk-like photonic properties. The fluorescence intensity from the 1D PC phosphors is examined during the pump photon energy scanning across the PBE. It is found that fluorescence from the 1D PC phosphor reaches its maximum when the pump photon energy coincides with the PBE, which is consistent with the theoretical prediction. In comparison with the reference phosphor, the fluorescence from the 1D PC phosphor is measured to be enhanced by a factor of 1.36.

Higher-order mode photonic crystal based nanofluidic sensor

NASA Astrophysics Data System (ADS)

Peng, Wang; Chen, Youping; Ai, Wu

2017-01-01

A higher-order photonic crystal (PC) based nanofluidic sensor, which worked at 532 nm, was designed and demonstrated. A systematical and detailed method for sculpturing a PC sensor for a given peak wavelength value (PWV) and specified materials was illuminated. It was the first time that the higher order mode was used to design PC based nanofluidic sensor, and the refractive index (RI) sensitivity of this sensor had been verified with FDTD simulation software from Lumerical. The enhanced electrical field of higher order mode structure was mostly confined in the channel area, where the enhance field is wholly interacting with the analytes in the channels. The comparison of RI sensitivity between fundamental mode and higher order mode shows the RI variation of higher order mode is 124.5 nm/RIU which is much larger than the fundamental mode. The proposed PC based nanofluidic structure pioneering a novel style for future optofluidic design.

Molecular imprinted opal closest-packing photonic crystals for the detection of trace 17β-estradiol in aqueous solution.

PubMed

Sai, Na; Wu, Yuntang; Sun, Zhong; Huang, Guowei; Gao, Zhixian

2015-11-01

A novel opal closest-packing (OCP) photonic crystal (PC) was prepared by the introduction of molecular imprinting technique into the OCP PC. This molecular imprinted (MI)-OCP PC was fabricated via a vertical convective self-assembly method using 17β-estradiol (E2) as template molecules for monitoring E2 in aqueous solution. Morphology characterization showed that the MI-OCP PC possessed a highly ordered three-dimensional (3D) periodically-ordered structure, showing the desired structural color. The proposed PC material displayed a reduced reflection intensity when detecting E2 in water environment, because the molecular imprinting recognition events make the optical characteristics of PC change. The Bragg diffraction intensity decreased by 19.864 a.u. with the increase of E2 concentration from 1.5 ng mL(-1) to 364.5 ng mL(-1) within 6 min, whereas there were no obvious peak intensity changes for estriol, estrone, cholesterol, testosterone and diethylstilbestrol, indicating that the MI-OCP PC had selective and rapid response for E2 molecules. The adsorption results showed that the OCP structure and homogeneous layers were created in the MI-OCP PC with higher adsorption capacity. Thus, it was learned the MI-OCP PC is a simple prepared, sensitive, selective, and easy operative material, which shows promising use in routine supervision for residue detection in food and environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Multiple-decker phthalocyaninato dinuclear lanthanoid(III) single-molecule magnets with dual-magnetic relaxation processes.

PubMed

Katoh, Keiichi; Horii, Yoji; Yasuda, Nobuhiro; Wernsdorfer, Wolfgang; Toriumi, Koshiro; Breedlove, Brian K; Yamashita, Masahiro

2012-11-28

The SMM behaviour of dinuclear Ln(III)-Pc multiple-decker complexes (Ln = Tb(3+) and Dy(3+)) with energy barriers and slow-relaxation behaviour were explained by using X-ray crystallography and static and dynamic susceptibility measurements. In particular, interactions among the 4f electrons of several dinuclear Ln(III)-Pc type SMMs have never been discussed on the basis of the crystal structure. For dinuclear Tb(III)-Pc complexes, a dual magnetic relaxation process was observed. The relaxation processes are due to the anisotropic centres. Our results clearly show that the two Tb(3+) ion sites are equivalent and are consistent with the crystal structure. On the other hand, the mononuclear Tb(III)-Pc complex exhibited only a single magnetic relaxation process. This is clear evidence that the magnetic relaxation mechanism depends heavily on the dipole-dipole (f-f) interactions between the Tb(3+) ions in the dinuclear systems. Furthermore, the SMM behaviour of dinuclear Dy(III)-Pc type SMMs with smaller energy barriers compared with that of Tb(III)-Pc and slow-relaxation behaviour was explained. Dinuclear Dy(III)-Pc SMMs exhibited single-component magnetic relaxation behaviour. The results indicate that the magnetic relaxation properties of dinuclear Ln(III)-Pc multiple-decker complexes are affected by the local molecular symmetry and are extremely sensitive to tiny distortions in the coordination geometry. In other words, the spatial arrangement of the Ln(3+) ions (f-f interactions) in the crystal is important. Our work shows that the SMM properties can be fine-tuned by introducing weak intermolecular magnetic interactions in a controlled SMM spatial arrangement.

Photo-crystallization in a-Se layer structures: Effects of film-substrate interface-rigidity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindberg, G. P.; Gross, N.; Weinstein, B. A.

Amorphous selenium (a-Se) films deposited on rigid substrates can undergo photo-induced crystallization (PC) even at temperatures (T) well below the glass transition, T{sub g} ∼ 313 K. Substrate-generated shear strain is known to promote the PC process. In the present work, we explore the influence of different substrates (Si and glass), and different film-layer-substrate combinations, on the PC in a variety of a-Se films and film-structures. The intermediate layers (indium tin oxide and polyimide) are chosen to promote conductivity and/or to be a buffer against interface strain in structures of interest for digital imaging applications. The PC characteristics in these samples are evaluatedmore » and compared using optical microscopy, atomic-force microscopy, Raman mapping, and T-dependent Raman spectroscopy. Both the presence of a soft intermediate layer, and the thermal softening that occurs for T increasing through T{sub g}, inhibit the tendency for the onset of PC. The extensive PC mapping results in the wide range of samples studied here, as well as the suppression of PC near T{sub g} in this array of samples, strongly support the generality of this behavior. As a consequence, one may expect that the stability of a-Se films against PC can be enhanced by decreasing the rigidity of the film-substrate interface. In this regard, advanced film structures that employ flexible substrates, soft intermediate layers, and/or are designed to be operated near T{sub g} should be explored.« less

Detection of Myoglobin with an Open-Cavity-Based Label-Free Photonic Crystal Biosensor.

PubMed

Zhang, Bailin; Tamez-Vela, Juan Manuel; Solis, Steven; Bustamante, Gilbert; Peterson, Ralph; Rahman, Shafiqur; Morales, Andres; Tang, Liang; Ye, Jing Yong

2013-01-01

The label-free detection of one of the cardiac biomarkers, myoglobin, using a photonic-crystal-based biosensor in a total-internal-reflection configuration (PC-TIR) is presented in this paper. The PC-TIR sensor possesses a unique open optical microcavity that allows for several key advantages in biomolecular assays. In contrast to a conventional closed microcavity, the open configuration allows easy functionalization of the sensing surface for rapid biomolecular binding assays. Moreover, the properties of PC structures make it easy to be designed and engineered for operating at any optical wavelength. Through fine design of the photonic crystal structure, biochemical modification of the sensor surface, and integration with a microfluidic system, we have demonstrated that the detection sensitivity of the sensor for myoglobin has reached the clinically significant concentration range, enabling potential usage of this biosensor for diagnosis of acute myocardial infarction. The real-time response of the sensor to the myoglobin binding may potentially provide point-of-care monitoring of patients and treatment effects.

Achieving an Accurate Surface Profile of a Photonic Crystal for Near-Unity Solar Absorption in a Super Thin-Film Architecture.

PubMed

Kuang, Ping; Eyderman, Sergey; Hsieh, Mei-Li; Post, Anthony; John, Sajeev; Lin, Shawn-Yu

2016-06-28

In this work, a teepee-like photonic crystal (PC) structure on crystalline silicon (c-Si) is experimentally demonstrated, which fulfills two critical criteria in solar energy harvesting by (i) its Gaussian-type gradient-index profile for excellent antireflection and (ii) near-orthogonal energy flow and vortex-like field concentration via the parallel-to-interface refraction effect inside the structure for enhanced light trapping. For the PC structure on 500-μm-thick c-Si, the average reflection is only ∼0.7% for λ = 400-1000 nm. For the same structure on a much thinner c-Si ( t = 10 μm), the absorption is near unity (A ∼ 99%) for visible wavelengths, while the absorption in the weakly absorbing range (λ ∼ 1000 nm) is significantly increased to 79%, comparing to only 6% absorption for a 10-μm-thick planar c-Si. In addition, the average absorption (∼94.7%) of the PC structure on 10 μm c-Si for λ = 400-1000 nm is only ∼3.8% less than the average absorption (∼98.5%) of the PC structure on 500 μm c-Si, while the equivalent silicon solid content is reduced by 50 times. Furthermore, the angular dependence measurements show that the high absorption is sustained over a wide angle range (θinc = 0-60°) for teepee-like PC structure on both 500 and 10-μm-thick c-Si.

The Lamb wave bandgap variation of a locally resonant phononic crystal subjected to thermal deformation

NASA Astrophysics Data System (ADS)

Zhu, Yun; Li, Zhen; Li, Yue-ming

2018-05-01

A study on dynamical characteristics of a ternary locally resonant phononic crystal (PC) plate (i.e., hard scatterer with soft coating periodically disperse in stiff host matrix) is carried out in this paper. The effect of thermal deformation on the structure stiffness, which plays an important role in the PC's dynamical characteristics, is considered. Results show that both the start and the stop frequency of bandgap shift to higher range with the thermal deformation. In particular, the characteristics of band structure change suddenly at critical buckling temperature. The effect of thermal deformation could be utilized for tuning of phononic band structures, which can promote their design and further applications.

EDITORIAL: Photonic Crystal Devices

NASA Astrophysics Data System (ADS)

Bhattacharya, Pallab K.

2007-05-01

The engineering of electromagnetic modes at optical frequencies in artificial dielectric structures with periodic and random variation of the refractive index, enabling control of the radiative properties of the materials and photon localization, was first proposed independently by Yablonovitch and John in 1987. It is possible to control the flow of light in the periodic dielectric structures, known as photonic crystals (PC). As light waves scatter within the photonic crystal, destructive interference cancels out light of certain wavelengths, thereby forming a photonic bandgap, similar to the energy bandgap for electron waves in a semiconductor. Photons whose energies lie within the gap cannot propagate through the periodic structure. This property can be used to make a low-loss cavity. If a point defect, such as one or more missing periods, is introduced into the periodic structure a region is obtained within which the otherwise forbidden wavelengths can be locally trapped. This property can be used to realize photonic microcavities. Similarly, a line of defects can serve as a waveguide. While the realization of three-dimensional (3D) photonic crystals received considerable attention initially, planar two-dimensional (2D) structures are currently favoured because of their relative ease of fabrication. 2D photonic crystal structures provide most of the functionality of 3D structures. These attributes have generated worldwide research and development of sub-μm and μm size active and passive photonic devices such as single-mode and non- classical light sources, guided wave devices, resonant cavity detection, and components for optical communication. More recently, photonic crystal guided wave devices are being investigated for application in microfludic and biochemical sensing. Photonic crystal devices have been realized with bulk, quantum well and quantum dot active regions. The Cluster of articles in this issue of Journal of Physics D: Applied Physics provides a glimpse of some of the most recent advances in the application of photonic crystals. The modelling of PC defect-mode cavities are described by Zhou et al. Ye and co-authors describe the concept and realization of a novel 3D silicon-based spiral PC. It is, in fact, the only article on 3D PCs. The design and realization of ultra-high Q heterostructure PC nanocavities are described by Song and co-authors. The concept of self-collimation of light in PCs and its applications are presented by Prather and co-workers. Experimental and numerical studies on the negative refraction related phenomenon in 2D PCs are the subject of the next article by Ozbay and co-authors. The emerging subject of slow light generation, control and propagation in PCs is presented in the next two articles by Baba and Mori and by Krauss. Finally, the progress made in the development of PC microcavity lasers and electrically injected microcavity light emitters and arrays is described, respectively, by O'Brien et al and by Chakravarty et al. It is hoped that readers will get a sense of the exciting developments and the possibilities presented by heterostructure photonic crystals and their devices from reading the articles in this Cluster.

Band gap in tubular pillar phononic crystal plate.

PubMed

Shu, Fengfeng; Liu, Yongshun; Wu, Junfeng; Wu, Yihui

2016-09-01

In this paper, a phononic crystal (PC) plate with tubular pillars is presented and investigated. The band structures and mode displacement profiles are calculated by using finite element method. The result shows that a complete band gap opens when the ratio of the pillar height to the plate thickness is about 1.6. However, for classic cylinder pillar structures, a band gap opens when the ratio is equal or greater than 3. A tubular pillar design with a void room in it enhances acoustic multiple scattering and gives rise to the opening of the band gap. In order to verify it, a PC structure with double tubular pillars different in size (one within the other) is introduced and a more than 2times band gap enlargement is observed. Furthermore, the coupling between the resonant mode and the plate mode around the band gap is characterized, as well as the effect of the geometrical parameters on the band gap. The behavior of such structure could be utilized to design a pillar PC with stronger structural stability and to enlarge band gaps. Copyright © 2016 Elsevier B.V. All rights reserved.

Microscopy and Chemical Inversing Techniques to Determine the Photonic Crystal Structure of Iridescent Beetle Scales in the Cerambycidae Family

NASA Astrophysics Data System (ADS)

Richey, Lauren; Gardner, John; Standing, Michael; Jorgensen, Matthew; Bartl, Michael

2010-10-01

Photonic crystals (PCs) are periodic structures that manipulate electromagnetic waves by defining allowed and forbidden frequency bands known as photonic band gaps. Despite production of PC structures operating at infrared wavelengths, visible counterparts are difficult to fabricate because periodicities must satisfy the diffraction criteria. As part of an ongoing search for naturally occurring PCs [1], a three-dimensional array of nanoscopic spheres in the iridescent scales of the Cerambycidae insects A. elegans and G. celestis has been found. Such arrays are similar to opal gemstones and self-assembled colloidal spheres which can be chemically inverted to create a lattice-like PC. Through a chemical replication process [2], scanning electron microscopy analysis, sequential focused ion beam slicing and three-dimensional modeling, we analyzed the structural arrangement of the nanoscopic spheres. The study of naturally occurring structures and their inversing techniques into PCs allows for diversity in optical PC fabrication. [1] J.W. Galusha et al., Phys. Rev. E 77 (2008) 050904. [2] J.W. Galusha et al., J. Mater. Chem. 20 (2010) 1277.

Selective nucleation of iron phthalocyanine crystals on micro-structured copper iodide.

PubMed

Rochford, Luke A; Ramadan, Alexandra J; Heutz, Sandrine; Jones, Tim S

2014-12-14

Morphological and structural control of organic semiconductors through structural templating is an efficient route by which to tune their physical properties. The preparation and characterisation of iron phthalocyanine (FePc)-copper iodide (CuI) bilayers at elevated substrate temperatures is presented. Thin CuI(111) layers are prepared which are composed of isolated islands rather than continuous films previously employed in device structures. Nucleation in the early stages of FePc growth is observed at the edges of islands rather than on the top (111) faces with the use of field emission scanning electron microscopy (FE-SEM). Structural measurements show two distinct polymorphs of FePc, with CuI islands edges nucleating high aspect ratio FePc crystallites with modified intermolecular spacing. By combining high substrate temperature growth and micro-structuring of the templating CuI(111) layer structural and morphological control of the organic film is demonstrated.

Enhanced photothermal lens using a photonic crystal surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Yunfei; Liu, Longju; Zhao, Xiangwei

2016-08-15

A photonic crystal (PC)-enhanced photothermal lens (PTL) is demonstrated for the detection of optically thin light absorption materials. The PC-enhanced PTL system is based on a pump-probe scheme consisting of a PC surface, pump laser beam, and probe laser beam. Heated by the pump beam, light absorption materials on the PC surface generate the PTL and cause a substantial change to the guided-mode resonance supported by the PC structure. The change of the PC resonance is detected using the probe laser beam by measuring its reflectivity from the PC surface. When applied to analyze dye molecules deposited on the PCmore » substrate, the developed system is capable of enhancing the PTL signal by 10-fold and reducing the lowest distinguishable concentration by 8-fold, in comparison to measuring without utilizing the PC resonance. The PC-enhanced PTL was also used to detect gold nanoparticles on the PC surface and exhibited a 20-fold improvement of the lowest distinguishable concentration. The PC-enhanced PTL technology offers a potential tool to obtain the absorption signatures of thin films in a broad spectral range with high sensitivity and inexpensive instrumentation. As a result, this technology will enable a broad range of applications of photothermal spectroscopy in chemical analysis and biomolecule sensing.« less

Atomic resolution ADF-STEM imaging of organic molecular crystal of halogenated copper phthalocyanine.

PubMed

Haruta, Mitsutaka; Yoshida, Kaname; Kurata, Hiroki; Isoda, Seiji

2008-05-01

Annular dark-field (ADF) scanning transmission electron microscopy (STEM) measurements are demonstrated for the first time to be applicable for acquiring Z-contrast images of organic molecules at atomic resolution. High-angle ADF imaging by STEM is a new technique that provides incoherent high-resolution Z-contrast images for organic molecules. In the present study, low-angle ADF-STEM is successfully employed to image the molecular crystal structure of hexadecachloro-Cu-phthalocyanine (Cl16-CuPc), an organic molecule. The structures of CuPc derivatives (polyhalogenated CuPc with Br and Cl) are determined quantitatively using the same technique to determine the occupancy of halogens at each chemical site. By comparing the image contrasts of atomic columns, the occupancy of Br is found to be ca. 56% at the inner position, slightly higher than that for random substitution and in good agreement with previous TEM results.

One-way mode transmission in one-dimensional phononic crystal plates

NASA Astrophysics Data System (ADS)

Zhu, Xuefeng; Zou, Xinye; Liang, Bin; Cheng, Jianchun

2010-12-01

We investigate theoretically the band structures of one-dimensional phononic crystal (PC) plates with both antisymmetric and symmetric structures, and show how unidirectional transmission behavior can be obtained for either antisymmetric waves (A modes) or symmetric waves (S modes) by exploiting mode conversion and selection in the linear plate systems. The theoretical approach is illustrated for one PC plate example where unidirectional transmission behavior is obtained in certain frequency bands. Employing harmonic frequency analysis, we numerically demonstrate the one-way mode transmission for the PC plate with finite superlattice by calculating the steady-state displacement fields under A modes source (or S modes source) in forward and backward direction, respectively. The results show that the incident waves from A modes source (or S modes source) are transformed into S modes waves (or A modes waves) after passing through the superlattice in the forward direction and the Lamb wave rejections in the backward direction are striking with a power extinction ratio of more than 1000. The present structure can be easily extended to two-dimensional PC plate and efficiently encourage practical studies of experimental realization which is believed to have much significance for one-way Lamb wave mode transmission.

3D light harnessing based on coupling engineering between 1D-2D Photonic Crystal membranes and metallic nano-antenna.

PubMed

Belarouci, Ali; Benyattou, Taha; Letartre, Xavier; Viktorovitch, Pierre

2010-09-13

A new approach is proposed for the optimum addressing of a metallic nano-antenna (NA) with a free space optical beam. This approach relies on the use of an intermediate resonator structure that provides the appropriate modal conversion of the incoming beam. More precisely, the intermediate resonator consists in a Photonic Crystal (PC) membrane resonant structure that takes benefit of surface addressable slow Bloch modes. First, a phenomenological approach including a deep physical understanding of the NA-PC coupling and its optimization is presented. In a second step, the main features of this analysis are confirmed by numerical simulations (FDTD).

Numerical investigation of diffraction of acoustic waves by phononic crystals

NASA Astrophysics Data System (ADS)

Moiseyenko, Rayisa P.; Declercq, Nico F.; Laude, Vincent

2012-05-01

Diffraction as well as transmission of acoustic waves by two-dimensional phononic crystals (PCs) composed of steel rods in water are investigated in this paper. The finite element simulations were performed in order to compute pressure fields generated by a line source that are incident on a finite size PC. Such field maps are analyzed based on the complex band structure for the infinite periodic PC. Finite size computations indicate that the exponential decrease of the transmission at deaf frequencies is much stronger than that in Bragg band gaps.

Training HBCU Faculty and Students in Prostate Cancer (PC) Research: Signal Transduction and Receptor-Inhibitor Interactions in the Progress of PC

DTIC Science & Technology

2007-03-01

Katrina. Nicole Bell has continued to work on the crystal structures of tyrosine kinase inhibitors. A senior, Aviva Baird , has joined the group and...Sabbatical Internship, Marian Merrell Dow Pharmaceuticals. Participated in drug discovery of compounds that I synthesized; techniques included tumor

Photonic crystals: emerging biosensors and their promise for point-of-care applications.

PubMed

Inan, Hakan; Poyraz, Muhammet; Inci, Fatih; Lifson, Mark A; Baday, Murat; Cunningham, Brian T; Demirci, Utkan

2017-01-23

Biosensors are extensively employed for diagnosing a broad array of diseases and disorders in clinical settings worldwide. The implementation of biosensors at the point-of-care (POC), such as at primary clinics or the bedside, faces impediments because they may require highly trained personnel, have long assay times, large sizes, and high instrumental cost. Thus, there exists a need to develop inexpensive, reliable, user-friendly, and compact biosensing systems at the POC. Biosensors incorporated with photonic crystal (PC) structures hold promise to address many of the aforementioned challenges facing the development of new POC diagnostics. Currently, PC-based biosensors have been employed for detecting a variety of biotargets, such as cells, pathogens, proteins, antibodies, and nucleic acids, with high efficiency and selectivity. In this review, we provide a broad overview of PCs by explaining their structures, fabrication techniques, and sensing principles. Furthermore, we discuss recent applications of PC-based biosensors incorporated with emerging technologies, including telemedicine, flexible and wearable sensing, smart materials and metamaterials. Finally, we discuss current challenges associated with existing biosensors, and provide an outlook for PC-based biosensors and their promise at the POC.

Huge light-enhancement by coupling a Bowtie Nano-antenna's plasmonic resonance to a photonic crystal mode.

PubMed

Eter, Ali El; Grosjean, Thierry; Viktorovitch, Pierre; Letartre, Xavier; Benyattou, Taha; Baida, Fadi I

2014-06-16

We numerically demonstrate a drastic enhancement of the light intensity in the vicinity of the gap of Bowtie Nano-antenna (BA) through its coupling with Photonic Crystal (PC) resonator. The resulting huge energy transfer toward the BA is based on the coupling between two optical resonators (BA and PC membrane) of strongly unbalanced quality factors. Thus, these two resonators are designed so that the PC is only slightly perturbed in term of resonance properties. The proposed hybrid dielectric-plasmonic structure may open new avenues in the generation of deeply subwavelength intense optical sources, with direct applications in various domains such as data storage, non-linear optics, optical trapping and manipulation, microscopy, etc.

2D photonic crystal complete band gap search using a cyclic cellular automaton refination

NASA Astrophysics Data System (ADS)

González-García, R.; Castañón, G.; Hernández-Figueroa, H. E.

2014-11-01

We present a refination method based on a cyclic cellular automaton (CCA) that simulates a crystallization-like process, aided with a heuristic evolutionary method called differential evolution (DE) used to perform an ordered search of full photonic band gaps (FPBGs) in a 2D photonic crystal (PC). The solution is proposed as a combinatorial optimization of the elements in a binary array. These elements represent the existence or absence of a dielectric material surrounded by air, thus representing a general geometry whose search space is defined by the number of elements in such array. A block-iterative frequency-domain method was used to compute the FPBGs on a PC, when present. DE has proved to be useful in combinatorial problems and we also present an implementation feature that takes advantage of the periodic nature of PCs to enhance the convergence of this algorithm. Finally, we used this methodology to find a PC structure with a 19% bandgap-to-midgap ratio without requiring previous information of suboptimal configurations and we made a statistical study of how it is affected by disorder in the borders of the structure compared with a previous work that uses a genetic algorithm.

Switchable Photonic Crystals Using One-Dimensional Confined Liquid Crystals for Photonic Device Application.

PubMed

Ryu, Seong Ho; Gim, Min-Jun; Lee, Wonsuk; Choi, Suk-Won; Yoon, Dong Ki

2017-01-25

Photonic crystals (PCs) have recently attracted considerable attention, with much effort devoted to photonic bandgap (PBG) control for varying the reflected color. Here, fabrication of a modulated one-dimensional (1D) anodic aluminum oxide (AAO) PC with a periodic porous structure is reported. The PBG of the fabricated PC can be reversibly changed by switching the ultraviolet (UV) light on/off. The AAO nanopores contain a mixture of photoresponsive liquid crystals (LCs) with irradiation-activated cis/trans photoisomerizable azobenzene. The resultant mixture of LCs in the porous AAO film exhibits a reversible PBG, depending on the cis/trans configuration of azobenzene molecules. The PBG switching is reliable over many cycles, suggesting that the fabricated device can be used in optical and photonic applications such as light modulators, smart windows, and sensors.

Synthesis, X-ray structure, magnetic resonance, and DFT analysis of a soluble copper(II) phthalocyanine lacking C-H bonds.

PubMed

Moons, Hans; Łapok, Łukasz; Loas, Andrei; Van Doorslaer, Sabine; Gorun, Sergiu M

2010-10-04

The synthesis, crystal structure, and electronic properties of perfluoro-isopropyl-substituted perfluorophthalocyanine bearing a copper atom in the central cavity (F(64)PcCu) are reported. While most halogenated phthalocyanines do not exhibit long-term order sufficient to form large single crystals, this is not the case for F(64)PcCu. Its crystal structure was determined by X-ray analysis and linked to the electronic properties determined by electron paramagnetic resonance (EPR). The findings are corroborated by density functional theory (DFT) computations, which agree well with the experiment. X-band continuous-wave EPR spectra of undiluted F(64)PcCu powder, indicate the existence of isolated metal centers. The electron-withdrawing effect of the perfluoroalkyl (R(f)) groups significantly enhances the complexes solubility in organic solvents like alcohols, including via their axial coordination. This coordination is confirmed by X-band (1)H HYSCORE experiments and is also seen in the solid state via the X-ray structure. Detailed X-band CW-EPR, X-band Davies and Mims ENDOR, and W-band electron spin-echo-detected EPR studies of F(64)PcCu in ethanol allow the determination of the principal g values and the hyperfine couplings of the metal, nitrogen, and fluorine nuclei. Comparison of the g and metal hyperfine values of F(64)PcCu and other PcCu complexes in different matrices reveals a dominant effect of the matrix on these EPR parameters, while variations in the ring substituents have only a secondary effect. The relatively strong axial coordination occurs despite the diminished covalency of the C-N bonds and potentially weakening Jahn-Teller effects. Surprisingly, natural abundance (13)C HYSCORE signals could be observed for a frozen ethanol solution of F(64)PcCu. The (13)C nuclei contributing to the HYSCORE spectra could be identified as the pyrrole carbons by means of DFT. Finally, (19)F ENDOR and easily observable paramagnetic NMR were found to relate well to the DFT computations, revealing negligible isotropic hyperfine (Fermi contact) contributions. The single-site isolation in solution and solid state and the relatively strong coordination of axial ligands, both attributed to the introduction of R(f) groups, are features important for materials and catalyst design.

Extremely low-frequency Lamb wave band gaps in a sandwich phononic crystal thin plate

NASA Astrophysics Data System (ADS)

Shen, Li; Wu, Jiu Hui; Liu, Zhangyi; Fu, Gang

2015-11-01

In this paper, a kind of sandwich phononic crystal (PC) plate with silicon rubber scatterers embedded in polymethyl methacrylate (PMMA) matrix is proposed to demonstrate its low-frequency Lamb wave band gap (BG) characteristics. The dispersion relationship and the displacement vector fields of the basic slab modes and the locally resonant modes are investigated to show the BG formation mechanism. The anti-symmetric Lamb wave BG is further studied due to its important function in reducing vibration. The analysis on the BG characteristics of the PC through changing their geometrical parameters is performed. By optimizing the structure, a sandwich PC plate with a thickness of only 3 mm and a lower boundary (as low as 23.9 Hz) of the first anti-symmetric BG is designed. Finally, sound insulation experiment on a sandwich PC plate with the thickness of only 2.5 mm is conducted, showing satisfactory noise reduction effect in the frequency range of the anti-symmetric Lamb BG. Therefore, this kind of sandwich PC plate has potential applications in controlling vibration and noise in low-frequency ranges.

Electronic structures at the interface between CuPc and black phosphorus

NASA Astrophysics Data System (ADS)

Wang, Can; Niu, Dongmei; Xie, Haipeng; Liu, Baoxing; Wang, Shitan; Zhu, Menglong; Gao, Yongli

2017-08-01

The electronic structure at the organic-inorganic semiconductor interface of π -conjugated copper phthalocyanine (CuPc) on a black phosphorus (BP) crystal surface is studied with photoemission spectroscopy and density functional theory calculations. From the photoemission spectra, we observe a shift of about 0.7 eV for the highest occupied molecular orbital, which originates from the transition of phase in the organic molecular thin film (from the interface phase to the bulk phase). On the other hand, we find 0.2 eV band bending at the CuPc/BP interface while the formation of an interface dipole is very small. According to our photoemission spectrum and theoretical simulation, we also define that the interaction between CuPc and BP is physisorption via van der Waals forces, rather than chemisorption. Our results provide a fundamental understanding of CuPc/BP interfacial interactions that could be important for future two-dimensional organic/inorganic heterostructure devices.

Morphological, structural and optical properties of MEH-PPV: PC70BM nanocomposite film

NASA Astrophysics Data System (ADS)

Mhamdi, Asya; Sweii, Fatma ben Slama; Saidi, Hamza; Saidi, Faouzi; Bouazizi, Abdelaziz

2018-05-01

In this report, the influence of annealing temperature and spin coating speed on the structural and morphological properties of a blend of poly (2-methoxy-5-(2-ethyl-oxy)-p-phenylene-vinylene) (MEH-PPV) and [6-6]-phenyl-C71-butyric acid methyl ester (PC70BM) layer has been investigated. The photoactive layer (MEH-PPV: PC70BM) was deposited on ZnO film deposited on top of indium tin oxide (ITO) substrate by spin-coating. The effect of spin coating speed via atomic force microscope (AFM) leads to conclude that high speed is favorable for a good homogeneity of the film surface and good aggregates dispersion. The optimized structure was studied by varying the annealing temperatures using X-ray diffraction (XRD). The XRD analysis indicates that annealing treatment promoted the ordered aggregation and crystallization of MEH-PPV: PC70BM films. Indeed, the blend ratio effect on the optical properties of MEH-PPV: PC70BM thin film was investigated. While, the effect of incorporation of PC70BM on the optical properties was studied using UV-Vis and photoluminescence (PL) measurement. We conclude that MEH-PPV: PC70BM (1:3) film leads to high charge transfer rate.

Specific phospholipid binding to Na,K-ATPase at two distinct sites.

PubMed

Habeck, Michael; Kapri-Pardes, Einat; Sharon, Michal; Karlish, Steven J D

2017-03-14

Membrane protein function can be affected by the physical state of the lipid bilayer and specific lipid-protein interactions. For Na,K-ATPase, bilayer properties can modulate pump activity, and, as observed in crystal structures, several lipids are bound within the transmembrane domain. Furthermore, Na,K-ATPase activity depends on phosphatidylserine (PS) and cholesterol, which stabilize the protein, and polyunsaturated phosphatidylcholine (PC) or phosphatidylethanolamine (PE), known to stimulate Na,K-ATPase activity. Based on lipid structural specificity and kinetic mechanisms, specific interactions of both PS and PC/PE have been inferred. Nevertheless, specific binding sites have not been identified definitively. We address this question with native mass spectrometry (MS) and site-directed mutagenesis. Native MS shows directly that one molecule each of 18:0/18:1 PS and 18:0/20:4 PC can bind specifically to purified human Na,K-ATPase (α 1 β 1 ). By replacing lysine residues at proposed phospholipid-binding sites with glutamines, the two sites have been identified. Mutations in the cytoplasmic αL8-9 loop destabilize the protein but do not affect Na,K-ATPase activity, whereas mutations in transmembrane helices (TM), αTM2 and αTM4, abolish the stimulation of activity by 18:0/20:4 PC but do not affect stability. When these data are linked to crystal structures, the underlying mechanism of PS and PC/PE effects emerges. PS (and cholesterol) bind between αTM 8, 9, 10, near the FXYD subunit, and maintain topological integrity of the labile C terminus of the α subunit (site A). PC/PE binds between αTM2, 4, 6, and 9 and accelerates the rate-limiting E 1 P-E 2 P conformational transition (site B). We discuss the potential physiological implications.

High-throughput and in situ EDXRD investigation on the formation of two new metal aminoethylphosphonates - Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) and Ca(OH)(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3}){center_dot}2H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmidt, Corinna; Feyand, Mark; Rothkirch, Andre

2012-04-15

The system Ca{sup 2+}/2-aminoethylphosphonic acid/H{sub 2}O/NaOH was systematically investigated using high-throughput methods. The experiments led to one new compound Ca(O{sub 3}PC{sub 2} H{sub 4}NH{sub 2}) (1) and the crystal structure was determined using in house X-ray powder diffraction data (monoclinic, P2{sub 1}/c, a=9.7753(3), b=6.4931(2), c=8.4473(2) A, {beta}=106.46(2) Degree-Sign , V=514.20(2) A{sup 3}, Z=4). The formation of 1 was investigated by in situ energy dispersive X-ray diffraction measurements (EDXRD) at beamline F3 at HASYLAB (light source DORIS III), DESY, Hamburg. An intermediate, Ca(OH)(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3}){center_dot}2H{sub 2}O (2), was observed and could be isolated from the reaction mixture at ambientmore » temperatures by quenching the reaction. The crystal structure of 2 was determined from XRPD data using synchrotron radiation (monoclinic, P2{sub 1}/m, a=11.2193(7), b=7.1488(3), c=5.0635(2) A, {beta}=100.13(4) Degree-Sign , V=399.78(3) A{sup 3}, Z=2). - Graphical abstarct: The detailed in situ energy dispersive X-ray diffraction (EDXRD) investigation on the formation of the new inorganic-organic hybrid compound Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) leads to the discovery of a new crystalline intermediate phase. Both crystal structures were elucidated using X-ray powder diffraction data. Highlights: Black-Right-Pointing-Pointer High-throughput investigation led to new metal aminoethylphosphonate Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}). Black-Right-Pointing-Pointer The formation of Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) was followed by in situ EDXRD measurements. Black-Right-Pointing-Pointer The crystalline intermediate Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3})(OH){center_dot}2H{sub 2}O was discovered. Black-Right-Pointing-Pointer Isolation of Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3})(OH){center_dot}2H{sub 2}O was accomplished by quenching experiments. Black-Right-Pointing-Pointer The structures were determined using X-ray powder diffraction data.« less

Ultralong copper phthalocyanine nanowires with new crystal structure and broad optical absorption.

PubMed

Wang, Hai; Mauthoor, Soumaya; Din, Salahud; Gardener, Jules A; Chang, Rio; Warner, Marc; Aeppli, Gabriel; McComb, David W; Ryan, Mary P; Wu, Wei; Fisher, Andrew J; Stoneham, Marshall; Heutz, Sandrine

2010-07-27

The development of molecular nanostructures plays a major role in emerging organic electronic applications, as it leads to improved performance and is compatible with our increasing need for miniaturization. In particular, nanowires have been obtained from solution or vapor phase and have displayed high conductivity or large interfacial areas in solar cells. In all cases however, the crystal structure remains as in films or bulk, and the exploitation of wires requires extensive postgrowth manipulation as their orientations are random. Here we report copper phthalocyanine (CuPc) nanowires with diameters of 10-100 nm, high directionality, and unprecedented aspect ratios. We demonstrate that they adopt a new crystal phase, designated eta-CuPc, where the molecules stack along the long axis. The resulting high electronic overlap along the centimeter length stacks achieved in our wires mediates antiferromagnetic couplings and broadens the optical absorption spectrum. The ability to fabricate ultralong, flexible metal phthalocyanine nanowires opens new possibilities for applications of these simple molecules.

Subphthalocyanines Axially Substituted with a Tetracyanobuta-1,3-diene-Aniline Moiety: Synthesis, Structure, and Physicochemical Properties.

PubMed

Winterfeld, Kim A; Lavarda, Giulia; Guilleme, Julia; Sekita, Michael; Guldi, Dirk M; Torres, Tomás; Bottari, Giovanni

2017-04-19

A 1,1,4,4-tetracyanobuta-1,3-diene (TCBD)-aniline moiety has been introduced, for the first time, at the axial position of two subphthalocyanines (SubPcs) peripherally substituted with hydrogen (H 12 SubPc) or fluorine atoms (F 12 SubPc). Single-crystal X-ray analysis of both SubPc-TCBD-aniline systems showed that each conjugate is a racemic mixture of two atropisomers resulting from the almost orthogonal geometry adopted by the axial TCBD unit, which were separated by chiral high-performance liquid chromatography. Remarkably, the single-crystal X-ray structure of one atropisomer of each SubPc-TCBD-aniline conjugate has been solved, allowing to unambiguously assign the atropisomers' absolute configuration, something, to the best of our knowledge, unprecedented in TCBD-based conjugates. Moreover, the physicochemical properties of both SubPc-TCBD-aniline racemates have been investigated using a wide range of electrochemical as well as steady-state and time-resolved spectroscopic techniques. Each of the two SubPc-TCBD-aniline conjugates presents a unique photophysical feature never observed before in SubPc chemistry. As a matter of fact, H 12 SubPc-TCBD-aniline showed significant ground-state charge transfer interactions between the H 12 SubPc macrocycle and the electron-withdrawing TCBD unit directly attached at its axial position. In contrast, F 12 SubPc-TCBD-aniline gave rise to an intense, broad emission, which red shifts upon increasing the solvent polarity and stems from an excited complex (i.e., an exciplex). Such an exciplex emission, which has also no precedent in TCBD chemistry, results from intramolecular interactions in the excited state between the electron-rich aniline and the F 12 SubPc π-surface, two molecular fragments kept in spatial proximity by the "unique" three-dimensional geometry adopted by the F 12 SubPc-TCBD-aniline. Complementary transient absorption studies were carried out on both SubPc-TCBD-aniline derivatives, showing the occurrence, in both cases, of photoinduced charge separation and corroborating the formation of the aforementioned intramolecular exciplex in terms of a radical ion pair stabilized through-space.

Applications of Silicon-on-Insulator Photonic Crystal Structures in Miniature Spectrometer Designs

NASA Astrophysics Data System (ADS)

Gao, Boshen

Optical spectroscopy is one of the most important fundamental scientific techniques. It has been widely adopted in physics, chemistry, biology, medicine and many other research fields. However, the size and weight of a spectrometer as well as the difficulty to align and maintain it have long limited spectroscopy to be a laboratory-only procedure. With the recent advancement in semiconductor electronics and photonics, miniaturized spectrometers have been introduced to complete many tasks in daily life where mobility and portability are necessary. This thesis focuses on the study of several photonic crystal (PC) nano-structures potentially suitable for miniaturized on-chip spectrometer designs. Chapter 1 briefly introduces the concept of PCs and their band structures. By analyzing the band structure, the origin of the superprism effect is explained. Defect-based PC nano-cavities are also discussed, as well as a type of coupled cavity waveguides (CCW) composed of PC nano-cavities. Chapter 2 is devoted to the optimization of a flat-band superprism structure for spectroscopy application using numerical simulations. Chapter 3 reports a fabricated broad-band superprism and the experimental characterization of its wavelength resolving performance. In chapter 4, the idea of composing a miniature spectrometer based on a single tunable PC nano-cavity is proposed. The rest of this chapter discusses the experimental study of this design. Chapter 5 examines the slow-light performance of a CCW and discusses its potential application in slow-light interferometry. Chapter 6 serves as a conclusion of this thesis and proposes directions for possible future work to follow up.

Evidence of a Love wave bandgap in a quartz substrate coated with a phononic thin layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Ting-Wei; Wu, Tsung-Tsong, E-mail: wutt@ntu.edu.tw; Lin, Yu-Ching

This paper presents a numerical and experimental study of Love wave propagation in a micro-fabricated phononic crystal (PC) structure consisting of a 2D, periodically etched silica film deposited on a quartz substrate. The dispersion characteristics of Love waves in such a phononic structure were analyzed with various geometric parameters by using complex band structure calculations. For the experiment, we adopted reactive-ion etching with electron-beam lithography to fabricate a submicrometer phononic structure. The measured results exhibited consistency with the numerical prediction. The results of this study may serve as a basis for developing PC-based Love wave devices.

Interaction Between the Biotin Carboxyl Carrier Domain and the Biotin Carboxylase Domain in Pyruvate Carboxylase from Rhizobium etli†

PubMed Central

Lietzan, Adam D.; Menefee, Ann L.; Zeczycki, Tonya N.; Kumar, Sudhanshu; Attwood, Paul V.; Wallace, John C.; Cleland, W. Wallace; Maurice, Martin St.

2011-01-01

Pyruvate carboxylase (PC) catalyzes the ATP-dependent carboxylation of pyruvate to oxaloacetate, an important anaplerotic reaction in mammalian tissues. To effect catalysis, the tethered biotin of PC must gain access to active sites in both the biotin carboxylase domain and the carboxyl transferase domain. Previous studies have demonstrated that a mutation of threonine 882 to alanine in PC from Rhizobium etli renders the carboxyl transferase domain inactive and favors the positioning of biotin in the biotin carboxylase domain. We report the 2.4 Å resolution X-ray crystal structure of the Rhizobium etli PC T882A mutant which reveals the first high-resolution description of the domain interaction between the biotin carboxyl carrier protein domain and the biotin carboxylase domain. The overall quaternary arrangement of Rhizobium etli PC remains highly asymmetrical and is independent of the presence of allosteric activator. While biotin is observed in the biotin carboxylase domain, its access to the active site is precluded by the interaction between Arg353 and Glu248, revealing a mechanism for regulating carboxybiotin access to the BC domain active site. The binding location for the biotin carboxyl carrier protein domain demonstrates that tethered biotin cannot bind in the biotin carboxylase domain active site in the same orientation as free biotin, helping to explain the difference in catalysis observed between tethered biotin and free biotin substrates in biotin carboxylase enzymes. Electron density located in the biotin carboxylase domain active site is assigned to phosphonoacetate, offering a probable location for the putative carboxyphosphate intermediate formed during biotin carboxylation. The insights gained from the T882A Rhizobium etli PC crystal structure provide a new series of catalytic snapshots in PC and offer a revised perspective on catalysis in the biotin-dependent enzyme family. PMID:21958016

Optical Study of 2D Photonic Crystals in an InP/GaInAsP Slab Waveguide Structure

DTIC Science & Technology

2002-01-01

the values n,,,,. = 3.35 and n, ,, = 3.17 are assumed for the refraction index of GaInAsP and InP, respectively. The resulting structure is a multimode...contributes to increase out-of- plane scattering. On the other hand, when entering the PC, the hole pattern is felt as a low refractive index contrast...in an InP/GaInAsP step- index waveguide. Transmission (T) measurements through simple PC slabs and through one-dimensional (1D) Fabry-P6rot (FP

Theoretical modeling of the electronic structure and exchange interactions in Cu(II)Pc

NASA Astrophysics Data System (ADS)

Wu, Wei; Fisher, A. J.; Harrison, N. M.; Wang, Hai; Wu, Zhenlin; Gardener, Jules; Heutz, Sandrine; Jones, Tim; Aeppli, Gabriel

2012-12-01

We calculate the electronic structure and exchange interactions in a copper(II)phthalocyanine (Cu(II)Pc) crystal as a one-dimensional molecular chain using hybrid exchange density functional theory (DFT). In addition, the intermolecular exchange interactions are also calculated in a molecular dimer using Green's function perturbation theory (GFPT) to illustrate the underlying physics. We find that the exchange interactions depend strongly on the stacking angle, but weakly on the sliding angle (defined in the text). The hybrid DFT calculations also provide an insight into the electronic structure of the Cu(II)Pc molecular chain and demonstrate that on-site electron correlations have a significant effect on the nature of the ground state, the band gap and magnetic excitations. The exchange interactions predicted by our DFT calculations and GFPT calculations agree qualitatively with the recent experimental results on newly found η-Cu(II)Pc and the previous results for the α- and β-phases. This work provides a reliable theoretical basis for the further application of Cu(II)Pc to molecular spintronics and organic-based quantum information processing.

Theoretical modeling of the electronic structure and exchange interactions in a Cu(II)Pc one-dimensional chain

NASA Astrophysics Data System (ADS)

Wu, Wei; Fisher, A. J.; Harrison, N. M.

2011-07-01

We calculate the electronic structure and exchange interactions in a copper(II)phthalocyanine [Cu(II)Pc] crystal as a one-dimensional molecular chain using hybrid exchange density functional theory (DFT). In addition, the intermolecular exchange interactions are also calculated in a molecular dimer using Green’s function perturbation theory (GFPT) to illustrate the underlying physics. We find that the exchange interactions depend strongly on the stacking angle, but weakly on the sliding angle (defined in the text). The hybrid DFT calculations also provide an insight into the electronic structure of the Cu(II)Pc molecular chain and demonstrate that on-site electron correlations have a significant effect on the nature of the ground state, the band gap, and magnetic excitations. The exchange interactions predicted by our DFT calculations and GFPT calculations agree qualitatively with the recent experimental results on newly found η-Cu(II)Pc and the previous results for the α and β phases. This work provides a reliable theoretical basis for the further application of Cu(II)Pc to molecular spintronics and organic-based quantum information processing.

Effect of chain length on thermal conversion of alkoxy-substituted copper phthalocyanine precursors.

PubMed

Fukuda, Takamitsu; Kikukawa, Yuu; Tsuruya, Ryota; Fuyuhiro, Akira; Ishikawa, Naoto; Kobayashi, Nagao

2011-11-21

A series of dialkoxy-substituted copper phthalocyanine (CuPc) precursors (4a-4d) have been prepared by treating phthalonitrile with the corresponding lithium alkoxide under mild conditions. The precursors exhibited high solubilities in common organic solvents, including acetone, toluene, tetrahydrofuran (THF), CH(2)Cl(2), and CHCl(3). Elongation of the alkoxy chains improved the solubilities of the precursors effectively, and accordingly, the butoxy-substituted derivative (4d) showed the highest solubility among 4a-4d. X-ray crystallography clarified that the conjugated skeletons of 4a-4d are all isostructural, and have two alkoxy groups in a syn-conformation fashion, leading to highly bent structures. Thermal conversions of the precursors examined by thermogravimetry (TG) and differential thermal analysis (DTA) demonstrate that 4a was converted into CuPc via two distinct exothermic processes in the 200-250 °C temperature range, while 4d exhibits only one exothermic signal in the DTA. In the field emission scanning electron microscopy (FESEM) images of 4a, the presence of two types of distinct crystal morphology (prismatic and plate-like crystals) can be recognized, implying that the two observed exothermic processes in the DTA can be attributed to the different crystal morphologies of the samples rather than the step-by-step elimination of the alkoxy groups. The thermal formation of CuPc from the precursors has been unambiguously confirmed by X-ray powder diffraction, UV-vis spectroscopy, and elemental analysis. The precursors were converted into CuPc at lower temperature with increasing chain length, presumably because of the increased void volume in the crystals. Thermal conversion performed in the solution phase results in a bright blue-colored solution with prominent absorption bands in the 650-700 nm region, strongly supporting the formation of CuPc.

Magneto-phonon polaritons in two-dimension antiferromagnetic/ion-crystalic photonic crystals

NASA Astrophysics Data System (ADS)

Ta, J. X.; Song, Y. L.; Wang, X. Z.

2012-01-01

Magneto-phonon polaritons in a two-dimension photonic crystal (PC) are discussed. This PC is constructed by embedding a periodical square lattice of ionic-crystal cylinders into an antiferromagnet. The two media are dispersive, with their individual resonant frequencies near each other. We first set up an effective-medium method to obtain the effective magnetic permeability and dielectric permittivity of the PC, followed by the dispersion relations of surface and bulk polaritons. There are a number of new surface polaritons, and two new distinctive bulk polariton bands in which the negative refraction and left-handedness can appear. The numerical calculations are based on the example, FeF2/TlBr PC.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Shashaank; Belianinov, Alex; Okatan, Mahmut B

(001)pc textured K0.5Na0.5NbO3 (KNN) ceramic was found to exhibit a 65% improvement in the longitudinal piezoelectric response as compared to its random counterpart. Piezoresponse force microscopy study revealed the existence of larger 180 and non-180 domains for textured ceramic as compared to that of the random ceramic. Improvement in piezoresponse by the development of (001)pc texture is discussed in terms of the crystallographic nature of KNN and domain morphology. A comparative analysis performed with a rhombohedral composition suggested that the improvement in longitudinal piezoresponse of polycrystalline ceramics by the development of (001)pc texture is limited by the crystal structure.

Polymer blend effect on molecular alignment induced by contact freezing of mesogenic phthalocyanine

NASA Astrophysics Data System (ADS)

Kitagawa, Takahiro; Fiderana Ramananarivo, Mihary; Fujii, Akihiko; Ozaki, Masanori

2018-04-01

The polymer blend effect in the fabrication of uniaxially oriented thin films of a mesogenic phthalocyanine, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH2), by contact freezing was studied. Contact freezing was induced by thermal stimulation to a supercooled liquid crystal state of the mixture of C6PcH2 and poly(3-hexylthiophene) (P3HT). With the blending of P3HT with C6PcH2 at an appropriate blend ratio, the cracks observed in a pure C6PcH2 film disappeared while maintaining the uniaxial alignment of C6PcH2. The polymer blend effect was discussed by taking the anisotropic optical absorption and molecular stacking structure in the thin films into consideration.

Band structure of comb-like photonic crystals containing meta-materials

NASA Astrophysics Data System (ADS)

Weng, Yi; Wang, Zhi-Guo; Chen, Hong

2007-09-01

We study the transmission properties and band structure of comb-like photonic crystals (PC) with backbones constructed of meta-materials (negative-index materials) within the frame of the interface response theory. The result shows the existence of a special band gap at low frequency. This gap differs from the Bragg gaps in that it is insensitive to the geometrical scaling and disorder. In comparison with the zero-average-index gap in one-dimensional PC made of alternating positive- and negative-index materials, the gap is obviously deeper and broader, given the same system parameters. In addition, the behavior of its gap-edges is also different. One gap-edge is decided by the average permittivity whereas the other is only subject to the changing of the permeability of the backbone. Due to this asymmetry of the two gap-edges, the broadening of the gap could be realized with much freedom and facility.

Observations of cavity polaritons in one-dimensional photonic crystals containing a liquid-crystalline semiconductor based on perylene bisimide units

NASA Astrophysics Data System (ADS)

Sakata, T.; Suzuki, M.; Yamamoto, T.; Nakanishi, S.; Funahashi, M.; Tsurumachi, N.

2017-10-01

We investigated the optical transmission properties of one-dimensional photonic crystal (1D-PC) microcavity structures containing the liquid-crystalline (LC) perylene tetracarboxylic bisimide (PTCBI) derivative. We fabricated the microcavity structures for this study by two different methods and observed the cavity polaritons successfully in both samples. For one sample, since the PTCBI molecules were aligned in the cavity layer of the 1D-PC by utilizing a friction transfer method, vacuum Rabi splitting energy was strongly dependent on the polarization of the incident light produced by the peculiar optical features of the LC organic semiconductor. For the other sample, we did not utilize the friction transfer method and did not observe such polarization dependence. However, we did observe a relatively large Rabi splitting energy of 187 meV, probably due to the improvement of optical confinement effect.

Pressure-controlled terahertz filter based on 1D photonic crystal with a defective semiconductor

NASA Astrophysics Data System (ADS)

Qinwen, XUE; Xiaohua, WANG; Chenglin, LIU; Youwen, LIU

2018-03-01

The tunable terahertz (THz) filter has been designed and studied, which is composed of 1D photonic crystal (PC) containing a defect layer of semiconductor GaAs. The analytical solution of 1D defective PC (1DDPC) is deduced based on the transfer matrix method, and the electromagnetic plane wave numerical simulation of this 1DDPC is performed by using the finite element method. The calculated and simulated results have confirmed that the filtering transmittance of this 1DDPC in symmetric structure of air/(Si/SiO2) N /GaAs/(SiO2/Si) N /air is far higher than in asymmetric structure of air/(Si/SiO2) N /GaAs/(Si/SiO2) N /air, where the filtering frequency can be tuned by the external pressure. It can provide a feasible route to design the external pressure-controlled THz filter based on 1DPC with a defective semiconductor.

Meso-size Effect from Self-assembled Carbon Structures and Their Device Applications

DTIC Science & Technology

2013-08-23

electrical photoresponse from pentacene 1D disks and 2D wires, and 3) dramatic increase of solubility in water of zinc phthalocyanine (ZnPc) nanowires...Hong, M.; Son, M.; Choi, H. C.* “Crystal Plane-Dependent Photoluminescence Activity of Pentacene 1D Wire and 2D Disk Crystals.” Angew. Chem. Int...Ed. 2013, 52, 5997-6001. [7] Park, J. E.; Hong, M.; Son, M.; Choi, H. C.* “Crystal Plane-Dependent Photoluminescence Activity of Pentacene 1D Wire

Insertion of two-dimensional photonic crystal pattern on p-GaN layer of GaN-based light-emitting diodes using bi-layer nanoimprint lithography.

PubMed

Byeon, Kyeong-Jae; Hwang, Seon-Yong; Hong, Chang-Hee; Baek, Jong Hyeob; Lee, Heon

2008-10-01

Nanoimprint lithography (NIL) was adapted to fabricate two-dimensional (2-D) photonic crystal (PC) pattern on the p-GaN layer of InGaN/GaN multi quantum well light-emitting diodes (LEDs) structure to improve the light extraction efficiency. For the uniform transfer of the PC pattern, a bi-layer imprinting method with liquid phase resin was used. The p-GaN layer was patterned with a periodic array of holes by an inductively coupled plasma etching process, based on SiCl4/Ar plasmas. As a result, 2-D photonic crystal patterns with 144 nm, 200 nm and 347 nm diameter holes were uniformly formed on the p-GaN layer and the photoluminescence (PL) intensity of each patterned LED samples was increased by more than 2.6 times, as compared to that of the un-patterned LED sample.

Crystal structure of an antibody bound to an immunodominant peptide epitope: novel features in peptide-antibody recognition.

PubMed

Nair, D T; Singh, K; Sahu, N; Rao, K V; Salunke, D M

2000-12-15

The crystal structure of Fab of an Ab PC283 complexed with its corresponding peptide Ag, PS1 (HQLDPAFGANSTNPD), derived from the hepatitis B virus surface Ag was determined. The PS1 stretch Gln2P to Phe7P is present in the Ag binding site of the Ab, while the next three residues of the peptide are raised above the binding groove. The residues Ser11P, Thr12P, and Asn13P then loop back onto the Ag-binding site of the Ab. The last two residues, Pro14P and Asp15P, extend outside the binding site without forming any contacts with the Ab. The PC283-PS1 complex is among the few examples where the light chain complementarity-determining regions show more interactions than the heavy chain complementarity-determining regions, and a distal framework residue is involved in Ag binding. As seen from the crystal structure, most of the contacts between peptide and Ab are through the five residues, Leu3-Asp4-Pro5-Ala6-Phe7, of PS1. The paratope is predominantly hydrophobic with aromatic residues lining the binding pocket, although a salt bridge also contributes to stabilizing the Ag-Ab interaction. The molecular surface area buried upon PS1 binding is 756 A(2) for the peptide and 625 A(2) for the Fab, which is higher than what has been seen to date for Ab-peptide complexes. A comparison between PC283 structure and a homology model of its germline ancestor suggests that paratope optimization for PS1 occurs by improving both charge and shape complementarity.

Crystal Structure of Crataeva tapia Bark Protein (CrataBL) and Its Effect in Human Prostate Cancer Cell Lines

PubMed Central

Ferreira, Joana Gasperazzo; Silva, Mariana Cristina Cabral; Silva-Lucca, Rosemeire Aparecida; Mentele, Reinhard; Paredes-Gamero, Edgar Julian; Bertolin, Thiago Carlos; dos Santos Correia, Maria Tereza; Paiva, Patrícia Maria Guedes; Gustchina, Alla; Wlodawer, Alexander; Oliva, Maria Luiza Vilela

2013-01-01

A protein isolated from the bark of Crataeva tapia (CrataBL) is both a Kunitz-type plant protease inhibitor and a lectin. We have determined the amino acid sequence and three-dimensional structure of CrataBL, as well as characterized its selected biochemical and biological properties. We found two different isoforms of CrataBL isolated from the original source, differing in positions 31 (Pro/Leu); 92 (Ser/Leu); 93 (Ile/Thr); 95 (Arg/Gly) and 97 (Leu/Ser). CrataBL showed relatively weak inhibitory activity against trypsin (Kiapp = 43 µM) and was more potent against Factor Xa (Kiapp = 8.6 µM), but was not active against a number of other proteases. We have confirmed that CrataBL contains two glycosylation sites and forms a dimer at high concentration. The high-resolution crystal structures of two different crystal forms of isoform II verified the β-trefoil fold of CrataBL and have shown the presence of dimers consisting of two almost identical molecules making extensive contacts (∼645 Å2). The structure differs from those of the most closely related proteins by the lack of the N-terminal β-hairpin. In experiments aimed at investigating the biological properties of CrataBL, we have shown that addition of 40 µM of the protein for 48 h caused maximum growth inhibition in MTT assay (47% of DU145 cells and 43% of PC3 cells). The apoptosis of DU145 and PC3 cell lines was confirmed by flow cytometry using Annexin V/FITC and propidium iodide staining. Treatment with CrataBL resulted in the release of mitochondrial cytochrome c and in the activation of caspase-3 in DU145 and PC3 cells. PMID:23823708

Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li7La3Zr2O12 revealed by an internal friction technique.

PubMed

Wang, X P; Gao, Y X; Xia, Y P; Zhuang, Z; Zhang, T; Fang, Q F

2014-04-21

The correlation and transport mechanism of lithium ions with the crystal structure of a fast lithium ion conductor Li7La3Zr2O12 are mainly investigated by internal friction (IF) and AC impedance spectroscopy techniques. Compared with the poor conductivity of tetragonal Li7La3Zr2O12, the Al stabilized cubic phase exhibits a good ionic conductivity that can be up to 1.9 × 10(-4) S cm(-1) at room temperature, which can be ascribed to the disordered distribution of lithium ions in the cubic phase. A well-pronounced relaxation IF peak (labeled as peak PC) is observed in the cubic phase while a very weak IF peak (labeled as PT) is observed in the tetragonal phase, further evidencing the difference in lithium ion migration in the two phases. Peak PC can be decomposed into two sub-peaks with the activation energy and the pre-exponential factor of relaxation time being E1 = 0.41 eV and τ01 = 1.2 × 10(-14) s for the lower temperature peak PC1 and E2 = 0.35 eV and τ02 = 1.9 × 10(-15) s for the higher temperature PC2 peak, respectively. Based on the crystalline structure of a cubic garnet-type Li7La3Zr2O12 compound, an atomistic mechanism of lithium ion diffusion via vacancies is suggested, i.e. 48g(96h) ↔ 48g(96h) for peak PC1 and 48g(96h) ↔ 24d for peak PC2, respectively. The weak PT peak in the tetragonal phase is preliminarily interpreted as due to the short jump process among neighboring octahedral sites and vacant tetrahedral sites.

Training HBCU Faculty and Students in Prostate Cancer (PC) Research: Signal Transduction and Receptor-Inhibitor Interactions in the Progress of PC

DTIC Science & Technology

2008-03-01

thiocinnamide, and 4-[(3-bromophenyl) amino ]-6- propionylamidoquinazoline have been completed. We continue to crystallize samples of tyrosine kinase...been developed last year identify the geometric relationship between structural features of a set of molecules known to act as tyrosine kinase...L. Klein Stevens, “A Crystallographic Study of ErbB2 Tyrosine Kinase Inhibitors”, 230th American Chemical Society National Meeting, Washington, DC

CdTe-based Light-Controllable Frequency-Selective Photonic Crystal Switch for Millimeter Waves

DTIC Science & Technology

2011-09-01

position (magenta curves with circular points which correspond to different light pulses) 23 Fig. 11.3. (a) Phase of transmission wave (in...11.4. Transmission spectra of plastic-air PC with CdTe-coated triple -quartz-wafer insertion of the kind ‘6t-qvqvqs-6t’ (computed yellow and measured...experimental requirements of matching the frequency band of VNA facility (f = 75–110 GHz), PC structures with triple -wafer insertion layers

Controllable fabrication of copper phthalocyanine nanostructure crystals.

PubMed

Liu, Fangmei; Sun, Jia; Xiao, Si; Huang, Wenglong; Tao, Shaohua; Zhang, Yi; Gao, Yongli; Yang, Junliang

2015-06-05

Copper phthalocyanine (CuPc) nanostructure crystals, including nanoflower, nanoribbon, and nanowire, were controllably fabricated by temperature gradient physical vapor deposition (TG-PVD) through controlling the growth parameters. In a controllable growth system with carrier gas N2, nanoflower, nanoribbon, and nanowire crystals were formed in a high-temperature zone, medium-temperature zone, and low-temperature zone, respectively. They were proved to be β-phase, coexist of α-phase and β-phase, and α-phase respectively based on x-ray diffraction results. Furthermore, ultralong CuPc nanowires up to several millimeters could be fabricated by TG-PVD without carrier gas, and they were well-aligned to form large-area CuPc nanowire crystal arrays by the Langmuir-Blodgett method. The nanostructure crystals showed unusual optical absorption spectra from the ultraviolet-visible to near-infrared range, which was explained by the diffraction and scattering caused by the wavelength-sized nanostructures. These CuPc nanostructure crystals show potential applications in organic electronic and optoelectronic devices.

Structural heterogeneity leads to functional homogeneity in A. marina phycocyanin.

PubMed

Bar-Zvi, Shira; Lahav, Avital; Harris, Dvir; Niedzwiedzki, Dariusz M; Blankenship, Robert E; Adir, Noam

2018-07-01

The major light harvesting antenna in all cyanobacterial species is the phycobilisome (PBS). The smallest PBS identified to date is that of Acaryochloris marina (A. marina), composed of a single four-hexamer rod. We have determined the crystal structure of phycocyanin (AmPC), the major component of the A. marina PBS (AmPBS) to 2.1 Å. The basic unit of the AmPC is a heterodimer of two related subunits (α and β), and we show that the asymmetric unit contains a superposition of two α and two β isoforms, the products of the simultaneous expression of different genes. This is the first time to our knowledge that isolated proteins crystallized with such identifiable heterogeneity. We believe that the presence of the different isoforms allows the AmPBS to have a significant bathochromic shift in its fluorescence emission spectrum, allowing, in the total absence of allophycocyanin, a better overlap with absorption of the chlorophyll d-containing reaction centers. We show that this bathochromic shift exists in intact AmPBS as well as in its disassembled components, thus suggesting that AmPC can efficiently serve as the AmPBS terminal emitter. Copyright © 2018 Elsevier B.V. All rights reserved.

Phase modification of copper phthalocyanine semiconductor by converting powder to thin film

NASA Astrophysics Data System (ADS)

Ai, Xiaowei; Lin, Jiaxin; Chang, Yufang; Zhou, Lianqun; Zhang, Xianmin; Qin, Gaowu

2018-01-01

Thin films of copper phthalocyanine (CuPc) semiconductor were deposited on glass substrates by a thermal evaporation system using the CuPc powder in a high vacuum. The crystal structures of both the films and the powder were measured by the X-ray diffraction spectroscopy technique. It is observed that CuPc films only show one peak at 6.84°, indicating a high texture of α phase along (200) orientation. In comparison, CuPc powder shows a series of peaks, which are confirmed from the mixture of both α and β phases. The effects of substrate anneal temperature on the film structure, grain size and optical absorption property of CuPc films were also investigated. All the films are of α phase and the full width of half maximum for (200) diffraction peak becomes narrow with increasing the substrate temperatures. The average grain size calculated by the Scherrer's formula is 33.63 nm for the film without anneal, which is increased up to 58.29 nm for the film annealed at 200 °C. Scanning electron microscope was further measured to prove the growth of crystalline grain and to characterize the morphologies of CuPc films. Ultraviolet-visible absorption spectra were employed to study the structure effect on the optical properties of both CuPc films and powder. Fourier Transform infrared spectroscopy was used to identify the crystalline nature of both CuPc powder and film.

Inhibition mechanism of hydroxypropyl methylcellulose acetate succinate on drug crystallization in gastrointestinal fluid and drug permeability from a supersaturated solution.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Kataoka, Makoto; Yamashita, Shinji; Yamamoto, Keiji; Moribe, Kunikazu

2014-10-01

The effects of drug-crystallization inhibitor in bile acid/lipid micelles solution on drug permeation was evaluated during the drug crystallization process. Hydroxypropyl methylcellulose acetate succinate (HPMC-AS) was used as a drug-crystallization inhibitor, which efficiently suppressed dexamethasone (DEX) crystallization in a gastrointestinal fluid model containing sodium taurocholate (NaTC) and egg-phosphatidylcholine (egg-PC). Changes of molecular state of supersaturated DEX during the DEX crystallization process was monitored in real time using proton nuclear magnetic resonance (1H NMR). It revealed that DEX distribution to bulk water and micellar phases formed by NaTC and egg-PC was not changed during the DEX crystallization process even in the presence of HPMC-AS. DEX permeation during DEX crystallization was evaluated using dissolution/permeability system. The combination of crystallization inhibition by HPMC-AS and micellar encapsulation by NaTC and egg-PC led to considerably higher DEX concentrations and improvement of DEX permeation at the beginning of the DEX crystallization process. Crystallization inhibition by HPMC-AS can efficiently work even in the micellar solution, where NaTC/egg-PC micelles encapsulates some DEX. It was concluded that a crystallization inhibitor contributed to improvement of permeation of a poorly water-soluble drug in gastrointestinal fluid. Copyright © 2014 Elsevier B.V. All rights reserved.

Negative refraction of acoustic waves using a foam-like metallic structure

NASA Astrophysics Data System (ADS)

Hladky-Hennion, A.-C.; Vasseur, J. O.; Haw, G.; Croënne, C.; Haumesser, L.; Norris, A. N.

2013-04-01

A phononic crystal (PC) slab made of a single metallic phase is shown, theoretically and experimentally, to display perfect negative index matching and focusing capability when surrounded with water. The proposed PC slab is a centimeter scale hollow metallic foam-like structure in which acoustic energy is mediated via the metal lattice. The negative index property arises from an isolated branch of the dispersion curves corresponding to a mode that can be coupled to incident acoustic waves in surrounding water. This band also intercepts the water sound line at a frequency in the ultrasonic range. The metallic structure is consequently a candidate for the negative refraction of incident longitudinal waves.

Design on compatible stealth photonic crystal of nearmiddle infrared and 1.06 μm laser

NASA Astrophysics Data System (ADS)

Zhang, Ji-kui; Wang, Jia-Chun; Wang, Qi-Chao

2016-01-01

In the near and middle infrared atmospheric window, infrared stealth material require a low absorptivity (which means a low emissivity according to Kirchhoff's law of black body), at the same time, it also requires high absorptivity so as to decrease the reflectance at military laser wavelength of 1.06μm. Under this circumstances, compatible stealth of infrared and laser is an urgent demand, but the demand is ambivalent for conventional materials. Photonic crystal (PC), as a new type of artificial periodic structure function material, can realize broadband thermal infrared stealth based on its high-reflection photon forbidden band(also called photonic band gap). The high-reflection photon forbidden band of PC can be adjusted to near and middle infrared wave band through some rational methods. When a defect was added into the periodic structure of PC, a "hole-digging" reflection spectrum, which is high absorption at military laser wavelength of 1.06μm, can be achieved, so compatible stealth of near and middle infrared and military laser wavelength of 1.06μm can be achieved too. In this paper, we selected near and middle infrared-transparent materials, Te and MgF2 , as high refractive index and low refractive index material respectively, and designed a one-dimensional one-defect-mode PC whose photon forbidden band was broadened to 1-5μm by constructing two photonic crystals into one. The optical property of the PC was calculated by Transfer matrix method(TMM) of thin-film optical theory, and the results shows that the as-designed PC has a high spectral reflectance in the near and middle infrared band, among which the reflectivity in 1.68μm 5.26μm band reached more than 90%, and the 2.48 5.07μm band even reached 99.99%. The result also shows that between the band gap of 1-5μm, there are one defect mode locating in the wavelength of 1.06μm, whose reflectance is below 0.70%, which means its spectral absorptivity is greater than 99.30%. All the above we have discussed proved that this "hole-digging spectrum" PC can realize the compatible stealth of near and middle infrared and 1.06μm military laser.

One-dimensional photonic crystal optical limiter.

PubMed

Soon, Boon Yi; Haus, Joseph; Scalora, Michael; Sibilia, Concita

2003-08-25

We explore a new passive optical limiter design using transverse modulation instability in the one-dimensional photonic crystal (PC) using x(3) materials. The performance of PC optical limiters strongly depends on the choice of the materials and the geometry and it improves as the duration of the incident pulse is extended. PC optical limiter performance is compared with that of a device made from homogeneous material. We identify three criteria for benchmarking the PC optical limiter. We also include a discussion of the advantages and disadvantages of PC optical limiters for real world applications.

Ambipolar carrier transport properties and molecular packing structure of octahexyl-substituted copper phthalocyanine

NASA Astrophysics Data System (ADS)

Watanabe, Ken; Watanabe, Koichi; Tohnai, Norimitsu; Itani, Hiromichi; Shimizu, Yo; Fujii, Akihiko; Ozaki, Masanori

2018-04-01

The charge carrier mobility of a solution-processable low-molecular-weight organic semiconductor material, i.e., 1,4,8,11,15,18,22,25-octahexylphthalocyanine copper complex (C6PcCu), was investigated by the time-of-flight technique. The anomalous ambipolar carrier mobility was discussed from the viewpoint of the molecular packing structure, which was clarified by single-crystal X-ray structure analysis. In the comparison between the molecular packing structures of C6PcCu and its metal-free-type homologue, it was found that the difference in carrier mobility originates from the rotation of the molecule, which is caused by the steric hindrance due to the introduction of a center metal and the interpenetration of the nonperipheral alkyl chains.

Proton-coupled electron-transfer reduction of dioxygen catalyzed by a saddle-distorted cobalt phthalocyanine.

PubMed

Honda, Tatsuhiko; Kojima, Takahiko; Fukuzumi, Shunichi

2012-03-07

Proton-coupled electron-transfer reduction of dioxygen (O(2)) to afford hydrogen peroxide (H(2)O(2)) was investigated by using ferrocene derivatives as reductants and saddle-distorted (α-octaphenylphthalocyaninato)cobalt(II) (Co(II)(Ph(8)Pc)) as a catalyst under acidic conditions. The selective two-electron reduction of O(2) by dimethylferrocene (Me(2)Fc) and decamethylferrocene (Me(10)Fc) occurs to yield H(2)O(2) and the corresponding ferrocenium ions (Me(2)Fc(+) and Me(10)Fc(+), respectively). Mechanisms of the catalytic reduction of O(2) are discussed on the basis of detailed kinetics studies on the overall catalytic reactions as well as on each redox reaction in the catalytic cycle. The active species to react with O(2) in the catalytic reaction is switched from Co(II)(Ph(8)Pc) to protonated Co(I)(Ph(8)PcH), depending on the reducing ability of ferrocene derivatives employed. The protonation of Co(II)(Ph(8)Pc) inhibits the direct reduction of O(2); however, the proton-coupled electron transfer from Me(10)Fc to Co(II)(Ph(8)Pc) and the protonated [Co(II)(Ph(8)PcH)](+) occurs to produce Co(I)(Ph(8)PcH) and [Co(I)(Ph(8)PcH(2))](+), respectively, which react immediately with O(2). The rate-determining step is a proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) in the Co(II)(Ph(8)Pc)-catalyzed cycle with Me(2)Fc, whereas it is changed to the electron-transfer reduction of [Co(II)(Ph(8)PcH)](+) by Me(10)Fc in the Co(I)(Ph(8)PcH)-catalyzed cycle with Me(10)Fc. A single crystal of monoprotonated [Co(III)(Ph(8)Pc)](+), [Co(III)Cl(2)(Ph(8)PcH)], produced by the proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) with HCl, was obtained, and the crystal structure was determined in comparison with that of Co(II)(Ph(8)Pc). © 2012 American Chemical Society

Improving the efficiency and directivity of THz photoconductive antennas by using a defective photonic crystal substrate

NASA Astrophysics Data System (ADS)

Rahmati, Ehsan; Ahmadi-Boroujeni, Mehdi

2018-04-01

One of the shortcomings of photoconductive (PC) antennas in terahertz (THz) generation is low effective radiated power in the desirable direction. In this paper, we propose a defective photonic crystal (DPC) substrate consisting of a customized 2D array of air holes drilled into a solid substrate in order to improve the radiation characteristics of THz PC antennas. The effect of the proposed structure on the performance of a conventional THz PC antenna has been examined from several aspects including radiation efficiency, directivity, and field distribution. By comparing the radiation performance of the THz antenna on the proposed DPC substrate to that of the conventional solid substrate, it is shown that the proposed technique can significantly improve the efficiency and directivity of the THz PC antenna over a wide frequency range. It is achieved by reducing the amount of power coupled to the substrate surface waves and limiting the radiation in undesirable directions. In addition, it is found that the sensitivity of directivity to the substrate thickness is considerably decreased and the adverse Fabry-Perot effects of the thick substrate are reduced by the application of the proposed DPC substrate.

Structure and biological function of ENPP6, a choline-specific glycerophosphodiester-phosphodiesterase

PubMed Central

Morita, Junko; Kano, Kuniyuki; Kato, Kazuki; Takita, Hiroyuki; Sakagami, Hideki; Yamamoto, Yasuo; Mihara, Emiko; Ueda, Hirofumi; Sato, Takanao; Tokuyama, Hidetoshi; Arai, Hiroyuki; Asou, Hiroaki; Takagi, Junichi; Ishitani, Ryuichiro; Nishimasu, Hiroshi; Nureki, Osamu; Aoki, Junken

2016-01-01

Choline is an essential nutrient for all living cells and is produced extracellularly by sequential degradation of phosphatidylcholine (PC). However, little is known about how choline is produced extracellularly. Here, we report that ENPP6, a choline-specific phosphodiesterase, hydrolyzes glycerophosphocholine (GPC), a degradation product of PC, as a physiological substrate and participates in choline metabolism. ENPP6 is highly expressed in liver sinusoidal endothelial cells and developing oligodendrocytes, which actively incorporate choline and synthesize PC. ENPP6-deficient mice exhibited fatty liver and hypomyelination, well known choline-deficient phenotypes. The choline moiety of GPC was incorporated into PC in an ENPP6-dependent manner both in vivo and in vitro. The crystal structure of ENPP6 in complex with phosphocholine revealed that the choline moiety of the phosphocholine is recognized by a choline-binding pocket formed by conserved aromatic and acidic residues. The present study provides the molecular basis for ENPP6-mediated choline metabolism at atomic, cellular and tissue levels. PMID:26888014

Spectral plasmonic effect in the nano-cavity of dye-doped nanosphere-based photonic crystals.

PubMed

Yadav, Ashish; Danesh, Mohammad; Zhong, Liubiao; Cheng, Gary J; Jiang, Lin; Chi, Lifeng

2016-04-22

We demonstrated three-dimensional PMMA-based photonic crystal (3D-PC) nanostructures attached to Au nanoparticles (AuNPs), which undergo self-organization into super lattice planes and enhance the fluorescence properties. This new structure exhibited interesting tunable spectral, peak broadening plasmonic behavior because of strong plasmonic interaction at high laser powers. The presented work provides an important tool to improve the efficiency of dye laser applications.

Array integration of thousands of photonic crystal nanolasers

NASA Astrophysics Data System (ADS)

Watanabe, Takumi; Abe, Hiroshi; Nishijima, Yoshiaki; Baba, Toshihiko

2014-03-01

Photonic crystal (PC) nanolasers often consist of air-bridge PC slab, which enhances optical confinement while limiting its size to 30 × 30 μm2 due to the mechanical fragileness. This limit is broken by resin-mediated bonding of the PC slab on a host substrate. In this paper, we demonstrate a GaInAsP PC slab with a size of over 100 × 100 μm2 in which 1089, 2376, and 11 664 nanolasers showing high-yield laser operation are integrated.

Organic Light Emitting Diodes with Opal Photonic Crystal Layer and Carbon Nanotube Anode

NASA Astrophysics Data System (ADS)

Ovalle Robles, Raquel; Del Rocio Nava, Maria; Williams, Christopher; Zhang, Mei; Fang, Shaoli; Lee, Sergey; Baughman, Ray; Zakhidov, Anvar

2007-03-01

We report electroluminescence intensity and spectral changes in light emission from organic light emitting diode (OLEDs) structures, which have thin transparent films of opal photonic crystal (PC). The anode in such PC-OLED is laminated on opal layer from free standing optically transparent multiwall carbon nanotubes (T-CNT) sheets made by dry spinning from CVD grown forests. Silica and polystyrene opal films were grown on glass substrates by vertical sedimentation in colloids in thermal baths and the particle size of opal spheres ranges from 300 nm to 450 nm. The use of T-CNTs, (coated by PEDOT-PSS to avoid shorting) as hole injector, allows to eliminate the use of vacuum deposition of metals and permits to achieve tunneling hole injection regime from CNT tips into Alq^3 emission layer

Reversible thermochromic response based on photonic crystal structure in butterfly wing

NASA Astrophysics Data System (ADS)

Wang, Wanlin; Wang, Guo Ping; Zhang, Wang; Zhang, Di

2018-01-01

Subtle responsive properties can be achieved by the photonic crystal (PC) nanostructures of butterfly based on thermal expansion effect. The studies focused on making the sample visually distinct. However, the response is restricted by limited thermal expansion coefficients. We herein report a new class of reversible thermochromic response achieved by controlling the ambient refractive index in butterfly PC structure. The photonic ethanol-filled nanoarchitecture sample is simply assembled by sealing liquid ethanol filling Papilio ulysses butterfly wing. Volatile ethanol is used to modulate the ambient refractive index. The sample is sealed with glasses to ensure reversibility. Liquid ethanol filling butterfly wing demonstrated significant allochroic response to ambient refractive index, which can be controlled by the liquefaction and vaporization of ethanol. This design is capable of converting thermal energy into visual color signals. The mechanism of this distinct response is simulated and proven by band theory. The response properties are performed with different filled chemicals and different structure parameters. Thus, the reversible thermochromic response design might have potential use in the fields such as detection, photonic switch, displays, and so forth.

All-optical diode structure based on asymmetrical coupling by a micro-cavity and FP cavity at two sides of photonic crystal waveguide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Bin, E-mail: liubin-d@126.com; Liu, Yun-Feng; He, Xing-Dao

2016-06-15

A high efficiency all-optical diode based on photonic crystal (PC) waveguide has been proposed and numerically investigated by finite-difference time-domain (FDTD) method. The structure is asymmetrically coupled by a micro-cavity containing nonlinear Kerr medium and a FP cavity at sides of PC waveguide. Because of interference between two cavities, Fano peak and FP peak can both appear in transmission spectra and unidirectional transmission can be achieved. The working wavelength can set between two peaks and near to the Fano peak. For forward launch with suitable light intensity, nonlinear Kerr effect of micro-cavity can been excited. It will result in redmore » shift of Fano peak and achieving forward transmission. But for backward launch, a stronger incidence light is needed to the excite Kerr effect due to the design of asymmetric structure. This design has many advantages, including high maximum transmittance, high transmittance contrast ratio, low power threshold, short response time, and ease of integration.« less

Photoconductive and electro-optic effects in (Cd,Mg)Te single crystals measured in an experiment-on-chip configuration

DOE PAGES

Serafini, John; Hossain, A.; James, R. B.; ...

2017-07-03

We present our studies on both photoconductive (PC) and electro-optic (EO) responses of (Cd,Mg)Te single crystals. In an In-doped Cd 0.92Mg 0.08Te single crystal, subpicosecond electrical pulses were optically generated via a PC effect, coupled into a transmission line, and, subsequently, detected using an internal EO sampling scheme, all in the same (Cd,Mg)Te material. For photo-excitation and EO sampling, we used femtosecond optical pulses generated by the same Ti:sapphire laser with the wavelength 410 and 820 nm, respectively. The shortest transmission line distance between the optical excitation and EO sampling points was 75 μm. By measuring the transient waveforms atmore » different distances from the excitation point, we calculated the transmission-line complex propagation factor, as well as the THz frequency attenuation factor and the propagation velocity, all of which allowed us to reconstruct the electromagnetic transient generated directly at the excitation point, showing that the original PC transient was subpicosecond in duration with a fall time of ~500 fs. Finally, the measured EO retardation, together with the amount of the electric-field penetration, allowed us to determine the magnitude of the internal EO effect in our (Cd,Mg)Te crystal. The obtained THz-frequency EO coefficient was equal to 0.4 pm/V, which is at the lower end among the values reported for CdTe-based ternaries, due to a twinned structure and misalignment of the tested (Cd,Mg)Te crystal.« less

High-pressure Raman study on the superconducting pyrochlore oxide Cd2Re2O7

NASA Astrophysics Data System (ADS)

Matsubayashi, Yasuhito; Hasegawa, Takumi; Ogita, Norio; Yamaura, Jun-ichi; Hiroi, Zenji

2018-05-01

The superconducting pyrochlore oxide Cd2Re2O7 (Tc = 1 K), which is now considered as a candidate of the spin-orbit-coupled metal, shows an inversion-symmetry-breaking structural transition at Ts1 = 200 K . Ts1 decreases with increasing pressure and disappears at around Pc = 4.2 GPa , where at least four high-pressure phases with tiny structural distortions are suggested by means of powder X-ray diffraction [Yamaura PRB 2017]. We have carried out Raman scattering experiments to investigate changes in the crystal symmetry under high pressures up to 4.8 GPa. A structural transition at 1.9-3.0 GPa and the recovery of inversion symmetry above Pc are observed at 12 K.

Silicon on-chip bandpass filters for the multiplexing of high sensitivity photonic crystal microcavity biosensors

PubMed Central

Chakravarty, Swapnajit; Yang, Chun-Ju; Wang, Zheng; Tang, Naimei; Fan, Donglei; Chen, Ray T.

2015-01-01

A method for the dense integration of high sensitivity photonic crystal (PC) waveguide based biosensors is proposed and experimentally demonstrated on a silicon platform. By connecting an additional PC waveguide filter to a PC microcavity sensor in series, a transmission passband is created, containing the resonances of the PC microcavity for sensing purpose. With proper engineering of the passband, multiple high sensitivity PC microcavity sensors can be integrated into microarrays and be interrogated simultaneously between a single input and a single output port. The concept was demonstrated with a 2-channel L55 PC biosensor array containing PC waveguide filters. The experiment showed that the sensors on both channels can be monitored simultaneously from a single output spectrum. Less than 3 dB extra loss for the additional PC waveguide filter is observed. PMID:25829549

Photonic crystal enhanced fluorescence using a quartz substrate to reduce limits of detection

PubMed Central

Pokhriyal, Anusha; Lu, Meng; Chaudhery, Vikram; Huang, Cheng-Sheng; Schulz, Stephen; Cunningham, Brian T.

2010-01-01

A Photonic Crystal (PC) surface fabricated upon a quartz substrate using nanoimprint lithography has been demonstrated to enhance light emission from fluorescent molecules in close proximity to the PC surface. Quartz was selected for its low autofluorescence characteristics compared to polymer-based PCs, improving the detection sensitivity and signal-to-noise ratio (SNR) of PC Enhanced Fluorescence (PCEF). Nanoimprint lithography enables economical fabrication of the subwavelength PCEF surface structure over entire 1x3 in2 quartz slides. The demonstrated PCEF surface supports a transverse magnetic (TM) resonant mode at a wavelength of λ = 632.8 nm and an incident angle of θ = 11°, which amplifies the electric field magnitude experienced by surface-bound fluorophores. Meanwhile, another TM mode at a wavelength of λ = 690 nm and incident angle of θ = 0° efficiently directs the fluorescent emission toward the detection optics. An enhancement factor as high as 7500 × was achieved for the detection of LD-700 dye spin-coated upon the PC, compared to detecting the same material on an unpatterned glass surface. The detection of spotted Alexa-647 labeled polypeptide on the PC exhibits a 330 × SNR improvement. Using dose-response characterization of deposited fluorophore-tagged protein spots, the PCEF surface demonstrated a 140 × lower limit of detection compared to a conventional glass substrate. PMID:21164826

Frequency dependent steering with backward leaky waves via photonic crystal interface layer.

PubMed

Colak, Evrim; Caglayan, Humeyra; Cakmak, Atilla O; Villa, Alessandro D; Capolino, Filippo; Ozbay, Ekmel

2009-06-08

A Photonic Crystal (PC) with a surface defect layer (made of dimers) is studied in the microwave regime. The dispersion diagram is obtained with the Plane Wave Expansion Method. The dispersion diagram reveals that the dimer-layer supports a surface mode with negative slope. Two facts are noted: First, a guided (bounded) wave is present, propagating along the surface of the dimer-layer. Second, above the light line, the fast traveling mode couple to the propagating spectra and as a result a directive (narrow beam) radiation with backward characteristics is observed and measured. In this leaky mode regime, symmetrical radiation patterns with respect to the normal to the PC surface are attained. Beam steering is observed and measured in a 70 degrees angular range when frequency ranges in the 11.88-13.69 GHz interval. Thus, a PC based surface wave structure that acts as a frequency dependent leaky wave antenna is presented. Angular radiation pattern measurements are in agreement with those obtained via numerical simulations that employ the Finite Difference Time Domain Method (FDTD). Finally, the backward radiation characteristics that in turn suggest the existence of a backward leaky mode in the dimer-layer are experimentally verified using a halved dimer-layer structure.

Reducing support loss in micromechanical ring resonators using phononic band-gap structures

NASA Astrophysics Data System (ADS)

Hsu, Feng-Chia; Hsu, Jin-Chen; Huang, Tsun-Che; Wang, Chin-Hung; Chang, Pin

2011-09-01

In micromechanical resonators, energy loss via supports into the substrates may lead to a low quality factor. To eliminate the support loss, in this paper a phononic band-gap structure is employed. We demonstrate a design of phononic-crystal (PC) strips used to support extensional wine-glass mode ring resonators to increase the quality factor. The PC strips are introduced to stop elastic-wave propagation by the band-gap and deaf-band effects. Analyses of resonant characteristics of the ring resonators and the dispersion relations, eigenmodes, and transmission properties of the PC strips are presented. With the proposed resonator architecture, the finite-element simulations show that the leaky power is effectively reduced and the stored energy inside the resonators is enhanced simultaneously as the operating frequencies of the resonators are within the band gap or deaf bands. Realization of a high quality factor micromechanical ring resonator with minimized support loss is expected.

Bacteriophage T5 encodes a homolog of the eukaryotic transcription coactivator PC4 implicated in recombination-dependent DNA replication.

PubMed

Steigemann, Birthe; Schulz, Annina; Werten, Sebastiaan

2013-11-15

The RNA polymerase II cofactor PC4 globally regulates transcription of protein-encoding genes through interactions with unwinding DNA, the basal transcription machinery and transcription activators. Here, we report the surprising identification of PC4 homologs in all sequenced representatives of the T5 family of bacteriophages, as well as in an archaeon and seven phyla of eubacteria. We have solved the crystal structure of the full-length T5 protein at 1.9Å, revealing a striking resemblance to the characteristic single-stranded DNA (ssDNA)-binding core domain of PC4. Intriguing novel structural features include a potential regulatory region at the N-terminus and a C-terminal extension of the homodimerisation interface. The genome organisation of T5-related bacteriophages points at involvement of the PC4 homolog in recombination-dependent DNA replication, strongly suggesting that the protein corresponds to the hitherto elusive replicative ssDNA-binding protein of the T5 family. Our findings imply that PC4-like factors intervene in multiple unwinding-related processes by acting as versatile modifiers of nucleic acid conformation and raise the possibility that the eukaryotic transcription coactivator derives from ancestral DNA replication, recombination and repair factors. © 2013.

Silicon on-chip bandpass filters for the multiplexing of high sensitivity photonic crystal microcavity biosensors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Hai, E-mail: hai.yan@utexas.edu; Zou, Yi; Yang, Chun-Ju

A method for the dense integration of high sensitivity photonic crystal (PC) waveguide based biosensors is proposed and experimentally demonstrated on a silicon platform. By connecting an additional PC waveguide filter to a PC microcavity sensor in series, a transmission passband is created, containing the resonances of the PC microcavity for sensing purpose. With proper engineering of the passband, multiple high sensitivity PC microcavity sensors can be integrated into microarrays and be interrogated simultaneously between a single input and a single output port. The concept was demonstrated with a 2-channel L55 PC biosensor array containing PC waveguide filters. The experimentmore » showed that the sensors on both channels can be monitored simultaneously from a single output spectrum. Less than 3 dB extra loss for the additional PC waveguide filter is observed.« less

Characterization of LiBC by phase-contrast scanning transmission electron microscopy.

PubMed

Krumeich, Frank; Wörle, Michael; Reibisch, Philipp; Nesper, Reinhard

2014-08-01

LiBC was used as a model compound for probing the applicability of phase-contrast (PC) imaging in an aberration-corrected scanning transmission electron microscope (STEM) to visualize lithium distributions. In the LiBC structure, boron and carbon are arranged to hetero graphite layers between which lithium is incorporated. The crystal structure is reflected in the PC-STEM images recorded perpendicular to the layers. The experimental images and their defocus dependence match with multi-slice simulations calculated utilizing the reciprocity principle. The observation that a part of the Li positions is not occupied is likely an effect of the intense electron beam triggering Li displacement. Copyright © 2013 Elsevier Ltd. All rights reserved.

Coupling of free space sub-terahertz waves into dielectric slabs using PC waveguides.

PubMed

Ghattan, Z; Hasek, T; Shahabadi, M; Koch, M

2008-04-28

The paper presents theoretical and experimental results on photonic crystal structures which work under the self-collimation condition to couple free space waves into dielectric slabs in the sub-terahertz range. Using a standard machining process, two-dimensional photonic crystal structures consisting of a square array of air holes in the dielectric medium are fabricated. One of the structures has two adjacent parallel line-defects that improve the coupling efficiency. This leads to a combination of self-collimation and directional emission of electromagnetic waves. The experimental results are in good agreement with those of the Finite- Element-Method calculations. Experimentally we achieve a coupling efficiency of 63%.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Dongbo; Zhao, Jinfeng, E-mail: jinfeng.zhao@tongji.edu.cn; Li, Libing

In this work, we applied a robust and fully air-coupled method to investigate the propagation of the lowest-order antisymmetric Lamb (A{sub 0}) mode in both a stubbed and an air-drilled phononic-crystal (PC) plate. By measuring simply the radiative acoustic waves of A{sub 0} mode close to the plate surface, we observed the band gaps for the stubbed PC plate caused by either the local resonance or the Bragg scattering, in frequency ranges in good agreement with theoretical predictions. We measured then the complete band gap of A{sub 0} mode for the air-drilled PC plate, in good agreement with the bandmore » structures. Finally, we compared the measurements made using the air-coupled method with those obtained by the laser ultrasonic technique.« less

Membrane protein crystallization in meso: lipid type-tailoring of the cubic phase.

PubMed Central

Cherezov, Vadim; Clogston, Jeffrey; Misquitta, Yohann; Abdel-Gawad, Wissam; Caffrey, Martin

2002-01-01

Hydrated monoolein forms the cubic-Pn3m mesophase that has been used for in meso crystallization of membrane proteins. The crystals have subsequently provided high-resolution structures by crystallographic means. It is possible that the hosting cubic phase created by monoolein alone, which itself is not a common membrane component, will limit the range of membrane proteins crystallizable by the in meso method. With a view to expanding the range of applicability of the method, we investigated by x-ray diffraction the degree to which the reference cubic-Pn3m phase formed by hydrated monoolein could be modified by other lipid types. These included phosphatidylcholine (PC), phosphatidylethanolamine, phosphatidylserine, cardiolipin, lyso-PC, a polyethylene glycol-lipid, 2-monoolein, oleamide, and cholesterol. The results show that all nine lipids were accommodated in the cubic phase to some extent without altering phase identity. The positional isomer, 2-monoolein, was tolerated to the highest level. The least well tolerated were the anionic lipids, followed by lyso-PC. The others were accommodated to the extent of 20-25 mol %. Beyond a certain concentration limit, the lipid additives either triggered one or a series of phase transitions or saturated the phase and separated out as crystals, as seen with oleamide and cholesterol. The series of phases observed and their order of appearance were consistent with expectations in terms of interfacial curvature changes. The changes in phase type and microstructure have been rationalized on the basis of lipid molecular shape, interfacial curvature, and chain packing energy. The data should prove useful in the rational design of cubic phase crystallization matrices with different lipid profiles that match the needs of a greater range of membrane proteins. PMID:12496106

Positron Interactions with Oriented Polymers and with Chiral Quartz Crystals

NASA Astrophysics Data System (ADS)

Wu, Fei

Positron annihilation in various materials has been applied to characterize microstructure for decades. In this work, PALS was used to study material nanostructure, with a focus on the size and density of free volume and hole relaxation properties in polycarbonate (PC) and polymethylmethacrylate (PMMA); fundamental studies of polarized positron interaction with chiral crystals were also studied. Free volume relaxation in PC and PMMA with different levels of simple shear orientation was studied by PALS. Effects of applied pressure on the free volume recovery were evaluated. Combining the bulk- and pressure-dependent PALS analyses, the removal of applied pressure led to free-volume relaxation in all samples studied. The alignment of the polymer chains and free-volume holes imposes molecular restrictions on the molecular mobility of both PC and PMMA in their glassy states. Results indicated that the relaxation of the free volume holes at temperatures below glass transition is mostly reversible. Longitudinally polarized positron particles were used to reveal asymmetric interactions in chiral quartz crystals. Experimental results showed a significant intensity difference in free positronium annihilation for left handed (LH) and right handed (RH) chiral quartz crystals. Doppler broadening energy spectra (DBES) of z-cut LH or RH quartz disks at different angles were also measured by an "S parameter" to probe the observed difference. It was found that obtained annihilation energy difference of DBES was in agreement with the result of positron annihilation in bulk chiral crystals. PALS was used to compare different orientations and confirm asymmetric interactions in natural versus synthetic quartz LH and RH crystals in z and non-z orientations. Significant lifetime and intensity differences in free positronium annihilation for LH and RH quartz crystals were observed. The trend was found to be same in the related crystallographic orientations of the LH or RH crystals; the direction of incident positrons, z or non-z, did not affect the observed differences in lifetime and intensity trends. The results confirmed the existence of differential interactions of positronium with the asymmetric lattice structures of LH and RH quartz crystals.

Enhanced sensitivity to near-infrared with high fill factor in small molecular organic solar cells

NASA Astrophysics Data System (ADS)

Shim, Hyun-Sub; Kim, Hyo Jung; Kim, Ji Whan; Kim, Sei-Yong; Jeong, Won-Ik; Kim, Tae-Min; Kim, Jang-Joo

2012-09-01

High efficiency near-infrared (NIR) absorbing solar cells based on lead phthalocyanine (PbPc) are reported using copper iodide (CuI) as a templating layer to control the crystal structure of PbPc. Devices with CuI inserted between the ITO and PbPc layers exhibit a two times enhancement of the JSC compared to the case in the absence of the CuI layer. This is due to the increase of crystallinity in the molecules grown on the CuI templating layer, which is investigated via an x-ray diffraction study. Moreover, fill factor is also enhanced to 0.63 from 0.57 due to low series resistance although the additional CuI layer is inserted between the ITO and the PbPc layer. As a result, the corrected power conversion efficiency of 2.5% was obtained, which is the highest one reported up to now among the PbPc based solar cells.

Novel in-situ nanocomposites of phthalonitrile end-capped polyarylene ether nitrile/copper phthalocyanine

NASA Astrophysics Data System (ADS)

Tong, Lifen; Wei, Renbo; Liu, Xiaobo

2017-01-01

A novel phthalonitrile end-capped polyarylene ether nitrile (PEN-Ph)/copper phthalocyanine (CuPc) nanocomposites which possesses crosslinking reaction combined with crystallization behaviour were prepared successfully through in-situ reaction and hot-compression. In the presence of copper ion, CuPc were formed through crosslinking reaction among the phthalonitrile at the end of the PEN-Ph main chain and 1, 3, 5-Tri-(3, 4-dicyanophenoxy) benzene (TPh). Besides, the formed CuPc can play the role of nucleating agent to improve the crystallinity of the polymers. The influence of the crosslinking reaction and crystallization behaviour were investigated. The results show that the crystallization and crosslinking coexist in the system at the same time. Scanning electron microscope (SEM) images show that the crystals of the PEN-Ph grow after the hot-compressing procedure. Moreover, the glass transition temperature (Tg) increases while the crystallinity declines slightly with the low amount of copper ions. The increase of Tg is mainly caused by the crosslinking reaction, indicating that the copper can be used as a crosslinking agent in this system. Due to formation of the CuPc and the crystallization behaviour, the dielectric constant increased as expected from 3.2 to 4.9 while the dielectric loss decreased. Therefore, the PEN-Ph/CuPc in-situ nanocomposites will have a good prospect for application in electronic field.

Achieving omnidirectional photonic band gap in sputter deposited TiO{sub 2}/SiO{sub 2} one dimensional photonic crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jena, S., E-mail: shuvendujena9@gmail.com; Tokas, R. B.; Sarkar, P.

2015-06-24

The multilayer structure of TiO{sub 2}/SiO{sub 2} (11 layers) as one dimensional photonic crystal (1D PC) has been designed and then fabricated by using asymmetric bipolar pulse DC magnetron sputtering technique for omnidirectional photonic band gap. The experimentally measured photonic band gap (PBG) in the visible region is well matched with the theoretically calculated band structure (ω vs. k) diagram. The experimentally measured omnidirectional reflection band of 44 nm over the incident angle range of 0°-70° is found almost matching within the theoretically calculated band.

Nano-lithographically fabricated titanium dioxide based visible frequency three dimensional gap photonic crystal.

PubMed

Subramania, Ganapathi; Lee, Yun-Ju; Brener, Igal; Luk, Ting-Shan; Clem, Paul G

2007-10-01

Photonic crystals (PC) have emerged as important types of structures for light manipulation. Ultimate control of light is possible by creating PCs with a complete three dimensional (3D) gap [1, 2]. This has proven to be a considerable challenge in the visible and ultraviolet frequencies mainly due to complications in integrating transparent, high refractive index (n) materials with fabrication techniques to create ~ 100nm features with long range translational order. In this letter, we demonstrate a nano-lithography approach based on a multilevel electron beam direct write and physical vapor deposition, to fabricate four-layer titania woodpile PCs that potentially exhibit complete 3D gap at visible wavelengths. We achieved a short wavelength bandedge of 525nm with a 300nm lattice constant PC. Due to the nanoscale precision and capability for defect control, the nanolithography approach represents an important step toward novel visible photonic devices for lighting, lasers, sensing and biophotonics.

Patterned Colloidal Photonic Crystals.

PubMed

Hou, Jue; Li, Mingzhu; Song, Yanlin

2018-03-01

Colloidal photonic crystals (PCs) have been well developed because they are easy to prepare, cost-effective, and versatile with regards to modification and functionalization. Patterned colloidal PCs contribute a novel approach to constructing high-performance PC devices with unique structures and specific functions. In this review, an overview of the strategies for fabricating patterned colloidal PCs, including patterned substrate-induced assembly, inkjet printing, and selective immobilization and modification, is presented. The advantages of patterned PC devices are also discussed in detail, for example, improved detection sensitivity and response speed of the sensors, control over the flow direction and wicking rate of microfluidic channels, recognition of cross-reactive molecules through an array-patterned microchip, fabrication of display devices with tunable patterns, well-arranged RGB units, and wide viewing-angles, and the ability to construct anti-counterfeiting devices with different security strategies. Finally, the perspective of future developments and challenges is presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radical-lanthanide ferromagnetic interaction in a T bIII bis-phthalocyaninato complex

NASA Astrophysics Data System (ADS)

Komijani, Dorsa; Ghirri, Alberto; Bonizzoni, Claudio; Klyatskaya, Svetlana; Moreno-Pineda, Eufemio; Ruben, Mario; Soncini, Alessandro; Affronte, Marco; Hill, Stephen

2018-02-01

Recent studies have highlighted the importance of organic ligands in the field of molecular spintronics, via which delocalized electron-spin density can mediate magnetic coupling to otherwise localized 4 f moments of lanthanide ions, which show tremendous potential for single-molecule device applications. To this end, high-field/high-frequency electron paramagnetic resonance (EPR) spectroscopy is employed to study a neutral terbium bis-phthalocyaninato metalorganic complex, [TbPc2 ] 0, with the aim of understanding the magnetic interaction between the Ising-like moment of the lanthanide ion and the unpaired spin density on the coordinating organic radical ligand. The measurements were performed on a previously unknown [TbPc2 ] 0 structural phase crystallizing in the Pnma space group. EPR measurements on powder samples of [TbPc2 ] 0 reveal an anisotropic spectrum, which is attributed to the spin-1/2 radical coupled weakly to the EPR-silent T bIII ion. Extensive double-axis rotation studies on a single crystal reveal two independent spin-1/2 signals with differently oriented (albeit identical) uniaxial g -tensors, in complete agreement with x-ray structural studies that indicate two molecular orientations within the unit cell. The easy-axis nature of the radical EPR spectra thus reflects the coupling to the Ising-like T bIII moment. This is corroborated by studies of the isostructural [YPc2 ] 0 analog (where Y is nonmagnetic yttrium), which gives a completely isotropic radical EPR signal. The experimental results for the terbium complex are well explained on the basis of an effective model that introduces a weak ferromagnetic Heisenberg coupling between an isotropic spin-1/2 and an anisotropic spin-orbital moment, J =6 , that mimics the known, strong easy-axis Tb ⋯P c2 crystal-field interaction.

Synthesis, crystal structure, Hirshfeld surfaces analysis and anti-ischemic activity of cinnamide derivatives

NASA Astrophysics Data System (ADS)

Zhong, Jian-gang; Han, Jia-pei; Li, Xiao-feng; Xu, Yi; Zhong, Yan; Wu, Bin

2018-02-01

Two cinnamide derivatives, namely, (E)-1-(4-(bis(4-methylphenyl)- methyl)piperazin-1-yl)-3-(3,4-diethoxyphenyl)prop-2-en-1-one (5) and (E)-1-(4-(bis- (4-fluorophenyl)methyl)piperazin-1-yl)-3-(4-methoxyphenyl)prop-2-en-1-one (6), have been synthesized and characterized by IR spectra, High resolution mass spectra, 1H NMR spectra, 13C NMR spectra. The compound 5 is a novel compound and has never been reported in the literature. Their crystal structures were studied by single-crystal X-ray diffraction. They all crystallize in the monoclinic system. The single-crystal X-ray revealed that compound 5 has infinite X-shaped 1-D polymeric chains structure and compound 6 has a layered 3-D structure by intermolecular interactions. Hirshfeld surface analysis demonstrated the presence of H⋯H, O⋯H, C⋯H, F⋯H, Csbnd H⋯π and π⋯π intermolecular interactions. In addition, the MTT assay results indicated that the compounds 5 and 6 display effective activities against neurotoxicity which is induced by glutamine in PC12 cells. The in vivo experiment indicated that the compound 6 has a good protective effect on cerebral infarction.

Performance analysis of all-optical XOR gate with photonic crystal semiconductor optical amplifier-assisted Mach-Zehnder interferometer at 160 Gb/s

NASA Astrophysics Data System (ADS)

Kotb, Amer; Zoiros, Kyriakos E.

2017-11-01

The photonic crystal (PC) can be used to prohibit, confine, or control the propagation of light in a photonic band-gap. The performance of an ultrafast exclusive disjunction (XOR) gate-implemented with a photonic crystal semiconductor optical amplifier (PC-SOA)-assisted Mach-Zehnder interferometer (MZI) is numerically investigated and analyzed at a data rate of 160 Gb/s. The impact of the data signals and PC-SOA's critical parameters on the output quality factor (Q-factor) is examined and assessed. The simulation results demonstrate that the XOR gate which is based on the proposed scheme is capable of operating at the target data rate with logical correctness and high quality. This is achieved with better performance than when having conventional SOAs in the MZI, which justifies employing PC-SOAs as nonlinear elements.

Conformational Sampling and Binding Site Assessment of Suppression of Tumorigenicity 2 Ectodomain

PubMed Central

Yang, Chao-Yie; Delproposto, James; Chinnaswamy, Krishnapriya; Brown, William Clay; Wang, Shuying; Stuckey, Jeanne A.; Wang, Xinquan

2016-01-01

Suppression of Tumorigenicity 2 (ST2), a member of the interleukin-1 receptor (IL-1R) family, activates type 2 immune responses to pathogens and tissue damage via binding to IL-33. Dysregulated responses contribute to asthma, graft-versus-host and autoinflammatory diseases and disorders. To study ST2 structure for inhibitor development, we performed the principal component (PC) analysis on the crystal structures of IL1-1R1, IL1-1R2, ST2 and the refined ST2 ectodomain (ST2ECD) models, constructed from previously reported small-angle X-ray scattering data. The analysis facilitates mapping of the ST2ECD conformations to PC subspace for characterizing structural changes. Extensive coverage of ST2ECD conformations was then obtained using the accelerated molecular dynamics simulations started with the IL-33 bound ST2ECD structure as instructed by their projected locations on the PC subspace. Cluster analysis of all conformations further determined representative conformations of ST2ECD ensemble in solution. Alignment of the representative conformations with the ST2/IL-33 structure showed that the D3 domain of ST2ECD (containing D1-D3 domains) in most conformations exhibits no clashes with IL-33 in the crystal structure. Our experimental binding data informed that the D1-D2 domain of ST2ECD contributes predominantly to the interaction between ST2ECD and IL-33 underscoring the importance of the D1-D2 domain in binding. Computational binding site assessment revealed one third of the total detected binding sites in the representative conformations may be suitable for binding to potent small molecules. Locations of these sites include the D1-D2 domain ST2ECD and modulation sites conformed to ST2ECD conformations. Our study provides structural models and analyses of ST2ECD that could be useful for inhibitor discovery. PMID:26735493

Sensitive Detection of Protein and miRNA Cancer Biomarkers using Silicon-Based Photonic Crystals and A Resonance Coupling Laser Scanning Platform

PubMed Central

George, Sherine; Chaudhery, Vikram; Lu, Meng; Takagi, Miki; Amro, Nabil; Pokhriyal, Anusha; Tan, Yafang; Ferreira, Placid; Cunningham, Brian T.

2013-01-01

Enhancement of the fluorescent output of surface-based fluorescence assays by performing them upon nanostructured photonic crystal (PC) surfaces has been demonstrated to increase signal intensities by >8000×. Using the multiplicative effects of optical resonant coupling to the PC in increasing the electric field intensity experienced by fluorescent labels (“enhanced excitation”) and the spatially biased funneling of fluorophore emissions through coupling to PC resonances (“enhanced extraction”), PC enhanced fluorescence (PCEF) can be adapted to reduce the limits of detection of disease biomarker assays, and to reduce the size and cost of high sensitivity detection instrumentation. In this work, we demonstrate the first silicon-based PCEF detection platform for multiplexed biomarker assay. The sensor in this platform is a silicon-based PC structure, comprised of a SiO2 grating that is overcoated with a thin film of high refractive index TiO2 and is produced in a semiconductor foundry for low cost, uniform, and reproducible manufacturing. The compact detection instrument that completes this platform was designed to efficiently couples fluorescence excitation from a semiconductor laser to the resonant optical modes of the PC, resulting in elevated electric field strength that is highly concentrated within the region <100 nm from the PC surface. This instrument utilizes a cylindrically focused line to scan a microarray in <1 minute. To demonstrate the capabilities of this sensor-detector platform, microspot fluorescent sandwich immunoassays using secondary antibodies labeled with Cy5 for two cancer biomarkers (TNF-α and IL-3) were performed. Biomarkers were detected at concentrations as low as 0.1 pM. In a fluorescent microarray for detection of a breast cancer miRNA biomarker miR-21, the miRNA was detectable at a concentration of 0.6 pM. PMID:23963502

Synthesis, structures, and properties of crystalline salts with radical anions of metal-containing and metal-free phthalocyanines.

PubMed

Konarev, Dmitri V; Kuzmin, Alexey V; Faraonov, Maxim A; Ishikawa, Manabu; Khasanov, Salavat S; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

2015-01-12

Radical anion salts of metal-containing and metal-free phthalocyanines [MPc(3-)](·-), where M = Cu(II), Ni(II), H2, Sn(II), Pb(II), Ti(IV)O, and V(IV)O (1-10) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long C-Nimine bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1-10 show new bands at 833-1041 nm in the NIR range, whereas the Q- and Soret bands are blue-shifted by 0.13-0.25 eV (38-92 nm) and 0.04-0.07 eV (4-13 nm), respectively. Radical anions with Ni(II), Sn(II), Pb(II), and Ti(IV)O have S = 1/2 spin state, whereas [Cu(II)Pc(3-)](·-) and [V(IV)OPc(3-)](·-) containing paramagnetic Cu(II) and V(IV)O have two S = 1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal-free phthalocyanine radical anions [H2Pc(3-)](·-) (linewidth of 0.08-0.24 mT), broad EPR signals are manifested (linewidth of 2-70 mT) with g-factors and linewidths that are strongly temperature-dependent. Salt 11 containing the [Na(I)Pc(2-)](-) anions as well as previously studied [Fe(I)Pc(2-)](-) and [Co(I)Pc(2-)](-) anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of [MPc(3-)](·-) in 1-10. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of biotin and oxamate in the carboxyl transferase reaction of pyruvate carboxylase

PubMed Central

Lietzan, Adam D.; Lin, Yi; St. Maurice, Martin

2014-01-01

Pyruvate carboxylase (PC) is a biotin-dependent enzyme that catalyzes the MgATP-dependent carboxylation of pyruvate to oxaloacetate, an important anaplerotic reaction in central metabolism. During catalysis, carboxybiotin is translocated to the carboxyltransferase domain where the carboxyl group is transferred to the acceptor substrate, pyruvate. Many studies on the carboxyltransferase domain of PC have demonstrated an enhanced oxaloacetate decarboxylation activity in the presence of oxamate and it has been shown that oxamate accepts a carboxyl group from carboxybiotin during oxaloacetate decarboxylation. The X-ray crystal structure of the carboxyltransferase domain from Rhizobium etli PC reveals that oxamate is positioned in the active site in an identical manner to the substrate, pyruvate, and kinetic data are consistent with the oxamate-stimulated decarboxylation of oxaloacetate proceeding through a simple ping-pong bi bi mechanism in the absence of the biotin carboxylase domain. Additionally, analysis of truncated PC enzymes indicates that the BCCP domain devoid of biotin does not contribute directly to the enzymatic reaction and conclusively demonstrates a biotin-independent oxaloacetate decarboxylation activity in PC. These findings advance the description of catalysis in PC and can be extended to the study of related biotin-dependent enzymes. PMID:25157442

Waveform-preserved unidirectional acoustic transmission based on impedance-matched acoustic metasurface and phononic crystal

NASA Astrophysics Data System (ADS)

Song, Ai-Ling; Chen, Tian-Ning; Wang, Xiao-Peng; Wan, Le-Le

2016-08-01

The waveform distortion happens in most of the unidirectional acoustic transmission (UAT) devices proposed before. In this paper, a novel type of waveform-preserved UAT device composed of an impedance-matched acoustic metasurface (AMS) and a phononic crystal (PC) structure is proposed and numerically investigated. The acoustic pressure field distributions and transmittance are calculated by using the finite element method. The subwavelength AMS that can modulate the wavefront of the transmitted wave at will is designed and the band structure of the PC structure is calculated and analyzed. The sound pressure field distributions demonstrate that the unidirectional acoustic transmission can be realized by the proposed UAT device without changing the waveforms of the output waves, which is the distinctive feature compared with the previous UAT devices. The physical mechanism of the unidirectional acoustic transmission is discussed by analyzing the refraction angle changes and partial band gap map. The calculated transmission spectra show that the UAT device is valid within a relatively broad frequency range. The simulation results agree well with the theoretical predictions. The proposed UAT device provides a good reference for designing waveform-preserved UAT devices and has potential applications in many fields, such as medical ultrasound, acoustic rectifiers, and noise insulation.

Synthesis and X-ray crystal structures of (Mo(CO)(Et{sub 2}PC{sub 2}H{sub 4}PEt{sub 2}){sub 2}){sub 2}({mu}-N{sub 2}) with an end-on bridging dinitrogen ligand and Mo(CO)(Bu{sup i}{sub 2}PC{sub 2}H{sub 4}PBu{sup i}{sub 2}){sub 2} containing an agostic Mo...H-C interaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, X.L.; Kubas, G.J.; Burns, C.J.

1995-12-20

The compound formed by the reaction of trans-Mo(N{sub 2})(Et{sub 2}PC{sub 2}H{sub 4}PEt{sub 2}){sub 2} with ethyl acetate in refluxing toluene under argon has been formulated as the bridging dinitrogen complex (Mo(CO)(Et{sub 2}PC{sub 2}H{sub 4}PEt{sub 2}){sub 2}){sub 2}({mu}-N{sub 2}) (1), in contrast with the previously proposed formulation of Mo(CO)(Et{sub 2}PC{sub 2}H{sub 4}PEt{sub 2}){sub 2} (2). In refluxing p-xylene and under argon, compound 1 eliminates the bridging dinitrogen ligand to form the nitrogen-free compound 2. The reaction of trans-Mo(N{sub 2})(Bu{sup i}{sub 2}PC{sub 2}H{sub 4}PBu{sup i}{sub 2}){sub 2} (3). The molecular structures of compounds 1 and 3 have been determined by single-crystal X-raymore » diffraction studies. Compound 1 contains an end-on bridging dinitrogen ligand. Compound 3 attains a formal 18-electron configuration by virtue of an agostic Mo...H-C interaction between the molybdenum atom and an alphiatic {gamma}-C-H bond of the alkyldiphosphine ligand. On the basis of the agostic Mo...C and Mo...H distances, the agostic interaction in 3 appears to be stronger than that in the related compound Mo(CO)(Ph{sub 2}PC{sub 2}H{sub 4}PPh{sub 2}){sub 2} which involves an ortho aromatic C-H bond of the diphosphine ligand. Crystallographic data for 1: monoclinic, space group C2/c, a=24.270(2){angstrom}, b=44.233(4){angstrom}, c=20.378(2){angstrom}, {beta}=90.725(9){angstrom}, V=21875(3){angstrom}{sup 3}, Z=16, and R=0.048. Crystallographic data for 3: orthorhombic, space group Pna2{sub 1}, a=18.332(4){angstrom}, b=22.0664(4){angstrom}, c=10.589(2){angstrom}, V=4283(2){angstrom}{sup 3}, Z=4, and R=0.034.« less

Nanocrystal waveguide (NOW) laser

DOEpatents

Simpson, John T.; Simpson, Marcus L.; Withrow, Stephen P.; White, Clark W.; Jaiswal, Supriya L.

2005-02-08

A solid state laser includes an optical waveguide and a laser cavity including at least one subwavelength mirror disposed in or on the optical waveguide. A plurality of photoluminescent nanocrystals are disposed in the laser cavity. The reflective subwavelength mirror can be a pair of subwavelength resonant gratings (SWG), a pair of photonic crystal structures (PC), or a distributed feedback structure. In the case of a pair of mirrors, a PC which is substantially transmissive at an operating wavelength of the laser can be disposed in the laser cavity between the subwavelength mirrors to improve the mode structure, coherence and overall efficiency of the laser. A method for forming a solid state laser includes the steps of providing an optical waveguide, creating a laser cavity in the optical waveguide by disposing at least one subwavelength mirror on or in the waveguide, and positioning a plurality of photoluminescent nanocrystals in the laser cavity.

Polarization splitting phenomenon of photonic crystals constructed by two-fold rotationally symmetric unit-cells

NASA Astrophysics Data System (ADS)

Yasa, U. G.; Giden, I. H.; Turduev, M.; Kurt, H.

2017-09-01

We present an intrinsic polarization splitting characteristic of low-symmetric photonic crystals (PCs) formed by unit-cells with C 2 rotational symmetry. This behavior emerges from the polarization sensitive self-collimation effect for both transverse-magnetic (TM) and transverse-electric (TE) modes depending on the rotational orientations of the unit-cell elements. Numerical analyzes are performed in both frequency and time domains for different types of square lattice two-fold rotational symmetric PC structures. At incident wavelength of λ = 1550 nm, high polarization extinction ratios with ˜26 dB (for TE polarization) and ˜22 dB (for TM polarization) are obtained with an operating bandwidth of 59 nm. Moreover, fabrication feasibilities of the designed structure are analyzed to evaluate their robustness in terms of the unit-cell orientation: for the selected PC unit-cell composition, corresponding extinction ratios for both polarizations still remain to be over 18 dB for the unit-cell rotation interval of θ = [40°-55°]. Taking all these advantages, two-fold rotationally symmetric PCs could be considered as an essential component in photonic integrated circuits for polarization control of light.

Influence of the morphology of the copper(II) phthalocyanine thin film on the performance of organic field-effect transistors

NASA Astrophysics Data System (ADS)

Xu, Jing; Liu, Xueqiang; Wang, Hailong; Hou, Wenlong; Zhao, Lele; Zhang, Haiquan

2017-01-01

Organic thin-film transistors (OTFTs) with high crystallization copper phthalocyanine (CuPc) active layers were fabricated. The performance of CuPc OTFTs was studied without and with treatment by Solvent Vapor Annealing on CuPc film. The values of the threshold voltage without and with solvent-vapor annealing are -17 V and -10.5 V respectively. The field-effect mobility values in saturation region of CuPc thin-film transistors without and with Solvent Vapor Annealing are 0.00027 cm2/V s and 0.0025 cm2/V s respectively. Meanwhile, the high crystallization of the CuPc film with a larger grain size and less grain boundaries can be observed by investigating the morphology of the CuPc active layer through scanning electron microscopy and X-ray diffraction. The experimental results showed the decreased of the resistance of the conducting channel, that led to a performance improvement of the OTFTs.

Preparation, crystal structure, vibrational spectral and density functional studies of bis (4-nitrophenol)-2,4,6-triamino-1,3,5-triazine monohydrate

NASA Astrophysics Data System (ADS)

Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Renganathan, N. G.; Gunasekaran, S.; Anbalagan, G.

2013-10-01

An organic-organic salt, bis (4-nitrophenol) 2,4,6-triamino 1,3,5-triazine monohydrate (BNPM) has been prepared by slow evaporation technique at room temperature. Single crystal X-ray diffraction analysis reveals that the compound crystallizes in triclinic system with centrosymmetric space group P-1. IR and Raman spectra of BNPM have been recorded and analyzed. The study has been extended to confocal Raman spectral analysis. Band assignments have been made for the melamine and p-nitrophenol molecules. Vibrational spectra have also been discussed on the basis of quantum chemical density functional theory calculations using Firefly (PC GAMESS) Version 7.1 G. Vibrational frequencies are calculated and scaled values are compared with the experimental one. The Mulliken charges, HOMO-LUMO orbital energies are calculated and analyzed. The chemical structure of the compound was established by 1H NMR and 13C NMR spectra.

Optical characteristics of a one-dimensional photonic crystal with an additional regular layer

NASA Astrophysics Data System (ADS)

Tolmachev, V. A.; Baldycheva, A. V.; Krutkova, E. Yu.; Perova, T. S.; Berwick, K.

2009-06-01

In this paper, the forbidden Photonic Band Gaps (PBGs) of a one-dimensional Photonic Crystal (1D PC) with additional regular layer, t for the constant value of the lattice constant A and at normal incident of light beam were investigated. The additional regular layer was formed from both sides of the high-refractive index layer H. The gap map approach and the Transfer Matrix Method were used for numerical analysis of this structure. The limitation of filling fraction values caused by the presence of t-layer was taking into account during calculations of the Stop-Band (SB) regions for threecomponent PC. The red shift of SBs was observed at the introduction of t-layer to conventional two-component 1D PC with optical contrast of N=3.42/1. The blue edge of the first PBG occupied the intermediate position between the blue edges of SBs regions of conventional PCs with different optical contrast N. This gives the opportunity of tuning the optical contrast of PC by introduction of the additional layer, rather than using the filler, as well as fine tuning of the SB edge. The influence of the number of periods m and the optical contrast N on the properties of SBs was also investigated. The effect of the PBG disappearance in the gap map and in the regions of the PBGs of high order was revealed at certain parameters of the additional layer.

Ultrasensitive Sensing Material Based on Opal Photonic Crystal for Label-Free Monitoring of Transferrin.

PubMed

Wu, Enqi; Peng, Yuan; Zhang, Xihao; Bai, Jialei; Song, Yanqiu; He, Houluo; Fan, Longxing; Qu, Xiaochen; Gao, Zhixian; Liu, Ying; Ning, Baoan

2017-02-22

A new opal photonic crystal (PC) sensing material, allowing label-free detection of transferrin (TRF), is proposed in the current study. This photonic crystal was prepared via a vertical convective self-assembly method with monodisperse microspheres polymerized by methyl methacrylate (MMA) and 3-acrylamidophenylboronic acid (AAPBA). FTIR, TG, and DLS were used to characterize the components and particle size of the monodisperse microspheres. SEM was used to observe the morphology of the PC. The diffraction peak intensity decreases as the TRF concentration increase. This was due to the combination of TRF to the boronic acid group of the photonic crystal. After condition optimization, a standard curve was obtained and the linear range of TRF concentration was from 2 × 10 -3 ng/mL to 200 ng/mL. Measurement of TRF concentration in simulated urine sample was also investigated using the sensing material. The results indicated that the PC provided a cheap, label-free, and easy-to-use alternative for TRF determination in clinical diagnostics.

Multiple polymer architectures of human Polyhomeotic homolog 3 (PHC3) SAM

PubMed Central

Nanyes, David R.; Junco, Sarah E.; Taylor, Alexander B.; Robinson, Angela K.; Patterson, Nicolle L.; Shivarajpur, Ambika; Halloran, Jonathan; Hale, Seth M.; Kaur, Yogeet; Hart, P. John; Kim, Chongwoo A.

2014-01-01

The self-association of sterile alpha motifs (SAMs) into a helical polymer architecture is a critical functional component of many different and diverse array of proteins. For the Drosophila Polycomb group (PcG) protein Polyhomeotic (Ph), its SAM polymerization serves as the structural foundation to cluster multiple PcG complexes, helping to maintain a silenced chromatin state. Ph SAM shares 64% sequence identity with its human ortholog, PHC3 SAM, and both SAMs polymerize. However, in the context of their larger protein regions, PHC3 SAM forms longer polymers compared to Ph SAM. Motivated to establish the precise structural basis for the differences, if any, between Ph and PHC3 SAM, we determined the crystal structure of the PHC3 SAM polymer. PHC3 SAM utilizes the same SAM-SAM interaction as the Ph SAM six-fold repeat polymer. Yet, PHC3 SAM polymerizes utilizing just five SAMs per turn of the helical polymer rather than the typical six per turn observed for all SAM polymers reported to date. Structural analysis suggested that malleability of the PHC3 SAM would allow formation of not just the five-fold repeat structure but possibly others. Indeed, a second PHC3 SAM polymer in a different crystal form forms a six-fold repeat polymer. These results suggest that the polymers formed by PHC3 SAM, and likely others, are quite dynamic. The functional consequence of the variable PHC3 SAM polymers may be to create different chromatin architectures. PMID:25044168

Insights into the carboxyltransferase reaction of pyruvate carboxylase from the structures of bound product and intermediate analogues

PubMed Central

Lietzan, Adam D.; St. Maurice, Martin

2014-01-01

Pyruvate carboxylase (PC) is a biotin-dependent enzyme that catalyzes the MgATP- and bicarbonate-dependent carboxylation of pyruvate to oxaloacetate, an important anaplerotic reaction in central metabolism. The carboxyltransferase (CT) domain of PC catalyzes the transfer of a carboxyl group from carboxybiotin to the accepting substrate, pyruvate. It has been hypothesized that the reactive enolpyruvate intermediate is stabilized through a bidentate interaction with the metal ion in the CT domain active site. Whereas bidentate ligands are commonly observed in enzymes catalyzing reactions proceeding through an enolpyruvate intermediate, no bidentate interaction has yet been observed in the CT domain of PC. Here, we report three X-ray crystal structures of the Rhizobium etli PC CT domain with the bound inhibitors oxalate, 3-hydroxypyruvate, and 3-bromopyruvate. Oxalate, a stereoelectronic mimic of the enolpyruvate intermediate, does not interact directly with the metal ion. Instead, oxalate is buried in a pocket formed by several positively charged amino acid residues and the metal ion. Furthermore, both 3-hydroxypyruvate and 3-bromopyruvate, analogs of the reaction product oxaloacetate, bind in an identical manner to oxalate suggesting that the substrate maintains its orientation in the active site throughout catalysis. Together, these structures indicate that the substrates, products and intermediates in the PC-catalyzed reaction are not oriented in the active site as previously assumed. The absence of a bidentate interaction with the active site metal appears to be a unique mechanistic feature among the small group of biotin-dependent enzymes that act on α-keto acid substrates. PMID:24157795

Magnetic properties in polycrystalline and single crystal Ca-doped LaCoO3

NASA Astrophysics Data System (ADS)

Zeng, R.; Debnath, J. C.; Chen, D. P.; Shamba, P.; Wang, J. L.; Kennedy, S. J.; Campbell, S. J.; Silver, T.; Dou, S. X.

2011-04-01

Polycrystalline (PC) and single crystalline (SC) Ca-doped LaCoO3 (LCCO) samples with the perovskite structure were synthesized by conventional solid-state reaction and the floating-zone growth method. We present the results of a comprehensive investigation of the magnetic properties of the LCCO system. Systematic measurements have been conducted on dc magnetization, ac susceptibility, exchange-bias, and the magnetocaloric effect. These findings suggest that complex structural phases, ferromagnetic (FM), and spin-glass/cluster-spin-glass (CSG), and their transitions exist in PC samples, while there is a much simpler magnetic phase in SC samples. It was also of interest to discover that the CSG induced a magnetic field memory effect and an exchange-bias-like effect, and that a large inverse irreversible magnetocaloric effect exists in this system.

Microcontact imprinted quartz crystal microbalance nanosensor for protein C recognition.

PubMed

Bakhshpour, Monireh; Özgür, Erdoğan; Bereli, Nilay; Denizli, Adil

2017-03-01

Detection of protein C (PC) in human serum was performed by quartz crystal microbalance (QCM) based on molecular imprinting technique (MIP). The high-resolution and mass-sensitive QCM based sensor was integrated with high sensitivity and selectivity of the MIP technique. The PC microcontact imprinted (PC-μCIP) nanofilm was prepared on the glass surface. Then, the PC-μCIP/QCM sensor was prepared with 2-hydroxyethyl methacrylate (HEMA), ethylene glycol dimethacrylate (EGDMA) and N-methacryloyl l-histidine methylester (MAH) as the functional monomer with copper(II) ions. The polymerization was performed under UV light (100W and 365nm) for 20-25min under nitrogen atmosphere. The characterization studies of QCM sensor were done by observation using atomic force microscopy (AFM), contact angle measurements, ellipsometry and fourier transform infrared spectroscopy (FTIR). Detection of PC was investigated in a concentration range of 0.1-30μg/mL. Selectivity of PC-μCIP and PC non-imprinted/QCM (PC-non-μCIP) sensors for PC determination was investigated by using proteins namely hemoglobin (Hb), human serum albumin (HSA) and fibrinogen solutions. QCM sensor was also used for detection of PC molecules in aqueous solutions and human plasma. The detection limit was determined as 0.01μg/mL for PC analysis. The PC-μCIP/QCM sensor was used for five consecutive adsorption-desorption cycles. According to the results, the PC-μCIP/QCM sensor had obtained high selectivity and sensitivity for detection of PC molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhancement of the electrical characteristics of metal-free phthalocyanine films using cold isostatic pressing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsushima, Toshinori, E-mail: tmatusim@opera.kyushu-u.ac.jp, E-mail: adachi@cstf.kyushu-u.ac.jp; Adachi, Chihaya, E-mail: tmatusim@opera.kyushu-u.ac.jp, E-mail: adachi@cstf.kyushu-u.ac.jp; Japan Science and Technology Agency

2014-12-15

Spatial gaps between grains and other grains, substrates, or electrodes in organic electronic devices are one of the causes of the reduction in the electrical characteristics. In this study, we demonstrate that cold isostatic pressing (CIP) is an effective method to crush the gaps and enhance the electrical characteristics. CIP of metal-free phthalocyanine (H{sub 2}PC) films induced a decrease in the film thickness by 34%–40% because of the gap crush. The connection of smaller grains into a larger grain and planarization of the film surface were also observed in the CIP film. The crystal axes of the H{sub 2}PC crystallitesmore » were rearranged from the a-axis to the c-axis of the α-phase crystal structure in a direction perpendicular to the substrate by CIP, indicating favorable hole injection and transport in this direction because of a better overlap of π orbitals. Thermally stimulated current measurements showed that deep hole traps disappeared and the total hole-trap density decreased after CIP. These CIP-induced changes of the film thicknesses, crystal axes and the hole traps lead to a marked increase in the hole mobility of the H{sub 2}PC films from 2.0 × 10{sup −7} to 4.0 × 10{sup −4} cm{sup 2}/V s by 2000 times in the perpendicular direction. We believe that these findings are important for unveiling the underlying carrier injection and transport mechanisms of organic films and for enhancing the performance of future organic electronic devices.« less

Multi/demulti-plexer based on transverse mode conversion in photonic crystal waveguides.

PubMed

Zhou, Wen; Zhuang, Yuyang; Ji, Ke; Chen, He-ming

2015-09-21

A novel mode multiplexer and demultiplexer (MMUX/DEMMUX) based on 2-D photonic crystal (PC) at 1550 nm is proposed. The PC-based mode MMUX/DEMMUX including mode conversion function with a single-mode and multi-mode waveguides can be realized by quasi phase-matching TE(0) & TE(1) modes of two waveguides. 2DFinite-Difference-Time-Domain and beam propagation methods are used for simulation. The results show that PC-based mode MMUX/DEMMUX has the potential for high-capacity MDM optical communication systems with a low insertion loss (<0.36dB), low mode crosstalk (< -20.9 dB) and wide bandwidth (~100 nm).

Enhanced emission of quantum dots embedded within the high-index dielectric regions of photonic crystal slabs

DOE Office of Scientific and Technical Information (OSTI.GOV)

See, Gloria G.; Naughton, Matt S.; Kenis, Paul J. A.

2016-04-25

We demonstrate a method for combining sputtered TiO{sub 2} deposition with liquid phase dip-coating of a quantum dot (QD) layer that enables precise depth placement of QD emitters within a high-index dielectric film, using a photonic crystal (PC) slab resonator to demonstrate enhanced emission from the QDs when they are located at a specific depth within the film. The depth of the QDs within the PC is found to modulate the resonant wavelength of the PC as well as the emission enhancement efficiency, as the semiconducting material embedded within the dielectric changes its spatial overlap with the resonant mode.

Optimization of experimental conditions for the monitoring of nucleation and growth of racemic Diprophylline from the supercooled melt

NASA Astrophysics Data System (ADS)

Lemercier, Aurélien; Viel, Quentin; Brandel, Clément; Cartigny, Yohann; Dargent, Eric; Petit, Samuel; Coquerel, Gérard

2017-08-01

Since more and more pharmaceutical substances are developed as amorphous forms, it is nowadays of major relevance to get insights into the nucleation and growth mechanisms from supercooled melts (SCM). A step-by-step approach of recrystallization from a SCM is presented here, designed to elucidate the impact of various experimental parameters. Using the bronchodilator agent Diprophylline (DPL) as a model compound, it is shown that optimal conditions for informative observations of the crystallization behaviour from supercooled racemic DPL require to place samples between two cover slides with a maximum sample thickness of 20 μm, and to monitor recrystallization during an annealing step of 30 min at 70 °C, i.e. about 33 °C above the temperature of glass transition. In these optimized conditions, it could be established that DPL crystallization proceeds in two steps: spontaneous nucleation and growth of large and well-faceted particles of a new crystal form (primary crystals: PC) and subsequent crystallization of a previously known form (RII) that develops from specific surfaces of PC. The formation of PC particles therefore constitutes the key-step of the crystallization events and is shown to be favoured by at least 2.33 wt% of the major chemical impurity, Theophylline.

Modulation of Bacillus thuringiensis Phosphatidylinositol-Specific Phospholipase C Activity by Mutations in the Putative Dimerization Interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, X.; Shao, C; Zhang, X

2009-01-01

Cleavage of phosphatidylinositol (PI) to inositol 1,2-(cyclic)-phosphate (cIP) and cIP hydrolysis to inositol 1-phosphate by Bacillus thuringiensis phosphatidylinositol-specific phospholipase C are activated by the enzyme binding to phosphatidylcholine (PC) surfaces. Part of this reflects improved binding of the protein to interfaces. However, crystallographic analysis of an interfacially impaired phosphatidylinositol-specific phospholipase (W47A/W242A) suggested protein dimerization might occur on the membrane. In the W47A/W242A dimer, four tyrosine residues from one monomer interact with the same tyrosine cluster of the other, forming a tight dimer interface close to the membrane binding regions. We have constructed mutant proteins in which two or more ofmore » these tyrosine residues have been replaced with serine. Phospholipid binding and enzymatic activity of these mutants have been examined to assess the importance of these residues to enzyme function. Replacing two tyrosines had small effects on enzyme activity. However, removal of three or four tyrosine residues weakened PC binding and reduced PI cleavage by the enzyme as well as PC activation of cIP hydrolysis. Crystal structures of Y247S/Y251S in the absence and presence of myo-inositol as well as Y246S/Y247S/Y248S/Y251S indicate that both mutant proteins crystallized as monomers, were very similar to one another, and had no change in the active site region. Kinetic assays, lipid binding, and structural results indicate that either (i) a specific PC binding site, critical for vesicle activities and cIP activation, has been impaired, or (ii) the reduced dimerization potential for Y246S/Y247S/Y248S and Y246S/Y247S/Y248S/Y251S is responsible for their reduced catalytic activity in all assay systems.« less

Photonic crystal active and passive device components in III-V semiconductors

NASA Astrophysics Data System (ADS)

Sabarinathan, Jayshri

Photonic crystals (PC's) are emerging as potentially important candidates in propelling the development in planar photonic integrated circuits, high capacity optical fibers and nanoscopic lasers. Photonic crystals are expected to play a role analogous to that played by crystalline semiconductors in the development of electronic circuits. What makes these photonic crystals more interesting is that introducing "defects"---a missing period or phase slip, in the PC lattice introduces defect modes that lie within the bandgap of the PC. In this investigation, both two dimensional and three dimensional photonic crystals have been fabricated and studied using III-V compound semiconductors which are presently the most useful material systems for integrating with existing optoelectronic technology. A novel single step epitaxial technique to fabricate GaAs-based 3D photonic crystals with sub-micron feature size has been developed employing MBE growth on patterned substrates, ebeam and optical lithography, and lateral wet oxidation of AlGaAs. Transmission characteristics of the fabricated 3D PCs have been measured revealing a 10dB stopband centered at 1 mum for the smallest feature sizes. Electrically injected 2D photonic crystal defect microcavities were designed and fabricated to realize low threshold vertically emitting light sources. The electroluminescent devices were fabricated with GaAs- and InP-based quantum wells heterostructures with emission wavelengths at 0.94mum and 1.55 mum respectively. The light-current, spectral, near- and far-field characteristics of these devices have been studied in detail. The processing and high-aspect ratio etch techniques were carefully developed to create the 2D PCs embedded in the electrically injected apertures. Quantum dots with emission wavelength of 1.04 mum were incorporated into electrically injected 2D PC microcavities to study the electrical and optical confinement simultaneously provided in this configuration. Weak microcavity effects were observed in the fabricated devices. Passive 2D PC's with linear defects, which act as efficient waveguides to confine and channel light even around very sharp bends, have also been investigated. A novel microfluidic sensor using 2D GaAs-based photonic crystal waveguides to detect one or more fluids on the basis of their refractive index properties have been designed, fabricated and demonstrated for the first time.

Applied Crystallography - Proceedings of the XVth Conference

NASA Astrophysics Data System (ADS)

Morawiec, H.; Ströż, D.

1993-06-01

The Table of Contents for the full book PDF is as follows: * Foreword * The International Centre for Diffraction Data and Its Future Developments * The Rietveld Method - A Historical Perspective * Real Structure in Quantitative Powder Diffraction Phase Analysis * Neutron Focusing Optics in Applied Crystallography * The Crystal Structures of Oxygen Deficient Rare Earth Oxides * Short-Range Order in Layer-Structured Ba1-xSrxBi2Nb2O9 Ferroelectrics * Radial Distribution Function as a Tool of Structural Studies on Noncrystalline Materials * Determination of Radial Distribution Function (RDF) of Electrodeposited Cu-Cd Alloys After Annealing * Spheres Packing as a Factor Describing the Local Environment and Structure Stability * X-Ray Stress Measurement of Samples Combined with Diffraction Line Analysis * Phase Stability and Martensitic Transformation in Cu-Zn and Cu-Zn-Al Single Crystals * Order, Defects, Precipitates and the Martensitic Transformation in β Cu-Zn-Al * Effect of γ Precipitates on the Martensitic Transformation in Cu-Zn-Al Alloys * Phase Transitions and Shape Memory Effect in a Thermomechanically Treated NiTi Alloy * Structure of Martensite and Bainite in CuAlMn Alloys * Glass-Ceramics * Mechanism of Texture Formation at the Rolling of Low Stacking Fault Energy Metals and Alloys * Shear Texture of Zinc and the Conditions of Its Occuring * The Development of Texture of ZnAlMg Sheets Depending on Deformation Geometry * Texture Stability of the D.S. NiAlMoCrTi Alloy After Heat Treatment * X-Ray Diffraction Method for Controlling of Texture Evolution in Layers * Texture and Lattice Imperfections Study of Some Low Alloyed Copper Alloys * Selected Examples of the Calculation of the Orientation Distribution Function for Low Crystal and Sample Symmetries * Automatical X-Ray Quantitative Phase Analysis * Application of a PC Computer for Crystallographic Calculations * Electron Diffraction Analysis using a Personal Computer * CA.R.INE Crystallography Version 2.1-1992 * PC-MINREF: The Computer Program Package for Neutron Refinement of Incommensurate Multiphase Crystal and Magnetic Structures on IBM PC Computers * Possibilities of Deflections from Stoichiometry Investigation for Phases of b1-b37 Structure by X-Ray Method * A Computer Program: “Measurement of Elastic Constants of Phases in Nontextured Polycrystalline Materials by X-Ray Method” * Crystallite Sizes and Lattice Strains of Hydrogenatid Tungsten Carbid Powder * The Bragg-Case Images of Dislocations at Different Absorption * Extended X-Ray Bremsstrahlung Isochromat of Molybdenum * Size Distribution Determination of Heterogeneity Regions in Electrodeposited Metals by Saxs Method * The Possibility of the Application of the CH2I2 - Paraffin Oil Mixture as a Masking Liquid for Metal/Carrier Systems in Saxs Investigations * Investigation on Mechanical Alloying and Amorphisation Processes by the Rietveld Method * Growth of β' Phase Single Crystals of Sn-Sb Alloy * Effect of Oxygen Agglomeration on Structure of Annealed Cz-Si Single Crystal * X-Ray Investigation of Non-Uniform Stress Fields * Problem of Polytype Structures Series for Martensitic Phases of Metals and Alloys * Structure of Strain-Induced Martensite in β-CuZnAl Alloy * The Effect of Heat Treatment on the Phase Transitions in NiTiCo Shape Memory Alloy * 9R → 18R Phase Transformation in Cu-13Zn-8Al Alloy * Effect of Austenite Thermal Instability on Characteristics of Martensitic Transformation in Fe-Ni Alloys * Vacuum Annealing Study of Thin Ti Layers on High Carbon Steel Substrates * Vacuum Annealing Study of Thin Ta Layers on High Carbon Steel Substrates * Investigation of Speed of Ionic Sputtering of NiTi Alloys in Sea 02 Auger Spectrometer * Effect of Precipitation Hardening on Thermal Stability of Austenite in Fe-Ni Alloys * Structure of 18Cr-25Ni-Nb L Steel After Two Years Operation in Catalytic Tubes * Influence of Magnetic Field on Mechanical Barkhausen Effect Stress Dependence in Steel * Precipitation Structure in High Strength Aluminium Alloys * Morphology of Laser Treated Al-Zn and Al-Fe Alloys * Structure of Rapidly Solidified AlFe and AlFeNi Ribbons After Continuous Heating * X-Ray Diffractometric Investigations of Anatase—Rutile Titanium Dioxide Forms Transformation in the Presence of Some Additives * Investigations on Phase Transformation of Coprecipitated Iron-Magnesium Hydroxides * Determination of the Crystallinity of Polymer Blends by X-Ray Diffraction Method * XPD Study of the Selected Magnesium Compounds with the Expected Pharmacological Activity * Supermolecular Structure of the Nylon 6.10 Crystallized from the Melt and Its Changes During Heating * The Analysis of Substructural Parameters of PZT-Type Ferroelectric Ceramics

EPR study of a gamma-irradiated (2-hydroxyethyl)triphenylphosphonium chloride single crystal

NASA Astrophysics Data System (ADS)

Karakaş, E.; Türkkan, E.; Dereli, Ö.; Sayιn, Ü.; Tapramaz, R.

2011-12-01

In this study, gamma-irradiated single crystals of (2-hydroxyethyl)triphenylphosphonium chloride [CH2CH2OH P(C6H5)3Cl] were investigated with electron paramagnetic resonance (EPR) spectroscopy at room temperature for different orientations in the magnetic field. The single crystals were irradiated with a 60Co-γ-ray source at 0.818 kGy/h for about 36 h. Taking the chemical structure and the experimental spectra of the irradiated single crystal of the title compound into consideration, a paramagnetic species was produced with the unpaired electron delocalized around 31P and several 1H nuclei. The anisotropic hyperfine values due to the 31P nucleus, slightly anisotropic hyperfine values due to the 1H nuclei and the g-tensor of the radical were measured from the spectra. Depending on the molecular structure and measured parameters, three possible radicals were modeled using the B3LYP/6-31+G(d) level of density-functional theory, and EPR parameters were calculated for modeled radicals using the B3LYP/TZVP method/basis set combination. The calculated hyperfine coupling constants were found to be in good agreement with the observed EPR parameters. The experimental and theoretically simulated spectra for each of the three crystallographic axes were well matched with one of the modeled radicals (discussed in the text). We thus identified the radical C˙H2CH2 P(C 6H5)3 Cl as a paramagnetic species produced in a single crystal of the title compound in two magnetically distinct sites. The experimental g-factor and hyperfine coupling constants of the radical were found to be anisotropic, with the isotropic values g iso = 2.0032, ? G, ? G, ? G and ? G for site 1 and g iso=2.0031, ? G, ? G ? G and ? G for site 2.

Imaging the 'mosaic' structure of ICB by pre-critical PcP-PKiKP phases

NASA Astrophysics Data System (ADS)

Shen, Z.; Ai, Y.; He, Y.; Jiang, M.

2013-12-01

Slowly growing in highly homogeneous liquid outer core, earth inner core has been thought lacking of significant heterogeneous structure. However, seismic observations of recent decades have demonstrated hierarchical heterogeneous structure as hemispherical longitudinal dichotomy superimposed by coda-generating scattering heterogeneities with diameters of tens of kilometers, indicating complicity of inner core crystallizing environment and related dynamic process. Furthermore, as boundary of phase transform and energy-material exchange, ICB has been unveiled as patchy mosaic-like surface, based on high variety of global pre-critical PcP-PKiKP amplitude ratios. From dense arrays deployed across East and South China in the year 2005~2011 and 13 earthquakes of west Pacific subduction zone, we have collected over 150 clear pre-critical PcP-PKiKP waveforms of epicenter distance range between 14~35°, providing an ideal sampling to detect possible ICB regional variation of the East Asia area. The amplitude observation exhibits good geographical coherency which is characterized as region of high density contrast (>1.0g/cm3) located beneath East China demarcated by the low (around or lower than 0.6g/cm3) on the periphery, except the southeastward stretching. This contrasting depicts vividly the claimed 'mosaic' ICB and bridges the gap between hemispherical (~1000km order) and scatter-inducing (~10km order or less) scales of heterogeneity. On the other hand, travel time residues of PcP-PKiKP in our study reveal a complex pattern north of ~18°N perturbed strongly by shallow (crust and mantle) anomalies and remarkable delay of PKiKP in the south, implicating effects of undetected ULVZ below Celebes Sea. This research is supported by the National Natural Science Foundation of China (NSFC, grant 90914011, 41125015). Distribution of PcP-PKiKP relative amplitude ratio

Ultra-directional source of longitudinal acoustic waves based on a two-dimensional solid/solid phononic crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morvan, B.; Tinel, A.; Sainidou, R.

2014-12-07

Phononic crystals (PC) can be used to control the dispersion properties of acoustic waves, which are essential to direct their propagation. We use a PC-based two-dimensional solid/solid composite to demonstrate experimentally and theoretically the spatial filtering of a monochromatic non-directional wave source and its emission in a surrounding water medium as an ultra-directional beam with narrow angular distribution. The phenomenon relies on square-shaped equifrequency contours (EFC) enabling self-collimation of acoustic waves within the phononic crystal. Additionally, the angular width of collimated beams is controlled via the EFC size-shrinking when increasing frequency.

Two-dimensional photonic crystal arrays for polymer:fullerene solar cells.

PubMed

Nam, Sungho; Han, Jiyoung; Do, Young Rag; Kim, Hwajeong; Yim, Sanggyu; Kim, Youngkyoo

2011-11-18

We report the application of two-dimensional (2D) photonic crystal (PC) array substrates for polymer:fullerene solar cells of which the active layer is made with blended films of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The 2D PC array substrates were fabricated by employing a nanosphere lithography technique. Two different hole depths (200 and 300 nm) were introduced for the 2D PC arrays to examine the hole depth effect on the light harvesting (trapping). The optical effect by the 2D PC arrays was investigated by the measurement of optical transmittance either in the direction normal to the substrate (direct transmittance) or in all directions (integrated transmittance). The results showed that the integrated transmittance was higher for the 2D PC array substrates than the conventional planar substrate at the wavelengths of ca. 400 nm, even though the direct transmittance of 2D PC array substrates was much lower over the entire visible light range. The short circuit current density (J(SC)) was higher for the device with the 2D PC array (200 nm hole depth) than the reference device. However, the device with the 2D PC array (300 nm hole depth) showed a slightly lower J(SC) value at a high light intensity in spite of its light harvesting effect proven at a lower light intensity.

Laser Scanning Holographic Lithography for Flexible 3D Fabrication of Multi-Scale Integrated Nano-structures and Optical Biosensors

PubMed Central

Yuan, Liang (Leon); Herman, Peter R.

2016-01-01

Three-dimensional (3D) periodic nanostructures underpin a promising research direction on the frontiers of nanoscience and technology to generate advanced materials for exploiting novel photonic crystal (PC) and nanofluidic functionalities. However, formation of uniform and defect-free 3D periodic structures over large areas that can further integrate into multifunctional devices has remained a major challenge. Here, we introduce a laser scanning holographic method for 3D exposure in thick photoresist that combines the unique advantages of large area 3D holographic interference lithography (HIL) with the flexible patterning of laser direct writing to form both micro- and nano-structures in a single exposure step. Phase mask interference patterns accumulated over multiple overlapping scans are shown to stitch seamlessly and form uniform 3D nanostructure with beam size scaled to small 200 μm diameter. In this way, laser scanning is presented as a facile means to embed 3D PC structure within microfluidic channels for integration into an optofluidic lab-on-chip, demonstrating a new laser HIL writing approach for creating multi-scale integrated microsystems. PMID:26922872

Photonic crystals on copolymer film for label-free detection of DNA hybridization.

PubMed

Su, Han; Cheng, Xin R; Endo, Tatsuro; Kerman, Kagan

2018-04-30

The presence of a single-nucleotide polymorphism in Apolipoprotein E4 gene is implicated with the increased risk of developing Alzheimer's disease (AD). In this study, detection of AD-related DNA oligonucleotide sequence associated with Apolipoprotein E4 gene sequence was achieved using localized-surface plasmon resonance (LSPR) on 2D-Photonic crystal (2D-PC) and Au-coated 2D-PC surfaces. 2D-PC surfaces were fabricated on a flexible copolymer film using nano-imprint lithography (NIL). The film surface was then coated with a dual-functionalized polymer to react with surface immobilized DNA probe. DNA hybridization was detected by monitoring the optical responses of either a Fresnel decrease in reflectance on 2D-PC surfaces or an increase in LSPR on Au-coated 2D-PC surfaces. The change in response due to DNA hybridization on the modified surfaces was also investigated using mismatched and non-complementary oligonucleotides sequences. The proof-of-concept results are promising towards the development of 2D-PC on copolymer film surfaces as miniaturized and wearable biosensors for various diagnostic and defense applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical sensing of copper phthalocyanine sol-gel glass through organic vapors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ridhi, R.; Gawri, Isha; Abbas, Saeed J.

2015-05-15

The sensitivities of metallophthalocyanine to vapor phase electron donors has gained significance in many areas and disciplines due to their sensing properties and ease of operation. In the present study the interaction mechanism of organic vapors in Copper Phthalocyanine (CuPc) sol-gel glass has been studied. The interaction mechanism is affected by many factors like morphology, electrical or optical properties of film. CuPc sol-gel glass has been synthesized using chemical route sol-gel method. Its structural characterization was conducted using XRD and the amorphous nature of the silicate glass was observed with characteristic α polymorph phase of CuPc at around 6.64° withmore » 13.30Å interplanar spacing. The size of the particle as determined using Debbye Scherre’s formula comes out around 15.5 nm. The presence of α phase of CuPc was confirmed using FTIR with the appearance of crystal parameter marker band at 787 cm-1. Apart from this A2u and Eu symmetry bands of CuPc have also been observed. The UV absorption spectrum of CuPc exhibits absorption peaks owing to π→ π* and n→ π* transitions. A blue shift in the prepared CuPc glass has been observed as compared to the dopant CuPc salt indicating increase of band gap. A split in B (Soret) band and Q band appears as observed with the help of Lorentzian fitting. CuPc sol gel glass has been exposed with chemical vapors of Methanol, Benzene and Bromine individually and the electrical measurements have been carried out. These measurements show the variation in conductivity and the interaction mechanism has been analyzed.« less

Molecular resolution friction microscopy of Cu phthalocyanine thin films on dolomite (104) in water

NASA Astrophysics Data System (ADS)

Nita, Paweł; Pimentel, Carlos; Luo, Feng; Milián-Medina, Begoña; Gierschner, Johannes; Pina, Carlos M.; Gnecco, Enrico

2014-06-01

The reliability of ultrathin organic layers as active components for molecular electronic devices depends ultimately on an accurate characterization of the layer morphology and ability to withstand mechanical stresses on the nanoscale. To this end, since the molecular layers need to be electrically decoupled using thick insulating substrates, the use of AFM becomes mandatory. Here, we show how friction force microscopy (FFM) in water allows us to identify the orientation of copper(ii)phthalocyanine (CuPc) molecules previously self-assembled on a dolomite (104) mineral surface in ultra-high vacuum. The molecular features observed in the friction images show that the CuPc molecules are stacked in parallel rows with no preferential orientation with respect to the dolomite lattice, while the stacking features resemble well the single CuPc crystal structure. This proves that the substrate induction is low and makes friction force microscopy in water a suitable alternative to more demanding dynamic AFM techniques in ultra-high vacuum.

Molecular resolution friction microscopy of Cu phthalocyanine thin films on dolomite (104) in water.

PubMed

Nita, Paweł; Pimentel, Carlos; Luo, Feng; Milián-Medina, Begoña; Gierschner, Johannes; Pina, Carlos M; Gnecco, Enrico

2014-07-21

The reliability of ultrathin organic layers as active components for molecular electronic devices depends ultimately on an accurate characterization of the layer morphology and ability to withstand mechanical stresses on the nanoscale. To this end, since the molecular layers need to be electrically decoupled using thick insulating substrates, the use of AFM becomes mandatory. Here, we show how friction force microscopy (FFM) in water allows us to identify the orientation of copper(ii)phthalocyanine (CuPc) molecules previously self-assembled on a dolomite (104) mineral surface in ultra-high vacuum. The molecular features observed in the friction images show that the CuPc molecules are stacked in parallel rows with no preferential orientation with respect to the dolomite lattice, while the stacking features resemble well the single CuPc crystal structure. This proves that the substrate induction is low and makes friction force microscopy in water a suitable alternative to more demanding dynamic AFM techniques in ultra-high vacuum.

Narrow Band Filter at 1550 nm Based on Quasi-One-Dimensional Photonic Crystal with a Mirror-Symmetric Heterostructure.

PubMed

Wang, Fang; Cheng, Yong Zhi; Wang, Xian; Zhang, Yi Nan; Nie, Yan; Gong, Rong Zhou

2018-06-27

In this paper, we present a high-efficiency narrow band filter (NBF) based on quasi-one-dimensional photonic crystal (PC) with a mirror symmetric heterostructure. Similarly to the Fabry-Perot-like resonance cavity, the alternately-arranged dielectric layers on both sides act as the high reflectance and the junction layers used as the defect mode of the quasi-one-dimensional PC, which can be designed as a NBF. The critical conditions for the narrow pass band with high transmittance are demonstrated and analyzed by simulation and experiment. The simulation results indicate that the transmission peak of the quasi-one-dimensional PC-based NBF is up to 95.99% at the telecommunication wavelength of 1550 nm, which agrees well with the experiment. Furthermore, the influences of the periodicity and thickness of dielectric layers on the transmission properties of the PC-based NBF also have been studied numerically. Due to its favorable properties of PC-based NBF, it is can be found to have many potential applications, such as detection, sensing, and communication.

Solar cells of metal-free phthalocyanine dispersed in polyvinyl carbazole. 1: Effects of the recrystallization of H2PC on cell characteristics

NASA Technical Reports Server (NTRS)

Shimura, M.; Baba, H.

1983-01-01

The development of an organic semiconductor solar cell and the effects of the recrystallization of metal free phthalocyanine (H2PC) on the characteristics of NESA/H2PC-PVK/Au sandwich cells were investigated. Alfa-H2PC sandwich cells showed photovoltage and photocurrent in a two direction opposite to that shown y as supplied H2PC cells, which consists mainly of beta-H2PC. Some difference was observed in the response times of the two cells. It is suggested that photocharacteristics change with the specific resistance of the H2PC, which is related to its crystal forms. In the cells with low resistance H2PC carriers are generated in H2PC by illumination, while in high resistance H2PC cells, carriers are generated in PVK which is sensitized with H2PC.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cody, Vivian, E-mail: cody@hwi.buffalo.edu; University of Buffalo, Buffalo, NY 14260; Pace, Jim

The structures of mouse DHFR holo enzyme and a ternary complex with NADPH and a potent inhibitor are described. It has been shown that 2, 4-diamino-6-arylmethylpteridines and 2, 4-diamino-5-arylmethylpyrimidines containing an O-carboxylalkyloxy group in the aryl moiety are potent and selective inhibitors of the dihydrofolate reductase (DHFR) from opportunistic pathogens such as Pneumocystis carinii, the causative agent of Pneumocystis pneumonia in HIV/AIDS patients. In order to understand the structure–activity profile observed for a series of substituted dibenz[b, f]azepine antifolates, the crystal structures of mouse DHFR (mDHFR; a mammalian homologue) holo and ternary complexes with NADPH and the inhibitor 2, 4-diamino-6-(2′-hydroxydibenz[b,more » f]azepin-5-yl)methylpteridine were determined to 1.9 and 1.4 Å resolution, respectively. Structural data for the ternary complex with the potent O-(3-carboxypropyl) inhibitor PT684 revealed no electron density for the O-carboxylalkyloxy side chain. The side chain was either cleaved or completely disordered. The electron density fitted the less potent hydroxyl compound PT684a. Additionally, cocrystallization of mDHFR with NADPH and the less potent 2′-(4-carboxybenzyl) inhibitor PT682 showed no electron density for the inhibitor and resulted in the first report of a holoenzyme complex despite several attempts at crystallization of a ternary complex. Modeling data of PT682 in the active site of mDHFR and P. carinii DHFR (pcDHFR) indicate that binding would require ligand-induced conformational changes to the enzyme for the inhibitor to fit into the active site or that the inhibitor side chain would have to adopt an alternative binding mode to that observed for other carboxyalkyloxy inhibitors. These data also show that the mDHFR complexes have a decreased active-site volume as reflected in the relative shift of helix C (residues 59–64) by 0.6 Å compared with pcDHFR ternary complexes. These data are consistent with the greater inhibitory potency against pcDHFR.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cody, V.; Pace, J.; Rosowsky, A.

It has been shown that 2,4-diamino-6-arylmethylpteridines and 2,4-diamino-5-arylmethylpyrimidines containing an O-carboxylalkyloxy group in the aryl moiety are potent and selective inhibitors of the dihydrofolate reductase (DHFR) from opportunistic pathogens such as Pneumocystis carinii, the causative agent of Pneumocystis pneumonia in HIV/AIDS patients. In order to understand the structure-activity profile observed for a series of substituted dibenz[b,f]azepine antifolates, the crystal structures of mouse DHFR (mDHFR; a mammalian homologue) holo and ternary complexes with NADPH and the inhibitor 2,4-diamino-6-(2{prime}-hydroxydibenz[b,f]azepin-5-yl)methylpteridine were determined to 1.9 and 1.4 A resolution, respectively. Structural data for the ternary complex with the potent O-(3-carboxypropyl) inhibitor PT684 revealed nomore » electron density for the O-carboxylalkyloxy side chain. The side chain was either cleaved or completely disordered. The electron density fitted the less potent hydroxyl compound PT684a. Additionally, cocrystallization of mDHFR with NADPH and the less potent 2{prime}-(4-carboxybenzyl) inhibitor PT682 showed no electron density for the inhibitor and resulted in the first report of a holoenzyme complex despite several attempts at crystallization of a ternary complex. Modeling data of PT682 in the active site of mDHFR and P. carinii DHFR (pcDHFR) indicate that binding would require ligand-induced conformational changes to the enzyme for the inhibitor to fit into the active site or that the inhibitor side chain would have to adopt an alternative binding mode to that observed for other carboxyalkyloxy inhibitors. These data also show that the mDHFR complexes have a decreased active-site volume as reflected in the relative shift of helix C (residues 59-64) by 0.6 A compared with pcDHFR ternary complexes. These data are consistent with the greater inhibitory potency against pcDHFR.« less

A visual water vapor photonic crystal sensor with PVA/SiO2 opal structure

NASA Astrophysics Data System (ADS)

Yang, Haowei; Pan, Lei; Han, Yingping; Ma, Lihua; Li, Yao; Xu, Hongbo; Zhao, Jiupeng

2017-11-01

In study, we proposed a simple yet fast optical sensing motif based on thimbleful of polyvinyl alcohol (PVA) infiltrated photonic crystal (PC), which allows for high efficiency in vapor sensing through changes in their inter-layer space. Linear response to a broad dynamic range of vapor concentration was realized. Ultrafast response time (<1 s) and excellent recyclability were also demonstrated. Selective response to a vapor was exhibited, reflecting well the characteristic sorption properties of PVA, with which colorimetric reporting was readily achieved. These substantial improvements in performance are attributed to the efficacy of signal transduction and the enhanced signal transduction because of thimbleful PVA infiltrated space between adjacent SiO2 nanospheres.

Crystal Data

National Institute of Standards and Technology Data Gateway

SRD 3 NIST Crystal Data (PC database for purchase)   NIST Crystal Data contains chemical, physical, and crystallographic information useful to characterize more than 237,671 inorganic and organic crystalline materials. The data include the standard cell parameters, cell volume, space group number and symbol, calculated density, chemical formula, chemical name, and classification by chemical type.

Four-Dimensional Screening Anti-Counterfeiting Pattern by Inkjet Printed Photonic Crystals.

PubMed

Hou, Jue; Zhang, Huacheng; Su, Bin; Li, Mingzhu; Yang, Qiang; Jiang, Lei; Song, Yanlin

2016-10-06

A four-dimensional screening anti-counterfeiting QR code composed of differently shaped photonic crystal (PC) dots has been fabricated that could display four images depending on different lighting conditions. By controlling the rheology of poly(dimethylsiloxane) (PDMS), three kinds of PC dots could be sequentially integrated into one pattern using the layer-by-layer printing strategy. The information can be encoded and stored in shapes and read out by the difference in optical properties. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiwavelength ultralow-threshold lasing in quantum dot photonic crystal microcavities.

PubMed

Chakravarty, S; Bhattacharya, P; Chakrabarti, S; Mi, Z

2007-05-15

We demonstrate multiwavelength lasing of resonant modes in linear (L3) microcavities in a triangular-lattice 2D photonic crystal (PC) slab. The broad spontaneous emission spectrum from coupled quantum dots, modified by the PC microcavity, is studied as a function of the intensity of incident optical excitation. We observe lasing with an ultralow-threshold power of approximately 600 nW and an output efficiency of approximately 3% at threshold. Two other resonant modes exhibit weaker turnon characteristics and thresholds of approximately 2.5 and 200 microW, respectively.

Study of optical reflectance properties in 1D annular photonic crystal containing double negative (DNG) metamaterials

NASA Astrophysics Data System (ADS)

Srivastava, Sanjeev K.; Aghajamali, Alireza

2016-05-01

Theoretical investigation of photonic band gaps or reflection bands in one-dimensional annular photonic crystal (APC) containing double negative (DNG) metamaterials and air has been presented. The proposed structure consists of the alternate layers of dispersive DNG material and air immersed in free space. In order to study photonic band gaps we obtain the reflectance spectrum of the annular PC by employing the transfer matrix method (TMM) in the cylindrical waves for both TE and TM polarizations. In this work we study the effect of azimuthal mode number (m) and starting radius (ρ0) on the three band gaps viz. zero averaged refractive index (zero-nbar) gap, zero permittivity (zero- ε) and zero permeability (zero- μ) gaps. It is found that for m ≥ 1 , zero- μ gap appears in TE mode and zero- ε gap appears in TM mode. The width of both zero- μ and zero- ε gap increases by increasing m values, but the enhancement of zero- μ gap is more appreciable. Also, the effect of ρ0 on the three band gaps (reflection bands) of annular PC structure at the given m-number has been studied, for both TE and TM polarizations. The result shows that in both polarizations zero- ε and zero- μ gaps decreases when ρ0 increases, whereas zero-nbar gap remains invariant.

Crystal structure of bis-[(phenyl-methanamine-κN)(phthalocyaninato-κ(4) N)zinc] phenyl-methan-amine tris-olvate.

PubMed

Shamsudin, Norzianah; Tan, Ai Ling; Wimmer, Franz L; Young, David J; Tiekink, Edward R T

2015-09-01

The asymmetric unit of the title compound, 2[Zn(C32H16N8)(C7H9N)]·3C7H9N, comprises two independent complex mol-ecules and three benzyl-amine solvent mol-ecules. Each complex mol-ecule features a penta-coordinated Zn(2+) ion within a square-pyramidal geometry, whereby the N5 donor set is defined by four atoms of the phthalocyaninate dianion (PC) and an N-bound benzyl-amine mol-ecule; it is the relative orientations of the latter that differentiate between the independent complex mol-ecules. The uncoordinated benzyl-amine mol-ecules display different conformations in the structure, with syn-Car-Car-Cm-N (ar = aromatic, m = methyl-ene) torsion angles spanning the range -28.7 (10) to 35.1 (14)°. In the crystal, N-H⋯N and N-H⋯π inter-actions lead to supra-molecular layers in the ab plane. The layers have a zigzag topology, have the coordinating and non-coordinating benzyl-amine mol-ecules directed to the inside, and present the essentially flat PC resides to the outside. This arrangement enables adjacent layers to associate via π-π inter-actions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593 (2) Å] so that a three-dimensional architecture is formed.

Photonic-crystal membranes for optical detection of single nano-particles, designed for biosensor application.

PubMed

Grepstad, Jon Olav; Kaspar, Peter; Solgaard, Olav; Johansen, Ib-Rune; Sudbø, Aasmund S

2012-03-26

A sensor designed to detect bio-molecules is presented. The sensor exploits a planar 2D photonic crystal (PC) membrane with sub-micron thickness and through holes, to induce high optical fields that allow detection of nano-particles smaller than the diffraction limit of an optical microscope. We report on our design and fabrication of a PC membrane with a nano-particle trapped inside. We have also designed and built an imaging system where an optical microscope and a CCD camera are used to take images of the PC membrane. Results show how the trapped nano-particle appears as a bright spot in the image. In a first experimental realization of the imaging system, single particles with a radius of 75 nm can be detected.

Optical properties of opal photonic crystals

NASA Astrophysics Data System (ADS)

Eradat-Oskouei, Nayer

2001-10-01

Photonic crystals (PC) are a class of artificial structures with a periodic dielectric function in one, two, or three dimensions, in which the propagation of electromagnetic waves within a certain frequency band is forbidden. This forbidden frequency band has been dubbed photonic band gap (PBG). The position, width, depth, and shape of the PBG strongly depend on the periodicity, symmetry properties, dielectric constant contrast, and internal lattice structure of the unit cell. There is a common belief that PCs will perform many functions with light that ordinary crystals do with electrons. At the same time, PCs are of great promise to become a laboratory for testing fundamental processes involving interactions of radiation with matter in novel conditions. We have studied the optical properties of opal PCs that are infiltrated with metals, laser dyes, π-conjugated polymers, and J-aggregates. Opals are self-assembled structures of silica (SiO2) spheres mostly packed in a face centered cubic (fcc) lattice. Our research is summarized in the following six chapters. Chapter 1 is a review on the concepts related to PBG and PC, eigenvalue problem of electromagnetism, material systems that exhibit PBG. Chapter 2 covers all the fabrication and measurement techniques including angle resolved reflectivity, transmission, photoluminescence, photo-induced absorption, and coherent backscattering. Chapter 3 focuses on the relationship between a polaritonic gap and a photonic stop-band when they resonantly coexist in the same structure. Infiltration of opal with polarizable molecules combines the polaritonic and Bragg diffractive effects. The experimental results on reflectivity and its dependence on the impinging angle and concentration of the polarizable medium are in agreement with the theoretical calculations. In Chapter 4, the optical studies of three-dimensional metallic mesh composites are reported. Photonic and electronic properties of these PCs strongly depend on their geometry. Dramatic differences in the reflectivity spectra of two kinds of metallic structures, with network or cermet topologies, were observed. Bragg diffraction occurs from both topologies. In addition, highly interconnected metallic PC structures showed about one order of magnitude decrease in the effective plasma frequency. These properties may be used to create transparent metals. Coherent backscattering measurements showed a much larger optical mean free path for the metal-infiltrated opals compared to the skin depth of the metals. Chapter 5 deals with the enhancement and inhibition of the spontaneous emission in PCs. In addition, the effect of the PBG on the photo-induced absorption (PA) of a π-conjugated polymer, when the absorption band lies within the PBG, is investigated for the first time. Changes in the PA spectrum of a π-conjugated polymer, DOO-PPP, infiltrated in opals were observed that are probably influenced by the photonic stop-band. This dissertation ends with some suggestions in Chapter 6 for future experiments.

Tetranuclear clusters containing a CrIII-doped MnIII4O2 core: syntheses, structures, and magnetic properties.

PubMed

Ma, Yun-Sheng; Li, Yi-Zhi; Song, You; Zheng, Li-Min

2008-06-02

The oxidation of MnII carboxylates by (NBu4)Cr2O7 in the presence of different phosphonic acids and chelating ligands results in six CrIII-doped tetranuclear manganese clusters formulated [Mn3CrO2(O2CCH3)4(O3PC5H4N)2(bpy)2] (1), [Mn3CrO2(O2CCH3)4(O3PC5H4N)2(phen)2] (2), [Mn3CrO2(O2CPh)4(O3PC5H4NO)2(phen)2] (3), [Mn3CrO2(O2CPh)4(O3PC6H11)2(bpy)2] (4), [Mn 3CrO2(O2CPh)4(O3PC6H11)2(phen) 2] (5), and [Mn3CrO2(O2CCH3)4(O3PC6H11)2(bpy)2] (6). Single-crystal X-ray analyses reveal that all the compounds contain similar [M4O2]8+ cores with the four metal sites arranged in planar topologies. The metal ions within the core are bridged by both carboxylate and phosphonate ligands. Temperature-dependent magnetic measurements show that in all cases dominant antiferromagnetic interactions are propagated between the metal centers. The ac magnetic measurements on compounds 5 and 6 reveal that both the in-phase and the out-of-phase signals are frequency dependent, characteristic of single-molecule magnet behaviors.

Up-regulated expression of cartilage intermediate-layer protein and ANK in articular hyaline cartilage from patients with calcium pyrophosphate dihydrate crystal deposition disease.

PubMed

Hirose, Jun; Ryan, Lawrence M; Masuda, Ikuko

2002-12-01

Excess accumulation of extracellular inorganic pyrophosphate (ePPi) in aged human cartilage is crucial in calcium pyrophosphate dihydrate (CPPD) crystal formation in cartilage matrix. Two sources of ePPi are ePPi-generating ectoenzymes (NTPPPH) and extracellular transport of intracellular PPi by ANK. This study was undertaken to evaluate the role of NTPPPH and ANK in ePPi elaboration, by investigating expression of NTPPPH enzymes (cartilage intermediate-layer protein [CILP] and plasma cell membrane glycoprotein 1 [PC-1]) and ANK in human chondrocytes from osteoarthritic (OA) articular cartilage containing CPPD crystals and without crystals. Chondrocytes were harvested from knee cartilage at the time of arthroplasty (OA with CPPD crystals [CPPD], n = 8; OA without crystals [OA], n = 10). Normal adult human chondrocytes (n = 1) were used as a control. Chondrocytes were cultured with transforming growth factor beta1 (TGFbeta1), which stimulates ePPi elaboration, and/or insulin-like growth factor 1 (IGF-1), which inhibits ePPi elaboration. NTPPPH and ePPi were measured in the media at 48 hours. Media CILP, PC-1, and ANK were determined by dot-immunoblot analysis. Chondrocyte messenger RNA (mRNA) was extracted for reverse transcriptase-polymerase chain reaction to study expression of mRNA for CILP, PC-1, and ANK. NTPPPH and ANK mRNA and protein were also studied in fresh frozen cartilage. Basal ePPi elaboration and NTPPPH activity in conditioned media from CPPD chondrocytes were elevated compared with normal chondrocytes, and tended to be higher compared with OA chondrocytes. Basal expression of mRNA for CILP (chondrocytes) and ANK (cartilage) was higher in both CPPD chondrocytes and CPPD cartilage extract than in OA or normal samples. PC-1 mRNA was less abundant in CPPD chondrocytes and cartilage extract than in OA chondrocytes and extract, although the difference was not significant. CILP, PC-1, and ANK protein levels were similar in CPPD, OA, and normal chondrocytes or cartilage extracts. Both CILP and ANK mRNA expression and ePPi elaboration were stimulated by TGFbeta1 and inhibited by IGF-1 in chondrocytes from all sources. CILP and ANK mRNA expression correlates with chondrocyte ePPi accumulation around CPPD and OA chondrocytes, and all respond similarly to growth factor stimulation. These findings suggest that up-regulated CILP and ANK expression contributes to higher ePPi accumulation from CPPD crystal-forming cartilage.

Insights into radiation damage from atomic resolution scanning transmission electron microscopy imaging of mono-layer CuPcCl16 films on graphene.

PubMed

Mittelberger, Andreas; Kramberger, Christian; Meyer, Jannik C

2018-03-19

Atomically resolved images of monolayer organic crystals have only been obtained with scanning probe methods so far. On the one hand, they are usually prepared on surfaces of bulk materials, which are not accessible by (scanning) transmission electron microscopy. On the other hand, the critical electron dose of a monolayer organic crystal is orders of magnitudes lower than the one for bulk crystals, making (scanning) transmission electron microscopy characterization very challenging. In this work we present an atomically resolved study on the dynamics of a monolayer CuPcCl 16 crystal under the electron beam as well as an image of the undamaged molecules obtained by low-dose electron microscopy. The results show the dynamics and the radiation damage mechanisms in the 2D layer of this material, complementing what has been found for bulk crystals in earlier studies. Furthermore, being able to image the undamaged molecular crystal allows the characterization of new composites consisting of 2D materials and organic molecules.

Controllable preparation of copper phthalocyanine single crystal nano column and its chlorine gas sensing properties

NASA Astrophysics Data System (ADS)

Zhao, Jianhong; Qiao, Zhenfang; Zhang, Yumin; Zou, Taoyu; Yu, Leiming; Luo, Li; Wang, Xiaoyan; Yang, Yiji; Wang, Hai; Tang, Libin

2016-09-01

The unsubstituted copper phthalocyanine (CuPc) single crystal nano columns were fabricated for the first time as chlorine (Cl2) gas sensors in this paper. The nano columns of CuPc have been prepared on different substrates via template-free physical vapor deposition (PVD) approach. The growth mechanism of CuPc nano column on quartz was explored and the same condition used on other substrates including glass, sapphire (C-plane<0001>, M-plane<10 1 ¯ 0 >, R-plane<1 1 ¯ 02 >), Si and SiO2/Si came to a same conclusion, which confirmed that the aligned growth of CuPc nano column is not substrate-dependent. And then the CuPc nano column with special morphology was integrated as in-situ sensor device which exhibits high sensitivity and selectivity towards Cl2 at room temperature with a minimum detection limit as low as 0.08 ppm. The response of sensor was found to increase linearly (26 ˜659 % ) with the increase for Cl2 within concentration range (0.08 ˜4.0 ppm ) . These results clearly demonstrate the great potential of the nano column growth and device integration approach for sensor device.

Syntheses, crystal structures and characterization of nitrogen-rich salts based on bis (1H-tetrazol-5-yl) methanone oxime

NASA Astrophysics Data System (ADS)

Lin, Xinyu; Guo, Weiming; Zhang, Tianhe; Huang, Jingru; Tong, Yi; Zhang, Tonglai

2017-08-01

Two nitrogen-rich energetic salts (NH4)2(bto) (1) and (NH3OH)2(bto)·H2O (2) [H2bto = Bis (1H-tetrazol-5-yl) methanone oxime] were synthesized by an improved method in which water was used as solvent. These compounds were characterized by FT-IR spectroscopy, elemental analysis and single crystal X-ray diffraction. Their crystal structures were confirmed to belong to monoclinic system with space group P21 for 1 and Pc for 2, respectively. The detailed thermal behaviours were investigated by using differential scanning calorimetry (DSC) and thermogravimetric method (TG) (decomposition temperature >250 °C). The enthalpies of formation were calculated through the experimental values of combustion enthalpy. In addition, the sensitivities toward impact and friction were tested with standard methods, and those results indicated that two compounds are all insensitive (impact >40 J and friction >360 N). In short, both of the compounds show potential usages as energetic materials. The improved process opens a door for exploring nitrogen-rich salts based on Bis (1H-tetrazol-5-yl) methanone oxime.

Fabrication of Crack-Free Photonic Crystal Films on Superhydrophobic Nanopin Surface.

PubMed

Xia, Tian; Luo, Wenhao; Hu, Fan; Qiu, Wu; Zhang, Zhisen; Lin, Youhui; Liu, Xiang Yang

2017-07-05

On the basis of their superior optical performance, photonic crystals (PCs) have been investigated as excellent candidates for widespread applications including sensors, displays, separation processes, and catalysis. However, fabrication of structurally controllable large-area PC assemblies with no defects is still a tough task. Herein, we develop an effective strategy for preparing centimeter-scale crack-free photonic crystal films by the combined effects of soft assembly and superhydrophobic nanopin surfaces. Owing to its large contact angle and low-adhesive force on the superhydrophobic substrate, the colloidal suspension exhibits a continuous retraction of the three-phase (gas-liquid-solid) contact line (TCL) in the process of solvent (water molecules) evaporation. The constantly receding TCL can bring the colloidal spheres closer to each other, which could timely close the gaps due to the loss of water molecules. As a result, close-packed and well-ordered assembly structures can be easily obtained. We expect that this work may pave the way to utilize novel superhydrophobic materials for designing and developing high-quality PCs and to apply PCs in different fields.

Dynamics of photogenerated nonequilibrium electronic states in Ar+-ion-irradiated SrTiO3

NASA Astrophysics Data System (ADS)

Kumar, Dushyant; Hossain, Z.; Budhani, R. C.

2015-05-01

A metallic surface is realized on stoichiometric and insulating (100) SrTiO3 by Ar+-ion irradiation. The sheet carrier density and Hall mobility of the layer are ˜4.0 ×1014cm-2 and ˜2 ×103cm2/Vs , respectively, at 15 K for the irradiation dose of ˜4.2 ×1018ions/cm2 . These samples display ultraviolet light sensitive photoconductivity (PC) which is enhanced abruptly below the temperature (≈100 K) where SrTiO3 crystal undergoes an antiferrodistortive cubic-to-tetragonal (Oh1→D4h 18 ) structural phase transition. This behavior of PC maps well with the temperature dependence of dielectric function and electric field induced conductivity. The longevity of the PC state also shows a distinct change below ≈100 K. At T >100 K its decay is thermally activated with an energy barrier of ≈36 meV, whereas at T <100 K it becomes independent of temperature. We have examined the effect of electrostatic gating on the lifetime of the PC state. One nontrivial result is the ambient temperature quenching of the photoconducting state by the negative gate field. This observation opens avenues for designing a solid state photoelectric switch. The origin and lifetime of the PC state are understood in the light of field effect induced band bending, defect dynamics, and thermal relaxation processes.

Theoretical and experimental investigations of asymmetric light transport in graded index photonic crystal waveguides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Giden, I. H., E-mail: igiden@etu.edu.tr; Yilmaz, D.; Turduev, M.

To provide asymmetric propagation of light, we propose a graded index photonic crystal (GRIN PC) based waveguide configuration that is formed by introducing line and point defects as well as intentional perturbations inside the structure. The designed system utilizes isotropic materials and is purely reciprocal, linear, and time-independent, since neither magneto-optical materials are used nor time-reversal symmetry is broken. The numerical results show that the proposed scheme based on the spatial-inversion symmetry breaking has different forward (with a peak value of 49.8%) and backward transmissions (4.11% at most) as well as relatively small round-trip transmission (at most 7.11%) in amore » large operational bandwidth of 52.6 nm. The signal contrast ratio of the designed configuration is above 0.80 in the telecom wavelengths of 1523.5–1576.1 nm. An experimental measurement is also conducted in the microwave regime: A strong asymmetric propagation characteristic is observed within the frequency interval of 12.8 GHz–13.3 GHz. The numerical and experimental results confirm the asymmetric transmission behavior of the proposed GRIN PC waveguide.« less

Enhanced optical power of GaN-based light-emitting diode with compound photonic crystals by multiple-exposure nanosphere-lens lithography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yonghui; Wei, Tongbo, E-mail: tbwei@semi.ac.cn; Xiong, Zhuo

2014-07-07

The light-emitting diodes (LEDs) with single, twin, triple, and quadruple photonic crystals (PCs) on p-GaN are fabricated by multiple-exposure nanosphere-lens lithography (MENLL) process utilizing the focusing behavior of polystyrene spheres. Such a technique is easy and economical for use in fabricating compound nano-patterns. The optimized tilted angle is decided to be 26.6° through mathematic calculation to try to avoid the overlay of patterns. The results of scanning electron microscopy and simulations reveal that the pattern produced by MENLL is a combination of multiple ovals. Compared to planar-LED, the light output power of LEDs with single, twin, triple, and quadruple PCsmore » is increased by 14.78%, 36.03%, 53.68%, and 44.85% under a drive current 350 mA, respectively. Furthermore, all PC-structures result in no degradation of the electrical properties. The stimulated results indicate that the highest light extraction efficiency of LED with the clover-shape triple PC is due to the largest scattering effect on propagation of light from GaN into air.« less

Study of temperature-dependent Raman spectroscopy and electrical properties in [001]-oriented 0.35Pb(In1/2Nb1/2)O3-0.35Pb(Mg1/3Nb2/3)O3-0.30PbTiO3-Mn single crystals

NASA Astrophysics Data System (ADS)

Liu, Xing; Fang, Bijun; Deng, Ji; Yan, Hong; Deng, Hao; Yue, Qingwen; Ding, Jianning; Zhao, Xiangyong; Luo, Haosu

2016-01-01

In this work, the temperature-dependent Raman spectra and electrical properties of the [001]-oriented 0.5 mol. % Mn-doped 0.35Pb(In1/2Nb1/2)O3-0.35Pb(Mg1/3Nb2/3)O3-0.30PbTiO3-Mn (PIMNT-Mn) single crystals were investigated. All the unpoled and poled PIMNT-Mn single crystals experience a ferroelectric tetragonal phase to paraelectric cubic phase transition (FET-PC) around 183 °C (TC), which exhibits a second-order transition behavior. Whereas, the poled PIMNT-Mn single crystals exhibit another two dielectric anomalies around 130 °C (TRM) and 148 °C (TMT), in which the ferroelectric rhombohedral phase to ferroelectric monoclinic phase (FER-FEM) and the ferroelectric monoclinic phase to ferroelectric tetragonal phase (FEM-FET) transitions take place, respectively. Both the two ferroelectric phase transitions exhibit a first-order transition behavior. The discontinuous change of the phase degree (θ) and frequencies (fr and fa) around TRM suggest the occurrence of the FER-FEM phase transition in the poled PIMNT-Mn single crystals. The narrowing of the 510 cm-1 and 582 cm-1 Raman modes around the TRM, TMT, and TC temperatures shown in the temperature-dependent Raman spectra suggests their increased ordering of the local structure. The intensity ratio of I272 cm-1/I801 cm-1 increases obviously around the phase transition temperatures (TRM, TMT, and TC), indicating the reduction of the long-range order. The anomalous broadening of the 272 cm-1 Raman mode around the TRM, TMT, and TC temperatures indicates the occurrence of the successive ferroelectric phase transitions (FER-FEM, FEM-FET, and FET-PC) with increasing temperature in the poled PIMNT-Mn single crystals.

Giant photonic Hall effect in magnetophotonic crystals.

PubMed

Merzlikin, A M; Vinogradov, A P; Inoue, M; Granovsky, A B

2005-10-01

We have considered a simple, square, two-dimensional (2D) PC built of a magneto-optic matrix with square holes. It is shown that using such a magnetophotonic crystal it is possible to deflect a light beam at very large angles by applying a nonzero external magnetic field. The effect is called the giant photonic Hall effect (GPHE) or the magnetic superprism effect. The GPHE is based on magneto-optical properties, as is the photonic Hall effect [B. A. van Tiggelen and G. L. J. A. Rikken, in, edited by V. M. Shalaev (Springer-Verlag, Berlin, 2002), p. 275]; however GPHE is not caused by asymmetrical light scattering but rather by the influence of an external magnetic field on the photonic band structure.

Dielectric and Energy Storage Properties of the Heterogeneous P(VDF-HFP)/PC Composite Films

NASA Astrophysics Data System (ADS)

Zhao, Xiaojia; Peng, Guirong; Zhan, Zaiji

2017-12-01

Polymer-based materials with a high discharge energy and low energy loss have attracted considerable attention for energy storage applications. A new class of polymer-based composite films composed of amorphous polycarbonate (PC) and poly(vinylidene fluoride-hexafluoropropylene) [P(VDF-HFP)] has been fabricated by simply solution blending followed by thermal treatment under vacuum. The results show that the diameter of the spherical phase for PC and the melting temperature of P(VDF-HFP) increase, and the crystallinity and crystallization temperature of P(VDF-HFP) decrease with increasing PC content. The phase transition from the polar β phase to weak polarity γ phase is induced by PC addition. Moreover, the Curie temperature of the P(VDF-HFP)/PC composite films shifts to a lower temperature. With the addition of PC, the permittivity, polarization and discharge energy of the P(VDF-HFP)/PC composite films slightly decrease. However, the energy loss is significantly reduced.

The coordination structure of the extracted copper(II) complex with a synergistic mixture containing dinonylnaphthalene sulfonic acid and n-hexyl 3-pyridinecarboxylate ester

NASA Astrophysics Data System (ADS)

Zhu, Shan; Hu, Huiping; Hu, Jiugang; Li, Jiyuan; Hu, Fang; Wang, Yongxi

2017-09-01

In continuation of our interest in the coordination structure of the nickel(II) complex with dinonylnaphthalene sulfonic acid (HDNNS) and 2-ethylhexyl 4-pyridinecarboxylate ester (4PC), it was observed that the coordination sphere was completed by the coordination of two N atoms of pyridine rings in ligands 4PC and four water molecules while no direct interaction between Ni(II) and deprotonated HDNNS was observed. To investigate whether the coordination structure of nickel(II) with the synergistic mixture containing HDNNS and 4PC predominates or not in the copper(II) complex with the synergistic mixtures containing HDNNS and pyridinecarboxylate esters, a copper(II) synergist complex with n-hexyl 3-pyridinecarboxylate ester (L) and naphthalene-2-sulfonic acid (HNS, the short chain analogue of HDNNS), was prepared and studied by X-ray single crystal diffraction, elemental analyses and thermo gravimetric analysis (TGA), respectively. It was shown that the composition of the copper(II) synergist complex was [Cu(H2O)2(L)2(NS)2] and formed a trans-form distorted octahedral coordination structure. Two oxygen atoms of the two coordinated water molecules and two N atoms of the pyridine rings in the ligands L defined the basal plane while two O atoms from two sulfonate anions of the deprotonated HNS ligands occupied the apical positions by direct coordination with Cu(II), which was distinguished from the coordination structure of the nickel(II) synergist complex as reported in our previous work. In the crystal lattice, neighboring molecules [Cu(H2O)2L2(NS)2] were linked through the intermolecular hydrogen bonds between the hydrogen atoms of the coordinated water molecules and the oxygen atoms of the sulfonate anions in the copper(II) synergist complex to form a 2D plane. In order to bridge the gap between the solid state structure of the copper(II) synergist complex and the solution structure of the extracted copper(II) complex with the actual synergistic mixture containing L and HDNNS in the non-polar organic phase, the structures of the two copper(II) complexes were further investigated by Fourier transform infrared spectroscopy (FT-IR) and electrospray ionization mass spectrometry (ESI-MS), and the results indicated that the extracted copper(II) complex in the non-polar organic phase might possess a similar coordination structure as the copper(II) synergist complex.

Spectral scalability and optical spectra of fractal multilayer structures: FDTD analysis

NASA Astrophysics Data System (ADS)

Simsek, Sevket; Palaz, Selami; Mamedov, Amirullah M.; Ozbay, Ekmel

2017-01-01

An investigation of the optical properties and band structures for the conventional and Fibonacci photonic crystals (PCs) based on SrTiO3 and Sb2Te3 is made in the present research. Here, we use one-dimensional SrTiO3- and Sb2Te3-based layers. We have theoretically calculated the photonic band structure and transmission spectra of SrTiO3- and Sb2Te3-based PC superlattices. The position of minima in the transmission spectrum correlates with the gaps obtained in the calculation. The intensity of the transmission depths is more intense in the case of higher refractive index contrast between the layers.

Critical CuI buffer layer surface density for organic molecular crystal orientation change

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahn, Kwangseok; Kim, Jong Beom; Lee, Dong Ryeol, E-mail: drlee@ssu.ac.kr

We have determined the critical surface density of the CuI buffer layer inserted to change the preferred orientation of copper phthalocyanine (CuPc) crystals grown on the buffer layer. X-ray reflectivity measurements were performed to obtain the density profiles of the buffer layers and out-of-plane and 2D grazing-incidence X-ray diffraction measurements were performed to determine the preferred orientations of the molecular crystals. Remarkably, it was found that the preferred orientation of the CuPc film is completely changed from edge-on (1 0 0) to face-on (1 1 −2) by a CuI buffer layer with a very low surface density, so low thatmore » a large proportion of the substrate surface is bare.« less

Structural Context of Disease-Associated Mutations and Putative Mechanism of Autoinhibition Revealed by X-Ray Crystallographic Analysis of the EZH2-SET Domain

PubMed Central

Antonysamy, Stephen; Condon, Bradley; Druzina, Zhanna; Bonanno, Jeffrey B.; Gheyi, Tarun; Zhang, Feiyu; MacEwan, Iain; Zhang, Aiping; Ashok, Sheela; Rodgers, Logan; Russell, Marijane; Gately Luz, John

2013-01-01

The enhancer-of-zeste homolog 2 (EZH2) gene product is an 87 kDa polycomb group (PcG) protein containing a C-terminal methyltransferase SET domain. EZH2, along with binding partners, i.e., EED and SUZ12, upon which it is dependent for activity forms the core of the polycomb repressive complex 2 (PRC2). PRC2 regulates gene silencing by catalyzing the methylation of histone H3 at lysine 27. Both overexpression and mutation of EZH2 are associated with the incidence and aggressiveness of various cancers. The novel crystal structure of the SET domain was determined in order to understand disease-associated EZH2 mutations and derive an explanation for its inactivity independent of complex formation. The 2.00 Å crystal structure reveals that, in its uncomplexed form, the EZH2 C-terminus folds back into the active site blocking engagement with substrate. Furthermore, the S-adenosyl-L-methionine (SAM) binding pocket observed in the crystal structure of homologous SET domains is notably absent. This suggests that a conformational change in the EZH2 SET domain, dependent upon complex formation, must take place for cofactor and substrate binding activities to be recapitulated. In addition, the data provide a structural context for clinically significant mutations found in the EZH2 SET domain. PMID:24367637

Distinctive effect on nerve growth factor-induced PC12 cell neurite outgrowth by two unique neolignan enantiomers from Illicium merrillianum

PubMed Central

Tian, Xinhui; Yue, Rongcai; Zeng, Huawu; Li, Honglin; Shan, Lei; He, Weiwei; Shen, Yunheng; Zhang, Weidong

2015-01-01

Merrillianoid (1), a racemic neolignan possessing the characteristic benzo-2,7-dioxabicyclo[3.2.1]octane moiety, was isolated from the branches and leaves of Illicium merrillianum. Chiral separation of 1 gave two enantiomers (+)−1 and (−)−1. The structure of 1 was established by comprehensive spectroscopic analysis and single crystal X-ray diffraction. The absolute configurations of enantiomers were determined by quantum mechanical calculation. Compound (+)−1 exhibited a better neurotrophic activity than racemate 1 by promoting nerve growth factor (NGF) induced PC12 cell neurite outgrowth, while (−)−1 showed a distinctive inhibitory effect. Furthermore, a mechanism study indicated that the two enantiomers influenced NGF-induced neurite outgrowth of PC12 cells possibly by interacting with the trkA receptor, and extracellular signal regulated kinases 1/2 (ERK1/2) and mitogen-activated protein kinase (MEK) in Ras/ERK signal cascade. But the phosphorylation level of serine/threonine kinase Akt1 and Akt2 in PI3K/Akt signal pathway showed no significant difference between (+)−1 and (−)−1. PMID:26585042

Bis(tri-n-hexylsilyl oxide) silicon phthalocyanine: a unique additive in ternary bulk heterojunction organic photovoltaic devices.

PubMed

Lessard, Benoît H; Dang, Jeremy D; Grant, Trevor M; Gao, Dong; Seferos, Dwight S; Bender, Timothy P

2014-09-10

Previous studies have shown that the use of bis(tri-n-hexylsilyl oxide) silicon phthalocyanine ((3HS)2-SiPc) as an additive in a P3HT:PC61BM cascade ternary bulk heterojunction organic photovoltaic (BHJ OPV) device results in an increase in the short circuit current (J(SC)) and efficiency (η(eff)) of up to 25% and 20%, respectively. The previous studies have attributed the increase in performance to the presence of (3HS)2-SiPc at the BHJ interface. In this study, we explored the molecular characteristics of (3HS)2-SiPc which makes it so effective in increasing the OPV device J(SC) and η(eff. Initially, we synthesized phthalocyanine-based additives using different core elements such as germanium and boron instead of silicon, each having similar frontier orbital energies compared to (3HS)2-SiPc and tested their effect on BHJ OPV device performance. We observed that addition of bis(tri-n-hexylsilyl oxide) germanium phthalocyanine ((3HS)2-GePc) or tri-n-hexylsilyl oxide boron subphthalocyanine (3HS-BsubPc) resulted in a nonstatistically significant increase in JSC and η(eff). Secondly, we kept the silicon phthalocyanine core and substituted the tri-n-hexylsilyl solubilizing groups with pentadecyl phenoxy groups and tested the resulting dye in a BHJ OPV. While an increase in JSC and η(eff) was observed at low (PDP)2-SiPc loadings, the increase was not as significant as (3HS)2-SiPc; therefore, (3HS)2-SiPc is a unique additive. During our study, we observed that (3HS)2-SiPc had an extraordinary tendency to crystallize compared to the other compounds in this study and our general experience. On the basis of this observation, we have offered a hypothesis that when (3HS)2-SiPc migrates to the P3HT:PC61BM interface the reason for its unique performance is not solely due to its frontier orbital energies but also might be due to a high driving force for crystallization.

Phononic band gap and wave propagation on polyvinylidene fluoride-based acoustic metamaterials

NASA Astrophysics Data System (ADS)

Oltulu, Oral; Simsek, Sevket; Mamedov, Amirullah M.; Ozbay, Ekmel

2016-12-01

In the present work, the acoustic band structure of a two-dimensional phononic crystal (PC) containing an organic ferroelectric (PVDF-polyvinylidene fluoride) and topological insulator (SnTe) was investigated by the plane-wave-expansion (PWE) method. Two-dimensional PC with square lattices composed of SnTe cylindrical rods embedded in the PVDF matrix is studied to find the allowed and stop bands for the waves of certain energy. Phononic band diagram ω = ω(k) for a 2D PC, in which non-dimensional frequencies ωa/2πc (c-velocity of wave) were plotted vs. the wavevector k along the Г-X-M-Г path in the square Brillouin zone shows five stop bands in the frequency range between 10 and 110 kHz. The ferroelectric properties of PVDF and the unusual properties of SnTe as a topological material give us the ability to control the wave propagation through the PC over a wide frequency range of 103-106 Hz. SnTe is a discrete component that allows conducting electricity on its surface but shows insulator properties through its bulk volume. Tin telluride is considered as an acoustic topological insulator as the extension of topological insulators into the field of "topological phononics".

Photonic Crystal Structures with Tunable Structure Color as Colorimetric Sensors

PubMed Central

Wang, Hui; Zhang, Ke-Qin

2013-01-01

Colorimetric sensing, which transduces environmental changes into visible color changes, provides a simple yet powerful detection mechanism that is well-suited to the development of low-cost and low-power sensors. A new approach in colorimetric sensing exploits the structural color of photonic crystals (PCs) to create environmentally-influenced color-changeable materials. PCs are composed of periodic dielectrics or metallo-dielectric nanostructures that affect the propagation of electromagnetic waves (EM) by defining the allowed and forbidden photonic bands. Simultaneously, an amazing variety of naturally occurring biological systems exhibit iridescent color due to the presence of PC structures throughout multi-dimensional space. In particular, some kinds of the structural colors in living organisms can be reversibly changed in reaction to external stimuli. Based on the lessons learned from natural photonic structures, some specific examples of PCs-based colorimetric sensors are presented in detail to demonstrate their unprecedented potential in practical applications, such as the detections of temperature, pH, ionic species, solvents, vapor, humidity, pressure and biomolecules. The combination of the nanofabrication technique, useful design methodologies inspired by biological systems and colorimetric sensing will lead to substantial developments in low-cost, miniaturized and widely deployable optical sensors. PMID:23539027

Tetra-methyl substituted copper (II) phthalocyanine as a hole injection enhancer in organic light-emitting diodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yu-Long; Xu, Jia-Ju; Lin, Yi-Wei

2015-10-15

We have enhanced hole injection and lifetime in organic light-emitting diodes (OLEDs) by incorporating the isomeric metal phthalocyanine, CuMePc, as a hole injection enhancer. The OLED devices containing CuMePc as a hole injection layer (HIL) exhibited higher luminous efficiency and operational lifetime than those using a CuPc layer and without a HIL. The effect of CuMePc thickness on device performance was investigated. Atomic force microscope (AFM) studies revealed that the thin films were smooth and uniform because the mixture of CuMePc isomers depressed crystallization within the layer. This may have caused the observed enhanced hole injection, indicating that CuMePc ismore » a promising HIL material for highly efficient OLEDs.« less

Possible Domain Formation In PE/PC Bilayers Containing High Cholesterol

NASA Astrophysics Data System (ADS)

Hein, Matthew; Hussain, Fazle; Huang, Juyang

2015-03-01

Cholesterol is a significant component of animal cell membranes, and its presence has the effects of not only adding rigidity to the lipid bilayer, but also leading to the formation of lipid domains. Two other lipids of interest are phosphatidylethanolamine (PE), which constitutes about 45 percent of the phospholipids found in human nervous tissues, and phosphatidylcholine (PC), which is found in every cell of the human body. The maximum solubility of cholesterol is the highest mole fraction of cholesterol that the lipid bilayer can retain, at which point cholesterol begins to precipitate out to form cholesterol monohydrate crystals. We have measured the maximum solubility of cholesterol in mixtures of 16:0-18:1PE and 16:0-18:1PC using a new light scattering technique, which utilizes the anisotropic nature of light scattering by cholesterol crystals. This new method is highly accurate and reproducible. Our results show that the maximum solubility of cholesterol increases linearly as a function of the molar ratio POPC/(POPE+POPC), which suggests possible domain formation in mixtures of PE and PC containing maximum amount of cholesterol.

High-resolution charge carrier mobility mapping of heterogeneous organic semiconductors

NASA Astrophysics Data System (ADS)

Button, Steven W.; Mativetsky, Jeffrey M.

2017-08-01

Organic electronic device performance is contingent on charge transport across a heterogeneous landscape of structural features. Methods are therefore needed to unravel the effects of local structure on overall electrical performance. Using conductive atomic force microscopy, we construct high-resolution out-of-plane hole mobility maps from arrays of 5000 to 16 000 current-voltage curves. To demonstrate the efficacy of this non-invasive approach for quantifying and mapping local differences in electrical performance due to structural heterogeneities, we investigate two thin film test systems, one bearing a heterogeneous crystal structure [solvent vapor annealed 5,11-Bis(triethylsilylethynyl)anthradithiophene (TES-ADT)—a small molecule organic semiconductor] and one bearing a heterogeneous chemical composition [p-DTS(FBTTh2)2:PC71BM—a high-performance organic photovoltaic active layer]. TES-ADT shows nearly an order of magnitude difference in hole mobility between semicrystalline and crystalline areas, along with a distinct boundary between the two regions, while p-DTS(FBTTh2)2:PC71BM exhibits subtle local variations in hole mobility and a nanoscale domain structure with features below 10 nm in size. We also demonstrate mapping of the built-in potential, which plays a significant role in organic light emitting diode and organic solar cell operation.

Sb-Te Phase-change Materials under Nanoscale Confinement

NASA Astrophysics Data System (ADS)

Ihalawela, Chandrasiri A.

Size, speed and efficiency are the major challenges of next generation nonvolatile memory (NVM), and phase-change memory (PCM) has captured a great attention due to its promising features. The key for PCM is rapid and reversible switching between amorphous and crystalline phases with optical or electrical excitation. The structural transition is associated with significant contrast in material properties which can be utilized in optical (CD, DVD, BD) and electronic (PCRAM) memory applications. Importantly, both the functionality and the success of PCM technology significantly depend on the core material and its properties. So investigating PC materials is crucial for the development of PCM technology to realized enhanced solutions. In regards to PC materials, Sb-Te binary plays a significant role as a basis to the well-known Ge-Sb-Te system. Unlike the conventional deposition methods (sputtering, evaporation), electrochemical deposition method is used due to its multiple advantages, such as conformality, via filling capability, etc. First, the controllable synthesis of Sb-Te thin films was studied for a wide range of compositions using this novel deposition method. Secondly, the solid electrolytic nature of stoichiometric Sb2Te3 was studied with respect to precious metals. With the understanding of 2D thin film synthesis, Sb-Te 1D nanowires (18 - 220 nm) were synthesized using templated electrodeposition, where nanoporous anodic aluminum oxide (AAO) was used as a template for the growth of nanowires. In order to gain the controllability over the deposition in high aspect ratio structures, growth mechanisms of both the thin films and nanowires were investigated. Systematic understanding gained thorough previous studies helped to formulate the ultimate goal of this dissertation. In this dissertation, the main objective is to understand the size effect of PC materials on their phase transition properties. The reduction of effective memory cell size in conjunction with multilevel cells could be promising to achieve high data densities. However the size reduction may result in changes in material properties. If phase transition properties of the materials are also tunable with respect to the size, then more attractive solutions could be realized. So we have reported the size effect on crystallization temperature of prototypical Sb2Te3 nanowires synthesized in AAO templates. Moreover, we have found that the reduction of nanowire size can elevate the crystallization temperature, which is crucial for data retention in PCM technology. Energy dispersive X-ray spectroscopy, X-ray diffraction, electron microscopy and electrical resistivity measurements were used to characterize the composition, structure, morphology, and phase transition properties of the materials. We believe that this dissertation will provide new insights into the size effect of PC materials in addition to the controllable synthesis of PC thin films and nanowires through the novel electrochemical method.

Control of Mechanical Properties of Thermoplastic Polyurethane Elastomers by Restriction of Crystallization of Soft Segment

PubMed Central

Kojio, Ken; Furukawa, Mutsuhisa; Nonaka, Yoshiteru; Nakamura, Sadaharu

2010-01-01

Mechanical properties of thermoplastic polyurethane elastomers based on either polyether or polycarbonate (PC)-glycols, 4,4’-dipheylmethane diisocyanate (1,1’-methylenebis(4-isocyanatobenzene)), 1,4-butanediol, were controlled by restriction of crystallization of polymer glycols. For the polyether glycol based-polyurethane elastomers (PUEs), poly(oxytetramethylene) glycol (PTMG), and PTMG incorporating dimethyl groups (PTG-X) and methyl side groups (PTG-L) were employed as a polymer glycol. For the PC-glycol, the randomly copolymerized PC-glycols with hexamethylene (C6) and tetramethylene (C4) units between carbonate groups with various composition ratios (C4/C6 = 0/100, 50/50, 70/30 and 90/10) were employed. The degree of microphase separation and mechanical properties of both the PUEs were investigated using differential scanning calorimetry, dynamic viscoelastic property measurements and tensile testing. Mechanical properties could be controlled by changing the molar ratio of two different monomer components. PMID:28883371

Porous Coordination Polymer Based on Bipyridinium Carboxylate Linkers with High and Reversible Ammonia Uptake.

PubMed

Leroux, Maxime; Mercier, Nicolas; Allain, Magali; Dul, Marie-Claire; Dittmer, Jens; Kassiba, Abdel Hadi; Bellat, Jean-Pierre; Weber, Guy; Bezverkhyy, Igor

2016-09-06

The zwitterionic bipyridinium carboxylate ligand 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium (pc1) in the presence of cadmium chloride affords novel porous coordination polymers (PCPs): [Cd4(pc1)3Cl6]·CdCl4·guest (1) crystallizing in the P3̅1c space group. In the structure, [Cd4Cl6(CO2)6] building units are linked together by six pc1 ligands, leading to a 3D high-symmetrical network exhibiting hexagonal channels along the c axis. The walls of this PCP consist of cationic electron-acceptor bipyridinium units. The PCP 1 reversibly adsorbs H2O and CH3OH up to about 0.1 g/g at saturation showing the adsorption isotherms characteristic of a moderately hydrophilic sorbent. Adsorption of ammonia (NH3) follows a different pattern, reaching an exceptional uptake of 0.39 g/g (22.3 mmol/g) after the first adsorption cycle. Although the crystalline structure of 1 collapses after the first adsorption, the solid can be regenerated and maintains the capacity of 0.29 g/g (17 mmol/g) in the following cycles. We found that the high NH3 uptake is due to a combination of pore filling taking place below 150 h·Pa and chemisorption occurring at higher pressures. The latter process was shown to involve two phenomena: (i) coordination of NH3 molecules to Cd(2+) cations as follows from (113)Cd NMR and (ii) strong donor-acceptor interactions between NH3 molecules and pc1 ligands.

Off-axis spectral beam combining of Bragg reflection waveguide photonic crystal diode lasers

NASA Astrophysics Data System (ADS)

Sun, Fangyuan; Wang, Lijie; Zhao, Yufei; Hou, Guanyu; Shu, Shili; Zhang, Jun; Peng, Hangyu; Tian, Sicong; Tong, Cunzhu; Wang, Lijun

2018-06-01

The spectral beam combining (SBC) of Bragg reflection waveguide photonic crystal (BRW-PC) diode lasers was studied for the first time. An off-axis feedback system was constructed using a stripe mirror and a spatial filter to control beam quality in the external cavity. It was found that the BRW-PC diode lasers with a low divergence and a circular beam provided a simplified and cost-effective SBC. The off-axis feedback broke the beam quality limit of a single element, and an M 2 factor of 3.8 times lower than that of a single emitter in the slow axis was demonstrated.

A General Method for Discovering Inhibitors of Protein–DNA Interactions Using Photonic Crystal Biosensors

PubMed Central

Chan, Leo L.; Pineda, Maria; Heeres, James T.; Hergenrother, Paul J.; Cunningham, Brian T.

2009-01-01

Protein–DNA interactions are essential for fundamental cellular processes such as transcription, DNA damage repair, and apoptosis. As such, small molecule disruptors of these interactions could be powerful tools for investigation of these biological processes, and such compounds would have great potential as therapeutics. Unfortunately, there are few methods available for the rapid identification of compounds that disrupt protein–DNA interactions. Here we show that photonic crystal (PC) technology can be utilized to detect protein–DNA interactions, and can be used in a high-throughput screening mode to identify compounds that prevent protein–DNA binding. The PC technology is used to detect binding between protein–DNA interactions that are DNA-sequence-dependent (the bacterial toxin–antitoxin system MazEF) and those that are DNA-sequence-independent (the human apoptosis inducing factor (AIF)). The PC technology was further utilized in a screen for inhibitors of the AIF–DNA interaction, and through this screen aurin tricarboxylic acid was identified as the first in vitro inhibitor of AIF. The generality and simplicity of the photonic crystal method should enable this technology to find broad utility for identification of compounds that inhibit protein–DNA binding. PMID:18582039

Effect of temperature on terahertz photonic and omnidirectional band gaps in one-dimensional quasi-periodic photonic crystals composed of semiconductor InSb.

PubMed

Singh, Bipin K; Pandey, Praveen C

2016-07-20

Engineering of thermally tunable terahertz photonic and omnidirectional bandgaps has been demonstrated theoretically in one-dimensional quasi-periodic photonic crystals (PCs) containing semiconductor and dielectric materials. The considered quasi-periodic structures are taken in the form of Fibonacci, Thue-Morse, and double periodic sequences. We have shown that the photonic and omnidirectional bandgaps in the quasi-periodic structures with semiconductor constituents are strongly depend on the temperature, thickness of the constituted semiconductor and dielectric material layers, and generations of the quasi-periodic sequences. It has been found that the number of photonic bandgaps increases with layer thickness and generation of the quasi-periodic sequences. Omnidirectional bandgaps in the structures have also been obtained. Results show that the bandwidths of photonic and omnidirectional bandgaps are tunable by changing the temperature and lattice parameters of the structures. The generation of quasi-periodic sequences can also change the properties of photonic and omnidirectional bandgaps remarkably. The frequency range of the photonic and omnidirectional bandgaps can be tuned by the change of temperature and layer thickness of the considered quasi-periodic structures. This work will be useful to design tunable terahertz PC devices.

Photoconductive and electro-optic effects in (Cd,Mg)Te single crystals measured in an experiment-on-chip configuration

NASA Astrophysics Data System (ADS)

Serafini, John; Hossain, A.; James, R. B.; Guziewicz, M.; Kruszka, R.; Słysz, W.; Kochanowska, D.; Domagala, J. Z.; Mycielski, A.; Sobolewski, Roman

2017-07-01

We present our studies on both photoconductive (PC) and electro-optic (EO) responses of (Cd,Mg)Te single crystals. In an In-doped Cd0.92Mg0.08Te single crystal, subpicosecond electrical pulses were optically generated via a PC effect, coupled into a transmission line, and, subsequently, detected using an internal EO sampling scheme, all in the same (Cd,Mg)Te material. For photo-excitation and EO sampling, we used femtosecond optical pulses generated by the same Ti:sapphire laser with the wavelengths of 410 and 820 nm, respectively. The shortest transmission line distance between the optical excitation and EO sampling points was 75 μm. By measuring the transient waveforms at different distances from the excitation point, we calculated the transmission-line complex propagation factor, as well as the THz frequency attenuation factor and the propagation velocity, all of which allowed us to reconstruct the electromagnetic transient generated directly at the excitation point, showing that the original PC transient was subpicosecond in duration with a fall time of ˜500 fs. Finally, the measured EO retardation, together with the amount of the electric-field penetration, allowed us to determine the magnitude of the internal EO effect in our (Cd,Mg)Te crystal. The obtained THz-frequency EO coefficient was equal to 0.4 pm/V, which is at the lower end among the values reported for CdTe-based ternaries, apparently, due to the disorientation of the tested crystal that resulted in the non-optimal EO measurement condition.

Low temperature structural transformation in T[Ni(CN){sub 4}].xpyz with x=1,2; T=Mn,Co,Ni,Zn,Cd; pyz=pyrazine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez-Hernandez, J.; Instituto de Ciencia y Tecnologia de Materiales, Universidad de La Habana; Lemus-Santana, A.A.

2010-01-15

The materials under study are pillared solids T[Ni(CN){sub 4}].xpyz with one and two (x=1,2) pyrazine (pyz) molecules and where T=Mn, Co, Ni, Zn, Cd. Stimulated by their structural features and potential role as prototype of porous solids for hydrogen storage, the structural stability under cryogenic conditions for this series of pillared solids was studied. At low temperature, in the 100-200 K range, the occurrence of a reversible structural transformation was found. For T=Mn, Co, Zn, Cd, with x=2, the structural transformation was observed to occur around 185 K, and the low temperature phase crystallizes with a monoclinic unit cell (spacemore » group Pc). This structure change results from certain charge redistribution on cooling within the involved ligands. For T=Ni with x=1, both the low and high temperature phases crystallize with unit cells of tetragonal symmetry, within the same space group but with a different unit cell volume. In this case the structure change is observed around 120 K. Above that temperature the rotational states for the pyrazine molecule are thermally excited and all the pyrazine molecules in the structure become equivalent. Under this condition the material structure is described using a smaller structural unit. The structural study using X-ray powder diffraction data was complemented with calorimetric and Raman spectroscopy measurements. For the low temperature phases the crystal structures were solved from Patterson methods and then refined using the Rietveld method. - Graphical abstract: Low temperature ordered structure for pyrazine in T[Ni(CN){sub 4}].pyz.« less

Origin of temporal compositional trends in monogenetic vent eruptions: Insights from the crystal cargo in the Papoose Canyon sequence, Big Pine Volcanic Field, CA

NASA Astrophysics Data System (ADS)

Gao, Ruohan; Lassiter, John C.; Ramirez, Gabrielle

2017-01-01

Many monogenetic vents display systematic temporal-compositional variations over the course of eruption. Previous studies have proposed that these trends may reflect variable degrees of crustal assimilation, or melting and mixing of heterogeneous mantle source(s). Discrimination between these two endmember hypotheses is critical for understanding the plumbing systems of monogenetic volcanoes, which pose a significant volcanic hazard in many areas. In this study, we examine the Papoose Canyon (PC) monogenetic vent in the Big Pine Volcanic Field (BPVF), which had been well characterized for temporal-compositional variations in erupted basalts. We present new major and trace element and Sr-Nd-Pb-O isotopic data from the PC "crystal cargo" (phenocrysts and xenoliths). Comparison of "crystal cargo" and host basalt provides new constraints on the history of magma storage, fractionation, and crustal contamination that are obscured in the bulk basalts due to pre- and syn-eruptive magma mixing processes. The abundances of phenocrysts and ultramafic xenoliths in the PC sequence decrease up-section. Olivine and clinopyroxene phenocrysts span a wide range of Mg# (77-89). The majority of phenocrysts are more evolved than olivine or clinopyroxene in equilibrium with their host basalts (Mg# = 68- 71, equilibrium Fo ≈ 85- 89). In addition, the ultramafic xenoliths display cumulate textures. Olivine and clinopyroxene from ultramafic xenoliths have Mg# (73-87) similar to the phenocrysts, and lower than typical mantle peridotites. Sr-Nd-Pb isotope compositions of the xenoliths are similar to early PC basalts. Finally, many clinopyroxene phenocrysts and clinopyroxene in xenoliths have trace element abundances in equilibrium with melts that are more enriched than the erupted basalts. These features suggest that the phenocrysts and xenoliths derive from melt that is more fractionated and enriched than erupted PC basalts. Pressure constraints suggest phenocrysts and ultramafic xenoliths crystallized at ∼5-7 kbar, corresponding to mid-crust depths. Correlations between HFSE depletion and Sr-Nd-Pb isotopic compositions, high δ18 O values in olivines, and radiogenic Os isotopic compositions in whole rocks also suggest incorporation of a crustally contaminated component. We propose that the phenocrysts and ultramafic xenoliths derive from melts that ponded and fractionated and assimilated continental crust, possibly in mid-crustal sills. These melts were drained and mixed with more primitive melts as the eruption began, and the temporal-compositional trends and decreasing crystal phase abundances reflect gradual deflation and exhaustion of these sills as the eruption progressed. The isotopic variations in the PC sequence span much of the compositional range observed in the BPVF. Evidence for variable crustal contamination of PC basalts suggests that much of the isotopic variation observed in the BPVF may also reflect crustal contamination rather than mantle source heterogeneity as previously proposed. In addition, evidence of pre-eruptive magma ponding and fractionation, if applicable to other monogenetic vents, may have significant implications for monitoring and hazard assessment of monogenetic volcano fields.

Stochastic optimization of broadband reflecting photonic structures.

PubMed

Estrada-Wiese, D; Del Río-Chanona, E A; Del Río, J A

2018-01-19

Photonic crystals (PCs) are built to control the propagation of light within their structure. These can be used for an assortment of applications where custom designed devices are of interest. Among them, one-dimensional PCs can be produced to achieve the reflection of specific and broad wavelength ranges. However, their design and fabrication are challenging due to the diversity of periodic arrangement and layer configuration that each different PC needs. In this study, we present a framework to design high reflecting PCs for any desired wavelength range. Our method combines three stochastic optimization algorithms (Random Search, Particle Swarm Optimization and Simulated Annealing) along with a reduced space-search methodology to obtain a custom and optimized PC configuration. The optimization procedure is evaluated through theoretical reflectance spectra calculated by using the Equispaced Thickness Method, which improves the simulations due to the consideration of incoherent light transmission. We prove the viability of our procedure by fabricating different reflecting PCs made of porous silicon and obtain good agreement between experiment and theory using a merit function. With this methodology, diverse reflecting PCs can be designed for any applications and fabricated with different materials.

(M)- and (P)-bicelaphanol A, dimeric trinorditerpenes with promising neuroprotective activity from Celastrus orbiculatus.

PubMed

Wang, Luo-Yi; Wu, Jian; Yang, Zhuo; Wang, Xu-Jie; Fu, Yan; Liu, Shuang-Zhu; Wang, Hong-Min; Zhu, Wei-Liang; Zhang, Hai-Yan; Zhao, Wei-Min

2013-04-26

(M)-Bicelaphanol A (1) and (P)-bicelaphanol A (2), two unprecedented dimeric trinorditerpenes existing as atropisomers, together with their monomer celaphanol A (3), were isolated from the root bark of Celastrus orbiculatus. The structures and absolute configurations of 1 and 2 were determined by spectroscopic and single-crystal X-ray diffraction analyses. Compound 1 exhibited a significant in vitro neuroprotective effect against a hydrogen peroxide-induced cell viability decrease in PC12 cells at 1 μM, while compounds 2 and 3 showed such effects at 10 μM.

Structural basis of DNA target recognition by the B3 domain of Arabidopsis epigenome reader VAL1

PubMed Central

Sasnauskas, Giedrius; Kauneckaitė, Kotryna; Siksnys, Virginijus

2018-01-01

Abstract Arabidopsis thaliana requires a prolonged period of cold exposure during winter to initiate flowering in a process termed vernalization. Exposure to cold induces epigenetic silencing of the FLOWERING LOCUS C (FLC) gene by Polycomb group (PcG) proteins. A key role in this epigenetic switch is played by transcriptional repressors VAL1 and VAL2, which specifically recognize Sph/RY DNA sequences within FLC via B3 DNA binding domains, and mediate recruitment of PcG silencing machinery. To understand the structural mechanism of site-specific DNA recognition by VAL1, we have solved the crystal structure of VAL1 B3 domain (VAL1-B3) bound to a 12 bp oligoduplex containing the canonical Sph/RY DNA sequence 5′-CATGCA-3′/5′-TGCATG-3′. We find that VAL1-B3 makes H-bonds and van der Waals contacts to DNA bases of all six positions of the canonical Sph/RY element. In agreement with the structure, in vitro DNA binding studies show that VAL1-B3 does not tolerate substitutions at any position of the 5′-TGCATG-3′ sequence. The VAL1-B3–DNA structure presented here provides a structural model for understanding the specificity of plant B3 domains interacting with the Sph/RY and other DNA sequences. PMID:29660015

Graphene-enhanced intermolecular interaction at interface between copper- and cobalt-phthalocyanines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dou, Wei-Dong; Center of Super-Diamond and Advanced Films; Huang, Shu-Ping

2015-10-07

Interfacial electronic structures of copper-phthalocyanine (CuPc), cobalt-phthalocyanine (CoPc), and graphene were investigated experimentally by using photoelectron spectroscopy. While the CuPc/graphene interface shows flat band structure and negligible interfacial dipole indicating quite weak molecule-substrate interaction, the CuPc/CoPc/graphene interface shows a large interfacial dipole and obvious energy level bending. Controlled experiments ruled out possible influences from the change in film structure of CuPc and pure π–π interaction between CoPc and CuPc. Analysis based on X-ray photoelectron spectroscopy and density functional theory reveals that the decrease in the work function for the CuPc/CoPc/graphene system is induced by the intermolecular interaction between CuPc andmore » CoPc which is enhanced owning to the peculiar electronic properties at the CoPc-graphene interface.« less

Bottom-up photonic crystal cavities formed by patterned III-V nanopillars.

PubMed

Scofield, Adam C; Shapiro, Joshua N; Lin, Andrew; Williams, Alex D; Wong, Ping-Show; Liang, Baolai L; Huffaker, Diana L

2011-06-08

We report on the formation and optical properties of bottom-up photonic crystal (PC) cavities formed by III-V nanopillars (NPs) via catalyst-free selective-area metal-organic chemical vapor deposition on masked GaAs substrates. This method of NP synthesis allows for precise lithographic control of NP position and diameter enabling simultaneous formation of both the photonic band gap (PBG) region and active gain region. The PBG and cavity resonance are determined by independently tuning the NP radius r, pitch a, and height h in the respective masked areas. Near-infrared emission at 970 nm is achieved from axial GaAs/InGaAs heterostructures with in situ passivation by laterally grown InGaP shells. To achieve out-of-plane optical confinement, the PC cavities are embedded in polydimethylsiloxane (PDMS) and removed from the growth substrate. Spatially and spectrally resolved 77 K photoluminescence demonstrates a strong influence of the PBG resonance on device emission. Resonant peaks are observed in the emission spectra of PC cavities embedded in PDMS.

Co-polymerization of methyl methacrylate and styrene via surfactant-free emulsion polymerization, as a potential material for photonic crystal application

NASA Astrophysics Data System (ADS)

Kassim, Syara; Zahari, Siti Balqis; Tahrin, Rabiatul Addawiyah Azwa; Harun, Noor Aniza

2017-09-01

Photonic crystals are being the great interest of researcher to studies due to a variety of potential application for the interaction of light including the solar cells, optical sensors and paints. In order to evaluate the fabrication of photonic crystals thin film, a free-emulsifier emulsion copolymerization of styrene and methyl methacrylate was carried out. By using the self -assembly approach, this method offers the opportunity to produce crystalline polymer sphere in more ease operation, low cost and environmental friendly. The influences of the mixing ratio of monomer and amount of initiators were studied. In advance, the presence of styrene as co-monomer had improved the thermal degradation of polymer methyl methacrylate. While in changing the mixing ratio of styrene and methyl methacrylate resulted in particle size of the sphere. The size of polymer particles slightly increased on increasing volume of styrene monomer ratio. This occurred because the properties of styrene in water where it sparingly soluble and lead to coagulation of particles. This simple, yet effective method for preparing functional complex 3D structures has the potential to be used generically to fabricate a variety of functional porous 3D structures that could find application not only in new or improved photonic crystal (PC) devices but also in areas such as catalysis, solar cell, separation, fuel cells technology, microelectronics and optoelectronics.

Ring-patterned plasmonic photonic crystal thermal light source for miniaturized near-infrared spectrometers

NASA Astrophysics Data System (ADS)

Labib, Shady R.; Elsayed, Ahmed A.; Sabry, Yasser M.; Khalil, Diaa

2018-02-01

There is a growing number of spectroscopy applications in the near-infrared (NIR) range including gas sensing, food analysis, pharmaceutical and industrial applications that requires highly efficient, more compact and low-cost miniaturized spectrometers. One of the key components for such systems is the wideband light source that can be fabricated using Silicon technology and hence integrated with other components on the same chip. In this work, we report a ring-patterned plasmonic photonic crystal (PC) thermal light source for miniaturized near-infrared spectrometers. The design is based on silicon and tuned to achieve wavelength selectivity in the emitted spectrum. The design is optimized by using Rigorous Coupled-Wave Analysis (RCWA) simulation, which is used to compute the power reflectance and transmittance that are used to predict the emissivity of the structure. The design consists of a PC of silicon rings coated with platinum. The period of the structure is about 2 μm and the silicon is highly-doped with n-type doping level in the order of 1019-1020 cm-3 to enhance the free-carrier absorption. The ring etching depth, diameter and shell thickness are optimized to increase its emissivity within a specific wavelength range of interest. The simulation results show an emissivity exceeding 0.9 in the NIR range up to 2.5 μm, while the emissivity is decreased significantly for longer wavelengths suppressing the emission out of the range of interest, and hence increasing the efficiency for the source. The reported results open the door for black body radiation engineering in integrated silicon sources for spectrometer miniaturization.

Microstructural and electrical properties of Al/n-type Si Schottky diodes with Au-CuPc nanocomposite films as interlayer

NASA Astrophysics Data System (ADS)

Reddy, P. R. Sekhar; Janardhanam, V.; Jyothi, I.; Chang, Han-Soo; Lee, Sung-Nam; Lee, Myung Sun; Reddy, V. Rajagopal; Choi, Chel-Jong

2017-11-01

Au-CuPc nanocomposite films were prepared by simultaneous evaporation of Au and CuPc with various Au and CuPc concentrations. Microstructural analysis of Au-CuPc films revealed elongated Au cluster formation from isolated Au nanoclusters with increasing Au concentration associated with coalescence of Au clusters. Au-CuPc films with different compositions were employed as interlayer in Al/n-Si Schottky diode. Barrier height and series resistance of the Al/n-Si Schottky diode with Au-CuPc interlayer decreased with increasing Au concentration. This could be associated with the enhancement of electron tunneling between neighboring clusters due to decrease in spacing of Au clusters and formation of conducting paths through the composite material. Interface state density of the Al/n-Si Schottky diode with Au-CuPc interlayer increased with increasing Au concentration. This might be because the inclusion of metal decreases the crystallinity and crystal size of the polymer matrix accompanied by the formation of local defect sites at the places of metal nucleation.

Polymer photonic crystal slab waveguides

NASA Astrophysics Data System (ADS)

Liguda, C.; Böttger, G.; Kuligk, A.; Blum, R.; Eich, M.; Roth, H.; Kunert, J.; Morgenroth, W.; Elsner, H.; Meyer, H. G.

2001-04-01

We present details of the fabrication, calculations, and transmission measurements for finite two-dimensional (2D) polymer photonic crystal (PC) slab waveguides, which were fabricated from a benzocyclobutene polymer on a low refractive index substrate from Teflon. A square air hole lattice (500 nm lattice constant, 300 nm hole diameter) was realized by electron beam lithography and reactive ion etching. Polarization and wavelength dependent transmission results show TE-like and TM-like stop gaps at 1.3 μm excitation wavelengths and are in good agreement with the calculated data obtained by 2D and three-dimensional finite difference time domain methods. Transmission was suppressed by 15 dB in the center of the TE-like stop gap for a PC length of ten lattice constants.

Electromagnetic diode based on photonic crystal cavity with embedded highly dispersive meta-interface

NASA Astrophysics Data System (ADS)

Chen, Yongqiang; Dong, Lijuan; Xu, Xiaohu; Jiang, Jun; Shi, Yunlong

2017-12-01

In this paper, we propose a scheme for subwavelength electromagnetic diodes by employing a photonic crystal (PC) cavity with embedded electromagnetically induced-transparency (EIT)-like highly dispersive meta-interface. A nonreciprocal response, with 21.5 dB transmission light contrast and 12.3 dBm working power, is conceptually demonstrated in a microstrip transmission line system with asymmetric absorption and nonlinear medium inclusion. Such high-contrast transmission and relatively low-threshold diode action stem from the composite PC-EIT mechanism. This mechanism not only possesses a large quality factor and strong localization of fields but also does not enlarge the device volume and drastically reduce transmittance. Our findings should be beneficial for the design of new and practical metamaterial-enabled nonlinear devices.

Morphology-defined interaction of copper phthalocyanine with O2/H2O

NASA Astrophysics Data System (ADS)

Muckley, Eric S.; Miller, Nicholas; Jacobs, Christopher B.; Gredig, Thomas; Ivanov, Ilia N.

2016-10-01

Copper phthalocyanine (CuPc) is an important hole transport layer for organic photovoltaics (OPVs), but interaction with ambient gas/vapor may lead to changes in its electronic properties and limit OPV device lifetimes. CuPc films of thickness 25 and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. We measured electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. CuPc films deposited at 250°C showed a factor of 5 higher uptake of O2 as detected by a quartz crystal microbalance (QCM), possibly due to the formation of β-CuPc at T>200°C which allows higher O2 mobility between stacked molecules. While weight-based measurements stabilize after ˜10 min of gas exposure, resistance response stabilizes over times >1 h, suggesting that mass change occurs by rapid adsorption at active surface sites whereas resistive response is dominated by slow diffusion of adsorbates into the bulk film. The 25 nm films exhibit higher resistive response than 100 nm films after an hour of O2/H2O exposure due to fast analyte diffusion down to the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold.

Hierarchical photonic structured stimuli-responsive materials as high-performance colorimetric sensors

NASA Astrophysics Data System (ADS)

Lu, Tao; Zhu, Shenmin; Chen, Zhixin; Wang, Wanlin; Zhang, Wang; Zhang, Di

2016-05-01

Hierarchical photonic structures in nature are of special interest because they can be used as templates for fabrication of stimuli-responsive photonic crystals (PCs) with unique structures beyond man-made synthesis. The current stimuli-responsive PCs templated directly from natural PCs showed a very weak external stimuli response and poor durability due to the limitations of natural templates. Herein, we tackle this problem by chemically coating functional polymers, polyacrylamide, on butterfly wing scales which have hierarchical photonic structures. As a result of the combination of the strong water absorption properties of the polyacrylamide and the PC structures of the butterfly wing scales, the designed materials demonstrated excellent humidity responsive properties and a tremendous colour change. The colour change is induced by the refractive index change which is in turn due to the swollen nature of the polymer when the relative humidity changes. The butterfly wing scales also showed an excellent durability which is due to the chemical bonds formed between the polymer and wing scales. The synthesis strategy provides an avenue for the promising applications of stimuli-responsive PCs with hierarchical structures.Hierarchical photonic structures in nature are of special interest because they can be used as templates for fabrication of stimuli-responsive photonic crystals (PCs) with unique structures beyond man-made synthesis. The current stimuli-responsive PCs templated directly from natural PCs showed a very weak external stimuli response and poor durability due to the limitations of natural templates. Herein, we tackle this problem by chemically coating functional polymers, polyacrylamide, on butterfly wing scales which have hierarchical photonic structures. As a result of the combination of the strong water absorption properties of the polyacrylamide and the PC structures of the butterfly wing scales, the designed materials demonstrated excellent humidity responsive properties and a tremendous colour change. The colour change is induced by the refractive index change which is in turn due to the swollen nature of the polymer when the relative humidity changes. The butterfly wing scales also showed an excellent durability which is due to the chemical bonds formed between the polymer and wing scales. The synthesis strategy provides an avenue for the promising applications of stimuli-responsive PCs with hierarchical structures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01875k

Distinguishing polymorphs of the semiconducting pigment copper phthalocyanine by solid-state NMR and Raman spectroscopy.

PubMed

Shaibat, Medhat A; Casabianca, Leah B; Siberio-Pérez, Diana Y; Matzger, Adam J; Ishii, Yoshitaka

2010-04-08

Cu(II)(phthalocyanine) (CuPc) is broadly utilized as an archetypal molecular semiconductor and is the most widely used blue printing pigment. CuPc crystallizes in six different forms; the chemical and physical properties are substantially modulated by its molecular packing among these polymorphs. Despite the growing importance of this system, spectroscopic identification of different polymorphs for CuPc has posed difficulties. This study presents the first example of spectroscopic distinction of alpha- and beta-forms of CuPc, the most widely used polymorphs, by solid-state NMR (SSNMR) and Raman spectroscopy. (13)C high-resolution SSNMR spectra of alpha- and beta-CuPc using very-fast magic angle spinning (VFMAS) at 20 kHz show that hyperfine shifts sensitively reflect polymorphs of CuPc. The experimental results were confirmed by ab initio chemical shift calculations. (13)C and (1)H SSNMR relaxation times of alpha- and beta-CuPc under VFMAS also showed marked differences, presumably because of the difference in electronic spin correlation times in the two forms. Raman spectroscopy also provided another reliable method of differentiation between the two polymorphs.

Competition between spin-orbit coupling, magnetism, and dimerization in the honeycomb iridates: α -Li2IrO3 under pressure

NASA Astrophysics Data System (ADS)

Hermann, V.; Altmeyer, M.; Ebad-Allah, J.; Freund, F.; Jesche, A.; Tsirlin, A. A.; Hanfland, M.; Gegenwart, P.; Mazin, I. I.; Khomskii, D. I.; Valentí, R.; Kuntscher, C. A.

2018-02-01

Single-crystal x-ray diffraction studies with synchrotron radiation on the honeycomb iridate α -Li2IrO3 reveal a pressure-induced structural phase transition with symmetry lowering from monoclinic to triclinic at a critical pressure of Pc=3.8 GPa. According to the evolution of the lattice parameters with pressure, the transition mainly affects the a b plane and thereby the Ir hexagon network, leading to the formation of Ir-Ir dimers. These observations are independently predicted and corroborated by our ab initio density functional theory calculations where we find that the appearance of Ir-Ir dimers at finite pressure is a consequence of a subtle interplay between magnetism, correlation, spin-orbit coupling, and covalent bonding. Our results further suggest that at Pc the system undergoes a magnetic collapse. Finally we provide a general picture of competing interactions for the honeycomb lattices A2M O3 with A =Li , Na and M =Ir , Ru.

Assessing the potential roles of silicon and germanium phthalocyanines in planar heterojunction organic photovoltaic devices and how pentafluoro phenoxylation can enhance π-π interactions and device performance.

PubMed

Lessard, Benoît H; White, Robin T; Al-Amar, Mohammad; Plint, Trevor; Castrucci, Jeffrey S; Josey, David S; Lu, Zheng-Hong; Bender, Timothy P

2015-03-11

In this study, we have assessed the potential application of dichloro silicon phthalocyanine (Cl2-SiPc) and dichloro germanium phthalocyanine (Cl2-GePc) in modern planar heterojunction organic photovoltaic (PHJ OPV) devices. We have determined that Cl2-SiPc can act as an electron donating material when paired with C60 and that Cl2-SiPc or Cl2-GePc can also act as an electron acceptor material when paired with pentacene. These two materials enabled the harvesting of triplet energy resulting from the singlet fission process in pentacene. However, contributions to the generation of photocurrent were observed for Cl2-SiPc with no evidence of photocurrent contribution from Cl2-GePc. The result of our initial assessment established the potential for the application of SiPc and GePc in PHJ OPV devices. Thereafter, bis(pentafluoro phenoxy) silicon phthalocyanine (F10-SiPc) and bis(pentafluoro phenoxy) germanium phthalocyanine (F10-GePc) were synthesized and characterized. During thermal processing, it was discovered that F10-SiPc and F10-GePc underwent a reaction forming small amounts of difluoro SiPc (F2-SiPc) and difluoro GePc (F2-GePc). This undesirable reaction could be circumvented for F10-SiPc but not for F10-GePc. Using single crystal X-ray diffraction, it was determined that F10-SiPc has significantly enhanced π-π interactions compared with that of Cl2-SiPc, which had little to none. Unoptimized PHJ OPV devices based on F10-SiPc were fabricated and directly compared to those constructed from Cl2-SiPc, and in all cases, PHJ OPV devices based on F10-SiPc had significantly improved device characteristics compared to Cl2-SiPc.

Phononic Crystal Tunable via Ferroelectric Phase Transition

NASA Astrophysics Data System (ADS)

Xu, Chaowei; Cai, Feiyan; Xie, Shuhong; Li, Fei; Sun, Rong; Fu, Xianzhu; Xiong, Rengen; Zhang, Yi; Zheng, Hairong; Li, Jiangyu

2015-09-01

Phononic crystals (PCs) consisting of periodic materials with different acoustic properties have potential applications in functional devices. To realize more smart functions, it is desirable to actively control the properties of PCs on demand, ideally within the same fabricated system. Here, we report a tunable PC made of Ba0.7Sr0.3Ti O3 (BST) ceramics, wherein a 20-K temperature change near room temperature results in a 20% frequency shift in the transmission spectra induced by a ferroelectric phase transition. The tunability phenomenon is attributed to the structure-induced resonant excitation of A0 and A1 Lamb modes that exist intrinsically in the uniform BST plate, while these Lamb modes are sensitive to the elastic properties of the plate and can be modulated by temperature in a BST plate around the Curie temperature. The study finds opportunities for creating tunable PCs and enables smart temperature-tuned devices such as the Lamb wave filter or sensor.

Band transition and topological interface modes in 1D elastic phononic crystals.

PubMed

Yin, Jianfei; Ruzzene, Massimo; Wen, Jihong; Yu, Dianlong; Cai, Li; Yue, Linfeng

2018-05-01

In this report, we design a one-dimensional elastic phononic crystal (PC) comprised of an Aluminum beam with periodically arranged cross-sections to study the inversion of bulk bands due to the change of topological phases. As the geometric parameters of the unit cell varies, the second bulk band closes and reopens forming a topological transition point. This phenomenon is confirmed for both longitudinal waves and bending waves. By constructing a structural system formed by two PCs with different topological phases, for the first time, we experimentally demonstrate the existence of interface mode within the bulk band gap as a result of topological transition for both longitudinal and bending modes in elastic systems, although for bending modes, additional conditions have to be met in order to have the interface mode due to the dispersive nature of the bending waves in uniform media compared to the longitudinal waves.

Maximally asymmetric transbilayer distribution of anionic lipids alters the structure and interaction with lipids of an amyloidogenic protein dimer bound to the membrane surface

PubMed Central

Cheng, Sara Y.; Chou, George; Buie, Creighton; Vaughn, Mark W.; Compton, Campbell; Cheng, Kwan H.

2016-01-01

We used molecular dynamics simulations to explore the effects of asymmetric transbilayer distribution of anionic phosphatidylserine (PS) lipids on the structure of a protein on the membrane surface and subsequent protein–lipid interactions. Our simulation systems consisted of an amyloidogenic, beta-sheet rich dimeric protein (D42) absorbed to the phosphatidylcholine (PC) leaflet, or protein-contact PC leaflet, of two membrane systems: a single-component PC bilayer and double PC/PS bilayers. The latter comprised of a stable but asymmetric transbilayer distribution of PS in the presence of counterions, with a 1-component PC leaflet coupled to a 1-component PS leaflet in each bilayer. The maximally asymmetric PC/PS bilayer had a non-zero transmembrane potential (TMP) difference and higher lipid order packing, whereas the symmetric PC bilayer had a zero TMP difference and lower lipid order packing under physiologically relevant conditions. Analysis of the adsorbed protein structures revealed weaker protein binding, more folding in the N-terminal domain, more aggregation of the N- and C-terminal domains and larger tilt angle of D42 on the PC leaflet surface of the PC/PS bilayer versus the PC bilayer. Also, analysis of protein-induced membrane structural disruption revealed more localized bilayer thinning in the PC/PS versus PC bilayer. Although the electric field profile in the non-protein-contact PS leaflet of the PC/PS bilayer differed significantly from that in the non-protein-contact PC leaflet of the PC bilayer, no significant difference in the electric field profile in the protein-contact PC leaflet of either bilayer was evident. We speculate that lipid packing has a larger effect on the surface adsorbed protein structure than the electric field for a maximally asymmetric PC/PS bilayer. Our results support the mechanism that the higher lipid packing in a lipid leaflet promotes stronger protein–protein but weaker protein–lipid interactions for a dimeric protein on membrane surfaces. PMID:26827904

Crystal structure of bis-[μ-(4-meth-oxy-phen-yl)methane-thiol-ato-κ(2) S:S]bis-[chlorido-(η(6)-1-isopropyl-4-methyl-benzene)-ruthenium(II)] chloro-form disolvate.

PubMed

Stíbal, David; Süss-Fink, Georg; Therrien, Bruno

2015-10-01

The mol-ecular structure of the title complex, [Ru2(C8H9OS)2Cl2(C10H14)2]·2CHCl3 or (p-MeC6H4Pr (i) )2Ru2(SCH2-p-C6H5-OCH3)2Cl2·2CHCl3, shows inversion symmetry. The two symmetry-related Ru(II) atoms are bridged by two 4-meth-oxy-α-toluene-thiol-ato [(4-meth-oxy-phen-yl)methane-thiol-ato] units. One chlorido ligand and the p-cymene ligand complete the typical piano-stool coordination environment of the Ru(II) atom. In the crystal, the CH moiety of the chloro-form mol-ecule inter-acts with the chlorido ligand of the dinuclear complex, while one Cl atom of the solvent inter-acts more weakly with the methyl group of the bridging 4-meth-oxy-α-toluene-thiol-ato unit. This assembly leads to the formation of supra-molecular chains extending parallel to [021].

Eco-friendly materials for large area piezoelectronics: self-oriented Rochelle salt in wood

NASA Astrophysics Data System (ADS)

Lemaire, E.; Ayela, C.; Atli, A.

2018-02-01

Upgraded biodegradable piezoelectric composite materials elaborated by incorporation of Rochelle salt (RS, Sodium potassium tartrate tetrahydrate) in wood were reported. RS crystals, known as the first discovered piezoelectric material, were grown in the micro-cavities of wood, having naturally a tubular structure, by soaking the wood into RS saturated water. Since most of the cavities in wood are oriented in the same direction, the piezoelectric effect was improved when the cavities were filled by RS crystals. The mechanical, structural and piezoelectric properties of RS incorporated wood composite samples were characterized. Both direct and converse piezoelectric effects are illustrated. The wood-base composite exhibits an effective piezoelectric constant d 33 of 11 pC N-1. Also, the flexural strength and modulus of elasticity were enhanced by inserting RS into the wood, nevertheless the samples became more brittle. The wood-based piezoelectric samples prepared in this work can be used as actuators, sensors or energy harvesters. The process developed here permits us to manufacture large area piezoelectric devices which are environmentally and economically unsurpassed.

Terahertz Sensor Using Photonic Crystal Cavity and Resonant Tunneling Diodes

NASA Astrophysics Data System (ADS)

Okamoto, Kazuma; Tsuruda, Kazuisao; Diebold, Sebastian; Hisatake, Shintaro; Fujita, Masayuki; Nagatsuma, Tadao

2017-09-01

In this paper, we report on a terahertz (THz) sensing system. Compared to previously reported systems, it has increased system sensitivity and reduced size. Both are achieved by using a photonic crystal (PC) cavity as a resonator and compact resonant tunneling diodes (RTDs) as signal source and as detector. The measured quality factor of the PC cavity is higher than 10,000, and its resonant frequency is 318 GHz. To demonstrate the operation of the refractive index sensing system, dielectric tapes of various thicknesses are attached to the PC cavity and the change in the resonator's refractive index is measured. The figure of merit of refractive index sensing using the developed system is one order higher than that of previous studies, which used metallic metamaterial resonators. The frequency of the RTD-based source can be swept from 316 to 321 GHz by varying the RTD direct current voltage. This effect is used to realize a compact frequency tunable signal source. Measurements using a commercial signal source and detector are carried out to verify the accuracy of the data obtained using RTDs as a signal source and as a detector.

Bio-inspired fabrication of stimuli-responsive photonic crystals with hierarchical structures and their applications

NASA Astrophysics Data System (ADS)

Lu, Tao; Peng, Wenhong; Zhu, Shenmin; Zhang, Di

2016-03-01

When the constitutive materials of photonic crystals (PCs) are stimuli-responsive, the resultant PCs exhibit optical properties that can be tuned by the stimuli. This can be exploited for promising applications in colour displays, biological and chemical sensors, inks and paints, and many optically active components. However, the preparation of the required photonic structures is the first issue to be solved. In the past two decades, approaches such as microfabrication and self-assembly have been developed to incorporate stimuli-responsive materials into existing periodic structures for the fabrication of PCs, either as the initial building blocks or as the surrounding matrix. Generally, the materials that respond to thermal, pH, chemical, optical, electrical, or magnetic stimuli are either soft or aggregate, which is why the manufacture of three-dimensional hierarchical photonic structures with responsive properties is a great challenge. Recently, inspired by biological PCs in nature which exhibit both flexible and responsive properties, researchers have developed various methods to synthesize metals and metal oxides with hierarchical structures by using a biological PC as the template. This review will focus on the recent developments in this field. In particular, PCs with biological hierarchical structures that can be tuned by external stimuli have recently been successfully fabricated. These findings offer innovative insights into the design of responsive PCs and should be of great importance for future applications of these materials.

Label-free in vitro prostate cancer cell detection via photonic-crystal biosensor

NASA Astrophysics Data System (ADS)

DeLuna, Frank; Ding, XiaoFei; Sagredo, Ismael; Bustamante, Gilbert; Sun, Lu-Zhe; Ye, Jing Yong

2018-02-01

Prostate-specific antigen (PSA) biomarker assays are the current clinical method for mass screening of prostate cancer. However, high false-positive rates are often reported due to PSA's low specificity, leading to an urgent need for the development of a more specific detection system independent of PSA levels. In our previous research, we demonstrated the feasibility of using cellular refractive indices (RI) as a unique contrast parameter to accomplish label-free detection of prostate cancer cells via variance testing, but were unable to determine if a specific cell was cancerous or noncancerous. In this paper, we report the use of our Photonic-Crystal biosensor in a Total-Internal-Reflection (PC-TIR) configuration to construct a label-free imaging system, which allows for the detection of individual prostate cancer cells utilizing cellular RI as the only contrast parameter. Noncancerous prostate (BPH-1) cells and prostate cancer (PC-3) cells were mixed at varied ratios and measured concurrently. Additionally, we isolated and induced PC-3 cells to undergo epithelial-mesenchymal transition (EMT) by exposing these cells to soluble factors such as TGF-β1. The biophysical characteristics of the cellular RI were quantified extensively in comparison to non-induced PC-3 cells as well as BPH-1 cells. EMT is a crucial mechanism for the invasion and metastasis of epithelial tumors characterized by the loss of cell-cell adhesion and increased cell mobility. Our study shows promising clinical potential in utilizing the PC-TIR biosensor imaging system to not only detect prostate cancer cells, but also evaluate prostate cancer progression.

Hydrogen bonds in PC{sub 61}BM solids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheng, Chun-Qi; Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121; Li, Wen-Jie

2015-09-15

We have studied the hydrogen bonds in PC{sub 61}BM solids. Inter-molecular interaction is analyzed theoretically for the well-defined monoclinic (P2{sub 1}/n) structure. The results indicate that PC{sub 61}BM combines into C–H⋯O{sub d} bonded molecular chains, where O{sub d} denotes the doubly-bonded O atom of PC{sub 61}BM. The molecular chains are linked together by C–H⋯O{sub s} bonds, where O{sub s} denotes the singly-bonded O atom of PC{sub 61}BM. To reveal the consequences of hydrogen bond formation on the structural properties of PC{sub 61}BM solids (not limited to the monoclinic structure), we design and perform some experiments for annealed samples with themore » monoclinic (P2{sub 1}/n) PC{sub 61}BM as starting material. The experiments include differential scanning calorimetry, X-ray diffraction and infrared absorption measurements. Structural phase transitions are observed below the melting point. The C–H⋯O{sub d} bonds seem persisting in the altered structures. The inter-molecular hydrogen bonds can help to understand the phase separation in polymer/PC{sub 61}BM blends and may be responsible for the existence of liquid PC{sub 61}BM.« less

Modeling the interactions of phthalocyanines in water: from the Cu(II)-tetrasulphonate to the metal-free phthalocyanine.

PubMed

Martín, Elisa I; Martínez, Jose M; Sánchez Marcos, Enrique

2011-01-14

A quantum and statistical study on the effects of the ions Cu(2+) and SO(3)(-) in the solvent structure around the metal-free phthalocyanine (H(2)Pc) is presented. We developed an ab initio interaction potential for the system CuPc-H(2)O based on quantum chemical calculations and studied its transferability to the H(2)Pc-H(2)O and [CuPc(SO(3))(4)](4-)-H(2)O interactions. The use of the molecular dynamics technique allows the determination of energetic and structural properties of CuPc, H(2)Pc, and [CuPc(SO(3))(4)](4-) in water and the understanding of the keys for the different behaviors of the three phthalocyanine (Pc) derivatives in water. The inclusion of the Cu(2+) cation in the Pc structure reinforces the appearance of two axial water molecules and second-shell water molecules in the solvent structure, whereas the presence of SO(3)(-) anions implies a well defined hydration shell of about eight water molecules around them making the macrocycle soluble in water. Debye-Waller factors for axial water molecules have been obtained in order to examine the potential sensitivity of the extended x-ray absorption fine structure technique to detect the axial water molecules.

Thermal, dielectric and barocaloric properties of NH4HSO4 crystallized from an aqueous solution and the melt

NASA Astrophysics Data System (ADS)

Mikhaleva, E. A.; Flerov, I. N.; Kartashev, A. V.; Gorev, M. V.; Bogdanov, E. V.; Bondarev, V. S.

2017-05-01

A study of heat capacity, thermal dilatation, permittivity, dielectric loops and susceptibility to hydrostatic pressure was carried out on quasi-ceramic samples of NH4HSO4 obtained from an aqueous solution as well as the melt. The main parameters of the successive P21/c (T1) ↔ Pc (T2) ↔ P1 phase transitions did not depend on the method of preparation of the samples, and were close to those determined in previous studies of single crystal and powder, except for the sign and magnitude of the baric coefficient for T2. Direct measurements of the pressure effect on the permittivity and thermal properties showed dT2/dp = -123 K·GPa-1, which is consistent in terms of magnitude and sign with the baric coefficient evaluated using dilatometric and calorimetric data in the framework of the Clausius-Clapeyron equation. Thus, the temperature region of the ferroelectric Pc phase existence is extended under pressure. A strong decrease in the entropy jump at the Pc ↔ P1 transformation with an increase in pressure, and the linear dependence of T2 on pressure, indicate that an increase in pressure shifts this phase transition towards the tricritical point on the T-p phase diagram. A significant barocaloric effect was found in the region of the Pc ↔ P1 phase transition.

Evaluation of a novel label-free photonic-crystal biosensor imaging system for the detection of prostate cancer cells

NASA Astrophysics Data System (ADS)

DeLuna, Frank; Ding, XiaoFie; Sun, Lu-Zhe; Ye, Jing Yong

2017-02-01

Biomarker screening for prostate-specific antigen (PSA) is the current clinical standard for detection of prostate cancer. However this method has shown many limitations, mainly in its specificity, which can lead to a high false positive rate. Thus, there is a growing need in developing a more specific detection system for prostate cancer. Using a Photonic- Crystal-based biosensor in a Total-Internal-Reflection (PC-TIR) configuration, we demonstrate the use of refractive index (RI) to accomplish label-free detection of prostate cancer cells against non-cancerous prostate epithelial cells. The PC-TIR biosensor possesses an open microcavity, which in contrast to traditional closed microcavities, allows for easier access of analyte molecules or cells to interact with its sensing surface. In this study, an imaging system was designed using the PC-TIR biosensor to quantify cell RI as the contrast parameter for prostate cancer detection. Non-cancerous BPH-1 prostate epithelial cells and prostate cancer PC-3 cells were placed on a single biosensor and measured concurrently. Recorded image data was then analyzed through a home-built MatLab program. Results demonstrate that RI is a suitable variable for differentiation between prostate cancer cells and non-cancerous prostate epithelial cells. Our study shows clinical potential in utilizing RI test for the detection of prostate cancer.

Pristine fullerenes mixed by vacuum-free solution process: Efficient electron transport layer for planar perovskite solar cells

NASA Astrophysics Data System (ADS)

Dai, Si-Min; Tian, Han-Rui; Zhang, Mei-Lin; Xing, Zhou; Wang, Lu-Yao; Wang, Xin; Wang, Tan; Deng, Lin-Long; Xie, Su-Yuan; Huang, Rong-Bin; Zheng, Lan-Sun

2017-01-01

Discovery of organic-inorganic hybrid perovskites ignites the dream of next-generation solar cells fabricated by low-cost solution processing. To date, fullerene derivative [6,6]-phenyl-C61- butyric acid methyl ester (PC61BM), is the most prevalently used electron transport layer for high efficiency p-i-n planar heterojunction perovskite solar cells. Compared with PC61BM, pristine fullerenes, such as C60 and C70, have shown superiority of higher electron mobility and much lower costs. Due to the poor solubility and strong tendency to crystallize for pristine fullerenes in solution process, it is still a challenge to deposit compact and continuous film of pristine fullerenes for p-i-n type perovskite solar cells by solution processing. Herein, solution processed pristine fullerenes (C60 and C70) were used as electron transport layers to replace PC61BM in perovskite solar cells with high performance and enhanced stability. Power conversion efficiency of 14.04% was obtained by using mixture of C60 and C70 as electron transport layer, which is comparable to that of PC61BM based device (13.74%). We demonstrated that the strong tendency of pristine fullerenes to crystallize during solvent removal can be largely mitigated by mixing different kinds of pristine fullerenes. These findings implicate pristine fullerenes as promising electron transport layers for high performance perovskite solar cells.

Mixed (phthalocyaninato)(Schiff-base) di-dysprosium sandwich complexes. Effect of magnetic coupling on the SMM behavior.

PubMed

Wang, Hailong; Liu, Chenxi; Liu, Tao; Zeng, Suyuan; Cao, Wei; Ma, Qi; Duan, Chunying; Dou, Jianmin; Jiang, Jianzhuang

2013-11-21

Reaction between Schiff-base ligand and half-sandwich complex M(Pc)(acac) led to the isolation of new sandwich-type mixed (phthalocyaninato)(Schiff-base) di-lanthanide compounds M2(Pc)2(L)H2O (M = Dy, Gd) (1, 2) [H2Pc = metal free phthalocyanine, Hacac = acetylacetone, H2L = N,N'-bis(3-methyloxysalicylidene)benzene-1,2-diamine] with the triple-decker molecular structure clearly revealed by single crystal X-ray diffraction analysis. For the comparative studies, sandwich triple-decker analogues with pure Schiff-base ligand M2(L)3H2O (M = Dy, Gd) (3, 4) were also prepared. Dynamic magnetic measurement result reveals the single-molecule magnet (SMM) nature of the di-dysprosium derivative 1, while the static magnetic investigation over both pure and the diamagnetic diluted samples of this compound discloses the interionic ferromagnetic coupling between the two dysprosium ions, which in turn effectively suppresses the QTM and enhances the energy barrier of this SMM. Nevertheless, comparative studies over the static magnetic properties of the di-dysprosium triple-decker complexes 1 and 3 indicate the stronger magnetic coupling between the two lanthanide ions in mixed (phthalocyaninato)(Schiff-base) species than in the pure Schiff-base triple-decker analogue, suggesting the special coordination sphere around the dysprosium ions in the former compound over the latter one on the more intense inter-ionic ferromagnetic coupling. As a very small step towards understanding the structure-property relationship, the present result will be surely helpful for the design and synthesis of the multinuclear lanthanide-based SMMs with good properties.

Maximally asymmetric transbilayer distribution of anionic lipids alters the structure and interaction with lipids of an amyloidogenic protein dimer bound to the membrane surface.

PubMed

Cheng, Sara Y; Chou, George; Buie, Creighton; Vaughn, Mark W; Compton, Campbell; Cheng, Kwan H

2016-03-01

We used molecular dynamics simulations to explore the effects of asymmetric transbilayer distribution of anionic phosphatidylserine (PS) lipids on the structure of a protein on the membrane surface and subsequent protein-lipid interactions. Our simulation systems consisted of an amyloidogenic, beta-sheet rich dimeric protein (D42) absorbed to the phosphatidylcholine (PC) leaflet, or protein-contact PC leaflet, of two membrane systems: a single-component PC bilayer and double PC/PS bilayers. The latter comprised of a stable but asymmetric transbilayer distribution of PS in the presence of counterions, with a 1-component PC leaflet coupled to a 1-component PS leaflet in each bilayer. The maximally asymmetric PC/PS bilayer had a non-zero transmembrane potential (TMP) difference and higher lipid order packing, whereas the symmetric PC bilayer had a zero TMP difference and lower lipid order packing under physiologically relevant conditions. Analysis of the adsorbed protein structures revealed weaker protein binding, more folding in the N-terminal domain, more aggregation of the N- and C-terminal domains and larger tilt angle of D42 on the PC leaflet surface of the PC/PS bilayer versus the PC bilayer. Also, analysis of protein-induced membrane structural disruption revealed more localized bilayer thinning in the PC/PS versus PC bilayer. Although the electric field profile in the non-protein-contact PS leaflet of the PC/PS bilayer differed significantly from that in the non-protein-contact PC leaflet of the PC bilayer, no significant difference in the electric field profile in the protein-contact PC leaflet of either bilayer was evident. We speculate that lipid packing has a larger effect on the surface adsorbed protein structure than the electric field for a maximally asymmetric PC/PS bilayer. Our results support the mechanism that the higher lipid packing in a lipid leaflet promotes stronger protein-protein but weaker protein-lipid interactions for a dimeric protein on membrane surfaces. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Distinguishing Polymorphs of the Semiconducting Pigment Copper Phthalocyanine by Solid-state NMR and Raman Spectroscopy

PubMed Central

Shaibat, Medhat A.; Casabianca, Leah B.; Siberio-Pérez, Diana Y.; Matzger, Adam J; Ishii, Yoshitaka

2010-01-01

Cu(II)(phthalocyanine) (CuPc) is broadly utilized as an archetypal molecular semiconductor and is the most widely used blue printing pigment. CuPc crystallizes in six different forms; the chemical and physical properties are substantially modulated by its molecular packing among these polymorphs. Despite the growing importance of this system, spectroscopic identification of different polymorphs for CuPc has posed difficulties. This study presents the first example of spectroscopic distinction of α- and β-forms of CuPc, the most widely used polymorphs, by solid-state NMR (SSNMR) and Raman spectroscopy. 13C high-resolution SSNMR spectra of α- and β-CuPc using very-fast magic angle spinning (VFMAS) at 20 kHz show that hyperfine shifts sensitively reflect polymorphs of CuPc. The experimental results were confirmed by ab initio chemical shift calculations. 13C and 1H SSNMR relaxation times of α- and β-CuPc under VFMAS also showed marked differences, presumably because of the difference in electronic spin correlation times in the two forms. Raman spectroscopy also provided another reliable method of differentiation between the two polymorphs. PMID:20225842

77 FR 42225 - Airworthiness Directives; PILATUS AIRCRAFT LTD. Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2012-07-18

... (AD) for all PILATUS AIRCRAFT LTD. Models PC 12, PC 12/45, PC 12/47, and PC 12/47E airplanes that... instructions and airworthiness limitations applicable to the Structure and Components of the PC-12 are... Pilatus Aircraft LTD. Models PC 12, PC 12/45, PC 12/47, and PC-12/47E airplanes, all manufacturer serial...

IR Sensor Synchronizing Active Shutter Glasses for 3D HDTV with Flexible Liquid Crystal Lenses

PubMed Central

Han, Jeong In

2013-01-01

IR sensor synchronizing active shutter glasses for three-dimensional high definition television (3D HDTV) were developed using a flexible liquid crystal (FLC) lens. The FLC lens was made on a polycarbonate (PC) substrate using conventional liquid crystal display (LCD) processes. The flexible liquid crystal lens displayed a maximum transmission of 32% and total response time of 2.56 ms. The transmittance, the contrast ratio and the response time of the flexible liquid crystal lens were superior to those of glass liquid crystal lenses. Microcontroller unit and drivers were developed as part of a reception module with power supply for the IR sensor synchronizing active shutter glasses with the flexible liquid crystal lens prototypes. IR sensor synchronizing active shutter glasses for 3D HDTV with flexible liquid crystal lenses produced excellent 3D images viewing characteristics.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bianchetti, Christopher M.; Takasuka, Taichi E.; Deutsch, Sam

The Carbohydrate Active Enzyme (CAZy) database indicates that glycoside hydrolase family 55 (GH55) contains both endo- and exo-β-1,3-glucanases. The founding structure in the GH55 is PcLam55A from the white rot fungus Phanerochaete chrysosporium. Here, we present high resolution crystal structures of bacterial SacteLam55A from the highly cellulolytic Streptomyces sp. SirexAA-E with bound substrates and product. These structures, along with mutagenesis and kinetic studies, implicate Glu-502 as the catalytic acid (as proposed earlier for Glu-663 in PcLam55A) and a proton relay network of four residues in activating water as the nucleophile. Further, a set of conserved aromatic residues that define themore » active site apparently enforce an exo-glucanase reactivity as demonstrated by exhaustive hydrolysis reactions with purified laminarioligosaccharides. Two additional aromatic residues that line the substrate-binding channel show substrate-dependent conformational flexibility that may promote processive reactivity of the bound oligosaccharide in the bacterial enzymes. Gene synthesis carried out on ~30% of the GH55 family gave 34 active enzymes (19% functional coverage of the nonredundant members of GH55). These active enzymes reacted with only laminarin from a panel of 10 different soluble and insoluble polysaccharides and displayed a broad range of specific activities and optima for pH and temperature. Furthermore, application of this experimental method provides a new, systematic way to annotate glycoside hydrolase phylogenetic space for functional properties.« less

Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures.

PubMed

Kanno, H; Kajiwara, K; Miyata, K

2010-05-21

Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for T(H) (homogeneous ice nucleation temperature) and T(m) (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the T(H) curve for a DMSO solution of R=20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at P(c2)= approximately 200 MPa and at T(c2)<-100 degrees C (P(c2): pressure of SCP, T(c2): temperature of SCP). The presence of two T(H) peaks for DMSO solutions (R=15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R

Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures

NASA Astrophysics Data System (ADS)

Kanno, H.; Kajiwara, K.; Miyata, K.

2010-05-01

Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for TH (homogeneous ice nucleation temperature) and Tm (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the TH curve for a DMSO solution of R =20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at Pc2=˜200 MPa and at Tc2<-100 °C (Pc2: pressure of SCP, Tc2: temperature of SCP). The presence of two TH peaks for DMSO solutions (R =15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R ≤15) at high pressures and low temperatures (<-90 °C). The pressure dependence of the two TH curves for DMSO solutions of R =10 and 12 indicates that the two phase-separated components in the DMSO solution of R =10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

Political, cultural and economic foundations of primary care in Europe.

PubMed

Kringos, Dionne S; Boerma, Wienke G W; van der Zee, Jouke; Groenewegen, Peter P

2013-12-01

This article explores various contributing factors to explain differences in the strength of the primary care (PC) structure and services delivery across Europe. Data on the strength of primary care in 31 European countries in 2009/10 were used. The results showed that the national political agenda, economy, prevailing values, and type of healthcare system are all important factors that influence the development of strong PC. Wealthier countries are associated with a weaker PC structure and lower PC accessibility, while Eastern European countries seemed to have used their growth in national income to strengthen the accessibility and continuity of PC. Countries governed by left-wing governments are associated with a stronger PC structure, accessibility and coordination of PC. Countries with a social-security based system are associated with a lower accessibility and continuity of PC; the opposite is true for transitional systems. Cultural values seemed to affect all aspects of PC. It can be concluded that strengthening PC means mobilising multiple leverage points, policy options, and political will in line with prevailing values in a country. Copyright © 2013 Elsevier Ltd. All rights reserved.

Synthesis and characterisation of new types of side chain cholesteryl polymers.

PubMed

Wang, Bin; Du, Haiyan; Zhang, Junhua

2011-01-01

A series of cholesterol derivatives have been synthesised via the alkylation reaction of the 3-hydroxyl group with the aliphatic bromide compounds with different chain lengths, namely 3β-alkyloxy-cholesterol. The double bond between the C5 and C6 positions in these cholesterol derivatives was oxidised into epoxy, followed by an epoxy-ring-opening reaction with the treatment with acrylic acid, resulting in a series of 3β-alkyloxy-5α-hydroxy-6β-acryloyloxycholesterol, C(n)OCh (n=1, 2, 4, 6, 8, 10, 12), The acrylate group is connected to the C6 position, which is confirmed by the single crystal structure analysis. The corresponding polymers, PC(n)OCh, were prepared via free radical polymerisation. The structure of monomers and the resulting polymers were characterised with nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). The thermal properties of PC(n)OCh were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). To determine the secondary structure of polymers, circular dichroism (CD) spectra were performed. It was found that not all monomers produce high-molecular-weight polymers because of steric hindrance. However, all polymers have a helical structure, which can be enhanced by increasing the alkoxy chain length. In addition, increasing the alkoxy chain length decreases the glass transition temperature and increases the decomposition temperature of the polymers. Copyright © 2010 Elsevier Inc. All rights reserved.

Ultracompact photonic crystal polarization beam splitter based on multimode interference.

PubMed

Lu, Ming-Feng; Liao, Shan-Mei; Huang, Yang-Tung

2010-02-01

We propose a theoretical design for a compact photonic crystal (PC) polarization beam splitter (PBS) based on the multimode interference (MMI) effect. The size of a conventional MMI device designed by the self-imaging principle is not compact enough; therefore, we design a compact PC PBS based on the difference of the interference effect between TE and TM modes. Within the MMI coupler, the dependence of interference of modes on propagation distance is weak for a TE wave and strong for a TM wave; as a result, the length of the MMI section can be only seven lattice constants. Simulation results show that the insertion losses are 0.32 and 0.89 dB, and the extinction ratios are 14.4 and 17.5 dB for Port 1 (TE mode) and Port 2 (TM mode), respectively.

Bistable four-wave mixing response in a semiconductor quantum dot coupled to a photonic crystal nanocavity.

PubMed

Li, Jian-Bo; Xiao, Si; Liang, Shan; He, Meng-Dong; Luo, Jian-Hua; Kim, Nam-Chol; Chen, Li-Qun

2017-10-16

We perform a theoretical study of the bistable four-wave mixing (FWM) response in a coupled system comprised of a semiconductor quantum dot (SQD) and a photonic crystal (PC) nanocavity in which the SQD is embedded. It is shown that the shape of the FWM spectrum can switch among single-peaked, double-peaked, triple-peaked, and four-peaked arising from the vacuum Rabi splitting and the exciton-nanocavity coupling. Especially, we map out bistability phase diagrams within a parameter subspace of the system, and find that it is easy to turn on or off the bistable FWM response by only adjusting the excitation frequency or the pumping intensity. Our results offer a feasible means for measuring the SQD-PC nanocavity coupling strength and open a new avenue to design optical switches and memories.

Bench-Scale Development of a Hot Carbonate Absorption Process with Crystallization-Enabled High-Pressure Stripping for Post-Combustion CO{sub 2} Capture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Yongqi; DeVries, Nicholas; Ruhter, David

A novel Hot Carbonate Absorption Process with Crystallization-Enabled High-Pressure Stripping (Hot-CAP) has been developed by the University of Illinois at Urbana-Champaign and Carbon Capture Scientific, LLC in this three-year, bench-scale project. The Hot-CAP features a concentrated carbonate solution (e.g., K{sub 2}CO{sub 3}) for CO{sub 2} absorption and a bicarbonate slurry (e.g., KHCO{sub 3}) for high-pressure CO{sub 2} stripping to overcome the energy use and other disadvantages associated with the benchmark monoethanolamine (MEA) process. The project was aimed at performing laboratory- and bench-scale experiments to prove its technical feasibility and generate process engineering and scale-up data, and conducting a techno-economic analysismore » (TEA) to demonstrate its energy use and cost competitiveness over MEA. To meet project goals and objectives, a combination of experimental, modeling, process simulation, and economic analysis studies were applied. Carefully designed and intensive experiments were conducted to measure thermodynamic and reaction engineering data relevant to four major unit operations in the Hot-CAP (i.e., CO{sub 2} absorption, CO{sub 2} stripping, bicarbonate crystallization, and sulfate reclamation). The rate promoters that could accelerate the CO{sub 2} absorption rate into the potassium carbonate/bicarbonate (PCB) solution to a level greater than that into the 5 M MEA solution were identified, and the superior performance of CO{sub 2} absorption into PCB was demonstrated in a bench-scale packed-bed column. Kinetic data on bicarbonate crystallization were developed and applied for crystallizer design and sizing. Parametric testing of high-pressure CO{sub 2} stripping with concentrated bicarbonate-dominant slurries at high temperatures ({>=}140{degrees}C) in a bench-scale stripping column demonstrated lower heat use than with MEA. The feasibility of a modified process for combining SO{sub 2} removal with CO{sub 2} capture was preliminarily demonstrated. In addition to the experimental studies, the technical challenges pertinent to fouling of slurry-handling equipment and the design of the crystallizer and stripper were addressed through consultation with vendors and engineering analyses. A process flow diagram of the Hot-CAP was then developed and a TEA was performed to compare the energy use and cost performance of a nominal 550-MWe subcritical pulverized coal (PC)-fired power plant without CO{sub 2} capture (DOE/NETL Case 9) with the benchmark MEA-based post-combustion CO{sub 2} capture (PCC; DOE/NETL Case 10) and the Hot-CAP-based PCC. The results revealed that the net power produced in the PC + Hot-CAP is 609 MWe, greater than the PC + MEA (550 MWe). The 20-year levelized cost of electricity (LCOE) for the PC + Hot-CAP, including CO{sub 2} transportation and storage, is 120.3 mills/kWh, a 60% increase over the base PC plant without CO{sub 2} capture. The LCOE increase for the Hot-CAP is 29% lower than that for MEA. TEA results demonstrated that the Hot-CAP is energy-efficient and cost-effective compared with the benchmark MEA process.« less

Acoustic scattering from phononic crystals with complex geometry.

PubMed

Kulpe, Jason A; Sabra, Karim G; Leamy, Michael J

2016-05-01

This work introduces a formalism for computing external acoustic scattering from phononic crystals (PCs) with arbitrary exterior shape using a Bloch wave expansion technique coupled with the Helmholtz-Kirchhoff integral (HKI). Similar to a Kirchhoff approximation, a geometrically complex PC's surface is broken into a set of facets in which the scattering from each facet is calculated as if it was a semi-infinite plane interface in the short wavelength limit. When excited by incident radiation, these facets introduce wave modes into the interior of the PC. Incorporation of these modes in the HKI, summed over all facets, then determines the externally scattered acoustic field. In particular, for frequencies in a complete bandgap (the usual operating frequency regime of many PC-based devices and the requisite operating regime of the presented theory), no need exists to solve for internal reflections from oppositely facing edges and, thus, the total scattered field can be computed without the need to consider internal multiple scattering. Several numerical examples are provided to verify the presented approach. Both harmonic and transient results are considered for spherical and bean-shaped PCs, each containing over 100 000 inclusions. This facet formalism is validated by comparison to an existing self-consistent scattering technique.

Excitations in opal photonic crystals infiltrated with polarizable media

NASA Astrophysics Data System (ADS)

Eradat, Nayer; Sivachenko, A. Y.; Raikh, Mikhail E.; Vardeny, Z. Valy; Zakhidov, Anvar A.; Li, S.; Baughman, Ray H.

2002-12-01

Photonic crystals (PC) are a class of artificial structures with a periodic dielectric function. PCs can be a laboratory for testing fundamental processes involving interactions of radiation with matter in novel conditions. We have studied the optical properties of opal PCs that are infiltrated with highly polarizable media such as j-aggregates of cyanine dyes. Opals are self-assembled structures of silica spheres. We report our studies on clarifying the relationship between a polaritonic gap and a photonic stop band (Bragg gap) when they resonantly coexist in the same structure. Infiltration of opal with polarizable molecules combines the polaritonic and Bragg diffractive effects. Both effects exist independently when the Bragg (at ω = ωB) and polaritonic (ω = ωT) resonances are well separated in frequency. A completely different situation occurs when ωT ~ωB. Such a condition was achieved in opals that were infiltrated with J-aggregates of cyanine dyes that have large Rabi frequency. Our measurements show some dramatic changes in the shape of the reflectivity plateaus, which are due to the interplay between the photonic band gap and the polaritonic gap. The experimental results on reflectivity and its dependence on the light propagation angle and concentration of the cyanie dyes are in agreement with the theoretical calculations.

Novel ethylenediamine-gallium phosphate containing 6-fold coordinated gallium atoms with unusual four equatorial Ga–N bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Torre-Fernández, Laura; Espina, Aránzazu; Khainakov, Sergei A.

2014-07-01

A novel ethylenediamine-gallium phosphate, formulated as Ga(H{sub 2}NCH{sub 2}CH{sub 2}NH{sub 2}){sub 2}PO{sub 4}·2H{sub 2}O, was synthesized under hydrothermal conditions. The crystal structure, including hydrogen positions, was determined using single-crystal X-ray diffraction data (monoclinic, a=9.4886(3) Å, b=6.0374(2) Å, c=10.2874(3) Å, and β=104.226(3)°, space group Pc) and the bulk was characterized by chemical (Ga–P–C–H–N) and thermal analysis (TG–MS and DSC), including activation energy data of its thermo-oxidative degradation, powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (SS-NMR) measurements, and transmission electron microscopy (TEM, SAED/NBD, and STEM BF-EDX). The crystal structure is built up of infinite zig-zag chains running along the c-axis, formedmore » by vertex-shared (PO{sub 4}) and (GaO{sub 2}N{sub 4}) polyhedra. The new compound is characterized by unusual four equatorial Ga–N bonds coming from two nonequivalent ethylenediamine molecules and exhibits strong blue emission at 430 nm (λ{sub ex}=350 nm) in the solid state at room temperature. - Graphical abstract: Single crystals of a new ethylenediamine-gallium phosphate, Ga(H{sub 2}NCH{sub 2}CH{sub 2}NH{sub 2}){sub 2}PO{sub 4}·2H{sub 2}O, were obtained and the structural features presented. This structure is one of the scarce examples of GaPO with Ga–N bonds reported. - Highlights: • A novel ethylenediamine-gallium phosphate was hydrothermally synthesized. • The new compound is characterized by unusual four equatorial Ga–N bonds. • Void-volume analysis shows cages and channels with sizes ideally suited to accommodate small molecules. • The new compound exhibits strong blue emission.« less

The effect of the protein corona on the interaction between nanoparticles and lipid bilayers.

PubMed

Di Silvio, Desirè; Maccarini, Marco; Parker, Roger; Mackie, Alan; Fragneto, Giovanna; Baldelli Bombelli, Francesca

2017-10-15

It is known that nanoparticles (NPs) in a biological fluid are immediately coated by a protein corona (PC), composed of a hard (strongly bounded) and a soft (loosely associated) layers, which represents the real nano-interface interacting with the cellular membrane in vivo. In this regard, supported lipid bilayers (SLB) have extensively been used as relevant model systems for elucidating the interaction between biomembranes and NPs. Herein we show how the presence of a PC on the NP surface changes the interaction between NPs and lipid bilayers with particular care on the effects induced by the NPs on the bilayer structure. In the present work we combined Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D) and Neutron Reflectometry (NR) experimental techniques to elucidate how the NP-membrane interaction is modulated by the presence of proteins in the environment and their effect on the lipid bilayer. Our study showed that the NP-membrane interaction is significantly affected by the presence of proteins and in particular we observed an important role of the soft corona in this phenomenon. Copyright © 2017 Elsevier Inc. All rights reserved.

Multinuclear Solid-State Magnetic Resonance as a Sensitive Probe of Structural Changes upon the Occurrence of Halogen Bonding in Co-crystals.

PubMed

Widdifield, Cory M; Cavallo, Gabriella; Facey, Glenn A; Pilati, Tullio; Lin, Jingxiang; Metrangolo, Pierangelo; Resnati, Giuseppe; Bryce, David L

2013-09-02

Although the understanding of intermolecular interactions, such as hydrogen bonding, is relatively well-developed, many additional weak interactions work both in tandem and competitively to stabilize a given crystal structure. Due to a wide array of potential applications, a substantial effort has been invested in understanding the halogen bond. Here, we explore the utility of multinuclear ((13)C, (14/15)N, (19)F, and (127)I) solid-state magnetic resonance experiments in characterizing the electronic and structural changes which take place upon the formation of five halogen-bonded co-crystalline product materials. Single-crystal X-ray diffraction (XRD) structures of three novel co-crystals which exhibit a 1:1 stoichiometry between decamethonium diiodide (i.e., [(CH3)3N(+)(CH2)10N(+)(CH3)3][2 I(-)]) and different para-dihalogen-substituted benzene moieties (i.e., p-C6X2Y4, X=Br, I; Y=H, F) are presented. (13)C and (15)N NMR experiments carried out on these and related systems validate sample purity, but also serve as indirect probes of the formation of a halogen bond in the co-crystal complexes in the solid state. Long-range changes in the electronic environment, which manifest through changes in the electric field gradient (EFG) tensor, are quantitatively measured using (14)N NMR spectroscopy, with a systematic decrease in the (14)N quadrupolar coupling constant (CQ) observed upon halogen bond formation. Attempts at (127)I solid-state NMR spectroscopy experiments are presented and variable-temperature (19)F NMR experiments are used to distinguish between dynamic and static disorder in selected product materials, which could not be conclusively established using solely XRD. Quantum chemical calculations using the gauge-including projector augmented-wave (GIPAW) or relativistic zeroth-order regular approximation (ZORA) density functional theory (DFT) approaches complement the experimental NMR measurements and provide theoretical corroboration for the changes in NMR parameters observed upon the formation of a halogen bond. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Photocurrent of Transparent CuFeO2 Photocathodes by Self-Light-Harvesting Architecture.

PubMed

Oh, Yunjung; Yang, Wooseok; Kim, Jimin; Jeong, Sunho; Moon, Jooho

2017-04-26

Efficient sunlight-driven water-splitting devices can be achieved by using an optically and energetically well-matched pair of photoelectrodes in a tandem configuration. The key for maximizing the photoelectrochemical efficiency is the use of a highly transparent front photoelectrode with a band gap below 2.0 eV. Herein, we propose two-dimensional (2D) photonic crystal (PC) structures consisting of a CuFeO 2 -decorated microsphere monolayer, which serve as self-light-harvesting architectures allowing for amplified light absorption and high transparency. The photocurrent densities are evaluated for three CuFeO 2 2D PC-based photoelectrodes with microspheres of different sizes. The optical analysis confirmed the presence of a photonic stop band that generates slow light and at the same time amplifies the absorption of light. The 410 nm sized CuFeO 2 -decorated microsphere 2D PC photocathode shows an exceptionally high visible light transmittance of 76.4% and a relatively high photocurrent of 0.2 mA cm -2 at 0.6 V vs a reversible hydrogen electrode. The effect of the microsphere size on the carrier collection efficiency was analyzed by in situ conductive atomic force microscopy observation under illumination. Our novel synthetic method to produce self-light-harvesting nanostructures provides a promising approach for the effective use of solar energy by highly transparent photocathodes.

A Method for Identifying Small-Molecule Aggregators Using Photonic Crystal Biosensor Microplates

PubMed Central

Chan, Leo L.; Lidstone, Erich A.; Finch, Kristin E.; Heeres, James T.; Hergenrother, Paul J.; Cunningham, Brian T.

2010-01-01

Small molecules identified through high-throughput screens are an essential element in pharmaceutical discovery programs. It is now recognized that a substantial fraction of small molecules exhibit aggregating behavior leading to false positive results in many screening assays, typically due to nonspecific attachment to target proteins. Therefore, the ability to efficiently identify compounds within a screening library that aggregate can streamline the screening process by eliminating unsuitable molecules from further consideration. In this work, we show that photonic crystal (PC) optical biosensor microplate technology can be used to identify and quantify small-molecule aggregation. A group of aggregators and nonaggregators were tested using the PC technology, and measurements were compared with those gathered by three alternative methods: dynamic light scattering (DLS), an α-chymotrypsin colorimetric assay, and scanning electron microscopy (SEM). The PC biosensor measurements of aggregation were confirmed by visual observation using SEM, and were in general agreement with the α-chymotrypsin assay. DLS measurements, in contrast, demonstrated inconsistent readings for many compounds that are found to form aggregates in shapes, very different from the classical spherical particles assumed in DLS modeling. As a label-free detection method, the PC biosensor aggregation assay is simple to implement and provides a quantitative direct measurement of the mass density of material adsorbed to the transducer surface, whereas the microplate-based sensor format enables compatibility with high-throughput automated liquid-handling methods used in pharmaceutical screening. PMID:20930952

Broadband and omnidirectional light harvesting enhancement in photovoltaic devices with aperiodic TiO2 nanotube photonic crystal

NASA Astrophysics Data System (ADS)

Guo, Min; Su, Haijun; Zhang, Jun; Liu, Lin; Fu, Nianqing; Yong, Zehui; Huang, Haitao; Xie, Keyu

2017-03-01

Design of more effective broadband light-trapping elements to improve the light harvesting efficiency under both normal and tilted light for solar cells and other photonic devices is highly desirable. Herein we present a theoretical analysis on the optical properties of a novel TiO2 nanotube aperiodic photonic crystal (NT APC) following an aperiodic sequences and its photocurrent enhancement effect for dye-sensitized solar cells (DSSCs) under various incidence angles. It is found that, compared to regular PC, the designed TiO2 NT APC owns broader reflection region and a desired omnidirectional reflection (ODR) bandgaps, leading to considerable and stable photocurrent enhancement under both normal and oblique light. The effects of the structural parameters of the TiO2 NT APC, including the average lattice constant and the common sequence difference, on the optical properties, ODR bandgaps and absorption magnification of the integrated DSSCs are investigated in detail. Moreover, the angular dependence of photocurrent enhancement and angular compensation effect of such TiO2 NT APCs are also provided to offer a guidance on the optimum structural parameters design under different engineering application conditions.

Up-conversion nanoparticles sensitized inverse opal photonic crystals enable efficient water purification under NIR irradiation

NASA Astrophysics Data System (ADS)

Zhang, Yuanyuan; Wang, Lili; Ma, Xiumei; Ren, Junfeng; Sun, Qinxing; Shi, Yongsheng; Li, Lin; Shi, Jinsheng

2018-03-01

A novel porous monolayer inverse opal (IO) structure was prepared by a simple sol-gel method combined with a self-assembly PS photonic crystal (PC) as template. By prolonging deposition time of PS spheres, three-dimensional multilayer TiO2 IOPC was also fabricated. Up-conversion nanoparticles (UCNPs) were selected to sensitize TiO2 IOPCs. Photocatalytic activity of as-prepared materials was investigated by disinfection of bacteria and organic pollutant degradation. Under NIR light irradiation, a large improvement in bacterial inactivation and photodegradation efficiency could be seen for NYF/TiO2 composites in comparison with other samples. As for monolayer NYF/TiO2, water disinfection of 100% inactivation of bacteria is realized within 11 h and kinetic constant of RhB degradation is 0.133 h-1, which is about 10 times higher than that of pure TiO2 IOPCs. Reasons of enhanced photocatalytic activity were systematically investigated and a possible mechanism for NIR-driven photocatalysis was reasonably proposed.

High-contrast controllable switching based on polystyrene nonlinear cavities in 2D hole-type photonic crystals

NASA Astrophysics Data System (ADS)

Paghousi, Roohollah; Fasihi, Kiazand

2018-05-01

We present a new high-contrast controllable switch, which is based on a polystyrene nonlinear cavity, and is implemented in a two dimensional (2D) hole-type photonic crystal (PC). We show that by applying a control signal, the input power can be transmitted to the output waveguide with a high contrast ratio. The operation of the proposed device is investigated through the use of coupled-mode theory (CMT) and finite-difference time-domain (FDTD) method. The contrast ratio of the proposed device varies between 18 and 23, which is higher than the corresponding value in the previous investigations. Based on the simulation results, with increasing the control power the range of operating power will be increased, while the contrast ratio will be decreased. It has been shown that in a modified structure, at the expense of the range of operating power and the contrast ratio, the control power can be decreased, considerably.

Fabrication of semiconductor-polymer compound nonlinear photonic crystal slab with highly uniform infiltration based on nano-imprint lithography technique.

PubMed

Qin, Fei; Meng, Zi-Ming; Zhong, Xiao-Lan; Liu, Ye; Li, Zhi-Yuan

2012-06-04

We present a versatile technique based on nano-imprint lithography to fabricate high-quality semiconductor-polymer compound nonlinear photonic crystal (NPC) slabs. The approach allows one to infiltrate uniformly polystyrene materials that possess large Kerr nonlinearity and ultrafast nonlinear response into the cylindrical air holes with diameter of hundred nanometers that are perforated in silicon membranes. Both the structural characterization via the cross-sectional scanning electron microscopy images and the optical characterization via the transmission spectrum measurement undoubtedly show that the fabricated compound NPC samples have uniform and dense polymer infiltration and are of high quality in optical properties. The compound NPC samples exhibit sharp transmission band edges and nondegraded high quality factor of microcavities compared with those in the bare silicon PC. The versatile method can be expanded to make general semiconductor-polymer hybrid optical nanostructures, and thus it may pave the way for reliable and efficient fabrication of ultrafast and ultralow power all-optical tunable integrated photonic devices and circuits.

Probing the influence of the center atom coordination structure in iron phthalocyanine multi-walled carbon nanotube-based oxygen reduction reaction catalysts by X-ray absorption fine structure spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Yingxiang; Li, Zhipan; Xia, Dingguo; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia

2015-09-01

Three different pentacoordinate iron phthalocyanine (FePc) electrocatalysts with an axial ligand (pyridyl group, Py) anchored to multi-walled carbon nanotubes (MWCNTs) are prepared by a microwave method as high performance composite electrocatalysts (FePc-Py/MWCNTs) for the oxygen reduction reaction (ORR). For comparison, tetracoordinate FePc electrocatalysts without an axial ligand anchored to MWCNTs (FePc/MWCNTs) are assembled in the same way. Ultraviolet-visible spectrophotometry (UV-Vis), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HRTEM) are used to characterize the obtained electrocatalysts. The electrocatalytic activity of the samples is measured by linear sweep voltammetry (LSV), and the onset potential of all of the FePc-Py/MWCNTs electrocatalysts is found to be more positive than that of their FePc/MWCNTs counterparts. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy are employed to elucidate the relationship between molecular structure and electrocatalytic activity. XPS indicates that higher concentrations of Fe3+ and pyridine-type nitrogen play critical roles in determining the electrocatalytic ORR activity of the samples. XAFS spectroscopy reveals that the FePc-Py/MWCNTs electrocatalysts have a coordination geometry around Fe that is closer to the square pyramidal structure, a higher concentration of Fe3+, and a smaller phthalocyanine ring radius compared with those of FePc/MWCNTs.

Polymer Energy Rechargeable System Battery Being Developed

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

2003-01-01

Long description. Illustrations of discotic liquid crystals, rod-coil polymers, lithium-ion conducting channel dilithium phthalocyanine (Li2Pc) from top and side, novel star polyethylene oxide structures, composite polyethylene oxide materials (showing polyethylene oxide + lithium salt, carbon atoms and oxygen atoms), homopolyrotaxanes, and diblock copolymers In fiscal year 2000, NASA established a program to develop the next generation, lithium-based, polymer electrolyte batteries for aerospace applications. The goal of this program, known as Polymer Energy Rechargeable Systems (PERS), is to develop a space-qualified, advanced battery system embodying polymer electrolyte and lithium-based electrode technologies and to establish world-class domestic manufacturing capabilities for advanced batteries with improved performance characteristics that address NASA s future aerospace battery requirements.

EVALUATIONS ON ASR DAMAGE OF CONCRETE STRUCTURE AND ITS STRUCTURAL PERFORMANCE

NASA Astrophysics Data System (ADS)

Ueda, Naoshi; Nakamura, Hikaru; Kunieda, Minoru; Maeno, Hirofumi; Morishit, Noriaki; Asai, Hiroshi

In this paper, experiments and finite element analyses were conducted in order to evaluate effects of ASR on structural performance of RC and PC structures. From the experimental results, it was confirmed that the ASR expansion was affected by the restraint of reinforcement and the magnitude of prestress. The material properties of concrete damaged by ASR had anisotropic characteristics depending on the degree of ASR expansion. Therefore, when the structural performance of RC and PC structures were evaluated by using the material properties of core concrete, the direction and place where cylinder specimens were cored should be considered. On the other hand, by means of proposed analytical method, ASR expansion behaviors of RC and PC beams and changing of their structural performance were evaluated. As the results, it was confirmed that PC structure had much advantage comparing with RC structure regarding the structural performance under ASR damage because of restraint by prestress against the ASR.

KSC-97PC1382

NASA Image and Video Library

1997-09-08

United States Microgravity Payload-4 (USMP-4) experiments are prepared to be flown on Space Shuttle mission STS-87 in the Space Station Processing Facility at Kennedy Space Center (KSC). This horizontal tube is known as MEPHISTO, the French acronym for a cooperative American-French investigation of the fundamentals of crystal growth. This experiment, designed for the study of solidification (or freezing) during the growth cycle of liquid materials used for semiconductor crystals, aims to aid in the development of techniques for growing higher quality crystals on Earth. All STS-87 experiments are scheduled for launch on Nov. 19 from KSC

NASA PC software evaluation project

NASA Technical Reports Server (NTRS)

Dominick, Wayne D. (Editor); Kuan, Julie C.

1986-01-01

The USL NASA PC software evaluation project is intended to provide a structured framework for facilitating the development of quality NASA PC software products. The project will assist NASA PC development staff to understand the characteristics and functions of NASA PC software products. Based on the results of the project teams' evaluations and recommendations, users can judge the reliability, usability, acceptability, maintainability and customizability of all the PC software products. The objective here is to provide initial, high-level specifications and guidelines for NASA PC software evaluation. The primary tasks to be addressed in this project are as follows: to gain a strong understanding of what software evaluation entails and how to organize a structured software evaluation process; to define a structured methodology for conducting the software evaluation process; to develop a set of PC software evaluation criteria and evaluation rating scales; and to conduct PC software evaluations in accordance with the identified methodology. Communication Packages, Network System Software, Graphics Support Software, Environment Management Software, General Utilities. This report represents one of the 72 attachment reports to the University of Southwestern Louisiana's Final Report on NASA Grant NGT-19-010-900. Accordingly, appropriate care should be taken in using this report out of context of the full Final Report.

Origin of the energy level alignment at organic/organic interfaces: The role of structural defects

NASA Astrophysics Data System (ADS)

Bussolotti, Fabio; Yang, Jinpeng; Hinderhofer, Alexander; Huang, Yuli; Chen, Wei; Kera, Satoshi; Wee, Andrew T. S.; Ueno, Nobuo

2014-03-01

In this paper, the electronic properties of as-deposited and N2-exposedCuPc/F16CuPc interface, a prototype system for organic photovoltaic applications, are investigated by using ultralow background, high-sensitivity photoemission spectroscopy. It is found that (i) N2 exposure significantly modifies the energy level alignment (ELA) at the interface between CuPc and F16CuPc layer and (ii) the direction of the N2-induced energy level shift of the CuPc depends on the position of the Fermi level (EF) in the CuPc highest occupied molecular orbital-lowest unoccupied molecular orbital gap of the as-deposited film. These observations are related to the changes in the density of gap states (DOGS) produced by structural imperfections in the molecular packing geometry, as introduced by the N2 penetration into the CuPc layer. This result demonstrates the key role of structure-induced DOGS in controlling the ELA at organic/organic interfaces.

Reduced Symmetry and Analogy to Chirality in Periodic Dielectric Media

NASA Astrophysics Data System (ADS)

Giden, I. H.; Turduev, M.; Kurt, H.

2014-10-01

Much attention has been paid to photonic applications based on periodic media. Meanwhile, quasi-periodic and disordered media have extended the research domain and provided additional novelties for manipulating and controlling light propagation. This review article attempts to highlight the benefits of symmetry reduction in highly symmetric periodic photonic media, and applies the concept of chirality to all-dielectric materials arranged in special orders. Two-dimensional periodic structures known as photonic crystals (PCs) are highly symmetric in terms of structural patterns, due to the lattice types and shape of the elements occupying the PC unit-cell. We propose the idea of intentionally introducing reduced-symmetry, to search for anomalous optical characteristics so that these types of PCs can be used in the design of novel optical devices. Breaking either translational or rotational symmetries of PCs provides enhanced and additional optical characteristics such as creation of a complete photonic bandgap, wavelength demultiplexing, super-collimation, tilted self-collimation, and beam deflecting/routing properties. Utilizing these characteristics allows the design of several types of photonic devices such as polarization-independent waveguides, wavelength demultiplexers, beam deflectors, and routers. Moreover, reducing the symmetry in the PC unit-cell scale produces a novel feature in all-dielectric PCs that is known as chirality. On the basis of above considerations, it is expected that low-symmetric PCs can be considered as a potential structure in photonic device applications, due to the rich inherent optical properties, providing broadband operation, and being free of absorption losses.

Active site and laminarin binding in glycoside hydrolase family 55

DOE PAGES

Bianchetti, Christopher M.; Takasuka, Taichi E.; Deutsch, Sam; ...

2015-03-09

The Carbohydrate Active Enzyme (CAZy) database indicates that glycoside hydrolase family 55 (GH55) contains both endo- and exo-β-1,3-glucanases. The founding structure in the GH55 is PcLam55A from the white rot fungus Phanerochaete chrysosporium. Here, we present high resolution crystal structures of bacterial SacteLam55A from the highly cellulolytic Streptomyces sp. SirexAA-E with bound substrates and product. These structures, along with mutagenesis and kinetic studies, implicate Glu-502 as the catalytic acid (as proposed earlier for Glu-663 in PcLam55A) and a proton relay network of four residues in activating water as the nucleophile. Further, a set of conserved aromatic residues that define themore » active site apparently enforce an exo-glucanase reactivity as demonstrated by exhaustive hydrolysis reactions with purified laminarioligosaccharides. Two additional aromatic residues that line the substrate-binding channel show substrate-dependent conformational flexibility that may promote processive reactivity of the bound oligosaccharide in the bacterial enzymes. Gene synthesis carried out on ~30% of the GH55 family gave 34 active enzymes (19% functional coverage of the nonredundant members of GH55). These active enzymes reacted with only laminarin from a panel of 10 different soluble and insoluble polysaccharides and displayed a broad range of specific activities and optima for pH and temperature. Furthermore, application of this experimental method provides a new, systematic way to annotate glycoside hydrolase phylogenetic space for functional properties.« less

?-BiPd: a clean noncentrosymmetric superconductor

NASA Astrophysics Data System (ADS)

Ramakrishnan, Srinivasan; Joshi, Bhanu; Thamizhavel, A.

2017-12-01

We present a comprehensive review of the normal and superconducting state properties of a high-quality single crystal of monoclinic BiPd (?-BiPd, space group ?). The superconductivity of this crystal below 3.8 K is established by measuring its properties using bulk as well as spectroscopic techniques. BiPd is one of the cleanest noncentrosymmetric superconductors that display superconductivity with multiple energy gaps. Evidence of multiple energy gaps was found in heat capacity, point contact (PC) spectroscopy, penetration depth, muon spin rotation, small angle neutron scattering and NMR/NQR measurements. Moreover, Muon spin rotation measurements also suggest strong field dependence of the penetration depth of this superconductor. Unusual superconducting properties due to possible s and p wave mixing are shown by the observation of Andreev bound state in PC measurements as well as the suppressed coherence peak in the temperature dependence of the spin-lattice relaxation in the NQR measurements. This surmise is at variance with the recent STM measurements (different crystal). The observed unusual properties and multiband superconductivity are extremely sensitive to disorder in BiPd. Finally, there is a possibility of tuning the electron correlations by selective substitution in BiPd, thus making it an important system for further investigations.

Composites Based on Core-Shell Structured HBCuPc@CNTs-Fe3O4 and Polyarylene Ether Nitriles with Excellent Dielectric and Mechanical Properties

NASA Astrophysics Data System (ADS)

Pu, Zejun; Zhong, Jiachun; Liu, Xiaobo

2017-10-01

Core-shell structured magnetic carbon nanotubes (CNTs-Fe3O4) coated with hyperbranched copper phthalocyanine (HBCuPc) (HBCuPc@CNTs-Fe3O4) hybrids were prepared by the solvent-thermal method. The results indicated that the HBCuPc molecules were decorated on the surface of CNTs-Fe3O4 through coordination behavior of phthalocyanines, and the CNTs-Fe3O4 core was completely coaxial wrapped by a functional intermediate HBCuPc shell. Then, polymer-based composites with a relatively high dielectric constant and low dielectric loss were fabricated by using core-shell structured HBCuPc@CNTs-Fe3O4 hybrids as fillers and polyarylene ether nitriles (PEN) as the polymer matrix. The cross-sectional scanning electron microscopy (SEM) images of composites showed that there is almost no agglomeration and internal delamination. In addition, the rheological analysis reveals that the core-shell structured HBCuPc@CNTs-Fe3O4 hybrids present better dispersion and stronger interface adhesion with the PEN matrix than CNTs-Fe3O4, thus resulting in significant improvement of the mechanical, thermal and dielectric properties of polymer-based composites.

Complete band gaps of phononic crystal plates with square rods.

PubMed

El-Naggar, Sahar A; Mostafa, Samia I; Rafat, Nadia H

2012-04-01

Much of previous work has been devoted in studying complete band gaps for bulk phononic crystal (PC). In this paper, we theoretically investigate the existence and widths of these gaps for PC plates. We focus our attention on steel rods of square cross sectional area embedded in epoxy matrix. The equations for calculating the dispersion relation for square rods in a square or a triangular lattice have been derived. Our analysis is based on super cell plane wave expansion (SC-PWE) method. The influence of inclusions filling factor and plate thickness on the existence and width of the phononic band gaps has been discussed. Our calculations show that there is a certain filling factor (f=0.55) below which arrangement of square rods in a triangular lattice is superior to the arrangement in a square lattice. A comparison between square and circular cross sectional rods reveals that the former has superior normalized gap width than the latter in case of a square lattice. This situation is switched in case of a triangular lattice. Moreover, a maximum normalized gap width of 0.7 can be achieved for PC plate of square rods embedded in a square lattice and having height 90% of the lattice constant. Copyright © 2011 Elsevier B.V. All rights reserved.

Podocalyxin as a major pluripotent marker and novel keratan sulfate proteoglycan in human embryonic and induced pluripotent stem cells.

PubMed

Toyoda, Hidenao; Nagai, Yuko; Kojima, Aya; Kinoshita-Toyoda, Akiko

2017-04-01

Podocalyxin (PC) was first identified as a heavily sialylated transmembrane protein of glomerular podocytes. Recent studies suggest that PC is a remarkable glycoconjugate that acts as a universal glyco-carrier. The glycoforms of PC are responsible for multiple functions in normal tissue, human cancer cells, human embryonic stem cells (hESCs), and human induced pluripotent stem cells (hiPSCs). PC is employed as a major pluripotent marker of hESCs and hiPSCs. Among the general antibodies for human PC, TRA-1-60 and TRA-1-81 recognize the keratan sulfate (KS)-related structures. Therefore, It is worthwhile to summarize the outstanding chemical characteristic of PC, including the KS-related structures. Here, we review the glycoforms of PC and discuss the potential of PC as a novel KS proteoglycan in undifferentiated hESCs and hiPSCs.

Slow light effect with high group index and wideband by saddle-like mode in PC-CROW

NASA Astrophysics Data System (ADS)

Wan, Yong; Jiang, Li-Jun; Xu, Sheng; Li, Meng-Xue; Liu, Meng-Nan; Jiang, Cheng-Yi; Yuan, Feng

2018-04-01

Slow light with high group index and wideband is achieved in photonic crystal coupled-resonator optical waveguides (PC-CROWs). According to the eye-shaped scatterers and various microcavities, saddle-like curves between the normalized frequency f and wave number k can be obtained by adjusting the parameters of the scatterers, parameters of the coupling microcavities, and positions of the scatterers. Slow light with decent flat band and group index can then be achieved by optimizing the parameters. Simulations prove that the maximal value of the group index is > 104, and the normalized delay bandwidth product within a new varying range of n g > 102 or n g > 103 can be a new and effective criterion of evaluation for the slow light in PC-CROWs.

The Redox-Active Chromium Phthalocyanine System: Isolation of Five Oxidation States from Pc4- CrI to Pc2- CrIII.

PubMed

Zhou, Wen; Thompson, John R; Leznoff, Clifford C; Leznoff, Daniel B

2017-02-16

The preparation and structural characterization of a series of chromium phthalocyanine complexes with multiple metal and ring oxidation states were achieved using PcCr II (1) (Pc=phthalocyanine) or PcCr II (THF) 2 (1⋅THF 2 ) as starting materials. The reaction of soluble 1⋅THF 2 with Br 2 or I 2 gave the PcCr III halide complexes PcCrX(THF) (X=I/I 3 , Br; 3, 4, respectively). Treatment of 1 with 0.5 equivalent of PhIO or air generated the dinuclear [PcCr(THF)] 2 (μ-O) (5), whereas the addition of one equivalent of AgSbF 6 to 1 resulted in oxidation to THF-solvated octahedral [PcCr III (THF) 2 ]SbF 6 (6). The reduction of 1 with three sequential equivalents of KEt 3 BH resulted in the isolation of [K(DME) 4 ][Pc 3- Cr II ] (7), [K(DME) 4 ] 2 [Pc 4- Cr II ] (8) and [K 6 (DME) 4 ][Pc 4- Cr I ] 2 (9), respectively. The reduced products are deep purple in colour, with visible absorption maxima between 500-580 nm. The ring-reduced complexes 7 and 8 are monomeric, whereas 9 is a 1D chain of dinuclear [PcCr] 2 units with intercalated K + cations and supported by Cr-Cr interactions of 2.988(2) Å. Addition of four equivalents of KC 8 resulted in the demetallated product PcK 2 (DME) 4 (10), which has a 1D chain structure. The isolation and structural characterization of new PcCr complexes spanning five oxidation states, including rare examples of crystalline reduced Pc-ring species emphasizes the broad redox activity and stability of phthalocyanine-based complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improvement Noise Insulation Performance of Polycarbonate Pane using Sandwich Structure

NASA Astrophysics Data System (ADS)

Shen, Min; Nagamura, Kazuteru; Nakagawa, Noritoshi; Okamura, Masaharu

Polycarbonate (PC) laminates offer the possibility of designing strong and light weight panes application in automobile. However, the noise insulation performance of PC pane is worse than glass pane because of its high rate of stiffness to low weight. In this work, a new ultra-thin(less than 10mm) sandwich pane is proposed to obtain high transmission loss(TL). The sandwich structure consists of two thin laminates plates of the same PC material and a thin lightweight damping core bonded between those plates. Then TL is predicted using decoupled equations representing symmetric and anti-symmetric motions for a sandwich PC pane. The effects of various structural and material parameters on noise insulation performance are investigated with numerical examples. Numerical results show that the shear rigidity has evident effect on coincidence frequency and proposed structure has better noise insulation properties than single layer PC pane of equivalent thickness.

Structural insight into GRIP1-PDZ6 in Alzheimer's disease: study from protein expression data to molecular dynamics simulations.

PubMed

Chatterjee, Paulami; Roy, Debjani

2017-08-01

Protein-protein interaction domain, PDZ, plays a critical role in efficient synaptic transmission in brain. Dysfunction of synaptic transmission is thought to be the underlying basis of many neuropsychiatric and neurodegenerative disorders including Alzheimer's disease (AD). In this study, Glutamate Receptor Interacting Protein1 (GRIP1) was identified as one of the most important differentially expressed, topologically significant proteins in the protein-protein interaction network. To date, very few studies have analyzed the detailed structural basis of PDZ-mediated protein interaction of GRIP1. In order to gain better understanding of structural and dynamic basis of these interactions, we employed molecular dynamics (MD) simulations of GRIP1-PDZ6 dimer bound with Liprin-alpha and GRIP1-PDZ6 dimer alone each with 100 ns simulations. The analyses of MD simulations of Liprin-alpha bound GRIP1-PDZ6 dimer show considerable conformational differences than that of peptide-free dimer in terms of SASA, hydrogen bonding patterns, and along principal component 1 (PC1). Our study also furnishes insight into the structural attunement of the PDZ6 domains of Liprin-alpha bound GRIP1 that is attributed by significant shift of the Liprin-alpha recognition helix in the simulated peptide-bound dimer compared to the crystal structure and simulated peptide-free dimer. It is evident that PDZ6 domains of peptide-bound dimer show differential movements along PC1 than that of peptide-free dimers. Thus, Liprin-alpha also serves an important role in conferring conformational changes along the dimeric interface of the peptide-bound dimer. Results reported here provide information that may lead to novel therapeutic approaches in AD.

Intensity-Modulated Radiotherapy of Head and Neck Cancer Aiming to Reduce Dysphagia: Early Dose-Effect Relationships for the Swallowing Structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Felix Y.; Kim, Hyungjin M.; Lyden, Teresa H.

2007-08-01

Purpose: To present initial results of a clinical trial of intensity-modulated radiotherapy (IMRT) aiming to spare the swallowing structures whose dysfunction after chemoradiation is a likely cause of dysphagia and aspiration, without compromising target doses. Methods and Materials: This was a prospective, longitudinal study of 36 patients with Stage III-IV oropharyngeal (31) or nasopharyngeal (5) cancer. Definitive chemo-IMRT spared salivary glands and swallowing structures: pharyngeal constrictors (PC), glottic and supraglottic larynx (GSL), and esophagus. Lateral but not medial retropharyngeal nodes were considered at risk. Dysphagia endpoints included objective swallowing dysfunction (videofluoroscopy), and both patient-reported and observer-rated scores. Correlations between dosesmore » and changes in these endpoints from pre-therapy to 3 months after therapy were assessed. Results: Significant correlations were observed between videofluoroscopy-based aspirations and the mean doses to the PC and GSL, as well as the partial volumes of these structures receiving 50-65 Gy; the highest correlations were associated with doses to the superior PC (p = 0.005). All patients with aspirations received mean PC doses >60 Gy or PC V{sub 65} >50%, and GSL V{sub 50} >50%. Reduced laryngeal elevation and epiglottic inversion were correlated with mean PC and GSL doses (p < 0.01). All 3 patients with strictures had PC V{sub 70} >50%. Worsening patient-reported liquid swallowing was correlated with mean PC (p = 0.05) and esophageal (p 0.02) doses. Only mean PC doses were correlated with worsening patient-reported solid swallowing (p = 0.04) and observer-rated swallowing scores (p = 0.04). Conclusions: These dose-volume-effect relationships provide initial IMRT optimization goals and motivate further efforts to reduce swallowing structures doses to reduce dysphagia and aspiration.« less

Impact of ambient environment on the electronic structure of CuPc/Au sample

NASA Astrophysics Data System (ADS)

Sinha, Sumona; Mukherjee, M.

2018-02-01

The performances of organic devices are crucially connected with their stability in the ambient environment. The impact of 24 h. Ambient environment exposure to the electronic structures of about 12 nm thick CuPc thin film on clean Au substrate have been studied employing UV photoemission spectroscopy technique. X-ray photoemission spectroscopy (XPS) was used to find out the origin of the change of the electronic structures in the sample with the exposure. The XPS study suggests that the oxidation occurs at the CuPc thin film. Due to the adsorption of oxygen in the CuPc film from the ambient air, charge carriers are formed within the CuPc film. Moreover, the XPS results imply that the CuPc film is sufficiently thinner for diffusing oxygen molecules through it and gets physically absorbed on Au substrate during the ambient exposure. Consequently, the hole injection barrier height of pristine CuPc film, grown on Au substrate, is reduced by about 0.50 eV and work-function of the pristine CuPc sample is enhanced by around 0.25 eV in the exposure. The findings will help to understand the mechanism that governs the degradation of performance of CuPc based devices in ambient environment.

Crystal structures of Mmm1 and Mdm12–Mmm1 reveal mechanistic insight into phospholipid trafficking at ER-mitochondria contact sites

PubMed Central

Jeong, Hanbin; Park, Jumi; Jun, Youngsoo; Lee, Changwook

2017-01-01

The endoplasmic reticulum (ER)-mitochondria encounter structure (ERMES) comprises mitochondrial distribution and morphology 12 (Mdm12), maintenance of mitochondrial morphology 1 (Mmm1), Mdm34, and Mdm10 and mediates physical membrane contact sites and nonvesicular lipid trafficking between the ER and mitochondria in yeast. Herein, we report two crystal structures of the synaptotagmin-like mitochondrial lipid-binding protein (SMP) domain of Mmm1 and the Mdm12–Mmm1 complex at 2.8 Å and 3.8 Å resolution, respectively. Mmm1 adopts a dimeric SMP structure augmented with two extra structural elements at the N and C termini that are involved in tight self-association and phospholipid coordination. Mmm1 binds two phospholipids inside the hydrophobic cavity, and the phosphate ion of the distal phospholipid is specifically recognized through extensive H-bonds. A positively charged concave surface on the SMP domain not only mediates ER membrane docking but also results in preferential binding to glycerophospholipids such as phosphatidylcholine (PC), phosphatidic acid (PA), phosphatidylglycerol (PG), and phosphatidylserine (PS), some of which are substrates for lipid-modifying enzymes in mitochondria. The Mdm12–Mmm1 structure reveals two Mdm12s binding to the SMP domains of the Mmm1 dimer in a pairwise head-to-tail manner. Direct association of Mmm1 and Mdm12 generates a 210-Å-long continuous hydrophobic tunnel that facilitates phospholipid transport. The Mdm12–Mmm1 complex binds all glycerophospholipids except for phosphatidylethanolamine (PE) in vitro. PMID:29078410

Topological Valley Transport in Two-dimensional Honeycomb Photonic Crystals.

PubMed

Yang, Yuting; Jiang, Hua; Hang, Zhi Hong

2018-01-25

Two-dimensional photonic crystals, in analogy to AB/BA stacking bilayer graphene in electronic system, are studied. Inequivalent valleys in the momentum space for photons can be manipulated by simply engineering diameters of cylinders in a honeycomb lattice. The inequivalent valleys in photonic crystal are selectively excited by a designed optical chiral source and bulk valley polarizations are visualized. Unidirectional valley interface states are proved to exist on a domain wall connecting two photonic crystals with different valley Chern numbers. With the similar optical vortex index, interface states can couple with bulk valley polarizations and thus valley filter and valley coupler can be designed. Our simple dielectric PC scheme can help to exploit the valley degree of freedom for future optical devices.

Hot Spots from Generated Defects in HMX Crystals

NASA Astrophysics Data System (ADS)

Sorensen, Christian; Cummock, Nicholas; O'Grady, Caitlin; Gunduz, I. Emre; Son, Steven

2017-06-01

There are several hot spot initiation mechanisms that have been proposed. However, direct observation of shock or impact compression of these mechanisms at macroscopic scale in explosives is difficult. Phase contrast imaging (PCI) may be applied to these systems. Here, high-speed video was used to record optical spectrum and for x-ray Phase Contrast Imaging (PCI) of shockwave interaction with low defect HMX crystals and crystals with engineered defects. Additionally, multiple crystals were arranged and observed under shock loading with PCI and optical high-speed video. Sample preparation techniques for generating voids and other engineered defects will be discussed. These methods include drilled holes and laser machined samples. Insight into hot spot mechanisms was obtained. Funding from ONR's PC@Xtreme MURI.

Interaction of the Bragg gap with polaritonic gap in opal photonic crystals

NASA Astrophysics Data System (ADS)

Nayer, Eradat; Sivachenko, Andrey Yu; Li, Sergey; Raikh, Mikhail E.; Valy Vardeny, Z.

2001-03-01

Photonic crystals (PC) are a class of artificial structures with a periodic dielectric function. PCs can be a laboratory for testing fundamental processes involving interactions of radiation with matter in novel conditions. We have studied the optical properties of opal PCs that are infiltrated with highly polarizable media such as j-aggregates of cyanine dyes. Opals are self- assembled structures of silica (SiO_2) spheres. We report our studies on clarifying the relationship between a polaritonic gap and a photonic stop band (Bragg gap) when they resonantly coexist in the same structure. Infiltration of opal with polarizable molecules combines the polaritonic and Bragg diffractive effects. Both effects exist independently when the Bragg (at ω=ω_B) and polaritonic (at ω=ω_T) resonances are well separated in frequency. A completely different situation occurs when ωT =ω_B. Such a condition was achieved in opals that were infiltrated with J-aggregates of cyanine dyes that have large Rabi frequency. Our measurements show some dramatic changes in the shape of the reflectivity plateaus, which are due to the interplay between the photonic band gap and the polaritonic gap. The experimental results on reflectivity and its dependence on the light propagation angle and concentration of the cyanie dyes are in agreement with the theoretical calculations. (The work was supported in part by Army Research office DAAD19-00-1-0406.)

Electronic properties of the interface between hexadecafluoro copper phthalocyanine and unsubstituted copper phthalocyanine films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Komolov, A. S., E-mail: akomolov07@ya.ru; Lazneva, E. F.; Pshenichnyuk, S. A.

2013-07-15

The formation of an interface during the deposition of unsubstituted copper phthalocyanine (CuPc) films on the surface of hexadecafluoro copper phthalocyanine (F{sub 16}-CuPc) films is studied. An incident low-energy electron beam with energies from 0 to 25 eV is used to test the surface under study according to the very-low-energy electron-diffraction technique (VLEED) in the mode of total current spectroscopy. For F{sub 16}-CuPc films, the structure of the maxima in the total current spectra and its main differences from the structure of the maxima for the CuPc film are determined in the energy range from 5 to 15 eV abovemore » the Fermi level. The differences in the structure of vacant electron orbitals for CuPc and F{sub 16}-CuPc are also revealed using density functional theory calculations. As a result of an analysis of variations in the intensities of the total current spectra of the CuPc and F{sub 16}-CuPc films, it is assumed that an intermediate layer up to 1 nm thick appears during the formation of an interface between these films, which is characterized by a spread of the features in the total current spectrum. The height, width, and change in the work function are determined for the studied F{sub 16}-CuPc/NuPc interface barrier. A decrease in the level of vacuum by 0.7 eV occurs in the boundary region, which corresponds to electron density transfer from the CuPc film toward the F{sub 16}-CuPc substrate.« less

Integration of both dense wavelength-division multiplexing and coarse wavelength-division multiplexing demultiplexer on one photonic crystal chip

NASA Astrophysics Data System (ADS)

Tian, Huiping; Shen, Guansheng; Liu, Weijia; Ji, Yuefeng

2013-07-01

An integrated model of photonic crystal (PC) demultiplexer that can be used to combine dense wavelength-division multiplexing (DWDM) and coarse wavelength-division multiplexing (CWDM) systems is first proposed. By applying the PC demultiplexer, dense channel spacing 0.8 nm and coarse channel spacing 20 nm are obtained at the same time. The transmission can be improved to nearly 90%, and the crosstalk can be decreased to less than -18 dB by enlarging the width of the bus waveguide. The total size of the device is 21×42 μm2. Four channels on one side of the demultiplexer can achieve DWDM in the wavelength range between 1575 and 1578 nm, and the other four channels on the other side can achieve CWDM in the wavelength range between 1490 and 1565 nm, respectively. The demonstrated demultiplexer can be applied in the future CWDM and DWDM system, and the architecture costs can be significantly reduced.

Analytical study of mode degeneracy in non-Hermitian photonic crystals with TM-like polarization

NASA Astrophysics Data System (ADS)

Yin, Xuefan; Liang, Yong; Ni, Liangfu; Wang, Zhixin; Peng, Chao; Li, Zhengbin

2017-08-01

We present a study of the mode degeneracy in non-Hermitian photonic crystals (PC) with TM-like polarization and C4 v symmetry from the perspective of the coupled-wave theory (CWT). The CWT framework is extended to include TE-TM coupling terms which are critical for modeling the accidental triple degeneracy within non-Hermitian PC systems. We derive the analytical form of the wave function and the condition of Dirac-like-cone dispersion when radiation loss is relatively small. We find that, similar to a real Dirac cone, the Dirac-like cone in non-Hermitian PCs possesses good linearity and isotropy, even with a ring of exceptional points (EPs) inevitably existing in the vicinity of the second-order Γ point. However, the Berry phase remains zero at the Γ point, indicating the cone does not obey the Dirac equation and is only a Dirac-like cone. The topological modal interchange phenomenon and nonzero Berry phase of the EPs are also discussed.

Room-temperature, solution-processable organic electron extraction layer for high-performance planar heterojunction perovskite solar cells

DOE PAGES

Kim, Jong H.; Chueh, Chu-Chen; Williams, Spencer T.; ...

2015-09-24

Here in this work, we describe a room-temperature, solution-processable organic electron extraction layer (EEL) for high-performance planar heterojunction perovskite solar cells (PHJ PVSCs). This EEL is composed of a bilayered fulleropyrrolidinium iodide (FPI)-polyethyleneimine (PEIE) and PC 61BM, which yields a promising power conversion efficiency (PCE) of 15.7% with insignificant hysteresis. We reveal that PC 61BM can serve as a surface modifier of FPI-PEIE to simultaneously facilitate the crystallization of perovskite and the charge extraction at FPI-PEIE/CH 3NH 3PbI 3 interface. Furthermore, the FPI-PEIE can also tune the work function of ITO and dope PC 61BM to promote the efficient electronmore » transport between ITO and PC 61BM. Based on the advantages of room-temperature processability and decent electrical property of FPI-PEIE/PC 61BM EEL, a high-performance flexible PVSC with a PCE ~10% is eventually demonstrated. Lastly, this study shows the potential of low-temperature processed organic EEL to replace transition metal oxide-based interlayers for highly printing compatible PVSCs with high-performance.« less

Thermal characterization and analysis of phase change random access memory

NASA Astrophysics Data System (ADS)

Giraud, V.; Cluzel, J.; Sousa, V.; Jacquot, A.; Dauscher, A.; Lenoir, B.; Scherrer, H.; Romer, S.

2005-07-01

The cross-plane thermal conductivity of Ge2Sb2Te5, either in its amorphous state or fcc crystallized state, and titanium nitride (TiN) thin films has been measured at room temperature by the 3ω method. These materials are involved in the fabrication of phase change random access memory (PC-RAM), Ge2Sb2Te5 and TiN being the PC and pseudoelectrode materials, respectively. The thermal conductivity of insulating SiO2 and ZnS :SiO2 layers was determined too. Each thermal conductivity measurement was performed by the means of at least two strip widths in order to check both the measurement self-consistency and the measurement accuracy. The performance of PC-RAM cells, i.e., the time needed to reach the melting temperature of the PC material and the cooling speed, has been evaluated as a function of both the measured thermal conductivity of the PC material and the reset current intensity independently of the thermal properties of the pseudoelectrodes by the way of analytical formula. The influence of the thickness and the thermal properties of the pseudoelectrodes on the performances have been determined by numerical simulations.

Electrical and Optical Characterization of Nanowire based Semiconductor Devices

NASA Astrophysics Data System (ADS)

Ayvazian, Talin

This research project is focused on a new strategy for the creation of nanowire based semiconductor devices. The main goal is to understand and optimize the electrical and optical properties of two types of nanoscale devices; in first type lithographically patterned nanowire electrodeposition (LPNE) method has been utilized to fabricate nanowire field effect transistors (NWFET) and second type involved the development of light emitting semiconductor nanowire arrays (NWLED). Field effect transistors (NWFETs) have been prepared from arrays of polycrystalline cadmium selenide (pc-CdSe) nanowires using a back gate configuration. pc-CdSe nanowires were fabricated using the lithographically patterned nanowire electrode- position (LPNE) process on SiO2 /Si substrates. After electrodeposition, pc-CdSe nanowires were thermally annealed at 300 °C x 4 h either with or without exposure to CdCl 2 in methanol a grain growth promoter. The influence of CdCl2 treatment was to increase the mean grain diameter as determined by X-ray diffraction pattern and to convert the crystal structure from cubic to wurtzite. Transfer characteristics showed an increase of the field effect mobility (mu eff) by an order of magnitude and increase of the Ion/I off ratio by a factor of 3-4. Light emitting devices (NW-LED) based on lithographically patterned pc-CdSe nanowire arrays have been investigated. Electroluminescence (EL) spectra of CdSe nanowires under various biases exhibited broad emission spectra centered at 750 nm close to the band gap of CdSe (1.7eV). To enhance the intensity of the emitted light and the external quantum efficiency (EQE), the distance between the contacts were reduced from 5 mum to less than 1 mum which increased the efficiency by an order of magnitude. Also, increasing the annealing temperature of nanowires from 300 °C x4 h to 450 This research project is focused on a new strategy for the creation of nanowire based semiconductor devices. The main goal is to understand and optimize the electrical and optical properties of two types of nanoscale devices; in first type lithographically patterned nanowire electrodeposition (LPNE) method has been utilized to fabricate nanowire field effect transistors (NWFET) and second type involved the development of light emitting semiconductor nanowire arrays (NWLED). Field effect transistors (NWFETs) have been prepared from arrays of polycrystalline cadmium selenide (pc-CdSe) nanowires using a back gate configuration. pc-CdSe nanowires were fabricated using the lithographically patterned nanowire electrode- position (LPNE) process on SiO2 /Si substrates. After electrodeposition, pc-CdSe nanowires were thermally annealed at 300 °C x 4 h either with or without exposure to CdCl2 in methanol- a grain growth promoter. The influence of CdCl2 treatment was to increase the mean grain diameter as determined by X-ray diffraction pattern and to convert the crystal structure from cubic to wurtzite. Transfer characteristics showed an increase of the field effect mobility (mueff<) by an order of magnitude and increase of the Ion/Ioff ratio by a factor of 3-4. Light emitting devices (NW-LED) based on lithographically patterned pc-CdSe nanowire arrays have been investigated. Electroluminescence (EL) spectra of CdSe nanowires under various biases exhibited broad emission spectra centered at 750 nm close to the band gap of CdSe (1.7eV). To enhance the intensity of the emitted light and the external quantum efficiency (EQE), the distance between the contacts were reduced from 5 mum to less than 1 mum which increased the efficiency by an order of magnitude. Also, increasing the annealing temperature of nanowires from 300 °C x4 h to 450 °C x 1h enhanced grain growth confirmed by structural characterization including X-ray diffraction (XRD), Scanning electron microscopy (SEM) and Raman Spectroscopy. Correspondingly the light emission intensity and EQE improved due to this grain growth. Kelvin probe force microscopy (KPFM) was utilized to understand mechanism of light emission in CdSe nanowires. Arrays of CdTe nanowires were electrodeposited using LPNE process where the elec- trodeposition of pc-CdTe was carried out at two temperatures: 20 °C (cold) and 55 °C (hot). Transmission electron microscopy (TEM) and X-ray diffraction (XRD) re- sults revealed higher crystallinity, larger grain size and presence of Te for nanowires prepared at 55°C compared to nanowires deposited at 20°C. Nanowires prepared at 55°C showed higher electrical conductivity and enhanced electroluminescence proper- ties, including higher light emission intensity and improved External Quantum Efficiency (EQE). Electrical conduction mechanism also investigated for CdTe nanowires. Thermionic emission over schottky barrier height was identified as the dominant charge transport mechanism in pc-CdTe nanowires.°C x 1h enhanced grain growth confirmed by structural characterization including X-ray diffraction (XRD), Scanning electron microscopy (SEM) and Raman Spectroscopy. Correspondingly the light emission intensity and EQE improved due to this grain growth. Kelvin probe force microscopy (KPFM) was utilized to understand mechanism of light emission in CdSe nanowires. Arrays of CdTe nanowires were electrodeposited using LPNE process where the electrodeposition of pc-CdTe was carried out at two temperatures: 20 °C (cold) and 55 °C (hot). Transmission electron microscopy (TEM) and X-ray diffraction (XRD) re- sults revealed higher crystallinity, larger grain size and presence of Te for nanowires prepared at 55°C compared to nanowires deposited at 20°C. Nanowires prepared at 55°C showed higher electrical conductivity and enhanced electroluminescence properties, including higher light emission intensity and improved External Quantum Efficiency (EQE). Electrical conduction mechanism also investigated for CdTe nanowires. Thermionic emission over schottky barrier height was identified as the dominant charge transport mechanism in pc-CdTe nanowires.

The Human Polycomb Group Complex Associates with Pericentromeric Heterochromatin to Form a Novel Nuclear Domain

PubMed Central

Saurin, Andrew J.; Shiels, Carol; Williamson, Jill; Satijn, David P.E.; Otte, Arie P.; Sheer, Denise; Freemont, Paul S.

1998-01-01

The Polycomb group (PcG) complex is a chromatin-associated multiprotein complex, involved in the stable repression of homeotic gene activity in Drosophila. Recently, a mammalian PcG complex has been identified with several PcG proteins implicated in the regulation of Hox gene expression. Although the mammalian PcG complex appears analogous to the complex in Drosophila, the molecular mechanisms and functions for the mammalian PcG complex remain unknown. Here we describe a detailed characterization of the human PcG complex in terms of cellular localization and chromosomal association. By using antibodies that specifically recognize three human PcG proteins— RING1, BMI1, and hPc2—we demonstrate in a number of human cell lines that the PcG complex forms a unique discrete nuclear structure that we term PcG bodies. PcG bodies are prominent novel nuclear structures with the larger PcG foci generally localized near the centromeres, as visualized with a kinetochore antibody marker. In both normal fetal and adult fibroblasts, PcG bodies are not randomly dispersed, but appear clustered into defined areas within the nucleus. We show in three different human cell lines that the PcG complex can tightly associate with large pericentromeric heterochromatin regions (1q12) on chromosome 1, and with related pericentromeric sequences on different chromosomes, providing evidence for a mammalian PcG–heterochromatin association. Furthermore, these heterochromatin-bound PcG complexes remain stably associated throughout mitosis, thereby allowing the potential inheritance of the PcG complex through successive cell divisions. We discuss these results in terms of the known function of the PcG complex as a transcriptional repression complex. PMID:9722603

Design for a broad non-transmission band gap of three-color filters using photonic heterostructures

NASA Astrophysics Data System (ADS)

Li, Hongfei; Guan, Huihuan; Han, Peide; Li, Yuping; Zhang, Caili

2013-01-01

The bandgap characteristics of one-dimensional (1D) photonic crystal (PC) heterostructures containing defects are studied using the transfer matrix method. The key is to search for the best combination style for different 1D PCs to form heterostructures containing Si/MgF2 multilayer films. The non-transmission range over the entire visible range can be enlarged substantially, and the phenomenon of three-color PC filters in blue-green-red light can be realized by adjusting the repeat cycle counts of various PCs. With perfect omnidirectional and high peak transmission three-color filters for the electric magnetic (TE) mode, this optimization design opens a promising way to fabricate three-color PC filters with a wide non-transmission range in the visible range, which can be applied to white LEDs.

Hybridization bandgap induced by an electrical resonance in piezoelectric metamaterial plates

NASA Astrophysics Data System (ADS)

Kherraz, N.; Haumesser, L.; Levassort, F.; Benard, P.; Morvan, B.

2018-03-01

We demonstrate numerically and experimentally the opening of a locally resonant bandgap in an active phononic crystal (PC) made of a homogeneous piezoelectric plate covered by a 1D periodic array of thin electrodes connected to inductive shunts. The application of periodic electrical boundary conditions (EBCs) enables an at will tailoring of the dispersion properties of the PC plate, thus leading to a control of the dispersion of the propagating guided elastic waves in the plate. Depending on the nature of the EBCs, several bandgaps open up, the most important being a Hybridization Bandgap (HBG) in the subwavelength regime. The PC behaves as a locally resonant metamaterial. The HBG originates from the interaction of propagating elastic waves (Lamb modes) with an electrical resonant mode whose dispersion can be effectively described through an equivalent transmission line model.

Structure of the polycystic kidney disease TRP channel Polycystin-2 (PC2).

PubMed

Grieben, Mariana; Pike, Ashley C W; Shintre, Chitra A; Venturi, Elisa; El-Ajouz, Sam; Tessitore, Annamaria; Shrestha, Leela; Mukhopadhyay, Shubhashish; Mahajan, Pravin; Chalk, Rod; Burgess-Brown, Nicola A; Sitsapesan, Rebecca; Huiskonen, Juha T; Carpenter, Elisabeth P

2017-02-01

Mutations in either polycystin-1 (PC1 or PKD1) or polycystin-2 (PC2, PKD2 or TRPP1) cause autosomal-dominant polycystic kidney disease (ADPKD) through unknown mechanisms. Here we present the structure of human PC2 in a closed conformation, solved by electron cryomicroscopy at 4.2-Å resolution. The structure reveals a novel polycystin-specific 'tetragonal opening for polycystins' (TOP) domain tightly bound to the top of a classic transient receptor potential (TRP) channel structure. The TOP domain is formed from two extensions to the voltage-sensor-like domain (VSLD); it covers the channel's endoplasmic reticulum lumen or extracellular surface and encloses an upper vestibule, above the pore filter, without blocking the ion-conduction pathway. The TOP-domain fold is conserved among the polycystins, including the homologous channel-like region of PC1, and is the site of a cluster of ADPKD-associated missense variants. Extensive contacts among the TOP-domain subunits, the pore and the VSLD provide ample scope for regulation through physical and chemical stimuli.

Influences of layer thickness on the compatibility and physical properties of polycarbonate/polystyrene multilayered film via nanolayer coextrusion

NASA Astrophysics Data System (ADS)

Cheng, Junfeng; Chen, Zhiru; Zhou, Jiaqi; Cao, Zheng; Wu, Dun; Liu, Chunlin; Pu, Hongting

2018-05-01

The effects of layer thickness on the compatibility between polycarbonate (PC) and polystyrene (PS) and physical properties of PC/PS multilayered film via nanolayer coextrusion are studied. The morphology of multilayered structure is observed using a scanning electron microscope. This multilayered structure may have a negative impact on the transparency, but it can improve the water resistance and heat resistance of film. To characterize the compatibility between PC and PS, differential scanning calorimetry is used to measure the glass transition temperature. The compatibility is found to be improved with the decrease of layer thickness. Therefore, the viscosity of multilayered film is also reduced with the decrease of layer thickness. In addition, the multilayered structure can improve the tensile strength with the increase of layer numbers. Because of the complete and continuous layer structure of PC, the PC/PS multilayered film can retain its mechanical strength at the temperature above Tg of PS.

FGF2 Stimulation of the Pyrophosphate-Generating Enzyme, PC-1, in Pre-Osteoblast Cells Is Mediated by RUNX2

PubMed Central

Hatch, Nan E; Li, Yan; Franceschi, Renny T

2009-01-01

Pyrophosphate is an established inhibitor of hydroxyapatite deposition and crystal growth, yet when hydrolyzed into phosphate, it becomes a substrate for hydroxyapatite deposition. Pyrophosphate-generating enzyme (PC-1), Ank, and tissue nonspecific alkaline phosphatase (Tnap) are three factors that regulate extracellular pyrophosphate levels through its generation, transport, and hydrolysis. We previously showed that fibroblast growth factor 2 (FGF2) induces PC-1 and Ank while inhibiting Tnap expression and mineralization in MC3T3E1(C4) calvarial pre-osteoblast cells. In this study, we showed similar FGF2 regulation of these genes in primary pre-osteoblast cultures. In contrast to Ank and Tnap that are regulated by FGF2 in multiple cell types, we found regulation of PC-1 to be selective to pre-osteoblastic cells and to require the osteoblast-related transcription factor, Runx2. Specifically, FGF2 was unable to induce PC-1 expression in Runx2-negative nonbone cells or in calvarial cells from Runx2-deficient mice. Transfection of these cells with a Runx2 expression vector restored FGF2 responsiveness. FGF2 was also shown to stimulate recruitment of Runx2 to the endogenous PC-1 promoter in MC3T3E1(C4) cells, as measured by chromatin immunoprecipitation. Taken together, our results establish that FGF2 is a specific inducer of PC-1 in pre-osteoblast cells and that FGF2 induces PC-1 expression through a mechanism involving Runx2. PMID:19049325

Adsorption of metal-phthalocyanine molecules onto the Si(111) surface passivated by δ doping: Ab initio calculations

NASA Astrophysics Data System (ADS)

Veiga, R. G. A.; Miwa, R. H.; McLean, A. B.

2016-03-01

We report first-principles calculations of the energetic stability and electronic properties of metal-phthalocyanine (MPc) molecules (M = Cr, Mn, Fe, Co, Ni, Cu, and Zn) adsorbed on the δ -doped Si(111)-B (√{3 }×√{3 }) reconstructed surface. (i) It can be seen that CrPc, MnPc, FePc, and CoPc are chemically anchored to the topmost Si atom. (ii) Contrastingly, the binding of the NiPc, CuPc, and ZnPc molecules to the Si (111 ) -B (√{3 }×√{3 }) surface is exclusively ruled by van der Waals interactions, the main implication being that these molecules may diffuse and rearrange to form clusters and/or self-organized structures on this surface. The electronic structure calculations reveal that in point (i), owing to the formation of the metal-Si covalent bond, the net magnetic moment of the molecule is quenched by 1 μB , remaining unchanged in point (ii). In particular, the magnetic moment of CuPc (1 μB ) is preserved after adsorption. Finally, we verify that the formation of ZnPc, CuPc, and NiPc molecular (self-assembled) arrangements on the Si(111)-B (√{3 }×√{3 } ) surface is energetically favorable, in good agreement with recent experimental findings.

Switchable multiwavelength erbium-doped photonic crystal fiber ring laser based on a length of polarization-maintaining photonic crystal fiber

NASA Astrophysics Data System (ADS)

Cheng, Jianqun; Ruan, Shuangchen

2011-11-01

A switchable multi-wavelength Erbium-doped photonic crystal fiber (ED-PCF) ring laser based on a length of polarization-maintaining photonic crystal fiber(PM-PCF) is presented and demonstrated experimentally. A segment of ED-PCF is used as linear gain medium in the resonant cavity. Due to the polarization hole burning (PHB) caused by the PM-PCF and a polarization controller (PC), the laser can operate in stable dual- or triple- wavelength modes at room temperature. The optical signal-to-noise ratio (OSNR) of the laser without any wavelength-selective components is greater than 30 dB. The amplitude variations of lasing peaks in ten minutes are less than 0.26dB for two different operating modes.

Switchable multiwavelength erbium-doped photonic crystal fiber ring laser based on a length of polarization-maintaining photonic crystal fiber

NASA Astrophysics Data System (ADS)

Cheng, Jianqun; Ruan, Shuangchen

2012-03-01

A switchable multi-wavelength Erbium-doped photonic crystal fiber (ED-PCF) ring laser based on a length of polarization-maintaining photonic crystal fiber(PM-PCF) is presented and demonstrated experimentally. A segment of ED-PCF is used as linear gain medium in the resonant cavity. Due to the polarization hole burning (PHB) caused by the PM-PCF and a polarization controller (PC), the laser can operate in stable dual- or triple- wavelength modes at room temperature. The optical signal-to-noise ratio (OSNR) of the laser without any wavelength-selective components is greater than 30 dB. The amplitude variations of lasing peaks in ten minutes are less than 0.26dB for two different operating modes.

Investigation of the Photocurrent in Hot-Wall-Epitaxy-Grown BaIn2S4 Layers

NASA Astrophysics Data System (ADS)

You, S. H.; Hong, K. J.; Jeong, T. S.; Youn, C. J.

2015-12-01

The photocurrent (PC) of hot-wall-epitaxy-grown BaIn2S4 layers was studied at different temperatures and for different photoresponse intensities. With increasing temperature, the position of the PC spectra tended to shift toward longer wavelength. These PC peaks corresponded to band-to-band transitions caused by intrinsic transitions from the valence band states to the conduction band states. Also, the bandgap variations were well matched by the equation E g( T) = E g(0) - 3.79 × 10-3 T 2/( T + 499), where E g(0) was estimated to be 3.0597 eV, 3.2301 eV, and 3.2606 eV for transitions corresponding to the valence band states Γ 4(z), Γ 5(x), and Γ 5(y), respectively. By use of the selection rule and results from the PC spectroscopy, the crystal field and the spin-orbit splitting were found to be 0.1703 and 0.0306 eV, respectively. Thus, the PC intensity gradually decreased with decreasing temperature. The decrease of PC intensity was caused by the presence of trapping centers associated with native defects in the BaIn2S4 layers. The trap level was found to be a shallow donor-level type of 20.4 meV, 1.6 meV below the conduction band. Consequently, these trap levels, which are related to native defects in BaIn2S4 layers, are believed to limit PC intensity with decreasing temperature.

Structure of the unliganded form of the proprotein convertase furin suggests activation by a substrate-induced mechanism

PubMed Central

Dahms, Sven O.; Arciniega, Marcelino; Steinmetzer, Torsten; Huber, Robert; Than, Manuel E.

2016-01-01

Proprotein convertases (PCs) are highly specific proteases required for the proteolytic modification of many secreted proteins. An unbalanced activity of these enzymes is connected to pathologies like cancer, atherosclerosis, hypercholesterolaemia, and infectious diseases. Novel protein crystallographic structures of the prototypical PC family member furin in different functional states were determined to 1.8–2.0 Å. These, together with biochemical data and modeling by molecular dynamics calculations, suggest essential elements underlying its unusually high substrate specificity. Furin shows a complex activation mechanism and exists in at least four defined states: (i) the “off state,” incompatible with substrate binding as seen in the unliganded enzyme; (ii) the active “on state” seen in inhibitor-bound furin; and the respective (iii) calcium-free and (iv) calcium-bound forms. The transition from the off to the on state is triggered by ligand binding at subsites S1 to S4 and appears to underlie the preferential recognition of the four-residue sequence motif of furin. The molecular dynamics simulations of the four structural states reflect the experimental observations in general and provide approximations of the respective stabilities. Ligation by calcium at the PC-specific binding site II influences the active-site geometry and determines the rotamer state of the oxyanion hole-forming Asn295, and thus adds a second level of the activity modulation of furin. The described crystal forms and the observations of different defined functional states may foster the development of new tools and strategies for pharmacological intervention targeting furin. PMID:27647913

Ab Initio Crystal Field for Lanthanides.

PubMed

Ungur, Liviu; Chibotaru, Liviu F

2017-03-13

An ab initio methodology for the first-principle derivation of crystal-field (CF) parameters for lanthanides is described. The methodology is applied to the analysis of CF parameters in [Tb(Pc) 2 ] - (Pc=phthalocyanine) and Dy 4 K 2 ([Dy 4 K 2 O(OtBu) 12 ]) complexes, and compared with often used approximate and model descriptions. It is found that the application of geometry symmetrization, and the use of electrostatic point-charge and phenomenological CF models, lead to unacceptably large deviations from predictions based on ab initio calculations for experimental geometry. It is shown how the predictions of standard CASSCF (Complete Active Space Self-Consistent Field) calculations (with 4f orbitals in the active space) can be systematically improved by including effects of dynamical electronic correlation (CASPT2 step) and by admixing electronic configurations of the 5d shell. This is exemplified for the well-studied Er-trensal complex (H 3 trensal=2,2',2"-tris(salicylideneimido)trimethylamine). The electrostatic contributions to CF parameters in this complex, calculated with true charge distributions in the ligands, yield less than half of the total CF splitting, thus pointing to the dominant role of covalent effects. This analysis allows the conclusion that ab initio crystal field is an essential tool for the decent description of lanthanides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Morphology-defined interaction of copper phthalocyanine with O 2/H 2O

DOE PAGES

Muckley, Eric S.; Miller, Nicholas; Jacobs, Christopher B.; ...

2016-11-01

Copper phthalocyanine (CuPc) is an important hole transport layer for organic photovoltaics (OPVs), but its interaction with ambient gas/vapor may lead to changes in electronic properties of the material which subsequently limits the lifetime of OPV devices. CuPc films of thickness 25 nm and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. Using a source-measure unit and a quartz crystal microbalance (QCM), we measured changes in electrical resistance and film mass in situ during exposure to controlled pulses of O 2 and H 2O vapor. Mass loading by O 2 wasmore » enhanced by a factor of 5 in films deposited at 250 C, possibly due to the ~200° C CuPc -> transition which allows higher O 2 mobility between stacked molecules. While gas/vapor sorption occurred over timescales of < 10 minutes, resistance change occurred over timescales > 1 hour, suggesting that mass change occurs by rapid adsorption at active surface sites, whereas resistive response is dominated by slow diffusion of adsorbates into the film bulk. Resistive response generally increases with film deposition temperature due to increased porosity associated with larger crystalline domains. The 25 nm thick films exhibit higher resistive response than 100 nm thick films after an hour of O 2/H 2O exposure due to the smaller analyte diffusion length required for reaching the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O 2/H 2O molecules on gold, which is consistent with findings of other studies.« less

Internal structure of copper(II)-phthalocyanine thin films on SiO2/Si substrates investigated by grazing incidence x-ray reflectometry

NASA Astrophysics Data System (ADS)

Brieva, A. C.; Jenkins, T. E.; Jones, D. G.; Strössner, F.; Evans, D. A.; Clark, G. F.

2006-04-01

The internal structure of copper(II)-phthalocyanine (CuPc) thin films grown on SiO2/Si by organic molecular beam deposition has been studied by grazing incidence x-ray reflectometry (GIXR) and atomic force microscopy. The electronic density profile is consistent with a structure formed by successive monolayers of molecules in the α form with the b axis lying in the substrate surface plane. The authors present an electronic density profile model of CuPc films grown on SiO2/Si. The excellent agreement between the model and experimental data allows postdeposition monitoring of the internal structure of the CuPc films with the nondestructive GIXR technique, providing a tool for accurate control of CuPc growth on silicon-based substrates. In addition, since the experiments have been carried out ex situ, they show that these structures can endure ambient conditions.

Molecular characterization of a Penicillium chrysogenum exo-rhamnogalacturonan lyase that is structurally distinct from other polysaccharide lyase family proteins.

PubMed

Iwai, Marin; Kawakami, Takuya; Ikemoto, Takeshi; Fujiwara, Daisuke; Takenaka, Shigeo; Nakazawa, Masami; Ueda, Mitsuhiro; Sakamoto, Tatsuji

2015-10-01

We previously described an endo-acting rhamnogalacturonan (RG) lyase, termed PcRGL4A, of Penicillium chrysogenum 31B. Here, we describe a second RG lyase, called PcRGLX. We determined the cDNA sequence of the Pcrglx gene, which encodes PcRGLX. Based on analyses using a BLAST search and a conserved domain search, PcRGLX was found to be structurally distinct from known RG lyases and might belong to a new polysaccharide lyase family together with uncharacterized fungal proteins of Nectria haematococca, Aspergillus oryzae, and Fusarium oxysporum. The Pcrglx cDNA gene product (rPcRGLX) expressed in Escherichia coli demonstrated specific activity against RG but not against homogalacturonan. Divalent cations were not essential for the enzymatic activity of rPcRGLX. rPcRGLX mainly released unsaturated galacturonosyl rhamnose (ΔGR) from RG backbones used as the substrate from the initial stage of the reaction, indicating that the enzyme can be classified as an exo-acting RG lyase (EC 4.2.2.24). This is the first report of an RG lyase with this mode of action in Eukaryota. rPcRGLX acted synergistically with PcRGL4A to degrade soybean RG and released ΔGR. This ΔGR was partially decorated with galactose (Gal) residues, indicating that rPcRGLX preferred oligomeric RGs to polymeric RGs, that the enzyme did not require Gal decoration of RG backbones for degradation, and that the enzyme bypassed the Gal side chains of RG backbones. These characteristics of rPcRGLX might be useful in the determination of complex structures of pectins.

Spin tuning of electron-doped metal-phthalocyanine layers.

PubMed

Stepanow, Sebastian; Lodi Rizzini, Alberto; Krull, Cornelius; Kavich, Jerald; Cezar, Julio C; Yakhou-Harris, Flora; Sheverdyaeva, Polina M; Moras, Paolo; Carbone, Carlo; Ceballos, Gustavo; Mugarza, Aitor; Gambardella, Pietro

2014-04-09

The spin state of organic-based magnets at interfaces is to a great extent determined by the organic environment and the nature of the spin-carrying metal center, which is further subject to modifications by the adsorbate-substrate coupling. Direct chemical doping offers an additional route for tailoring the electronic and magnetic characteristics of molecular magnets. Here we present a systematic investigation of the effects of alkali metal doping on the charge state and crystal field of 3d metal ions in Cu, Ni, Fe, and Mn phthalocyanine (Pc) monolayers adsorbed on Ag. Combined X-ray absorption spectroscopy and ligand field multiplet calculations show that Cu(II), Ni(II), and Fe(II) ions reduce to Cu(I), Ni(I), and Fe(I) upon alkali metal adsorption, whereas Mn maintains its formal oxidation state. The strength of the crystal field at the Ni, Fe, and Mn sites is strongly reduced upon doping. The combined effect of these changes is that the magnetic moment of high- and low-spin ions such as Cu and Ni can be entirely turned off or on, respectively, whereas the magnetic configuration of MnPc can be changed from intermediate (3/2) to high (5/2) spin. In the case of FePc a 10-fold increase of the orbital magnetic moment accompanies charge transfer and a transition to a high-spin state.

A Sensor-Type PC Strand with an Embedded FBG Sensor for Monitoring Prestress Forces

PubMed Central

Kim, Sung Tae; Park, YoungHwan; Park, Sung Yong; Cho, Keunhee; Cho, Jeong-Rae

2015-01-01

Prestressed Concrete Wire and Strand (PC) strands are the most used materials to introduce prestress in a Pre-Stressed Concrete (PSC) structure. However, it is difficult to evaluate the final prestress force of the PC strand after prestressing or its residual prestress force after completion of the structure on site. This impossibility to assess eventual loss of prestress of the PC strand has resulted in a number of serious accidents and even in the collapse of several structures. This situation stresses the necessity to maintain the prestress force residual or after prestressing for the evaluation of the health of the concrete structure throughout its lifespan. Recently, several researchers have studied methods enabling one to verify the prestress force by inserting an optical fiber sensor inside the strand but failed to provide simple techniques for the fabrication of these devices to fulfill measurement performance from the design prestress to failure. Moreover, these methods require the additional installation of electrical resistance strain gages, displacement sensors and load cells on the outer surface of the structure for long-term precise measurement. This paper proposes a method enabling one to evaluate precisely and effectively the prestress force of the PC strand and intends to verify the applicability of the proposed method on actual concrete structures. To that end, an innovative PC strand is developed by embedding a Fiber Bragg Grating (FBG) sensor in the core wire of the PC strand so as to enable short term as well as long term monitoring. The measurement performance of the developed strand is then evaluated experimentally and the reliability of the monitoring data is assessed. PMID:25580903

A sensor-type PC strand with an embedded FBG sensor for monitoring prestress forces.

PubMed

Kim, Sung Tae; Park, YoungHwan; Park, Sung Yong; Cho, Keunhee; Cho, Jeong-Rae

2015-01-08

Prestressed Concrete Wire and Strand (PC) strands are the most used materials to introduce prestress in a Pre-Stressed Concrete (PSC) structure. However, it is difficult to evaluate the final prestress force of the PC strand after prestressing or its residual prestress force after completion of the structure on site. This impossibility to assess eventual loss of prestress of the PC strand has resulted in a number of serious accidents and even in the collapse of several structures. This situation stresses the necessity to maintain the prestress force residual or after prestressing for the evaluation of the health of the concrete structure throughout its lifespan. Recently, several researchers have studied methods enabling one to verify the prestress force by inserting an optical fiber sensor inside the strand but failed to provide simple techniques for the fabrication of these devices to fulfill measurement performance from the design prestress to failure. Moreover, these methods require the additional installation of electrical resistance strain gages, displacement sensors and load cells on the outer surface of the structure for long-term precise measurement. This paper proposes a method enabling one to evaluate precisely and effectively the prestress force of the PC strand and intends to verify the applicability of the proposed method on actual concrete structures. To that end, an innovative PC strand is developed by embedding a Fiber Bragg Grating (FBG) sensor in the core wire of the PC strand so as to enable short term as well as long term monitoring. The measurement performance of the developed strand is then evaluated experimentally and the reliability of the monitoring data is assessed.

Immunoresponses to Neisseria meningitidis epitopes: suppression of secondary response to phosphorylcholine is carrier specific.

PubMed Central

Faro, J; Seoane, R; Eiras, A; Lareo, I; Couceiro, J; Regueiro, B J

1986-01-01

Results of our previous work have shown that Neisseria meningitidis serogroup B M986 can induce a phosphorylcholine (PC)-specific plaque-forming cell immunoresponse in mice. Also, a single injection of a relatively low dose of meningococci in NBF1 female mice induced a priming time-dependent suppression on subsequent meningococcus challenge. This suppression was not due to switching to another class of immunoglobulin nor to the presence of a capsule on N. meningitidis. In this study we show that suppression induced by meningococcus is carrier specific. Furthermore, we offer evidence suggesting that the structure(s) on meningococcus that trigger this suppression is heat labile and different from the antigenic structure(s) recognized by the suppressed B cells. In addition, we found that there is a gradual increase in antibody secretion rates of N. meningitidis-induced anti-PC plaque-forming cells that correlates with N. meningitidis priming time. Rather unexpected was the fact that pretreatment of mice with PC-keyhole limpet hemocyanin (thymus-dependent antigen) had a great influence on the subsequent PC-specific immunoresponses induced by N. meningitidis and PC-coupled heat-inactivated meningococcus [PC-(NMB)HI], as shown by (i) a striking decrease in T15 idiotype expression, (ii) concomitant direct anti-PC plaque-forming cells reduction, (iii) switching to immunoglobulin G (N. meningitidis-induced immunoresponse) or immunoglobulin G plus immunoglobulin A [PC-(NMB)HI-induced immunoresponse], and (iv) a significant increase in heterogeneity of plaque-forming cell secretion rates. The possibility that N. meningitidis, PC-(NMB)HI, and PC-KLH stimulate B lymphocytes pertaining to three different subpopulations embedded in distinct regulatory circuits is discussed, with emphasis on the interrelationships between T-dependent and T-independent lymphocyte compartments. We focus on the possibility of the existence of high-level regulatory circuits in which lymphocyte subpopulations or sets of lymphocyte subpopulations with different requirements of activation are connected. PMID:2416688

A new electrode design for ambipolar injection in organic semiconductors.

PubMed

Kanagasekaran, Thangavel; Shimotani, Hidekazu; Shimizu, Ryota; Hitosugi, Taro; Tanigaki, Katsumi

2017-10-17

Organic semiconductors have attracted much attention for low-cost, flexible and human-friendly optoelectronics. However, achieving high electron-injection efficiency is difficult from air-stable electrodes and cannot be equivalent to that of holes. Here, we present a novel concept of electrode composed of a bilayer of tetratetracontane (TTC) and polycrystalline organic semiconductors (pc-OSC) covered by a metal layer. Field-effect transistors of single-crystal organic semiconductors with the new electrodes of M/pc-OSC/TTC (M: Ca or Au) show both highly efficient electron and hole injection. Contact resistance for electron injection from Au/pc-OSC/TTC and hole injection from Ca/pc-OSC/TTC are comparable to those for electron injection from Ca and hole injection from Au, respectively. Furthermore, the highest field-effect mobilities of holes (22 cm 2  V -1  s -1 ) and electrons (5.0 cm 2  V -1  s -1 ) are observed in rubrene among field-effect transistors with electrodes so far proposed by employing Ca/pc-OSC/TTC and Au/pc-OSC/TTC electrodes for electron and hole injection, respectively.One of technological challenges building organic electronics is efficient injection of electrons at metal-semiconductor interfaces compared to that of holes. The authors show an air-stable electrode design with induced gap states, which support Fermi level pinning and thus ambipolar carrier injection.

Hybrid solar cells composed of perovskite and polymer photovoltaic structures

NASA Astrophysics Data System (ADS)

Phaometvarithorn, Apatsanan; Chuangchote, Surawut; Kumnorkaew, Pisist; Wootthikanokkhan, Jatuphorn

2018-06-01

Organic/inorganic lead halide perovskite solar cells have recently attracted much attention in photovoltaic research, due to the devices show promising ways to achieve high efficiencies. The perovskite devices with high efficiencies, however, are typically fabricated in tandem solar cell which is complicated. In this research work, we introduce a solar cell device with the combination of CH3NH3PbI3-xClx perovskite and bulk heterojunction PCDTBT:PC70BM polymer without any tandem structure. The new integrated perovskite/polymer hybrid structure of ITO/PEDOT:PSS/perovskite/PCDTBT:PC70BM/PC70BM/TiOx/Al provides higher power conversion efficiency (PCE) of devices compared with conventional perovskite cell structure. With the optimized PCDTBT:PC70BM thickness of ∼70 nm, the highest PCE of 11.67% is achieved. Variation of conducting donor polymers in this new structure is also preliminary demonstrated. This study provides an attractively innovative structure and a promising design for further development of the new-generation solar cells.

Impact of a Recombinant Biocontrol Bacterium, Pseudomonas fluorescens pc78, on Microbial Community in Tomato Rhizosphere.

PubMed

Kong, Hyun Gi; Kim, Nam Hee; Lee, Seung Yeup; Lee, Seon-Woo

2016-04-01

Pseudomonas fluorescens pc78 is an effective biocontrol agent for soil-borne fungal diseases. We previously constructed a P43-gfp tagged biocontrol bacteria P. fluorescens pc78-48 to investigate bacterial traits in natural ecosystem and the environmental risk of genetically modified biocontrol bacteria in tomato rhizosphere. Fluctuation of culturable bacteria profile, microbial community structure, and potential horizontal gene transfer was investigated over time after the bacteria treatment to the tomato rhizosphere. Tagged gene transfer to other organisms such as tomato plants and bacteria cultured on various media was examined by polymerase chain reaction, using gene specific primers. Transfer of chromosomally integrated P43-gfp from pc78 to other organisms was not apparent. Population and colony types of culturable bacteria were not significantly affected by the introduction of P. fluorescens pc78 or pc78-48 into tomato rhizosphere. Additionally, terminal restriction fragment length polymorphism profiles were investigated to estimate the influence on the microbial community structure in tomato rhizosphere between non-treated and pc78-48-treated samples. Interestingly, rhizosphere soil treated with strain pc78-48 exhibited a significantly different bacterial community structure compared to that of non-treated rhizosphere soil. Our results suggest that biocontrol bacteria treatment influences microbial community in tomato rhizosphere, while the chromosomally modified biocontrol bacteria may not pose any specific environmental risk in terms of gene transfer.

Electronic and structural properties at the interface between CuPc and graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, Yongsheng; College of Modern Science and Technology, China Jiliang University, Hangzhou 310018; Mao, Hongying

2015-01-07

The electronic and structural properties at Copper phthalocyanine (CuPc)/graphene have been studied using ultraviolet photoemission spectroscopy and first-principles density function theory calculation. The five emission features α, β, γ, δ, and ε originating from the CuPc molecules locate at 1.48, 3.66, 4.98, 6.90, and 9.04 eV, respectively. These features shift in binding energy with the increasing CuPc coverage. The feature α is mostly deriving from Cu 3d orbital with some contributions from C 2p orbital. Further theoretical calculation indicates that the adsorption of CuPc on a top site is the most favorable configuration, and the separation between the adsorbate and graphenemore » is about 3.47 Å. According to the density of states before and after CuPc adsorption, the LUMO of CuPc is slightly occupied, while the Dirac point of graphene slightly shift towards higher energy, suggesting that a small amount of electron transfer from graphene to CuPc upon contact.« less

Basic Research in Electronics (JSEP)

DTIC Science & Technology

1991-12-01

Single Crystal Growth Single crystals of Bi2Sr 2 CaCu2 O8 (BSCCO) have been prepared following the method of Mitzi , et al. [241. A mixture of oxides...P.C. van Son, H. van Kempen and P. Wyder, Phys. Rev. Lett., 50 2226 (1987). [24] D.B. Mitzi , L.W. Lombardo, A. Kapitulnik,/S.S. Laderman and R.D...Phys. Rev., 165 837 (1908). P.C. van Son, H. van Kempen and P. Wyder, Phys. Rev. Lett., 59 2228 (1987). D.B. Mitzi , L.W. Lombardo, A. Kapitulnik

Polarized micro-cavity organic light-emitting devices.

PubMed

Park, Byoungchoo; Kim, Mina; Park, Chan Hyuk

2009-04-27

We present the results of a study of light emissions from a polarized micro-cavity Organic Light-Emitting Device (OLED), which consisted of a flexible, anisotropic one-dimensional (1-D) photonic crystal (PC) film substrate. It is shown that luminous Electroluminescent (EL) emissions from the polarized micro-cavity OLED were produced at relatively low operating voltages. It was also found that the peak wavelengths of the emitted EL light corresponded to the two split eigen modes of the high-energy band edges of the anisotropic PC film, with a strong dependence on the polarization state of the emitting light. For polarization along the ordinary axis of the anisotropic PC film, the optical split micro-cavity modes occurred at the longer high-energy photonic band gap (PBG) edge, while for polarization along the extraordinary axis, the split micro-cavity modes occurred at the shorter high-energy PBG edge, with narrow bandwidths. We demonstrated that the polarization and emission mode of the micro-cavity OLED may be selected by choosing the appropriate optical axis of the anisotropic 1-D PC film.

Physical and Instrumental Considerations in the Use of Lithium Phthalocyanine for Measurements of the Concentration of the Oxygen

NASA Astrophysics Data System (ADS)

Smirnov, A. I.; Norby, S. W.; Walczak, T.; Liu, K. J.; Swartz, H. M.

The use of crystals of lithium phthalocyanine (LiPc) to measure the concentration of oxygen in vivo and in vitro by electron paramagnetic resonance leads to experimental constraints due to the very narrow EPR lines that may occur (as narrow as 11-13 mG in the absence of O 2), distortions induced by the automatic frequency control system, anisotropy in the spectra (orientation-dependent linewidth is 11-17 mG in the absence of O 2), microwave power saturation, and the effect of physiological motion. These constraints can be overcome if recognized. This article highlights the experimental and theoretical basis of these properties of the EPR signal of LiPc and suggests some technical solutions. It is most important to recognize that paramagnetic species such as LiPc present problems that are not commonly encountered in EPR spectroscopy.

Effect of structure and morphology on thermal and electrical properties of polycarbonate film capacitors

NASA Astrophysics Data System (ADS)

Yen, S. P. S.; Lewis, C. R.

Research is reported to identify polycarbonate (PC) film characteristics and fabrication procedures which extend the reliable performance range of PC capacitors to 125 C without derating, and establish quality control techniques and transfer technology to US PC film manufacturers. The approach chosen to solve these problems was to develop techniques for fabricating biaxially oriented (BX) 2 microns or thinner PC film with a low dissipation factor up to 140 C; isotropic dimensional stability; high crystallinity; and high voltage breakdown strength. The PC film structure and morphology was then correlated to thermal and electrical capacitor behavior. Analytical techniques were developed to monitor film quality during capacitor fabrication, and as a result, excellent performance was demonstrated during initial capacitor testing.

Tunneling electron induced chemisorption of copper phthalocyanine molecules on the Cu(111) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stock, T.; Nogami, J.

2014-02-17

The adsorption of up to one monolayer (ML) of copper phthalocyanine (CuPc) molecules on a room temperature Cu(111) surface has been studied using scanning tunneling microscopy (STM). Below 1 ML the molecules are in a fluid state and are highly mobile on the surface. At 1 ML coverage the molecules coalesce into a highly ordered 2D crystal phase. At sub-ML coverages, chemisorption of individual CuPc molecules can be induced through exposure to tunneling electrons at a tunneling bias voltage exceeding a threshold value. This tunneling electron induced effect has been exploited to perform molecular STM lithography.

Using small molecule reagents to help distinguish among prion structural models

USDA-ARS?s Scientific Manuscript database

The only demonstrated difference between infectious prions (PrPSc) and the isosequential normal cellular prion protein (PrPC) is conformation. The structure of PrPC has been determined by a variety of instrumental techniques. The structure of prions remains uncertain. Recent instrumental analysis h...

Porous silicon-copper phthalocyanine heterostructure based photoelectrochemical cell

NASA Astrophysics Data System (ADS)

A. Betty, C.; N, Padma; Arora, Shalav; Survaiya, Parth; Bhattacharya, Debarati; Choudhury, Sipra; Roy, Mainak

2018-01-01

A hybrid solar cell consisting of nanostructured p-type porous silicon (PS) deposited with visible light absorbing dye, Copper Phthalocyanine (CuPc) has been prepared in the photoelectrochemical cell configuration. P-type PS with (100) and (111) orientations which have different porous structures were used for studying the effects of the substrate morphology on the cell efficiency. Heterostructures were prepared by depositing three different thicknesses of CuPc for optimizing the cell efficiency. Structural and surface characterizations were studied using XRD, Raman, SEM and AFM on the PS-CuPc heterostructure. XRD spectrum on both plane silicon and porous silicon indicates the π-π stacking of CuPc with increased disorder for CuPc film on porous silicon. Electrochemical characterizations under sun light type radiation have been carried out to evaluate the photosensitivity of the heterostructure. Between the two different substrates, (100) PS gives better photocurrent, possibly due to the higher surface area and lower series resistance of the structure. Among the (100) PS substrates, (100) PS with 15 nm CuPc film gives Voc more than 1 V resulting in higher efficiency for the cell. The study suggests the scope for optimization of solar cell efficiency using various combinations of the substrate structure and thickness of the sensitizing layer.

Azaphenalene phthalocyanines: phthalocyanine analogues with six-membered-ring units instead of five-membered-ring units.

PubMed

Shimizu, Soji; Zhu, Hua; Kobayashi, Nagao

2010-09-24

Mixed-condensation reaction of 1,8-naphthalenedicarbonitrile and a 4,5-disubstituted phthalonitrile provided a series of phthalocyanine (Pc) analogues with azaphenalene (AP) moieties in place of the isoindole moieties. Monosubstituted species, APPc, and the two structural isomers of disubstituted species, adj-AP(2)Pc and opp-AP(2)Pc, were successfully isolated by gel-permeation chromatography on HPLC apparatus. Their structures were elucidated by (1)H NMR spectroscopy and X-ray crystallographic analysis. Replacement of the isoindole moieties with azaphenalene moieties created six-membered-ring units in the core and caused distortion of the molecular structures. The Q-band absorption shifted to the red upon an increase in the number of azaphenalene units; the shape of the absorption spectra depended on the molecular symmetries. APPc and opp-AP(2)Pc showed a large splitting of the Q band, whereas adj-AP(2)Pc exhibited a single broad Q band. These changes in the absorption spectra, as well as the unique electronic structures, are discussed in detail, based on magnetic circular dichroism spectra, electrochemical measurements, and density functional theory calculations.

Comparative study of I- V methods to extract Au/FePc/p-Si Schottky barrier diode parameters

NASA Astrophysics Data System (ADS)

Oruç, Çiğdem; Altındal, Ahmet

2018-01-01

So far, various methods have been proposed to extract the Schottky diode parameters from measured current-voltage characteristics. In this work, Schottky barrier diode with structure of Au/2(3),9(10),16(17),23(24)-tetra(4-(4-methoxyphenyl)-8-methylcoumarin-7 oxy) phthalocyaninatoiron(II) (FePc)/p-Si was fabricated and current-voltage measurements were carried out on it. In addition, current-voltage measurements were also performed on Au/p-Si structure, without FePc, to clarify the influence of the presence of an interface layer on the device performance. The measured current-voltage characteristics indicate that the interface properties of a Schottky barrier diode can be controlled by the presence of an organic interface layer. It is found that the room temperature barrier height of Au/FePc/p-Si structure is larger than that of the Au/p-Si structure. The obtained forward bias current-voltage characteristics of the Au/FePc/p-Si device was analysed by five different analytical methods. It is found that the extracted values of SBD parameters strongly depends on the method used.

Enhanced activity and stability of binuclear iron (III) phthalocyanine on graphene nanosheets for electrocatalytic oxygen reduction in acid

NASA Astrophysics Data System (ADS)

Li, Tengfei; Peng, Yingxiang; Li, Kai; Zhang, Rui; Zheng, Lirong; Xia, Dingguo; Zuo, Xia

2015-10-01

Binuclear iron (III) phthalocyanine (bi-FePc) and iron (III) phthalocyanine (FePc) are synthesized in situ on graphene nanosheets (GNS) by a microwave-assisted method. TEM, ultraviolet-visible spectroscopy and Raman spectroscopy confirm that bi-FePc is supported on GNS through π-π interactions. The catalytic activity of the bi-FePc/GNS and FePc/GNS composites in the oxygen reduction reaction (ORR) is investigated by CV and RDE measurements. The bi-FePc/GNS composite shows a more positive onset potential (0.12 V vs. Hg/Hg2SO4) for the ORR than FePc/GNS (-0.02 V vs. Hg/Hg2SO4), and a four-electron mechanism similar to commercial Pt/C (0.22 V vs. Hg/Hg2SO4). Moreover, bi-FePc/GNS exhibits good stability with 100% retention after 36,000 s, while Pt/C has a retention of only 50% after the same period. Additionally, bi-FePc/GNS shows higher tolerance toward methanol than the Pt/C catalyst. XPS and X-ray absorption fine structure spectroscopy demonstrate that compared with FePc/GNS, bi-FePc/GNS possesses a higher concentration of Fe3+ and smaller skeleton radius of the phthalocyanine ring, which has a square-planar structure that evidently favors the ORR. Thus, bi-FePc/GNS is a promising candidate as a cathode catalyst in direct methanol fuel cells.

A model of magnetic and relaxation properties of the mononuclear [Pc2Tb](-)TBA+ complex.

PubMed

Reu, O S; Palii, A V; Ostrovsky, S M; Tregenna-Piggott, P L W; Klokishner, S I

2012-10-15

The present work is aimed at the elaboration of the model of magnetic properties and magnetic relaxation in the mononuclear [Pc(2)Tb](-)TBA(+) complex that displays single-molecule magnet properties. We calculate the Stark structure of the ground (7)F(6) term of the Tb(3+) ion in the exchange charge model of the crystal field, taking account for covalence effects. The ground Stark level of the complex possesses the maximum value of the total angular momentum projection, while the energies of the excited Stark levels increase with decreasing |M(J)| values, thus giving rise to a barrier for the reversal of magnetization. The one-phonon transitions between the Stark levels of the Tb(3+) ion induced by electron-vibrational interaction are shown to lead to magnetization relaxation in the [Pc(2)Tb](-)TBA(+) complex. The rates of all possible transitions between the low-lying Stark levels are calculated in the temperature range 14 K

Absolute configuration of podophyllotoxone and its inhibitory activity against human prostate cancer cells.

PubMed

Li, Juan; Feng, Juan; Luo, Cheng; Herman, Ho-Yung Sung; Jiang, Ren-Wang

2015-01-01

Podophyllotoxone (1) was isolated from the roots of Dysosma versipellis. The structure was determined by spectroscopic analysis in combination with single-crystal X-ray analysis. The absolute configuration of compound 1 was assigned based on the Flack parameter. It showed significant inhibitory activities against human prostate cancer cells PC3 and DU145 with IC50 values being 14.7 and 20.6 μmol·L(-1), respectively. It also arrested the cells at G2/M phase. Tubulin polymerization assay showed that it inhibited the tubulin polymerization in a dose-dependent manner, and molecular docking analysis revealed a different binding mode with tubulin as compared with those known tubulin inhibitors. Copyright © 2015 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.

Improvement in the Viability of Cryopreserved Cells by Microencapsulation

NASA Astrophysics Data System (ADS)

Matsumoto, Yoshifumi; Morinaga, Yukihiro; Ujihira, Masanobu; Oka, Kotaro; Tanishita, Kazuo

The advantages of microencapsulated cells over those of suspended cells were evaluated for improving viability in cryopreservation. Rat pheochromocytoma (PC12) cells were selected as the test biological cells and then microencapsulated in alginate-polylysine-alginate membranes. These microencapsulated PC12 cells were frozen by differential scanning calorimetry (DSC) at various cooling rates, from 0.5 to 10°C/min. Their latent heat was measured during freezing from 4 to -80°C. The post-thaw viability was evaluated by dopamine-concentration measurement and by trypan blue exclusion assay. Results showed that at cooling rates of 0.5 and 1°C/min, the latent heat of microencapsulated PC12 cells was lower than that of suspended cells. This lower latent heat is caused by the fact that the extra-microcapsule froze and the intra-capsule remained unfrozen due to the formation of ice crystals in the extra-capsule space. The post-thaw viability of microencapsulated PC12 cells was improved when the cooling rate was 0.5 or 1°C/min, compared with that of suspended cells. Therefore, in microencapsulated PC12 cells, maintaining the intra-microcapsules in an unfrozen state during freezing reduces the solution effect and thus improves the post-thaw viability.

A near atomic structure of the active human apoptosome

PubMed Central

Cheng, Tat Cheung; Hong, Chuan; Akey, Ildikó V; Yuan, Shujun; Akey, Christopher W

2016-01-01

In response to cell death signals, an active apoptosome is assembled from Apaf-1 and procaspase-9 (pc-9). Here we report a near atomic structure of the active human apoptosome determined by cryo-electron microscopy. The resulting model gives insights into cytochrome c binding, nucleotide exchange and conformational changes that drive assembly. During activation an acentric disk is formed on the central hub of the apoptosome. This disk contains four Apaf-1/pc-9 CARD pairs arranged in a shallow spiral with the fourth pc-9 CARD at lower occupancy. On average, Apaf-1 CARDs recruit 3 to 5 pc-9 molecules to the apoptosome and one catalytic domain may be parked on the hub, when an odd number of zymogens are bound. This suggests a stoichiometry of one or at most, two pc-9 dimers per active apoptosome. Thus, our structure provides a molecular framework to understand the role of the apoptosome in programmed cell death and disease. DOI: http://dx.doi.org/10.7554/eLife.17755.001 PMID:27697150

[Risk analysis and assessment of occupational hazard fromindiumand its compounds in manufacture of liquid crystal display panel].

PubMed

Qiu, Haili; Zhou, Wei; Li, Zhimin; Tian, Dongchao; Weng, Shaofan; He, Juntao

2015-08-01

To understand the exposed positions and levels of indium and its compounds in manufacture of liquid crystal displays, and to evaluate the degree of occupational hazard from indium and its compounds. On-site investigation of occupational health, occupational hazard monitoring, and occupational health examination were used to evaluate the degree of occupational hazard from indium and its compounds in three manufacturers of liquid crystal display panel in Shenzhen, Guangdong, China. The time-weighted average (TWA) and short-term exposure limit (STEL) concentrations of indium and its compounds to which sputtering machine operating positions were exposed were less than 0.002~0.004 mg/m³ and 0.006~0.007 mg/m³, respectively, both of which complied with the National Hygienic Standard (PC-TWA = 0.1 mg/m³; PC-STEL = 0.3 mg/m³); the TWA and STEL concentrations of indium and its compounds to which grinding positions were exposed were 0.114~2.98 mg/m³ and 0.31~10.02 mg/m³, respectively, both of which exceeded the National Hygienic Standard with the highest concentration 33-fold higher than the standard. No significant health damages were found in exposed workers according to the results of occupational health examination. The grinding positions are the key to the control of occupational hazard from indium and its compounds in manufacture of liquid crystal display panel. The workers should be equipped with the anti-particulate full-face respirator, which is an effective way to prevent occupational hazard from indium and its compounds.

Temperature-assisted morphological transition in CuPc thin films

NASA Astrophysics Data System (ADS)

Bae, Yu Jeong; Pham, Thi Kim Hang; Kim, Tae Hee

2016-05-01

Ex-situ and in-situ morphological analyses were performed for Cu-phthalocyanine (CuPc) organic semiconductor films by using atomic force microscopy (AFM) and reflection high-energy electron diffraction (RHEED). The focus was the effects of post-annealing on the structural characteristics of CuPc films grown on MgO(001) layers by using an ultra-high-vacuum thermal evaporator. Sphere-to-nanofibril and 2-D to 3-D morphological transitions were observed with increasing CuPc thickness beyond 3 nm. The surface morphology and the crystallinity were drastically improved after an additional cooling of the post-annealed CuPc films thinner than 3 nm. Our results highlight that molecular orientation and structural ordering can be effectively controlled by using different temperature treatments and a proper combination of material, film thickness, and substrate.

Critical role of domain crystallinity, domain purity and domain interface sharpness for reduced bimolecular recombination in polymer solar cells

DOE PAGES

Venkatesan, Swaminathan; Chen, Jihua; Ngo, Evan C.; ...

2014-12-31

In this study, inverted bulk heterojunction solar cells were fabricated using poly(3-hexylthiophene) (P3HT) blended with two different fullerene derivatives namely phenyl-C61-butyric acid methyl ester (PC 60BM) and indene-C 60 bis-adduct (IC 60BA). The effects of annealing temperatures on the morphology, optical and structural properties were studied and correlated to differences in photovoltaic device performance. It was observed that annealing temperature significantly improved the performance of P3HT:IC 60BA solar cells while P3HT:PC 60BM cells showed relatively less improvement. The performance improvement is attributed to the extent of fullerene mixing with polymer domains. Energy filtered transmission electron microscopy (EFTEM) and x-ray diffractionmore » (XRD) results showed that ICBA mixes with disordered P3HT much more readily than PC 60BM which leads to lower short circuit current density and fill factor for P3HT:IC 60BA cells annealed below 120°C. Annealing above 120°C improves the crystallinity of P3HT in case of P3HT:IC 60BA whereas in P3HT:PC 60BM films, annealing above 80°C leads to negligible change in crystallinity. Crystallization of P3HT also leads to higher domain purity as seen EFTEM. Further it is seen that cells processed with additive nitrobenzene (NB) showed enhanced short circuit current density and power conversion efficiency regardless of the fullerene derivative used. Addition of NB led to nanoscale phase separation between purer polymer and fullerene domains. Kelvin probe force microscopy (KPFM) images showed that enhanced domain purity in additive casted films led to a sharper interface between polymer and fullerene. Lastly, enhanced domain purity and interfacial sharpness led to lower bimolecular recombination and higher mobility and charge carrier lifetime in NB modified devices.« less

How to achieve optimal organization of primary care service delivery at system level: lessons from Europe.

PubMed

Pelone, Ferruccio; Kringos, Dionne S; Spreeuwenberg, Peter; De Belvis, Antonio G; Groenewegen, Peter P

2013-09-01

To measure the relative efficiency of primary care (PC) in turning their structures into services delivery and turning their services delivery into quality outcomes. Cross-sectional study based on the dataset of the Primary Healthcare Activity Monitor for Europe project. Two Data Envelopment models were run to compare the relative technical efficiency. A sensitivity analysis of the resulting efficiency scores was performed. PC systems in 22 European countries in 2009/2010. Model 1 included data on PC governance, workforce development and economic conditions as inputs and access, coordination, continuity and comprehensiveness of care as outputs. Model 2 included the previous process dimensions as inputs and quality indicators as outputs. There is relatively reasonable efficiency in all countries at delivering as many as possible PC processes at a given level of PC structure. It is particularly important to invest in economic conditions to achieve an efficient structure-process balance. Only five countries have fully efficient PC systems in turning their services delivery into high quality outcomes, using a similar combination of access, continuity and comprehensiveness, although they differ on the adoption of coordination of services. There is a large variation in efficiency levels obtained by countries with inefficient PC in turning their services delivery into quality outcomes. Maximizing the individual functions of PC without taking into account the coherence within the health-care system is not sufficient from a policymaker's point of view when aiming to achieve efficiency.

Terahertz transmission properties of a triadic-Cantor-set photonic crystal containing a semiconductor

NASA Astrophysics Data System (ADS)

King, Tzu-Chyang; Liu, Chi-Chung; Huang, Chih-Hsi; Wu, Chien-Jang

2016-08-01

Terahertz transmission properties of a stage 3 triadic-Cantor-set photonic crystal (S3 TCS PC) containing a semiconductor of n-InSb are theoretically investigated. With the resonant frequency in the permittivity function of n-InSb, transmission responses can be classified as three regions. In the two regions with frequencies well above and below the resonant frequency, the permittivity functions are nearly a positive constant and n-InSb is dielectric-like. For these two regions, transmittance response of S3 TCS PC at a given number of periods Np reveals that, within a photonic band gap, there are two groups of defect modes with numbers of Np and Np-1, respectively. Defect modes are shown to be blue-shifted as the angle of incidence increases for both TE and TM waves. Additionally, adjusting the layer thickness enables us to control mode positions for the group of (Np-1)-mode, but the one with Np-mode is not able to be controlled. In a region of 5.1-6.2 THz, where the loss is large, there also are many transmission modes.

Dual-Responsive SPMA-Modified Polymer Photonic Crystals and Their Dynamic Display Patterns.

PubMed

Gao, Zewen; Gao, Dongsheng; Huang, Chao; Zhang, Hanbing; Guo, Jinbao; Wei, Jie

2018-05-28

Light and electrothermal responsive polymer photonic crystals (PCs) modified with 1'-acryloyl chloride-3',3'-dimethyl-6-nitro-spiro(2H-1-benzopyran-2,2'-indoline) (SPMA) are proposed, and their dynamic display patterns are achieved through the combination of the SPMA-modified PCs and a patterned graphite layer. These PCs exhibit fluorescence under UV light irradiation because of the isomerization of the SPMA, which is restricted in the shell of the polymer colloidal spheres. After a voltage is applied to the patterned graphite layer, the fluorescence of PCs in the specific area disappears, and dynamic display patterns are obtained. Under UV light irradiation, the PCs change from the "partial-fluorescence" state to the initial "fluorescence" state, and the patterns disappear. Using this technique, the PC pattern "M L N" on the glass substrate and PC patterns from "0" to "9" on the paper substrate are fabricated. Thus, these dual-responsive PCs have potential applications in information recording, anticounterfeiting, dynamic display, and photoelectric devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Detection and Site Localization of Phosphorylcholine-Modified Peptides by NanoLC-ESI-MS/MS Using Precursor Ion Scanning and Multiple Reaction Monitoring Experiments

NASA Astrophysics Data System (ADS)

Timm, Thomas; Lenz, Christof; Merkel, Dietrich; Sadiffo, Christian; Grabitzki, Julia; Klein, Jochen; Lochnit, Guenter

2015-03-01

Phosphorylcholine (PC)-modified biomolecules like lipopolysaccharides, glycosphingolipids, and (glyco)proteins are widespread, highly relevant antigens of parasites, since this small hapten shows potent immunomodulatory capacity, which allows the establishment of long-lasting infections of the host. Especially for PC-modified proteins, structural data is rare because of the zwitterionic nature of the PC substituent, resulting in low sensitivities and unusual but characteristic fragmentation patterns. We have developed a targeted mass spectrometric approach using hybrid triple quadrupole/linear ion trap (QTRAP) mass spectrometry coupled to nanoflow chromatography for the sensitive detection of PC-modified peptides from complex proteolytic digests, and the localization of the PC-modification within the peptide backbone. In a first step, proteolytic digests are screened using precursor ion scanning for the marker ions of choline ( m/z 104.1) and phosphorylcholine ( m/z 184.1) to establish the presence of PC-modified peptides. Potential PC-modified precursors are then subjected to a second analysis using multiple reaction monitoring (MRM)-triggered product ion spectra for the identification and site localization of the modified peptides. The approach was first established using synthetic PC-modified synthetic peptides and PC-modified model digests. Following the optimization of key parameters, we then successfully applied the method to the detection of PC-peptides in the background of a proteolytic digest of a whole proteome. This methodological invention will greatly facilitate the detection of PC-substituted biomolecules and their structural analysis.

Effect of film morphology on oxygen and water interaction with copper phthalocyanine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Nicholas; Gredig, Thomas; Ivanov, Ilia N

2016-01-01

Copper phthalocyanine (CuPc) films of thickness 25 nm and 100 nm were grown by thermal sublimation at 25 C, 150 C, and 250 C in order to vary morphology. Using a source-measure unit and a quartz crystal microbalance (QCM), we measured changes in electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. Mass loading by O2 was enhanced by a factor of 5 in films deposited at 250 C, possibly due to the ~200 C CuPc transition which allows higher O2 mobility between stacked molecules. While gas/vapor sorption occurred over timescales ofmore » < 10 minutes, resistance change occurred over timescales > 1 hour, suggesting that mass change occurs by rapid adsorption at active surface sites, whereas resistive response is dominated by slow diffusion of adsorbates into the film bulk. Resistive response generally increases with film deposition temperature due to increased porosity associated with larger crystalline domains. The 25 nm thick films exhibit higher resistive response than 100 nm thick films after an hour of O2/H2O exposure due to the smaller analyte diffusion length required for reaching the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold, which is consistent with findings of other studies.« less

Effect of film morphology on oxygen and water interaction with copper phthalocyanine

NASA Astrophysics Data System (ADS)

Muckley, Eric S.; Miller, Nicholas; Gredig, Thomas; Ivanov, Ilia N.

2016-09-01

Copper phthalocyanine (CuPc) films of thickness 25 nm and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. Using a source-measure unit and a quartz crystal microbalance (QCM), we measured changes in electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. Mass loading by O2 was enhanced by a factor of 5 in films deposited at 250°C, possibly due to the 200°C CuPc α->β transition which allows higher O2 mobility between stacked molecules. While gas/vapor sorption occurred over timescales of < 10 minutes, resistance change occurred over timescales < 1 hour, suggesting that mass change occurs by rapid adsorption at active surface sites, whereas resistive response is dominated by slow diffusion of adsorbates into the film bulk. Resistive response generally increases with film deposition temperature due to increased porosity associated with larger crystalline domains. The 25 nm thick films exhibit higher resistive response than 100 nm thick films after an hour of O2/H2O exposure due to the smaller analyte diffusion length required for reaching the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold, which is consistent with findings of other studies.

Responsive Photonic Crystal Carbohydrate Hydrogel Sensor Materials for Selective and Sensitive Lectin Protein Detection.

PubMed

Cai, Zhongyu; Sasmal, Aniruddha; Liu, Xinyu; Asher, Sanford A

2017-10-27

Lectin proteins, such as the highly toxic lectin protein, ricin, and the immunochemically important lectin, jacalin, play significant roles in many biological functions. It is highly desirable to develop a simple but efficient method to selectively detect lectin proteins. Here we report the development of carbohydrate containing responsive hydrogel sensing materials for the selective detection of lectin proteins. The copolymerization of a vinyl linked carbohydrate monomer with acrylamide and acrylic acid forms a carbohydrate hydrogel that shows specific "multivalent" binding to lectin proteins. The resulting carbohydrate hydrogels are attached to 2-D photonic crystals (PCs) that brightly diffract visible light. This diffraction provides an optical readout that sensitively monitors the hydrogel volume. We utilize lactose, galactose, and mannose containing hydrogels to fabricate a series of 2-D PC sensors that show strong selective binding to the lectin proteins ricin, jacalin, and concanavalin A (Con A). This binding causes a carbohydrate hydrogel shrinkage which significantly shifts the diffraction wavelength. The resulting 2-D PC sensors can selectively detect the lectin proteins ricin, jacalin, and Con A. These unoptimized 2-D PC hydrogel sensors show a limit of detection (LoD) of 7.5 × 10 -8 M for ricin, a LoD of 2.3 × 10 -7 M for jacalin, and a LoD of 3.8 × 10 -8 M for Con A, respectively. This sensor fabrication approach may enable numerous sensors for the selective detection of numerous lectin proteins.

Coagulation mechanism of salt solution-extracted active component in Moringa oleifera seeds.

PubMed

Okuda, T; Baes, A U; Nishijima, W; Okada, M

2001-03-01

This study focuses on the coagulation mechanism by the purified coagulant solution (MOC-SC-PC) with the coagulation active component extracted from M. oleifera seeds using salt solution. The addition of MOC-SC-PC tap water formed insoluble matters. This formation was responsible for kaolin coagulation. On the other hand, insoluble matters were not formed when the MOC-SC-PC was added into distilled water. The formation was affected by Ca2+ or other bivalent cations which may connect each molecule of the active coagulation component in MOC-SC-PC and form a net-like structure. The coagulation mechanism of MOC-SC-PC seemed to be an enmeshment of Kaolin by the insoluble matters with the net-like structure. In case of Ca2+ ion (bivalent cations), at least 0.2 mM was necessary for coagulation at 0.3 mgC l-1 dose of MOC-SC-PC. Other coagulation mechanisms like compression of double layer, interparticle bridging or charge neutralization were not responsible for the coagulation by MOC-SC-PC.

Behavior of temperature-dependent dc-photoconductivity in hot-wall deposited CaAl2Se4 layers

NASA Astrophysics Data System (ADS)

Jeong, J. W.; Hong, K. J.; Jeong, T. S.; Youn, C. J.

2017-10-01

The dc-photoconductive characteristic on the hot-wall grown CaAl2Se4 (CAS) layers was explored as a function of temperature. From the photocurrent (PC) measurement, three PC peaks A, B, and C corresponded to the intrinsic transitions, which represent the band-to-band transitions from the valence-band states of Γ2(A), Γ3 + Γ4(B), and Γ3 + Γ4(C) to the conduction-band state of Γ1, respectively. Based on these PC results, the optical band-gap energy was well matched by E g ( T) = E g (0) - 4.94 × 10-3 T 2/( T + 552), where E g (0) is found to be 3.8239, 3.8716, and 3.8801 eV for three peaks A, B, and C, respectively. Thus, the effect of the crystal field and spin-orbit splitting (These values were extracted out to be 47.7 and 8.5 meV, respectively.) was observed and calculated by means of the PC spectroscopy. However, PC intensity gradually decreased with decreasing temperature unlike an ordinary behavior. In the log J ph vs 1/ T plot, two dominant traplevels were observed to be 20.81 meV at temperatures of 300 - 70 K and 1.18 meV at temperatures below 70 K. Consequently, we extract out that these trapping centers caused by native defects in CAS confine the PC intensity as temperature decreases.

Interplay between crystal and magnetic structures in YFe{sub 2}(H{sub α}D{sub 1−α}){sub 4.2} compounds studied by neutron diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paul-Boncour, V., E-mail: paulbon@icmpe.cnrs.fr; Guillot, M.; Isnard, O.

We report a detailed magnetic structure investigation of YFe{sub 2}(H{sub α}D{sub 1−α}){sub 4.2} (α=0, 0.64, 1) compounds presenting a strong (H,D) isotope effect by neutron diffraction and Mössbauer spectroscopy analysis. They crystallize in the same monoclinic structure (Pc space group) with 8 inequivalent Fe sites having different H(D) environment. At low temperature, the compounds are ferromagnetic (FM) and show an easy magnetization axis perpendicular to the b axis and only slightly tilted away from the c axis. Upon heating, they display a first order transition from a ferromagnetic towards an antiferromagnetic (AFM) structure at T{sub M0} which is sensitive tomore » the H/D isotope nature. The AFM cell is described by doubling the crystal cell along the monoclinic b axis. It presents an unusual coexistence of non magnetic Fe layer sandwiched by two thicker ferromagnetic Fe layers which are antiparallel to each other. This FM-AFM transition is driven by the loss of ordered moment on one Fe site (Fe7) through an itinerant electron metamagnetic (IEM) behaviour. The key role of the Fe7 position is assigned to both its hydrogen rich atomic environment and its geometric position. Above T{sub M0} a field induced metamagnetic transition is observed from the AFM towards the FM structure accompanied by a cell volume increase. Both thermal and magnetic field dependence of the magnetic structure are found strongly related to the anisotropic cell distortion induced by (H,D) order in interstitial sites. - Graphical abstract: Representation of the FM-AFM magnetic structures of YFe{sub 2}D{sub 4.2} deuteride. - Highlights: • YFe{sub 2}(H,D){sub 4.2} compounds undergoes a isotope sensitive FM-AFM transition at T{sub M0}. • The FM structure is formed of Fe moments perpendicular to the monoclinic b axis. • AFM structure is formed by antiparallel Fe layers separated by non-magnetic Fe layer. • One Fe site among eight loses its moment at T{sub M0} due to larger Fe–H bonding. • Magnetic properties are driven by the monoclinic distortion induced by D order.« less

X-ray crystal structure and properties of Phanta, a weakly fluorescent photochromic GFP-like protein

DOE PAGES

Paul, Craig Don; Traore, Daouda A. K.; Olsen, Seth; ...

2015-04-29

Phanta is a reversibly photoswitching chromoprotein (Φ F, 0.003), useful for pcFRET, that was isolated from a mutagenesis screen of the bright green fluorescent eCGP123 (Φ F, 0.8). We have investigated the contribution of substitutions at positions His193, Thr69 and Gln62, individually and in combination, to the optical properties of Phanta. Single amino acid substitutions at position 193 resulted in proteins with very low Φ F, indicating the importance of this position in controlling the fluorescence efficiency of the variant proteins. The substitution Thr69Val in Phanta was important for supressing the formation of a protonated chromophore species observed in somemore » His193 substituted variants, whereas the substitution Gln62Met did not significantly contribute to the useful optical properties of Phanta. X-ray crystal structures for Phanta (2.3 Å), eCGP123 T69V (2.0 Å) and eCGP123 H193Q (2.2 Å) in their non-photoswitched state were determined, revealing the presence of a cis-coplanar chromophore. We conclude that changes in the hydrogen-bonding network supporting the cis-chromophore, and its contacts with the surrounding protein matrix, are responsible for the low fluorescence emission of eCGP123 variants containing a His193 substitution.« less

Controlled transition dipole alignment of energy donor and energy acceptor molecules in doped organic crystals, and the effect on intermolecular Förster energy transfer.

PubMed

Wang, Huan; Yue, Bailing; Xie, Zengqi; Gao, Bingrong; Xu, Yuanxiang; Liu, Linlin; Sun, Hongbo; Ma, Yuguang

2013-03-14

The orientation factor κ(2) ranging from 0 to 4, which depends on the relative orientation of the transition dipoles of the energy donor (D) and the energy acceptor (A) in space, is one of the pivotal factors deciding the efficiency and directionality of resonance energy transfer (RET) in a D-A molecular system. In this work, tetracene (Tc) and pentacene (Pc) are successfully doped in a trans-1,4-distyrylbenzene (DSB) crystalline lattice to form definite D-A mutually perpendicular transition dipole orientations. The cross D-A dipole arrangement results in an extremely small orientation factor, which is about two orders smaller than that in the disordered films. The energy transfer properties from the host (DSB) to the guest (Tc/Pc) were investigated in detail by steady-state as well as time-resolved fluorescence spectroscopy. Our experimental research results show that the small value of κ(2) allows less or partial energy transfer from the host (DSB) to the guest (Tc) in a wide range of guest concentration, with the Förster distance of around 1.5 nm. By controlling the doping concentrations in the Tc and Pc doubly doped DSB crystals, we demonstrate, as an example, for the first time the application of the restricted energy transfer by D-A cross transition dipole arrangement for preparation of a large-size, white-emissive organic crystal with the CIE coordinates of (0.36, 0.37) approaching an ideal white light. In contrast, Tc is also doped in an anthracene crystalline lattice to form head-to-tail D-A transition dipole alignment, which is proved to be highly effective to promote the intermolecular energy transfer. In this doped system, the orientation factor is relatively large and the Förster distance is around 7 nm.

Raw material variability of an active pharmaceutical ingredient and its relevance for processability in secondary continuous pharmaceutical manufacturing.

PubMed

Stauffer, F; Vanhoorne, V; Pilcer, G; Chavez, P-F; Rome, S; Schubert, M A; Aerts, L; De Beer, T

2018-06-01

Active Pharmaceutical Ingredients (API) raw material variability is not always thoroughly considered during pharmaceutical process development, mainly due to low quantities of drug substance available. However, synthesis, crystallization routes and production sites evolve during product development and product life cycle leading to changes in physical material attributes which can potentially affect their processability. Recent literature highlights the need for a global approach to understand the link between material synthesis, material variability, process and product quality. The study described in this article aims at explaining the raw material variability of an API using extensive material characterization on a restricted number of representative batches using multivariate data analysis. It is part of a larger investigation trying to link the API drug substance manufacturing process, the resulting physical API raw material attributes and the drug product continuous manufacturing process. Eight API batches produced using different synthetic routes, crystallization, drying, delumping processes and processing equipment were characterized, extensively. Seventeen properties from seven characterization techniques were retained for further analysis using Principal Component Analysis (PCA). Three principal components (PCs) were sufficient to explain 92.9% of the API raw material variability. The first PC was related to crystal length, agglomerate size and fraction, flowability and electrostatic charging. The second PC was driven by the span of the particle size distribution and the agglomerates strength. The third PC was related to surface energy. Additionally, the PCA allowed to summarize the API batch-to-batch variability in only three PCs which can be used in future drug product development studies to quantitatively evaluate the impact of the API raw material variability upon the drug product process. The approach described in this article could be applied to any other compound which is prone to batch-to-batch variability. Copyright © 2018 Elsevier B.V. All rights reserved.

Establishment of a dog primary prostate cancer organoid using the urine cancer stem cells.

PubMed

Usui, Tatsuya; Sakurai, Masashi; Nishikawa, Shimpei; Umata, Koji; Nemoto, Yuki; Haraguchi, Tomoya; Itamoto, Kazuhito; Mizuno, Takuya; Noguchi, Shunsuke; Mori, Takashi; Iwai, Satomi; Nakagawa, Takayuki; Yamawaki, Hideyuki; Ohama, Takashi; Sato, Koichi

2017-12-01

Dog spontaneously develop prostate cancer (PC) like humans. Because most dogs with PC have a poor prognosis, they could be used as a translational model for advanced PC in humans. Stem cell-derived 3-D organoid culture could recapitulate organ structures and physiology. Using patient tissues, a human PC organoid culture system was established. Recent study has shown that urine cells also possess the characteristic of stem cells. However, urine cell-derived PC organoids have never been produced. Therefore, we generated PC organoids using the dog urine samples. Urine organoids were successfully generated from each dog with PC. Each organoid showed cystic structures and resembled the epithelial structures of original tissues. Expression of an epithelial cell marker, E-cadherin, and a myofibloblast marker, α-SMA, was observed in the urine organoids. The organoids also expressed a basal cell marker, CK5, and a luminal cell marker, CK8. CD49f-sorted basal cell organoids rapidly grew compared with CD24-sorted luminal cell organoids. The population of CD44-positive cells was the highest in both organoids and the original urine cells. Tumors were successfully formed with the injection of the organoids into immunodeficient mice. Treatment with a microtubule inhibitor, docetaxel, but not a cyclooxygenase inhibitor, piroxicam, and an mTOR inhibitor, rapamycin, decreased the cell viability of organoids. Treatment with a Hedgehog signal inhibitor, GANT61, increased the radiosensitivity in the organoids. These findings revealed that PC organoids using urine might become a useful tool for investigating the mechanisms of the pathogenesis and treatment of PC in dogs. © 2017 The Authors. Cancer Science published by John Wiley & Sons Australia, Ltd on behalf of Japanese Cancer Association.

Effect of Ultrasonic Extraction on Production and Structural Changes of C-Phycocyanin from Marine Spirulina maxima.

PubMed

Choi, Woon Yong; Lee, Hyeon Yong

2018-01-11

This work first showed that very high amounts of phycocyanins, such as 11.3 mg/mL C-phycocyanin (C-PC), 3.1 mg/mL allophycocyanin (APC), and 0.8 mg/mL phycoerythrin (PE), can be obtained using an ultrasonic extraction process (UE) with a 60 kHz frequency and 3 h of process time at 25 °C, without any other pretreatments. These yields were higher than those from most conventional water extractions at 4 °C for 24 h (Control condition) or at 25 °C for 24 h (WE), namely, 9.8 and 5.7 mg/mL C-PC, 2.3 and 1.2 mg/mL APC, and 0.7 and 0.3 mg/mL PE, respectively. These yields were also shown to be even higher than yields from other reported data. Structural changes in C-PC in the extracts were also found for the first time, according to extraction conditions, showing that the total concentration of C-PC and of the α-subunit of C-PC in the UE were much higher than in the WE, with little difference in the amount of β-subunit of C-PC in the UE or WE. It was also shown that the structural changes in C-PC in the WE decreased both antioxidant and anti-inflammation activities-29.83% vs. 32.09% of α,α-diphenyl-β-picrylhydrazyl (DPPH) scavenging activity and 8.21 vs. 7.25 µM of NO production for the WE and UE, respectively-while the UE, with similar patterns to standard C-PC, showed very high biological effects, which may suggest that the biologically active part is the α-subunit of C-PC, not the β-subunit.

Effect of Ultrasonic Extraction on Production and Structural Changes of C-Phycocyanin from Marine Spirulina maxima

PubMed Central

Choi, Woon Yong; Lee, Hyeon Yong

2018-01-01

This work first showed that very high amounts of phycocyanins, such as 11.3 mg/mL C-phycocyanin (C-PC), 3.1 mg/mL allophycocyanin (APC), and 0.8 mg/mL phycoerythrin (PE), can be obtained using an ultrasonic extraction process (UE) with a 60 kHz frequency and 3 h of process time at 25 °C, without any other pretreatments. These yields were higher than those from most conventional water extractions at 4 °C for 24 h (Control condition) or at 25 °C for 24 h (WE), namely, 9.8 and 5.7 mg/mL C-PC, 2.3 and 1.2 mg/mL APC, and 0.7 and 0.3 mg/mL PE, respectively. These yields were also shown to be even higher than yields from other reported data. Structural changes in C-PC in the extracts were also found for the first time, according to extraction conditions, showing that the total concentration of C-PC and of the α-subunit of C-PC in the UE were much higher than in the WE, with little difference in the amount of β-subunit of C-PC in the UE or WE. It was also shown that the structural changes in C-PC in the WE decreased both antioxidant and anti-inflammation activities—29.83% vs. 32.09% of α,α-diphenyl-β-picrylhydrazyl (DPPH) scavenging activity and 8.21 vs. 7.25 µM of NO production for the WE and UE, respectively—while the UE, with similar patterns to standard C-PC, showed very high biological effects, which may suggest that the biologically active part is the α-subunit of C-PC, not the β-subunit. PMID:29324668

Synthetic and structural investigations of mercurous and mercuric organophosphonates and phenylarsonates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Padalwar, Nitin Balkrushna; Vidyasagar, Kanamaluru

2016-11-15

The following twelve mercurous and mercuric organophosphomates, bis/diphosphonates and phenylarsonates have been isolated and structurally characterized by single crystal X-ray diffraction, {sup 13}C-and {sup 31}P NMR, infrared and Raman spectroscopic methods: Hg{sub 2}(HO{sub 3}PC{sub 6}H{sub 5}){sub 2}(1), Hg{sub 2}(HO{sub 3}P(C{sub 6}H{sub 4})PO{sub 3}H)(2), Hg{sub 2}(HO{sub 3}P(C{sub 6}H{sub 4}){sub 2}PO{sub 3}H)(3), Hg{sub 2}(HO{sub 3}P(CH{sub 2}){sub 4}PO{sub 3}H)(4), Hg{sub 2}(O{sub 3}PC{sub 6}H{sub 5})·H{sub 2}O(5), (Hg{sub 2}){sub 2}(O{sub 3}P(CH{sub 2}){sub 2}PO{sub 3})(6), (Hg{sub 2}){sub 2}(O{sub 3}P(CH{sub 2}){sub 3}PO{sub 3})(7), Hg(O{sub 3}PC{sub 6}H{sub 5})·H{sub 2}O(8), Hg(O{sub 3}PCH{sub 2}C{sub 6}H{sub 5})·H{sub 2}O(9), Hg(O{sub 3}AsC{sub 6}H{sub 5})·H{sub 2}O(10), Hg{sub 3}(O{sub 3}AsC{sub 6}H{sub 5}){sub 2}(HO{sub 3}AsC{sub 6}H{submore » 5}){sub 2}(11) and (Hg{sub 2})Hg{sub 3}(O{sub 3}P(C{sub 6}H{sub 4})PO{sub 3}){sub 2}·2H{sub 2}O(12). Compounds 1–7 are the first examples of mercurous phosphonates and di/bisphosphonates. They contain Hg{sub 2}O{sub 6} units, which consist of Hg{sub 2}{sup 2+} cations with Hg-Hg bond of ~2.5 Å length. Phenylphosphonates 1 and 5 are layered compounds, whereas bis/diphosphonates 2, 3, 4, 6 and 7 have pillared-layered and three-dimensional structures. Compounds 8–11 are layered mercuric phosphonates and phenylarsonates. Compound 12 is a three-dimensional mixed-valent mercury phenylenebisphosphonate. - Graphical abstract: The first examples of mercurous organophosphonates and organodiphosphonates have layered, pillared-layered and three-dimensional structures.« less

Competition between Anion Binding and Dimerization Modulates Staphylococcus aureus Phosphatidylinositol-specific Phospholipase C Enzymatic Activity*

PubMed Central

Cheng, Jiongjia; Goldstein, Rebecca; Stec, Boguslaw; Gershenson, Anne; Roberts, Mary F.

2012-01-01

Staphylococcus aureus phosphatidylinositol-specific phospholipase C (PI-PLC) is a secreted virulence factor for this pathogenic bacterium. A novel crystal structure shows that this PI-PLC can form a dimer via helix B, a structural feature present in all secreted, bacterial PI-PLCs that is important for membrane binding. Despite the small size of this interface, it is critical for optimal enzyme activity. Kinetic evidence, increased enzyme specific activity with increasing enzyme concentration, supports a mechanism where the PI-PLC dimerization is enhanced in membranes containing phosphatidylcholine (PC). Mutagenesis of key residues confirm that the zwitterionic phospholipid acts not by specific binding to the protein, but rather by reducing anionic lipid interactions with a cationic pocket on the surface of the S. aureus enzyme that stabilizes monomeric protein. Despite its structural and sequence similarity to PI-PLCs from other Gram-positive pathogenic bacteria, S. aureus PI-PLC appears to have a unique mechanism where enzyme activity is modulated by competition between binding of soluble anions or anionic lipids to the cationic sensor and transient dimerization on the membrane. PMID:23038258

Magnetic properties of Co2Fe(Ga1-xSix) alloys

NASA Astrophysics Data System (ADS)

Deka, Bhargab; Chakraborty, Dibyashree; Srinivasan, Ananthakrishnan

2014-09-01

Magnetic and crystallographic properties of bulk Co2Fe(Ga1-xSix) alloys with 0≤x≤1 are reported in this work. The alloys with x=0.75 and 1.00 exhibit L21 structure whereas the alloys with x=0, 0.25 and 0.50 crystallized in the disordered A2 phase. Unit cell volume of this series of alloys decreased from 189.1 to 178.5 Å3 as x was increased from 0 to 1.00. All alloy compositions exhibit ferromagnetic behavior with a high Curie temperature (TC) which showed a systematic variation with x (1089 K, 1075 K, 1059 K, 1019 K and 1015 K for x=0, 0.25, 0.5, 0.75 and 1.00, respectively). The saturation magnetization moment Ms for the alloys with x=0, 0.25 and 0.50 are 5.05μB, 5.23μB, 5.49μB, respectively, in accordance with the Slater-Pauling rule, but alloys with x=0.75 and 1.00 deviated from this rule. The effective moment per magnetic atom (pc) of the alloys was estimated from the inverse DC magnetic susceptibility data above TC. A comparison of Ms with pc reveals the half-metallic character of the alloys.

Printable and Rewritable Full Block Copolymer Structural Color.

PubMed

Kang, Han Sol; Lee, Jinseong; Cho, Suk Man; Park, Tae Hyun; Kim, Min Ju; Park, Chanho; Lee, Seung Won; Kim, Kang Lib; Ryu, Du Yeol; Huh, June; Thomas, Edwin L; Park, Cheolmin

2017-08-01

Structural colors (SCs) of photonic crystals (PCs) arise from selective constructive interference of incident light. Here, an ink-jet printable and rewritable block copolymer (BCP) SC display is demonstrated, which can be quickly written and erased over 50 times with resolution nearly equivalent to that obtained with a commercial office ink-jet printer. Moreover, the writing process employs an easily modified printer for position- and concentration-controlled deposition of a single, colorless, water-based ink containing a reversible crosslinking agent, ammonium persulfate. Deposition of the ink onto a self-assembled BCP PC film comprising a 1D stack of alternating layers enables differential swelling of the written BCP film and produces a full-colored SC display of characters and images. Furthermore, the information can be readily erased and the system can be reset by application of hydrogen bromide. Subsequently, new information can be rewritten, resulting in a chemically rewritable BCP SC display. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge transfer complexes of metal-free phthalocyanine radical anions with decamethylmetallocenium cations: (Cp*2Co+)(H2Pc˙-)·solvent and (Cp*2Cr+)(H2Pc˙-)·4C6H4Cl2.

PubMed

Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

2017-03-14

Charge transfer complexes (Cp* 2 Co + )(H 2 Pc˙ - )·0.5C 6 H 4 Cl 2 ·0.7C 6 H 5 CN·0.3C 6 H 14 (1) and (Cp* 2 Cr + )(H 2 Pc˙ - )·4C 6 H 4 Cl 2 (2) have been obtained as single crystals. Both complexes contain metal-free phthalocyanine (Pc) radical anions and decamethylmetallocenium cations. Reduction of the Pc macrocycle leads to the appearance of new bands at 1026-1030 nm in the NIR range and blue shifts of both Soret and Q-bands of H 2 Pc in the spectra of 1 and 2. The geometry of the Pc macrocycles supports the formation of H 2 Pc˙ - by the alternation of shorter and longer C-N(imine) bonds in the macrocycles in 2. Complex 1 contains pairs of H 2 Pc˙ - having effective π-π interactions with two sandwiched Cp* 2 Co + cations, whereas complex 2 contains stacks composed of alternating Cp* 2 Cr + and H 2 Pc˙ - ions. The magnetic moment of 1 is 1.64 μ B at 300 K due to the contribution of the H 2 Pc˙ - spins with the S = 1/2 state and diamagnetism of Cp* 2 Co + . This is supported by the observation of a narrow EPR signal of 1 with g = 2.0032-2.0036 characteristic of H 2 Pc˙ - . Strong antiferromagnetic coupling of spins with a Weiss temperature of -23 K is observed between H 2 Pc˙ - in 1. This coupling is probably mediated by the Cp* 2 Co + cations. The magnetic moment of 2 is 4.18 μ B at 300 K indicating the contribution of both paramagnetic H 2 Pc˙ - (S = 1/2) and Cp* 2 Cr + (S = 3/2) species. In spite of the presence of stacks of alternating ions in 2, only weak magnetic coupling is observed with a Weiss temperature of -4 K most probably due to ineffective π-π interactions between Cp* 2 Cr + and H 2 Pc˙ - . The EPR spectrum of 2 contains an asymmetric signal attributed to Cr III (g 1 = 3.9059-3.9220) and a narrow Lorentzian signal from H 2 Pc˙ - with g 2 = 1.9943-1.9961. In addition to these signals, a broad EPR signal grows in intensity below 80 K with g 4 = 2.1085-2.2438 which can be attributed to both paramagnetic Cp* 2 Cr + and H 2 Pc˙ - species having exchange interactions.

Glycoform-independent prion conversion by highly efficient, cell-based, protein misfolding cyclic amplification

PubMed Central

Moudjou, Mohammed; Chapuis, Jérôme; Mekrouti, Mériem; Reine, Fabienne; Herzog, Laetitia; Sibille, Pierre; Laude, Hubert; Vilette, Didier; Andréoletti, Olivier; Rezaei, Human; Dron, Michel; Béringue, Vincent

2016-01-01

Prions are formed of misfolded assemblies (PrPSc) of the variably N-glycosylated cellular prion protein (PrPC). In infected species, prions replicate by seeding the conversion and polymerization of host PrPC. Distinct prion strains can be recognized, exhibiting defined PrPSc biochemical properties such as the glycotype and specific biological traits. While strain information is encoded within the conformation of PrPSc assemblies, the storage of the structural information and the molecular requirements for self-perpetuation remain uncertain. Here, we investigated the specific role of PrPC glycosylation status. First, we developed an efficient protein misfolding cyclic amplification method using cells expressing the PrPC species of interest as substrate. Applying the technique to PrPC glycosylation mutants expressing cells revealed that neither PrPC nor PrPSc glycoform stoichiometry was instrumental to PrPSc formation and strainness perpetuation. Our study supports the view that strain properties, including PrPSc glycotype are enciphered within PrPSc structural backbone, not in the attached glycans. PMID:27384922

Scanning tunneling microscopy investigation of copper phthalocyanine and truxenone derivative binary superstructures on graphite.

PubMed

Liu, Jia; Wang, Dong; Wang, Jie-Yu; Pei, Jian; Wan, Li-Jun

2011-02-01

The binary self-assembly of copper phthalocyanine (CuPc) and 2,3,7,8,12,13-hexahexyloxy-truxenone (TrO23) at the solid/liquid interface of highly oriented pyrolytic graphite (HOPG) was investigated by using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Pseduohexagonal and linear patterned superstructures of CuPc are obtained by co-adsorbing with TrO23. High-resolution STM images reveal the structural details of the arrangement of TrO23 and CuPc in the binary assembly structures. The molecular ratio between CuPc and TrO23 in the adlayer can be modulated by the CuPc concentration in liquid phase. The electronic properties of CuPc and TrO23 in the co-adsorbed self-assembly are investigated by STS. The results presented here are helpful to the design and fabrication of multi-component functional molecular nanostructures. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modification of symmetrically substituted phthalocyanines using click chemistry: phthalocyanine nanostructures by nanoimprint lithography.

PubMed

Chen, Xiaochun; Thomas, Jayan; Gangopadhyay, Palash; Norwood, Robert A; Peyghambarian, N; McGrath, Dominic V

2009-09-30

Phthalocyanines (Pcs) are commonly applied to advanced technologies such as optical limiting, photodynamic therapy (PDT), organic field-effect transistors (OFETs), and organic photovoltaic (OPV) devices, where they are used as the p-type layer. An approach to Pc structural diversity and the incorporation of a functional group that allows fabrication of solvent resistant Pc nanostructures formed by using a newly developed nanoimprint by melt processing (NIMP) technique, a variant of standard nanoimprint lithography (NIL), is reported. Copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC), a click chemistry reaction, serves as an approach to structural diversity in Pc macrocycles. We have prepared octaalkynyl Pc 1b and have modified this Pc using the CuAAC reaction to yield four Pc derivatives 5a-5d with different peripheral substituents on the macrocycle. One of these derivatives, 5c, has photo-cross-linkable cinnamate residues, and we have demonstrated the fabrication of robust cross-linked photopatterned and imprinted nanostructures from this material.

Modelling copper-phthalocyanine/cobalt-phthalocyanine chains: towards magnetic quantum metamaterials.

PubMed

Wu, Wei

2014-07-23

The magnetic properties of a theoretically designed molecular chain structure CuCoPc2, in which copper-phthalocyanine (CuPc) and cobalt-phthalocyanine (CoPc) alternate, have been investigated across a range of chain structures. The computed exchange interaction for the α-phase CuCoPc2 is ∼ 5 K (ferromagnetic), in strong contrast to the anti-ferromagnetic interaction recently observed in CuPc and CoPc. The computed exchange interactions are strongly dependent on the stacking angle but weakly on the sliding angle, and peak at 20 K (ferromagnetic). These ferromagnetic interactions are expected to arise from direct exchange with the strong suppression of super-exchange interaction. These first-principles calculations show that π-conjugated molecules, such as phthalocyanine, could be used as building blocks for the design of magnetic materials. This therefore extends the concept of quantum metamaterials further into magnetism. The resulting new magnetic materials could find applications in the studies such as organic spintronics.

Spatially selective photonic crystal enhanced fluorescence and application to background reduction for biomolecule detection assays

PubMed Central

Chaudhery, Vikram; Huang, Cheng-Sheng; Pokhriyal, Anusha; Polans, James; Cunningham, Brian T.

2011-01-01

By combining photonic crystal label-free biosensor imaging with photonic crystal enhanced fluorescence, it is possible to selectively enhance the fluorescence emission from regions of the PC surface based upon the density of immobilized capture molecules. A label-free image of the capture molecules enables determination of optimal coupling conditions of the laser used for fluorescence imaging of the photonic crystal surface on a pixel-by-pixel basis, allowing maximization of fluorescence enhancement factor from regions incorporating a biomolecule capture spot and minimization of background autofluorescence from areas between capture spots. This capability significantly improves the contrast of enhanced fluorescent images, and when applied to an antibody protein microarray, provides a substantial advantage over conventional fluorescence microscopy. Using the new approach, we demonstrate detection limits as low as 0.97 pg/ml for a representative protein biomarker in buffer. PMID:22109210

Spatially selective photonic crystal enhanced fluorescence and application to background reduction for biomolecule detection assays.

PubMed

Chaudhery, Vikram; Huang, Cheng-Sheng; Pokhriyal, Anusha; Polans, James; Cunningham, Brian T

2011-11-07

By combining photonic crystal label-free biosensor imaging with photonic crystal enhanced fluorescence, it is possible to selectively enhance the fluorescence emission from regions of the PC surface based upon the density of immobilized capture molecules. A label-free image of the capture molecules enables determination of optimal coupling conditions of the laser used for fluorescence imaging of the photonic crystal surface on a pixel-by-pixel basis, allowing maximization of fluorescence enhancement factor from regions incorporating a biomolecule capture spot and minimization of background autofluorescence from areas between capture spots. This capability significantly improves the contrast of enhanced fluorescent images, and when applied to an antibody protein microarray, provides a substantial advantage over conventional fluorescence microscopy. Using the new approach, we demonstrate detection limits as low as 0.97 pg/ml for a representative protein biomarker in buffer.

Robust inference of population structure for ancestry prediction and correction of stratification in the presence of relatedness.

PubMed

Conomos, Matthew P; Miller, Michael B; Thornton, Timothy A

2015-05-01

Population structure inference with genetic data has been motivated by a variety of applications in population genetics and genetic association studies. Several approaches have been proposed for the identification of genetic ancestry differences in samples where study participants are assumed to be unrelated, including principal components analysis (PCA), multidimensional scaling (MDS), and model-based methods for proportional ancestry estimation. Many genetic studies, however, include individuals with some degree of relatedness, and existing methods for inferring genetic ancestry fail in related samples. We present a method, PC-AiR, for robust population structure inference in the presence of known or cryptic relatedness. PC-AiR utilizes genome-screen data and an efficient algorithm to identify a diverse subset of unrelated individuals that is representative of all ancestries in the sample. The PC-AiR method directly performs PCA on the identified ancestry representative subset and then predicts components of variation for all remaining individuals based on genetic similarities. In simulation studies and in applications to real data from Phase III of the HapMap Project, we demonstrate that PC-AiR provides a substantial improvement over existing approaches for population structure inference in related samples. We also demonstrate significant efficiency gains, where a single axis of variation from PC-AiR provides better prediction of ancestry in a variety of structure settings than using 10 (or more) components of variation from widely used PCA and MDS approaches. Finally, we illustrate that PC-AiR can provide improved population stratification correction over existing methods in genetic association studies with population structure and relatedness. © 2015 WILEY PERIODICALS, INC.

Laser-Induced Periodic Surface Structures on P3HT and on Its Photovoltaic Blend with PC71BM.

PubMed

Cui, Jing; Rodríguez-Rodríguez, Álvaro; Hernández, Margarita; García-Gutiérrez, Mari-Cruz; Nogales, Aurora; Castillejo, Marta; Moseguí González, Daniel; Müller-Buschbaum, Peter; Ezquerra, Tiberio A; Rebollar, Esther

2016-11-23

We describe the conditions for optimal formation of laser-induced periodic surface structures (LIPSS) over poly(3-hexylthiophene) (P3HT) spin-coated films. Optimal LIPSS on P3HT are observed within a particular range of thicknesses and laser fluences. These conditions can be translated to the photovoltaic blend formed by the 1:1 mixture of P3HT and [6,6]-phenyl C 71 -butyric acid methyl ester (PC 71 BM) when deposited on an indium tin oxide (ITO) electrode coated with (poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS). Solar cells formed by using either a bilayer of P3HT structured by LIPSS covered by PC 71 BM or a bulk heterojunction with a P3HT:PC 71 BM blend structured by LIPSS exhibit generation of electrical photocurrent under light illumination. These results suggest that LIPSS could be a compatible technology with organic photovoltaic devices.

Comparative characterisation of the biofilm-production abilities of Staphylococcus epidermidis isolated from human skin and platelet concentrates.

PubMed

Taha, Mariam; Kohnen, Carissa; Mallya, Shruti; Kou, Yuntong; Zapata, Adriana; Ramirez-Arcos, Sandra

2018-02-01

Staphylococcus epidermidis is the predominant contaminant of platelet concentrates (PCs), a blood product used to treat patients with platelet deficiencies. This microorganism is able to form surface-attached aggregates (biofilms) in human skin. Herein, the abundance of S. epidermidis biofilm-producers in contaminated PCs compared to skin isolates was explored. Furthermore, the potential positive selection of S. epidermidis biofilm-producers during the blood donation process and PC manufacturing was investigated. Twenty-four S. epidermidis isolates obtained from contaminated PCs and 48 S. epidermidis isolates obtained from the venipuncture area of human volunteers were compared for their ability to form biofilms in laboratory media and in PCs using a semi quantitative crystal violet assay. Also, the presence of the biofilm-associated icaA and icaD genes was assessed by PCR-amplification.Results/Key findings.Biofilm production in laboratory media showed a higher number of S. epidermidis biofilm-producers in the skin-derived group (43.7 %) compared to the PC-derived isolates (25 %). However, all skin and PC isolates formed biofilms in PCs. The prevalence of ica-positive biofilm-producer isolates was similar in PC and skin isolates (16.6 and 18.8 %, respectively). In contrast, the abundance of ica-negative biofilm-producers was lower in PC isolates compared to skin isolates (8.3 vs 25 %, respectively). Positive selection of S. epidermidis biofilm-producers during blood donation and PC manufacturing was not observed. Interestingly, ica-negative biofilm-producers seem to be negatively affected by skin disinfection, blood processing and PC storage. Furthermore, this study shows that S. epidermidis adopts a biofilm-forming phenotype in PCs regardless of its genetic background or origin.

Cost Savings from Palliative Care Teams and Guidance for a Financially Viable Palliative Care Program

PubMed Central

McCarthy, Ian M; Robinson, Chessie; Huq, Sakib; Philastre, Martha; Fine, Robert L

2015-01-01

Objectives To quantify the cost savings of palliative care (PC) and identify differences in savings according to team structure, patient diagnosis, and timing of consult. Data Sources Hospital administrative records on all inpatient stays at five hospital campuses from January 2009 through June 2012. Study Design The analysis matched PC patients to non-PC patients (separately by discharge status) using propensity score methods. Weighted generalized linear model regressions of hospital costs were estimated for the matched groups. Data Collection Data were restricted to patients at least 18 years old with inpatient stays of between 7 and 30 days. Variables available included patient demographics, primary and secondary diagnoses, hospital costs incurred for the inpatient stay, and when/if the patient had a PC consult. Principal Findings We found overall cost savings from PC of $3,426 per patient for those dying in the hospital. No significant cost savings were found for patients discharged alive; however, significant cost savings for patients discharged alive could be achieved for certain diagnoses, PC team structures, or if consults occurred within 10 days of admission. Conclusions Appropriately selected and timed PC consults with physician and RN involvement can help ensure a financially viable PC program via cost savings to the hospital. PMID:25040226

Osteopontin splice variants expression is involved on docetaxel resistance in PC3 prostate cancer cells.

PubMed

Nakamura, K D M; Tilli, T M; Wanderley, J L; Palumbo, A; Mattos, R M; Ferreira, A C; Klumb, C E; Nasciutti, L E; Gimba, E R

2016-02-01

Osteopontin (OPN) is a phosphoprotein that activates several aspects of tumor progression. Alternative splicing of the OPN primary transcript generates three splicing isoforms, OPNa, OPNb and OPNc. In this report, we investigated some cellular mechanisms by which OPN splice variants could mediate PC3 prostate cancer (PCa) cell survival and growth in response to docetaxel (DXT)-induced cell death. Cell survival before and after DXT treatment was analyzed by phase-contrast microscopy and crystal-violet staining assays. Quantitative real-time PCR and immunocytochemical staining assays were used to evaluate the putative involvement of epithelial-mesenchymal transition (EMT) and OPN isoforms on mediating PC3 cell survival. Upon DXT treatment, PC3 cells overexpressing OPNb or OPNc isoforms showed higher cell densities, compared to cells overexpressing OPNa and controls. Notably, cells overexpressing OPNb or OPNc isoforms showed a downregulated pattern of EMT epithelial cell markers, while mesenchymal markers were mostly upregulated in these experimental conditions. We concluded that OPNc or OPNb overexpression in PC3 cells can mediate resistance and cell survival features in response to DXT-induced cell death. Our data also provide evidence the EMT program could be one of the molecular mechanisms mediating survival in OPNb- or OPNc-overexpressing cells in response to DXT treatment. These data could further contribute to a better understanding of the mechanisms by which PCa cells acquire resistance to DXT treatment.

X-ray structures of the Pseudomonas cichorii D-tagatose 3-epimerase mutant form C66S recognizing deoxy sugars as substrates.

PubMed

Yoshida, Hiromi; Yoshihara, Akihide; Ishii, Tomohiko; Izumori, Ken; Kamitori, Shigehiro

2016-12-01

Pseudomonas cichorii D-tagatose 3-epimerase (PcDTE), which has a broad substrate specificity, efficiently catalyzes the epimerization of not only D-tagatose to D-sorbose but also D-fructose to D-psicose (D-allulose) and also recognizes the deoxy sugars as substrates. In an attempt to elucidate the substrate recognition and catalytic reaction mechanisms of PcDTE for deoxy sugars, the X-ray structures of the PcDTE mutant form with the replacement of Cys66 by Ser (PcDTE_C66S) in complexes with deoxy sugars were determined. These X-ray structures showed that substrate recognition by the enzyme at the 1-, 2-, and 3-positions is responsible for enzymatic activity and that substrate-enzyme interactions at the 4-, 5-, and 6-positions are not essential for the catalytic reaction of the enzyme leading to the broad substrate specificity of PcDTE. They also showed that the epimerization site of 1-deoxy 3-keto D-galactitol is shifted from C3 to C4 and that 1-deoxy sugars may bind to the catalytic site in the inhibitor-binding mode. The hydrophobic groove that acts as an accessible surface for substrate binding is formed through the dimerization of PcDTE. In PcDTE_C66S/deoxy sugar complex structures, bound ligand molecules in both the linear and ring forms were detected in the hydrophobic groove, while bound ligand molecules in the catalytic site were in the linear form. This result suggests that the sugar-ring opening of a substrate may occur in the hydrophobic groove and also that the narrow channel of the passageway to the catalytic site allows a substrate in the linear form to pass through.

78 FR 17865 - Airworthiness Directives; PILATUS AIRCRAFT LTD. Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-25

... TBO were moved from Chapter 5: Time Limits/Maintenance Checks, to Chapter 4: Structural, Component and... Directives; PILATUS AIRCRAFT LTD. Airplanes AGENCY: Federal Aviation Administration (FAA), DOT. ACTION: Final... all PILATUS AIRCRAFT LTD. Models PC-12, PC-12/45, and PC-12/47 airplanes. This AD results from...

QSAR study of anthranilic acid sulfonamides as inhibitors of methionine aminopeptidase-2 using LS-SVM and GRNN based on principal components.

PubMed

Shahlaei, Mohsen; Sabet, Razieh; Ziari, Maryam Bahman; Moeinifard, Behzad; Fassihi, Afshin; Karbakhsh, Reza

2010-10-01

Quantitative relationships between molecular structure and methionine aminopeptidase-2 inhibitory activity of a series of cytotoxic anthranilic acid sulfonamide derivatives were discovered. We have demonstrated the detailed application of two efficient nonlinear methods for evaluation of quantitative structure-activity relationships of the studied compounds. Components produced by principal component analysis as input of developed nonlinear models were used. The performance of the developed models namely PC-GRNN and PC-LS-SVM were tested by several validation methods. The resulted PC-LS-SVM model had a high statistical quality (R(2)=0.91 and R(CV)(2)=0.81) for predicting the cytotoxic activity of the compounds. Comparison between predictability of PC-GRNN and PC-LS-SVM indicates that later method has higher ability to predict the activity of the studied molecules. Copyright (c) 2010 Elsevier Masson SAS. All rights reserved.

Binding Modes of Phthalocyanines to Amyloid β Peptide and Their Effects on Amyloid Fibril Formation.

PubMed

Valiente-Gabioud, Ariel A; Riedel, Dietmar; Outeiro, Tiago F; Menacho-Márquez, Mauricio A; Griesinger, Christian; Fernández, Claudio O

2018-03-13

The inherent tendency of proteins to convert from their native states into amyloid aggregates is associated with a range of human disorders, including Alzheimer's and Parkinson's diseases. In that sense, the use of small molecules as probes for the structural and toxic mechanism related to amyloid aggregation has become an active area of research. Compared with other compounds, the structural and molecular basis behind the inhibitory interaction of phthalocyanine tetrasulfonate (PcTS) with proteins such as αS and tau has been well established, contributing to a better understanding of the amyloid aggregation process in these proteins. We present here the structural characterization of the binding of PcTS and its Cu(II) and Zn(II)-loaded forms to the amyloid β-peptide (Aβ) and the impact of these interactions on the peptide amyloid fibril assembly. Elucidation of the PcTS binding modes to Aβ 40 revealed the involvement of specific aromatic and hydrophobic interactions in the formation of the Aβ 40 -PcTS complex, ascribed to a binding mode in which the planarity and hydrophobicity of the aromatic ring system in the phthalocyanine act as main structural determinants for the interaction. Our results demonstrated that formation of the Aβ 40 -PcTS complex does not interfere with the progression of the peptide toward the formation of amyloid fibrils. On the other hand, conjugation of Zn(II) but not Cu(II) at the center of the PcTS macrocyclic ring modified substantially the binding profile of this phthalocyanine to Aβ 40 and became crucial to reverse the effects of metal-free PcTS on the fibril assembly of the peptide. Overall, our results provide a firm basis to understand the structural rules directing phthalocyanine-protein interactions and their implications on the amyloid fibril assembly of the target proteins; in particular, our results contradict the hypothesis that PcTS might have similar mechanisms of action in slowing the formation of a variety of pathological aggregates. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Enhancing the bioavailability of mebendazole by integrating the principles solid dispersion and nanocrystal techniques, for safe and effective management of human echinococcosis.

PubMed

Chaudhary, Sushant; Garg, Tarun; Rath, Goutam; Murthy, Rs Rayasa; Goyal, Amit K

2016-05-01

The method based on integrating the principles of solid dispersion and nanocrystal techniques was developed to prepare polymer crystals (PCs) of mebendazole (MBZ) and polyethylene glycol (PEG). Powder X-Ray diffraction (PXRD) of the PC crystals shows the required integrated crystalline and amorphous regions. The in vitro solubility studies showed a 32-fold increase in the solubility of the drug. Tests of dissolution of the PCs showed that the crystals have an enhanced dissolution rate in comparison to those in the MF. The results of the pharmacokinetic study showed a 2.12-fold increase in the bioavailability of the drug. Thus, the present study has proved the potential in enhancing solubility, dissolution, and bioavailability of the drug.

Biological evaluation of water soluble arene Ru(II) enantiomers with amino-oxime ligands.

PubMed

de la Cueva-Alique, Isabel; Sierra, Sara; Muñoz-Moreno, Laura; Pérez-Redondo, Adrián; Bajo, Ana M; Marzo, Isabel; Gude, Lourdes; Cuenca, Tomás; Royo, Eva

2018-06-01

New water soluble, enantiopure arene ruthenium compound S Ru S N -(1R,4S)-[(η 6 -p-cymene)Ru{ĸNH(Bn),ĸNOH}Cl]Cl (Bn = benzyl, 1a') has been synthesized. The novel compound along with that previously described R Ru R N -(1S,4R)-[(η 6 -p-cymene)Ru{ĸNH(Bn),ĸNOH}Cl]Cl (1a) was evaluated by polarimetry, ultra-violet and circular dichroism spectroscopy. The structure of novel ruthenium derivative 1a' was determined by single crystal X-ray crystallography. Both enantiomers have been tested against several cancer cell lines in vitro: prostate PC-3, lung A-549, pancreas MIA PaCa-2, colorectal HCT-116, leukemia Jurkat and cervical HeLa. Both enantiomers are active and versatile cytotoxic agents, showing IC 50 values from 2 to 12 times lower than those found for cisplatin in the different cell lines evaluated. The mechanism of cell death induced by the metal compounds was analyzed in A-549 and Jurkat cell lines. Derivatives 1a and 1a' induced apoptotic cell death of A-549 cells while dose-dependent cell death mechanisms have been found in the Jurkat cell line. Compound-DNA interactions have been investigated by equilibrium dialysis, Fluorescence Resonance Energy Transfer (FRET) melting assays and viscometric titrations, revealing moderate binding affinity of 1a and 1a' towards duplex DNA. Finally, the efficacy of 1a in a preliminary in vivo assay of PC-3 xenografts in nude mice has been evaluated, resulting in a promising inhibition of tumor growth by 45%. Analysis of tumor tissue also showed a significant decrease of levels of crucial molecules in the invasive phenotype of PC-3 cells. Copyright © 2018 Elsevier Inc. All rights reserved.

Surface Polarity and Self-Structured Nanogrooves Collaboratively Oriented Molecular Packing for High Crystallinity toward Efficient Charge Transport.

PubMed

Ji, Deyang; Xu, Xiaomin; Jiang, Longfeng; Amirjalayer, Saeed; Jiang, Lang; Zhen, Yonggang; Zou, Ye; Yao, Yifan; Dong, Huanli; Yu, Junsheng; Fuchs, Harald; Hu, Wenping

2017-02-22

Efficient charge transport in organic semiconductors is essential for construction of high performance optoelectronic devices. Herein, for the first time, we demonstrate that poly(amic acid) (PAA), a facilely deposited and annealing-free dielectric layer, can tailor the growth of organic semiconductor films with large area and high crystallinity toward efficient charge transport and high mobility in their thin film transistors. Pentacene is used as a model system to demonstrate the concept with mobility up to 30.6 cm 2 V -1 s -1 , comparable to its high quality single crystal devices. The structure of PAA has corrugations with OH groups pointing out of the surface, and the presence of an amide bond further allows adjacent polymer strands to interact via hydrogen bonding, leading to a self-rippled surface perpendicular to the corrugation. On the other hand, the strong polar groups (-COOH/-CONH) of PAA could provide repulsive forces between PAA and pentacene, which results in the vertical orientation of pentacene on the dielectric surface. Indeed, in comparison with its imidized counterpart polyimide (PI), PAA dielectric significantly enhances the film crystallinity, drastically increases the domain size, and decreases the interface trap density, giving rise to superior device performance with high mobility. This concept can be extended to more organic semiconducting systems, e.g., 2,6-diphenylanthracene (DPA), tetracene, copper phthalocyanine (CuPc), and copper hexadecafluorophthalocyanine (F 16 CuPc), demonstrating the general applicability. The results show the importance of combining surface nanogrooves with the strong polarity in orienting the molecular arrangement for high crystallinity toward efficient charge transport in organic semiconductors.

Properties of copper (fluoro-)phthalocyanine layers deposited on epitaxial graphene.

PubMed

Ren, Jun; Meng, Sheng; Wang, Yi-Lin; Ma, Xu-Cun; Xue, Qi-Kun; Kaxiras, Efthimios

2011-05-21

We investigate the atomic structure and electronic properties of monolayers of copper phthalocyanines (CuPc) deposited on epitaxial graphene substrate. We focus in particular on hexadecafluorophthalocyanine (F(16)CuPc), using both theoretical and experimental (scanning tunneling microscopy - STM) studies. For the individual CuPc and F(16)CuPc molecules, we calculated the electronic and optical properties using density functional theory (DFT) and time-dependent DFT and found a red-shift in the absorption peaks of F(16)CuPc relative to those of CuPc. In F(16)CuPc, the electronic wavefunctions are more polarized toward the electronegative fluorine atoms and away from the Cu atom at the center of the molecule. When adsorbed on graphene, the molecules lie flat and form closely packed patterns: F(16)CuPc forms a hexagonal pattern with two well-ordered alternating α and β stripes while CuPc arranges into a square lattice. The competition between molecule-substrate and intermolecular van der Waals interactions plays a crucial role in establishing the molecular patterns leading to tunable electron transfer from graphene to the molecules. This transfer is controlled by the layer thickness of, or the applied voltage on, epitaxial graphene resulting in selective F(16)CuPc adsorption, as observed in STM experiments. In addition, phthalocyanine adsorption modifies the electronic structure of the underlying graphene substrate introducing intensity smoothing in the range of 2-3 eV below the Dirac point (E(D)) and a small peak in the density of states at ∼0.4 eV above E(D). © 2011 American Institute of Physics.

Rich Variety of Three-Dimensional Nanostructures Enabled by Geometrically Constraining Star-like Block Copolymers.

PubMed

Wang, Chao; Xu, Yuci; Li, Weihua; Lin, Zhiqun

2016-08-09

The influence of star-like architecture on phase behavior of star-like block copolymer under cylindrical confinement differs largely from the bulk (i.e., nonconfinement). A set of intriguing self-assembled morphologies and the corresponding phase diagrams of star-like (AB)f diblock copolymers with different numbers of arms f (i.e., f = 3, 9, 15, and 21) in four scenarios (ϕA = 0.3 and V0 > 0; ϕA = 0.3 and V0 < 0; ϕA = 0.7 and V0 > 0; and ϕA = 0.7 and V0 < 0 (where ϕA is the volume fraction of A block) and V0 < 0 and V0 > 0 represent that the pore wall of cylindrical confinement prefers the inner A block (i.e., A-preferential) and B block (i.e., B-preferential), respectively) were for the first time scrutinized by employing the pseudospectral method of self-consistent mean-field theory. Surprisingly, a new nanoscopic phase, that is, perforated-lamellae-on-cylinder (denoted PC), was observed in star-like (AB)3 diblock copolymer at ϕA = 0.3 and V0 > 0. With a further increase in f, a single lamellae (denoted L1) was found to possess a larger phase region. Under the confinement of A-preferential wall (i.e., V0 < 0) at ϕA = 0.3, PC phase became metastable and its free energy increased as f increased. Quite intriguingly, when ϕA = 0.7 and V0 > 0, where an inverted cylinder was formed in bulk, the PC phase became stable, and its free energy decreased as f increased, suggesting the propensity to form PC phase under this condition. Moreover, in stark contrast to the phase transition of C1 → L1 → PC (C1, a single cylindrical microdmain) at ϕA = 0.3 and V0 > 0, when subjected to the A-preferential wall (ϕA = 0.7), a different phase transition sequence (i.e., C1 → PC → L1) was identified due to the formation of a double-layer structure. On the basis of our calculations, the influence of star-like architecture on (AB)f diblock copolymer under the imposed cylindrical confinement, particularly the shift of the phase boundaries as a function of f, was thoroughly understood. These self-assembled nanostructures may hold the promise for applications as lithographic templates for nanowires, photonic crystals, and nanotechnology.

Nanoscale Insight and Control of Structural and Electronic Properties of Organic Semiconductor / Metal Interfaces

NASA Astrophysics Data System (ADS)

Maughan, Bret

Organic semiconductor interfaces are promising materials for use in next-generation electronic and optoelectronic devices. Current models for metal-organic interfacial electronic structure and dynamics are inadequate for strongly hybridized systems. This work aims to address this issue by identifying the factors most important for understanding chemisorbed interfaces with an eye towards tuning the interfacial properties. Here, I present the results of my research on chemisorbed interfaces formed between thin-films of phthalocyanine molecules grown on monocrystalline Cu(110). Using atomically-resolved nanoscale imaging in combination with surface-sensitive photoemission techniques, I show that single-molecule level interactions control the structural and electronic properties of the interface. I then demonstrate that surface modifications aimed at controlling interfacial interactions are an effective way to tailor the physical and electronic structure of the interface. This dissertation details a systematic investigation of the effect of molecular and surface functionalization on interfacial interactions. To understand the role of molecular structure, two types of phthalocyanine (Pc) molecules are studied: non-planar, dipolar molecules (TiOPc), and planar, non-polar molecules (H2Pc and CuPc). Multiple adsorption configurations for TiOPc lead to configuration-dependent self-assembly, Kondo screening, and electronic energy-level alignment. To understand the role of surface structure, the Cu(110) surface is textured and passivated by oxygen chemisorption prior to molecular deposition, which gives control over thin-film growth and interfacial electronic structure in H2Pc and CuPc films. Overall, the work presented here demonstrates a method for understanding interfacial electronic structure of strongly hybridized interfaces, an important first step towards developing more robust models for metal-organic interfaces, and reliable, predictive tuning of interfacial properties.

Does methionine oxidation influence the progression of classical or atypical scrapie

USDA-ARS?s Scientific Manuscript database

Introduction Prions are pathological proteins that propagate by converting a normal cellular prion protein (PrPC) into a prion (PrPSc). PrPC and PrPSc possess identical covalent structures and only differ in their conformations. The conversion of the PrPC conformation to the PrPSc one is template ...

Fucosylated haptoglobin is a novel marker for pancreatic cancer: detailed analyses of oligosaccharide structures.

PubMed

Miyoshi, Eiji; Nakano, Miyako

2008-08-01

Changes in oligosaccharide structures have been reported in certain types of malignant transformation and thus can be used as tumor markers in certain types of cancer. In the case of pancreatic cancer (PC) cell lines, a variety of fucosylated proteins are secreted into the conditioned media. To identify fucosylated proteins in the sera of patients with PC, we performed Western blot analysis using Aleuria Aurantia Lectin (AAL), which is specific for fucosylated structures. An approximately 40 kD protein was found to be highly fucosylated in PC and N-terminal analysis revealed that it was the beta chain of haptoglobin. While the appearance of fucosylated haptoglobin has been reported in other diseases such as hepatocellular carcinoma, liver cirrhosis, gastric cancer, and colorectal cancer, the incidence was significantly higher in the case of PC. Fucosylated haptoglobin was observed more frequently at the advanced stage of PC and disappeared after operation. Haptoglobin has four sites of N-glycans and site-directed oligosaccharide analysis involving MS was performed. Site-specific increases in fucosylation of bi-antennary glycans of sites 2 and 4, and of tri-antennary glycans of all sites were observed in PC, compared to in normal volunteers and chronic pancreatitis. Therefore, increases in fucosylation seem to be not due to inflammation, but cancer itself. Coculturing of a human hepatoma cell line, Hep3B, with PC cells-induced production of fucosylated haptoglobin, suggesting that PC produces a factor that induces the production of fucosylated haptoglobin. On clinical investigation of 100 cases of colorectal cancer, cases in which it was located near the liver showed a higher positive rate of fucosylated haptoglobin, suggesting that the location of the cancer might also be an important factor for fucosylated haptoglobin if cancer tissues produce such inducible factors. Thus, fucosylated haptoglobin could become a novel tumor marker for PC and complicated mechanisms would be involved in its production.

Switchable dual-wavelength fiber laser based on PCF Sagnac loop and broadband FBG

NASA Astrophysics Data System (ADS)

Chen, Weiguo; Lou, Shuqin; Feng, Suchun; Wang, Liwen; Li, Honglei; Guo, Tieying; Jian, Shuisheng

2009-11-01

Switchable dual-wavelength fiber laser with photonic crystal fiber (PCF) Sagnac loop and broadband fiber Bragg grating (BFBG) at room temperature is demonstrated. By adjusting the polarization controller (PC) appropriately, the laser can be switched between the stable single- and dual-wavelength lasing operations by exploiting polarization hole burning (PHB) and spectral hole burning effects (SHB).

Photonic crystal ring resonator-based four-channel dense wavelength division multiplexing demultiplexer on silicon on insulator platform: design and analysis

NASA Astrophysics Data System (ADS)

Sreenivasulu, Tupakula; Bhowmick, Kaustav; Samad, Shafeek A.; Yadunath, Thamerassery Illam R.; Badrinarayana, Tarimala; Hegde, Gopalkrishna; Srinivas, Talabattula

2018-04-01

A micro/nanofabrication feasible compact photonic crystal (PC) ring-resonator-based channel drop filter has been designed and analyzed for operation in C and L bands of communication window. The four-channel demultiplexer consists of ring resonators of holes in two-dimensional PC slab. The proposed assembly design of dense wavelength division multiplexing setup is shown to achieve optimal quality factor, without altering the lattice parameters or resonator size or inclusion of scattering holes. Transmission characteristics are analyzed using the three-dimensional finite-difference time-domain simulation approach. The radiation loss of the ring resonator was minimized by forced cancelation of radiation fields by fine-tuning the air holes inside the ring resonator. An average cross talk of -34 dB has been achieved between the adjacent channels maintaining an average quality factor of 5000. Demultiplexing is achieved by engineering only the air holes inside the ring, which makes it a simple and tolerant design from the fabrication perspective. Also, the device footprint of 500 μm2 on silicon on insulator platform makes it easy to fabricate the device using e-beam lithography technique.

Understanding the fast phase-change mechanism of tetrahedrally bonded Cu2GeTe3 : Comprehensive analyses of electronic structure and transport phenomena

NASA Astrophysics Data System (ADS)

Kobayashi, Keisuke; Skelton, Jonathan M.; Saito, Yuta; Shindo, Satoshi; Kobata, Masaaki; Fons, Paul; Kolobov, Alexander V.; Elliott, Stephen; Ando, Daisuke; Sutou, Yuji

2018-05-01

Cu2GeTe3 (CGT) phase-change material, a promising candidate for advanced fast nonvolatile random-access-memory devices, has a chalcopyritelike structure with s p3 bonding in the crystalline phase; thus, the phase-change (PC) mechanism is considered to be essentially different from that of the standard PC materials (e.g., Ge-Sb-Te) with threefold to sixfold p -like bonding. In order to reveal the PC mechanism of CGT, the electronic structure change due to PC has been investigated by laboratory hard x-ray photoelectron spectroscopy and combined first-principles density-functional theory molecular-dynamics simulations. The valence-band spectra, in both crystalline and amorphous phases, are well simulated by the calculations. An inherent tendency of Te 5 s lone-pair formation and an enhanced participation of Cu 3 d orbitals in the bonding are found to play dominant roles in the PC mechanism. The electrical conductivity of as-deposited films and its change during the PC process is investigated in connection with valence-band spectral changes near the Fermi level. The results are successfully analyzed, based on a model proposed by Davis and Mott for chalcogenide amorphous semiconductors. The results suggest that robustness of the defect-band states against thermal stress is a key to the practical application of this material for memory devices.

Structuring a palliative care service in Brazil: experience report.

PubMed

Garcia, João Batista Santos; Rodrigues, Rayssa Fiterman; Lima, Sara Fiterman

2014-01-01

in Brazil, palliative care (PC) is not properly structured and that reality transforms this theme in a public health problem; therefore, initiatives become relevant in this context. This paper aims to share the experience that occurred in an oncology referral hospital in the State of Maranhão and present initiatives that helped in the development of PC Service. the hospital had an outpatient Pain and PC Service, but without specialized beds. The terminally ill patients stayed in common wards, which caused much unrest. A sensitization process was initiated in the hospital through initiatives, such as a photo contest called Flashes of Life and a ward called Room of Dreams, designed in partnership with the architecture course at the Universidade Estadual do Maranhão. The process culminated in the granting of wards to the PC and in the commitment of the Foundation, sponsor of the hospital, to run the project. this experience was a reproducible local initiative for the establishment of PC in a cancer hospital. Local initiatives are valuable in Brazil because they favor a significant number of patients and show its effectiveness in practice to governments and society. To structure a PC service, it is essential to establish priorities that include the assignment of drugs for management of symptoms, humanization, multidisciplinarity, sensitization and education of professionals. Copyright © 2013 Sociedade Brasileira de Anestesiologia. Published by Elsevier Editora Ltda. All rights reserved.

[Structuring a palliative care service in Brazil: experience report].

PubMed

Garcia, João Batista Santos; Rodrigues, Rayssa Fiterman; Lima, Sara Fiterman

2014-01-01

In Brazil, palliative care (PC) is not properly structured and that reality transforms this theme in a public health problem; therefore, initiatives become relevant in this context. This paper aims to share the experience that occurred in an oncology referral hospital in the State of Maranhão and present initiatives that helped in the development of PC Service. The hospital had an outpatient Pain and PC Service, but without specialized beds. The terminally ill patients stayed in common wards, which caused much unrest. A sensitization process was initiated in the hospital through initiatives, such as a photo contest called Flashes of Life and a ward called Room of Dreams, designed in partnership with the architecture course at the Universidade Estadual do Maranhão. The process culminated in the granting of wards to the PC and in the commitment of the Foundation, sponsor of the hospital, to run the project. This experience was a reproducible local initiative for the establishment of PC in a cancer hospital. Local initiatives are valuable in Brazil because they favor a significant number of patients and show its effectiveness in practice to governments and society. To structure a PC service, it is essential to establish priorities that include the assignment of drugs for management of symptoms, humanization, multidisciplinarity, sensitization and education of professionals. Copyright © 2013 Sociedade Brasileira de Anestesiologia. Publicado por Elsevier Editora Ltda. All rights reserved.

Spectroscopic interaction studies of substituted and unsubstituted copper phthalocyanine with adsorbed organic vapours

NASA Astrophysics Data System (ADS)

Ridhi, R.; Kang, Jasmeen; Saini, G. S. S.; Tripathi, S. K.

2018-05-01

The present study deals with comparing the interaction mechanism of adsorbed organic vapours with Copper Phthalocyanine thin films in its substituted and unsubstituted forms. For this purpose, the variations in vibrational levels of substituted CuPc (CuPcS) functionalized with tetrasulfonic acid tetrasodium salt and unsubstituted CuPc after exposure with methanol and benzene vapours is analyzed. Fourier transform infrared (FTIR) is used to study the interaction behaviour. The bulkier group tetrasulfonic acid tetrasodium salt added to CuPc leads to occupation of more space in the molecular arrangement as compared to unsubstituted CuPc and hence alteration of its properties. FTIR spectra of CuPc and CuPcS before and after vapours exposures highlighted the effect of these vapours on the various bonds and the role of functional group in altering the molecular structure of CuPcS during interaction with adsorbed vapours.

Direct characterization of the energy level alignments and molecular components in an organic hetero-junction by integrated photoemission spectroscopy and reflection electron energy loss spectroscopy analysis.

PubMed

Yun, Dong-Jin; Shin, Weon-Ho; Bulliard, Xavier; Park, Jong Hwan; Kim, Seyun; Chung, Jae Gwan; Kim, Yongsu; Heo, Sung; Kim, Seong Heon

2016-08-26

A novel, direct method for the characterization of the energy level alignments at bulk-heterojunction (BHJ)/electrode interfaces on the basis of electronic spectroscopy measurements is proposed. The home-made in situ photoemission system is used to perform x-ray/ultraviolet photoemission spectroscopy (XPS/UPS), reflection electron energy loss spectroscopy (REELS) and inverse photoemission spectroscopy of organic-semiconductors (OSCs) deposited onto a Au substrate. Through this analysis system, we are able to obtain the electronic structures of a boron subphthalocyanine chloride:fullerene (SubPC:C60) BHJ and those of the separate OSC/electrode structures (SubPC/Au and C60/Au). Morphology and chemical composition analyses confirm that the original SubPC and C60 electronic structures remain unchanged in the electrodes prepared. Using this technique, we ascertain that the position and area of the nearest peak to the Fermi energy (EF = 0 eV) in the UPS (REELS) spectra of SubPC:C60 BHJ provide information on the highest occupied molecular orbital level (optical band gap) and combination ratio of the materials, respectively. Thus, extracting the adjusted spectrum from the corresponding SubPC:C60 BHJ UPS (REELS) spectrum reveals its electronic structure, equivalent to that of the C60 materials. This novel analytical approach allows complete energy-level determination for each combination ratio by separating its electronic structure information from the BHJ spectrum.

Oil and drug control the release rate from lyotropic liquid crystals.

PubMed

Martiel, Isabelle; Baumann, Nicole; Vallooran, Jijo J; Bergfreund, Jotam; Sagalowicz, Laurent; Mezzenga, Raffaele

2015-04-28

The control of the diffusion coefficient by the dimensionality d of the structure appears as a most promising lever to efficiently tune the release rate from lyotropic liquid crystalline (LLC) phases and dispersed particles towards sustained, controlled and targeted release. By using phosphatidylcholine (PC)- and monolinoleine (MLO)-based mesophases with various apolar structural modifiers and water-soluble drugs, we present a comprehensive study of the dimensional structural control of hydrophilic drug release, including 3-d bicontinuous cubic, 2-d lamellar, 1-d hexagonal and 0-d micellar cubic phases in excess water. We investigate how the surfactant, the oil properties and the drug hydrophilicity mitigate or even cancel the effect of structure variation on the drug release rate. Unexpectedly, the observed behavior cannot be fully explained by the thermodynamic partition of the drug into the lipid matrix, which points out to previously overlooked kinetic effects. We therefore interpret our results by discussing the mechanism of structural control of the diffusion rate in terms of drug permeation through the lipid membrane, which includes exchange kinetics. A wide range of implications follow regarding formulation and future developments, both for dispersed LLC delivery systems and topical applications in bulk phase. Copyright © 2015 Elsevier B.V. All rights reserved.

Applications of AMPS-1D for solar cell simulation

NASA Astrophysics Data System (ADS)

Zhu, Hong; Kalkan, Ali Kaan; Hou, Jingya; Fonash, Stephen J.

1999-03-01

The AMPS-1D PC computer program is now used by over 70 groups world-wide for detector and solar cell analysis. It has proved to be a very powerful tool in understanding device operation and physics for single crystal, poly-crystalline and amorphous structures. For example, AMPS-1D has been successful in explaining the "red kink" [1] and the "transient effect" in CdS/CIGS poly-crystalline solar cells. It has been used to show that thin film poly-Si structures, with reasonable light trapping, are capable of competitive solar cell conversion efficiencies. In the case of a-Si:H structures, it has been used, for example, to settle the discrepancies in bandgap measurement, to predict the effective QE>1 phenomenon later seen in these materials [2], to determine the relative roles of interface and bulk properties, and to point the direction toward 16% triple junction structures. In general AMPS-1D is used for cell and detector design, material parameter sensitivity studies, and parameter extraction. Recently we have shown that it can be used to determine optimum structure and light and voltage biasing conditions in the material parameter extraction function. Information on AMPS can be found at www.psu.edu/dept/AMPS/amps_web/AMPS.html and at other web sites set up by user groups.

Chemical and enzymatic catalytic routes to polyesters and oligopeptides biobased materials

NASA Astrophysics Data System (ADS)

Zhu, Jianhui

My Ph.D research focuses on the synthesis and property studies of different biobased materials, including polyesters, polyurethanes and oligopeptides. The first study describes the synthesis, crystal structure and physico-mechanical properties of a bio-based polyester prepared from 2,5-furandicarboxylic acid (FDCA) and 1,4-butanediol. Melt-polycondensation experiments were conducted by a two-stage polymerization using titanium tetraisopropoxide (Ti[OiPr] 4) as catalyst. Polymerization conditions (catalyst concentration, reaction time and 2nd stage reaction temperature) were varied to optimize poly(butylene furan dicarboxylate), PBF, molecular weight. A series of PBFs with different Mw were characterized by Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), Dynamic Mechanical Thermal Analysis (DMTA), X-Ray diffraction and tensile testing. Influence of molecular weight and melting/crystallization enthalpy on PBF material tensile properties was explored. Cold-drawing tensile tests at room temperature for PBF with Mw 16K to 27K showed a brittle-to-ductile transition. When Mw reaches 38K, the Young's Modulus of PBF remains above 900 MPa, and the elongation at break increases to above 1000%. The mechanical properties, thermal properties and crystal structures of PBF were similar to petroleum derived poly(butylenes terephthalate), PBT. Fiber diagrams of uniaxially stretched PBF films were collected, indexed, and the unit cell was determined as triclinic (a=4.78(3) A, b=6.03(5) A, c=12.3(1) A, alpha=110.1(2)°, beta=121.1(3)°, gamma=100.6(2)°). A crystal structure was derived from this data and final atomic coordinates are reported. We concluded that there is a close similarity of the PBF structure to PBT alpha- and beta-forms. In the second study, a biobased long chain polyester polyol (PC14-OH) was synthesized from o-hydroxytetradecanoic acid (o-HOC14) and 1,4-butanediol. The first section about polyester polyurethanes describes the synthesis and physico-mechanical properties for two series of linear polyurethane elastomers built from polyol polyesters which contain bio-based o-hydroxytetradecanoic acid (o-HOC14) repeat units. Varied quantities of o-HOC14 was converted by a condensation polymerization catalyzed by titanium tetraisopropoxide (Ti[OiPr]4) to polyester polyol with Mn around 2K. By end-cap the polyols with excess amount of 1,4-butanediol, low number of carbonyl end group can be achieved so that the polyols can be further used as soft segment of thermoplastic polyurethanes (TPU). We have studied the thermo-mechanical properties of two-series polyurethanes with different polyester polyols or polyester polyols mixtures. With increasing amount of o-HOC14 content in the soft segment polyols of polyurethanes, tensile strength of the polyurethanes kept increasing from 30MPa to 470MPa while at the same time their elongation ratio decreased from 900% to 300%. Their mechanical behavior shifted from elastomer to semi-crystalline plastic. In the second section about polyether polyurethanes, PC14-OH and poly(tetrahydrofuran) mixtures were used as soft segment in linear polyurethane elastomer synthesis. Similar thermal and mechanical property changing trends were observed with increasing amount of PC14-OH up to 30 wt% of total soft segments. In this study, the functions of PC14-OH in thermoplastic polyurethane elastomers were identified, and there are several benefits of incorporating this long chain fatty acid. In the third study, seven amphiphilic alternating oligopeptides were synthesized via chemo-enzymatic routes. Four proteases (papain, bromelain, alpha-chymotrypsin, and trypsin) were evaluated to determine their efficiency in synthesizing alternating peptides. The first series is hydrophobic-anionic alternating oligopeptides targeting for self assembly smart material design. So far, beta-sheet secondary structure of the anionic alternating oligopeptides was not observed very clearly at low pH comparing to the cationic alternating oligopeptides (KL)x, which is probably due to the short chain length of the oligopeptides. Combination of cationic and anionic alternating oligopeptides has been tested by (KL)x and (LD)x mixtures at 1:1 weight ratio, beta-sheet secondary structure started to appear at neutral pH. The preliminary CD results of the mixtures have shown the potential to manipulate self assembly behavior at different pHs. The second series is alternating oligo(Lys-Trp) targeting for antimicrobial agent design. The alternating (KW)x was successfully synthesized by alpha-chymotrypsin in mixed solvent medium. Chain length of (KW)x can be varied when using different mixed solvent medium. In order to increase the solubility of (KW)x-OEt, C-terminal ethyl ester moiety was modified by reaction with ethylene diamine. Antimicrobial activities of (KW)x with different chain lengths have been tested against E.coli and S. aureus. Our work utilizes a simplified synthetic method to prepare alternating peptides at the cost of chain length uniformity. However, (KW)x-OEt (n=3--6) alternating peptide mixtures still possesses quite good antimicrobial activity while the preparation method is much more easier and greener, which means this method is more economical and environmental friendly. Moreover, the adjustment of reaction conditions and proteases can successfully enhance the control over KW alternating peptide chain length to better achieve more antimicrobial active products. (Abstract shortened by UMI.).

Electronic structure of the organic semiconductor copper phthalocyanine: experiment and theory.

PubMed

Aristov, V Yu; Molodtsova, O V; Maslyuk, V V; Vyalikh, D V; Zhilin, V M; Ossipyan, Yu A; Bredow, T; Mertig, I; Knupfer, M

2008-01-21

The electronic structure of the organic semiconductor copper-phthalocyanine (CuPc) has been determined by a combination of conventional and resonant photoemission, near-edge x-ray absorption, as well as by the first-principles calculations. The experimentally obtained electronic valence band structure of CuPc is in very good agreement with the calculated density of states results, allowing the derivation of detailed site specific information.

The ground support equipment for the LAUE project

NASA Astrophysics Data System (ADS)

Caroli, E.; Auricchio, N.; Basili, A.; Carassiti, V.; Cassese, F.; Del Sordo, S.; Frontera, F.; Pecora, M.; Recanatesi, L.; Schiavone, F.; Silvestri, S.; Squerzanti, S.; Stephen, J. B.; Virgilli, E.

2013-09-01

The development of wide band Laue lens imaging technology is challenging, but has important potential applications in hard X- and γ-ray space instrumentation for the coming decades. The Italian Space Agency has funded a project dedicated to the development of a reliable technology to assemble a wide band Laue lens for use in space. The ground support equipment (GSE) for this project was fundamental to its eventual success... The GSE was implemented in a hard X-ray beam line built at the University of Ferrara and had the main purpose of controlling the assembly of crystals onto the Laue lens petal and to verify its final performance. The GSE incorporates the management and control of all the movements of the beam line mechanical subsystems and of the precision positioner (based on a Hexapod tool) of crystals on the petal, as well as the acquisition, storing and analysis of data obtained from the focal plane detectors (an HPGe spectrometer and an X-ray flat panel imager). The GSE is based on two PC's connected through a local network: one, placed inside the beam line, to which all the movement subsystems and the detector I/O interface and on which all the management and acquisition S/W runs, the other in the control room allows the remote control and implements the offline analysis S/W of the data obtained from the detectors. Herein we report on the GSE structure with its interface with the beam line mechanical system, with the fine crystal positioner and with the focal plane detector. Furthermore we describe the SW developed for the handling of the mechanical movement subsystems and for the analysis of the detector data with the procedure adopted for the correct orientation of the crystals before their bonding on the lens petal support.

Does legal physician-assisted dying impede development of palliative care? The Belgian and Benelux experience.

PubMed

Chambaere, Kenneth; Bernheim, Jan L

2015-08-01

In 2002, physician-assisted dying was legally regulated in the Netherlands and Belgium, followed in 2009 by Luxembourg. An internationally frequently expressed concern is that such legislation could stunt the development of palliative care (PC) and erode its culture. To study this, we describe changes in PC development 2005-2012 in the permissive Benelux countries and compare them with non-permissive countries. Focusing on the seven European countries with the highest development of PC, which include the three euthanasia-permissive and four non-permissive countries, we compared the structural service indicators for 2005 and 2012 from successive editions of the European Atlas of Palliative Care. As an indicator for output delivery of services to patients, we collected the amounts of governmental funding of PC 2002-2011 in Belgium, the only country where we could find these data. The rate of increase in the number of structural PC provisions among the compared countries was the highest in the Netherlands and Luxembourg, while Belgium stayed on a par with the UK, the benchmark country. Belgian government expenditure for PC doubled between 2002 and 2011. Basic PC expanded much more than endowment-restricted specialised PC. The hypothesis that legal regulation of physician-assisted dying slows development of PC is not supported by the Benelux experience. On the contrary, regulation appears to have promoted the expansion of PC. Continued monitoring of both permissive and non-permissive countries, preferably also including indicators of quantity and quality of delivered care, is needed to evaluate longer-term effects. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

Red-emitting phosphor Rb2TiF6:Mn4+ with high thermal-quenching resistance for wide color-gamut white light-emitting diodes

NASA Astrophysics Data System (ADS)

Wang, Zhengliang; Yang, Zhiyu; Tan, Huiying; Brik, Mikhail G.; Zhou, Qiang; Chen, Guo; Liang, Hongbin

2017-10-01

Red-emitting phosphor plays a critical role in improving performance of the phosphor-converted white light-emitting diodes (pc-WLEDs). Herein, a red-emitting phosphor, Rb2TiF6:Mn4+, was synthesized via the ion exchange method under mild condition. The crystal structure and morphology were characterized by the powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The Rietveld refinements of Rb2TiF6:Mn4+ indicate that this sample is of single phase with hexagonal crystal structure. The as-prepared Rb2TiF6:Mn4+ has sharp red emissions with broad excitation band at ∼460 nm. The luminescent behavior of Mn4+ was discussed in detail. The temperature-dependent emission spectra of Rb2TiF6:Mn4+ indicate that this phosphor shares high thermal quenching resistance and excellent color stability. A series of WLEDs with tunable color rendering index and color temperature were fabricated by combining commercial Y3Al5O12:Ce3+ and Rb2TiF6:Mn4+ on blue GaN-LED chips. With the addition of Rb2TiF6:Mn4+, WLED with wide gamut was obtained with low color temperature (3123 K), high color rendering index (91.5) and high luminous efficacy (187.9 lm/W). These findings show this phosphor could be a promising commercial red phosphor in wide color-gamut WLEDs.

[Three-dimensional genome organization: a lesson from the Polycomb-Group proteins].

PubMed

Bantignies, Frédéric

2013-01-01

As more and more genomes are being explored and annotated, important features of three-dimensional (3D) genome organization are just being uncovered. In the light of what we know about Polycomb group (PcG) proteins, we will present the latest findings on this topic. The PcG proteins are well-conserved chromatin factors that repress transcription of numerous target genes. They bind the genome at specific sites, forming chromatin domains of associated histone modifications as well as higher-order chromatin structures. These 3D chromatin structures involve the interactions between PcG-bound regulatory regions at short- and long-range distances, and may significantly contribute to PcG function. Recent high throughput "Chromosome Conformation Capture" (3C) analyses have revealed many other higher order structures along the chromatin fiber, partitioning the genomes into well demarcated topological domains. This revealed an unprecedented link between linear epigenetic domains and chromosome architecture, which might be intimately connected to genome function. © Société de Biologie, 2013.

Fabrication of field-effect transistor utilizing oriented thin film of octahexyl-substituted phthalocyanine and its electrical anisotropy based on columnar structure

NASA Astrophysics Data System (ADS)

Ohmori, Masashi; Nakatani, Mitsuhiro; Kajii, Hirotake; Miyamoto, Ayano; Yoneya, Makoto; Fujii, Akihiko; Ozaki, Masanori

2018-03-01

Field-effect transistors with molecularly oriented thin films of metal-free non-peripherally octahexyl-substituted phthalocyanine (C6PcH2), which characteristically form a columnar structure, have been fabricated, and the electrical anisotropy of C6PcH2 has been investigated. The molecularly oriented thin films of C6PcH2 were prepared by the bar-coating technique, and the uniform orientation in a large area and the surface roughness at a molecular level were observed by polarized spectroscopy and atomic force microscopy, respectively. The field effect mobilities parallel and perpendicular to the column axis of C6PcH2 were estimated to be (1.54 ± 0.24) × 10-2 and (2.10 ± 0.23) × 10-3 cm2 V-1 s-1, respectively. The electrical anisotropy based on the columnar structure has been discussed by taking the simulated results obtained by density functional theory calculation into consideration.

On the solvation of the phosphocholine headgroup in an aqueous propylene glycol solution

NASA Astrophysics Data System (ADS)

Rhys, Natasha H.; Al-Badri, Mohamed Ali; Ziolek, Robert M.; Gillams, Richard J.; Collins, Louise E.; Lawrence, M. Jayne; Lorenz, Christian D.; McLain, Sylvia E.

2018-04-01

The atomic-scale structure of the phosphocholine (PC) headgroup in 30 mol. % propylene glycol (PG) in an aqueous solution has been investigated using a combination of neutron diffraction with isotopic substitution experiments and computer simulation techniques—molecular dynamics and empirical potential structure refinement. Here, the hydration of the PC headgroup remains largely intact compared with the hydration of this group in a bilayer and in a bulk water solution, with the PG molecules showing limited interactions with the headgroup. When direct PG interactions with PC do occur, they are most likely to coordinate to the 3+N (CH 3 ) motifs. Further, PG does not affect the bulk water structure and the addition of PC does not perturb the PG-solvent interactions. This suggests that the reason why PG is able to penetrate into membranes easily is that it does not form strong-hydrogen bonding or electrostatic interactions with the headgroup allowing it to easily move across the membrane barrier.

Fast modulations of pulsating proton aurora related to subpacket structures of Pc1 geomagnetic pulsations at subauroral latitudes

DOE PAGES

Ozaki, M.; Shiokawa, K.; Miyoshi, Y.; ...

2016-08-16

To understand the role of electromagnetic ion cyclotron (EMIC) waves in determining the temporal features of pulsating proton aurora (PPA) via wave-particle interactions at subauroral latitudes, high-time-resolution (1/8 s) images of proton-induced N 2>+ emissions were recorded using a new electron multiplying charge-coupled device camera, along with related Pc1 pulsations on the ground. The observed Pc1 pulsations consisted of successive rising-tone elements with a spacing for each element of 100 s and subpacket structures, which manifest as amplitude modulations with a period of a few tens of seconds. In accordance with the temporal features of the Pc1 pulsations, the auroralmore » intensity showed a similar repetition period of 100 s and an unpredicted fast modulation of a few tens of seconds. Furthermore, these results indicate that PPA is generated by pitch angle scattering, nonlinearly interacting with Pc1/EMIC waves at the magnetic equator.« less

Fast modulations of pulsating proton aurora related to subpacket structures of Pc1 geomagnetic pulsations at subauroral latitudes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ozaki, M.; Shiokawa, K.; Miyoshi, Y.

To understand the role of electromagnetic ion cyclotron (EMIC) waves in determining the temporal features of pulsating proton aurora (PPA) via wave-particle interactions at subauroral latitudes, high-time-resolution (1/8 s) images of proton-induced N 2>+ emissions were recorded using a new electron multiplying charge-coupled device camera, along with related Pc1 pulsations on the ground. The observed Pc1 pulsations consisted of successive rising-tone elements with a spacing for each element of 100 s and subpacket structures, which manifest as amplitude modulations with a period of a few tens of seconds. In accordance with the temporal features of the Pc1 pulsations, the auroralmore » intensity showed a similar repetition period of 100 s and an unpredicted fast modulation of a few tens of seconds. Furthermore, these results indicate that PPA is generated by pitch angle scattering, nonlinearly interacting with Pc1/EMIC waves at the magnetic equator.« less

β-Octabromo- and β-Octakis(trifluoromethyl)isocorroles: New Sterically Constrained Macrocyclic Ligands

DOE PAGES

Thomas, Kolle E.; Beavers, Christine M.; Gagnon, Kevin J.; ...

2017-05-26

Here, we present a study of the acid-induced demetalation of two sterically hindered copper corroles, Cu β-octabromo-meso-triphenylcorrole (Cu[Br 8TPC]) and β-octakis(trifluoromethyl)-meso-tris(p-methoxyphenyl)corrole (Cu[(CF 3) 8TpOMePC]). Unlike reductive demetalation, which affords the free-base β-octabromocorrole, demetalation of Cu[Br 8TPC] under non- reductive conditions (CHCl 3/H 2SO 4) resulted in moderate yields of free-base 5- and 10-hydroxy isocorroles. The isomeric free bases could be complexed to Co II and Ni II, affording stable complexes. Only reductive demetalation was found to work for Cu[(CF 3) 8TpOMePC], affording a highly saddled, hydrated corrole, H 3[5-OH,10-H-(CF 3) 8TpOMePC], where the elements of water had added across C5more » and C10. Interaction of this novel free base with Co II resulted in Co[iso-10-H-[CF 3) 8TpOMePC], a Co II 10-hydro isocorrole. Finally, the new metal complexes were all characterized by single-crystal X-ray diffraction analysis and, despite their sterically hindered nature, were found to exhibit almost perfectly planar isocorrole cores.« less

Design of anti- and pro-aggregation variants to assess the effects of methionine oxidation in human prion protein

PubMed Central

Wolschner, Christina; Giese, Armin; Kretzschmar, Hans A.; Huber, Robert; Moroder, Luis; Budisa, Nediljko

2009-01-01

Prion disease is characterized by the α→β structural conversion of the cellular prion protein (PrPC) into the misfolded and aggregated “scrapie” (PrPSc) isoform. It has been speculated that methionine (Met) oxidation in PrPC may have a special role in this process, but has not been detailed and assigned individually to the 9 Met residues of full-length, recombinant human PrPC [rhPrPC(23-231)]. To better understand this oxidative event in PrP aggregation, the extent of periodate-induced Met oxidation was monitored by electrospray ionization-MS and correlated with aggregation propensity. Also, the Met residues were replaced with isosteric and chemically stable, nonoxidizable analogs, i.e., with the more hydrophobic norleucine (Nle) and the highly hydrophilic methoxinine (Mox). The Nle-rhPrPC variant is an α-helix rich protein (like Met-rhPrPC) resistant to oxidation that lacks the in vitro aggregation properties of the parent protein. Conversely, the Mox-rhPrPC variant is a β-sheet rich protein that features strong proaggregation behavior. In contrast to the parent Met-rhPrPC, the Nle/Mox-containing variants are not sensitive to periodate-induced in vitro aggregation. The experimental results fully support a direct correlation of the α→β secondary structure conversion in rhPrPC with the conformational preferences of Met/Nle/Mox residues. Accordingly, sporadic prion and other neurodegenerative diseases, as well as various aging processes, might also be caused by oxidative stress leading to Met oxidation. PMID:19416900

Fabrication of a highly oriented line structure on an aluminum surface and the nanoscale patterning on the nanoscale structure using highly functional molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watanabe, Y.; Kato, H.; Takemura, S.

2009-07-15

The surface of an Al plate was treated with a combination of chemical and electrochemical processes for fabrication of surface nanoscale structures on Al plates. Chemical treatments by using acetone and pure water under supersonic waves were conducted on an Al surface. Additional electrochemical process in H{sub 2}SO{sub 4} solution created a finer and oriented nanoscale structure on the Al surface. Dynamic force microscopy (DFM) measurement clarified that the nanoscale highly oriented line structure was successfully created on the Al surface. The line distance was estimated approximately 30-40 nm. At the next stage, molecular patterning on the highly oriented linemore » structure by functional molecules such as copper phthalocyanine (CuPc) and fullerene C{sub 60} was also conducted. CuPc or C{sub 60} molecules were deposited on the highly oriented line structure on Al. A toluene droplet containing CuPc molecules was cast on the nanostructured Al plate and was extended on the surface. CuPc or C{sub 60} deposition on the nanostructured Al surface proceeded by evaporation of toluene. DFM and x-ray photoemission spectroscopy measurements demonstrated that a unique molecular pattern was fabricated so that the highly oriented groove channels were filled with the functional molecules.« less

5.5 W near-diffraction-limited power from resonant leaky-wave coupled phase-locked arrays of quantum cascade lasers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirch, J. D.; Chang, C.-C.; Boyle, C.

2015-02-09

Five, 8.36 μm-emitting quantum-cascade lasers (QCLs) have been monolithically phase-locked in the in-phase array mode via resonant leaky-wave coupling. The structure is fabricated by etch and regrowth which provides large index steps (Δn = 0.10) between antiguided-array elements and interelement regions. Such high index contrast photonic-crystal (PC) lasers have more than an order of magnitude higher index contrast than PC-distributed feedback lasers previously used for coherent beam combining in QCLs. Absorption loss to metal layers inserted in the interelement regions provides a wide (∼1.0 μm) range in interelement width over which the resonant in-phase mode is strongly favored to lase. Room-temperature, in-phase-mode operation withmore » ∼2.2 kA/cm{sup 2} threshold-current density is obtained from 105 μm-wide aperture devices. The far-field beam pattern has lobewidths 1.65× diffraction limit (D.L.) and 82% of the light in the main lobe, up to 1.8× threshold. Peak pulsed near-D.L. power of 5.5 W is obtained, with 4.5 W emitted in the main lobe. Means of how to increase the device internal efficiency are discussed.« less

Chemometric and multivariate statistical analysis of time-of-flight secondary ion mass spectrometry spectra from complex Cu-Fe sulfides.

PubMed

Kalegowda, Yogesh; Harmer, Sarah L

2012-03-20

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) spectra of mineral samples are complex, comprised of large mass ranges and many peaks. Consequently, characterization and classification analysis of these systems is challenging. In this study, different chemometric and statistical data evaluation methods, based on monolayer sensitive TOF-SIMS data, have been tested for the characterization and classification of copper-iron sulfide minerals (chalcopyrite, chalcocite, bornite, and pyrite) at different flotation pulp conditions (feed, conditioned feed, and Eh modified). The complex mass spectral data sets were analyzed using the following chemometric and statistical techniques: principal component analysis (PCA); principal component-discriminant functional analysis (PC-DFA); soft independent modeling of class analogy (SIMCA); and k-Nearest Neighbor (k-NN) classification. PCA was found to be an important first step in multivariate analysis, providing insight into both the relative grouping of samples and the elemental/molecular basis for those groupings. For samples exposed to oxidative conditions (at Eh ~430 mV), each technique (PCA, PC-DFA, SIMCA, and k-NN) was found to produce excellent classification. For samples at reductive conditions (at Eh ~ -200 mV SHE), k-NN and SIMCA produced the most accurate classification. Phase identification of particles that contain the same elements but a different crystal structure in a mixed multimetal mineral system has been achieved.

The cmc-value of a bolalipid with two phosphocholine headgroups and a C24 alkyl chain: Unusual binding properties of fluorescence probes to bolalipid aggregates.

PubMed

Kordts, Martin; Kerth, Andreas; Drescher, Simon; Ott, Maria; Blume, Alfred

2017-09-01

Bolalipids with a long alkyl chain and two phosphocholine polar groups self-assemble in water into two different types of aggregate structures, namely helical nanofibers at low temperature and two types of micellar aggregates at higher temperature. We tried to determine the critical aggregation concentration (cac) or critical micellar concentration (cmc) of the bolalipid tetracosane-1,24-bis(phosphocholine) (PC-C24-PC) by using different fluorescent probes. The use of pyrene or pyrene derivatives as fluorophores failed, whereas the probes 1,8-ANS and particularly bis-ANS gave consistent results. The structure of the bolalipid aggregates obviously hinders partitioning or binding of pyrene derivatives into the micellar interior, whereas 1,8-ANS and bis-ANS can bind to the surface of the aggregate structures. The observed large increase in fluorescence intensity of bis-ANS indicates that binding to the hydrophobic surface of the aggregates leads to a reduction of the dye mobility. However, binding of bis-ANS is relatively weak, so that the determination of a cac/cmc-value is difficult. Simulations of the intensity curves for PC-C24-PC lead to estimates of the cac/cmc-value of 0.3-1.0×10 -6 M, depending on the structure of the aggregates. Single molecule fluorescence correlation spectroscopy was used to determine the mobility of bis-ANS as a function of concentration of PC-C24-PC. The dye diffusion time and the molecular brightness are lower at low bolalipid concentration, when only free dye is present, and increase at higher concentration when bis-ANS is bound to the aggregates. The experimental cac/cmc-values are higher than those estimated, using an incremental method for the change in Gibbs free energy for micellization with n-alkyl-phosphocholines with only one polar group as a comparison. Apparently, for PC-C24-PC in micellar or fibrous aggregates, more CH 2 groups are exposed to water than in a conventional micelle of an n-alkyl-phosphocholine. Copyright © 2017 Elsevier Inc. All rights reserved.

The Structural Architecture of an Infectious Mammalian Prion Using Electron Cryomicroscopy.

PubMed

Vázquez-Fernández, Ester; Vos, Matthijn R; Afanasyev, Pavel; Cebey, Lino; Sevillano, Alejandro M; Vidal, Enric; Rosa, Isaac; Renault, Ludovic; Ramos, Adriana; Peters, Peter J; Fernández, José Jesús; van Heel, Marin; Young, Howard S; Requena, Jesús R; Wille, Holger

2016-09-01

The structure of the infectious prion protein (PrPSc), which is responsible for Creutzfeldt-Jakob disease in humans and bovine spongiform encephalopathy, has escaped all attempts at elucidation due to its insolubility and propensity to aggregate. PrPSc replicates by converting the non-infectious, cellular prion protein (PrPC) into the misfolded, infectious conformer through an unknown mechanism. PrPSc and its N-terminally truncated variant, PrP 27-30, aggregate into amorphous aggregates, 2D crystals, and amyloid fibrils. The structure of these infectious conformers is essential to understanding prion replication and the development of structure-based therapeutic interventions. Here we used the repetitive organization inherent to GPI-anchorless PrP 27-30 amyloid fibrils to analyze their structure via electron cryomicroscopy. Fourier-transform analyses of averaged fibril segments indicate a repeating unit of 19.1 Å. 3D reconstructions of these fibrils revealed two distinct protofilaments, and, together with a molecular volume of 18,990 Å3, predicted the height of each PrP 27-30 molecule as ~17.7 Å. Together, the data indicate a four-rung β-solenoid structure as a key feature for the architecture of infectious mammalian prions. Furthermore, they allow to formulate a molecular mechanism for the replication of prions. Knowledge of the prion structure will provide important insights into the self-propagation mechanisms of protein misfolding.

Dielectric relaxation and magnetic properties of Ti and Zn co-doped GaFeO3

NASA Astrophysics Data System (ADS)

Raies, Imen; Dulmani, Shara A.; Amami, Mongi

2018-06-01

polycrystalline GaFeO3 and Ga0.98Zn0.02Fe0.98Ti0.02O3 were prepared by solid state reaction. They showed an orthorhombic crystal structure with Pc21n space group. The magnetic transition temperature decrease due to the dilution of the magnetic interaction. A noteworthy effect of substitution of multiple elements at the Ga and Fe-sites on dielectric constant and tangent loss of GaFeO3 has been observed. Complete studies of temperature (180-400 K) and frequency (10-107 Hz) dependence of dielectric constant and impedance have provided the effect of grains and grain boundaries on the conduction mechanism and dielectric relaxation of the material. Impedance spectroscopy results in the temperature range 160-400 K have revealed a distinct conduction process at grain and grain boundaries.

Neo-clerodane and abietane diterpenoids with neurotrophic activities from the aerial parts of Salvia leucantha Cav.

PubMed

Li, Lai-Wei; Qi, Yan-Yan; Liu, Shi-Xi; Wu, Xing-De; Zhao, Qin-Shi

2018-04-04

Four new neoclerodane diterpenoids, leucansalvialins FI (1-4), and one rare 18(4 → 3)-abeo-abietane diterpenoid, leucansalvialin J (5), were isolated from the aerial part of Salvia leucantha Cav., along with 14 known analogues. Leucansalvialin F (1) represents the first rearranged salvigenane type clerodane-17,12:18,6-diolide. Their structures were elucidated by 1D and 2D NMR spectroscopic data analysis, and the absolute configurations of 1, 2, 3, and 5 were determinded by X-ray diffraction crystal analysis and the ECD technique. All of the isolated components were evaluated for their neurotrophic activities on PC12 cells and all new compounds were evaluated for their cytotoxicity against five human cancer cell lines (HL-60, A-549, SMMC-7721, MCF-7, and SW480). Compounds 2 and 5 showed moderate neuroprotective effects in an in vitro assay. Copyright © 2018. Published by Elsevier B.V.

Synthesis, crystal structure and effect of indeno[1,2-b]indole derivatives on prostate cancer in vitro. Potential effect against MMP-9.

PubMed

Lobo, Gricela; Monasterios, Melina; Rodrigues, Juan; Gamboa, Neira; Capparelli, Mario V; Martínez-Cuevas, Javier; Lein, Michael; Jung, Klaus; Abramjuk, Claudia; Charris, Jaime

2015-01-01

A highly regiospecific synthesis of a series of indenoindoles is reported, together with X-ray studies and their activity against human prostate cancer cells PC-3 and LNCaP in vitro. The most effective compound 7,7-dimethyl-5-[(3,4-dichlorophenyl)]-(4bRS,9bRS)-dihydroxy-4b,5,6,7,8,9bhexahydro-indeno[1,2-b]indole-9,10-dione 7q reduced the viability in both cell lines in a time and dose-dependent manner. Inhibitory effects were also observed on the adhesion, migration, and invasion of the prostate cancer cells as well as on clonogenic possibly by inhibition of MMP-9 activity. Molecular docking of 7q and 6k into MMP-9 human active site was also performed to determine the probable binding mode. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Charge Effects on the Efflorescence in Single Levitated Droplets.

PubMed

Hermann, Gunter; Zhang, Yan; Wassermann, Bernhard; Fischer, Henry; Quennet, Marcel; Rühl, Eckart

2017-09-14

The influence of electrical excess charges on the crystallization from supersaturated aqueous sodium chloride solutions is reported. This is accomplished by efflorescence studies on single levitated microdroplets using optical and electrodynamic levitation. Specifically, a strong increase in efflorescence humidity is observed as a function of the droplet's negative excess charge, ranging up to -2.1 pC, with a distinct threshold behavior, increasing the relative efflorescence humidity, at which spontaneous nucleation occurs, from 44% for the neutral microparticle to 60%. These findings are interpreted by using molecular dynamics simulations for determining plausible structural patterns located near the particle surface that could serve as suitable precursors for the formation of critical clusters overcoming the nucleation barrier. These results, facilitating heterogeneous nucleation in the case of negatively charged microparticles, are compared to recent work on charge-induced nucleation of neat supercooled water, where a distinctly different nucleation behavior as a function of droplet charge has been observed.

(Cryptand-222)potassium(+) (hydrogensulfido)[5,10,15,20-tetra­kis(2-pival­amido­phen­yl)porphyrinato]ferrate(II)

PubMed Central

Dhifet, Mondher; Belkhiria, Mohamed Salah; Daran, Jean-Claude; Nasri, Habib

2009-01-01

As part of a systematic investigation for a number of FeII porphyrin complexes used as biomimetic models for cytochrome P450, crystals of the title compound, [K(C18H36N2O6)][FeII(C64H64N8O4)(HS)], were prepared. The compound exhibits a non-planar conformation with major ruffling and saddling distortions. The average equatorial iron–pyrrole N atom [Fe—Np = 2.102 (2) Å] bond length and the distance between the FeII atom and the 24-atom core of the porphyrin ring (Fe—PC= 0.558 Å) are typical for high-spin iron(II) penta­coordinate porphyrinates. One of the tert-butyl groups in the structure is disordered over two sets with occupancies of 0.84 and 0.16. PMID:21583412

Efficient light harvesting within a C153@Zr-based MOF embedded in a polymeric film: spectral and dynamical characterization.

PubMed

Gutiérrez, M; López-González, M; Sánchez, F; Douhal, A

2017-07-21

Light harvesting is a natural phenomenon that scientists try to mimic in artificial systems. Having this in mind, attention has been focused on using new smart-materials for photonics. Herein, we report on the photobehaviour of a Zr-NDC MOF (NDC = dimethyl 2,6-naphthalenedicarboxylate) and its composite material, Coumarin153@Zr-NDC, embedded within a polymeric membrane of poly[bisphenol A carbonate-co-4,4'-(3,3,5-trimethylcyclohexylidene)diphenol carbonate] (PC). For the mixed matrix membrane (MMM) Zr-NDC/PC, we observed interparticle excimer-like formation, taking place in times shorter than 15 ps and giving rise to a red-shifted broad emission band. The interparticle interactions are supported by the SEM images, as they reflect the contact between the MOF crystals. The C153@Zr-NDC/PC material presents an energy transfer (ET) process from the excited MOF to the trapped C153 molecules in 820 ps, with a 35 nm red-shifted emission band corresponding to C153 in PC. The fluorescence quantum yield, as a result of this ET from the MOF, is high enough (25%) to explore the possibility of using this new composite material in a LED device. To elucidate the observed photobehavior, we compared it with those of C153/PC and (2,6-NDC + C153)/PC films. These results shed light on the spectroscopic and dynamical properties of these new composite materials formed by a highly fluorescent molecule, and easily synthesized MOFs and polymeric matrices, opening the way for more research based on these mixed inorganic and organic compounds for possible applications in the fields of luminescence sensing and emitting devices.

Electron transport properties in fluorinated copper-phthalocyanine films: importance of vibrational reorganization energy and molecular microstructure.

PubMed

Wu, Fu-Chiao; Cheng, Horng-Long; Yen, Chen-Hsiang; Lin, Jyu-Wun; Liu, Shyh-Jiun; Chou, Wei-Yang; Tang, Fu-Ching

2010-03-07

Electron transport (ET) properties of a series of fluorinated copper-phthalocyanine (F(16)CuPc) thin films, which were deposited at different substrate temperatures (T(sub)) ranging from 30 to 150 degrees C, have been investigated by quantum mechanical calculations of the reorganization energy (lambda(reorg)), X-ray diffraction (XRD), atomic force microscopy (AFM), and microRaman spectroscopy. Density functional theory calculations were used to predict the vibrational frequencies, normal mode displacement vectors, and electron-vibrational lambda(reorg) for the F(16)CuPc molecule. The electron mobilities (mu(e)) of F(16)CuPc thin films are strongly dependent on the T(sub), and the value of mu(e) increases with increasing T(sub) from 30 to 120 degrees C, at which point it reaches its maximum value. The importance of electron-vibrational coupling and molecular microstructures for ET properties in F(16)CuPc thin films are discussed on the basis of theoretical vibrational lambda(reorg) calculations and experimental observations of resonance Raman spectra. We observed a good correlation between mu(e) and the full-width-at-half-maximum of the vibrational bands, which greatly contributed to lambda(reorg) and/or which reflects the molecular microstructural quality of the active channel. In contrast, the crystal size analysis by XRD and surface grain morphology by AFM did not reveal a clear correlation with the ET behaviours for these different F(16)CuPc thin films. Therefore, we suggest that for organic films with weak intermolecular interactions, such as F(16)CuPc, optimized microscopic molecular-scale parameters are highly important for efficient long-range charge transport in the macroscopic devices.

Potential for Imaging Engineered Tissues with X-Ray Phase Contrast

PubMed Central

Appel, Alyssa; Anastasio, Mark A.

2011-01-01

As the field of tissue engineering advances, it is crucial to develop imaging methods capable of providing detailed three-dimensional information on tissue structure. X-ray imaging techniques based on phase-contrast (PC) have great potential for a number of biomedical applications due to their ability to provide information about soft tissue structure without exogenous contrast agents. X-ray PC techniques retain the excellent spatial resolution, tissue penetration, and calcified tissue contrast of conventional X-ray techniques while providing drastically improved imaging of soft tissue and biomaterials. This suggests that X-ray PC techniques are very promising for evaluation of engineered tissues. In this review, four different implementations of X-ray PC imaging are described and applications to tissues of relevance to tissue engineering reviewed. In addition, recent applications of X-ray PC to the evaluation of biomaterial scaffolds and engineered tissues are presented and areas for further development and application of these techniques are discussed. Imaging techniques based on X-ray PC have significant potential for improving our ability to image and characterize engineered tissues, and their continued development and optimization could have significant impact on the field of tissue engineering. PMID:21682604

Novel Kunitz-like Peptides Discovered in the Zoanthid Palythoa caribaeorum through Transcriptome Sequencing.

PubMed

Liao, Qiwen; Li, Shengnan; Siu, Shirley Weng In; Yang, Binrui; Huang, Chen; Chan, Judy Yuet-Wa; Morlighem, Jean-Étienne R L; Wong, Clarence Tsun Ting; Rádis-Baptista, Gandhi; Lee, Simon Ming-Yuen

2018-02-02

Palythoa caribaeorum (class Anthozoa) is a zoanthid that together jellyfishes, hydra, and sea anemones, which are venomous and predatory, belongs to the Phyllum Cnidaria. The distinguished feature in these marine animals is the cnidocytes in the body tissues, responsible for toxin production and injection that are used majorly for prey capture and defense. With exception for other anthozoans, the toxin cocktails of zoanthids have been scarcely studied and are poorly known. Here, on the basis of the analysis of P. caribaeorum transcriptome, numerous predicted venom-featured polypeptides were identified including allergens, neurotoxins, membrane-active, and Kunitz-like peptides (PcKuz). The three predicted PcKuz isotoxins (1-3) were selected for functional studies. Through computational processing comprising structural phylogenetic analysis, molecular docking, and dynamics simulation, PcKuz3 was shown to be a potential voltage gated potassium-channel inhibitor. PcKuz3 fitted well as new functional Kunitz-type toxins with strong antilocomotor activity as in vivo assessed in zebrafish larvae, with weak inhibitory effect toward proteases, as evaluated in vitro. Notably, PcKuz3 can suppress, at low concentration, the 6-OHDA-induced neurotoxicity on the locomotive behavior of zebrafish, which indicated PcKuz3 may have a neuroprotective effect. Taken together, PcKuz3 figures as a novel neurotoxin structure, which differs from known homologous peptides expressed in sea anemone. Moreover, the novel PcKuz3 provides an insightful hint for biodrug development for prospective neurodegenerative disease treatment.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krumeich, F., E-mail: krumeich@inorg.chem.ethz.ch; Mueller, E.; Wepf, R.A.

While HRTEM is the well-established method to characterize the structure of dodecagonal tantalum (vanadium) telluride quasicrystals and their periodic approximants, phase-contrast imaging performed on an aberration-corrected scanning transmission electron microscope (STEM) represents a favorable alternative. The (Ta,V){sub 151}Te{sub 74} clusters, the basic structural unit in all these phases, can be visualized with high resolution. A dependence of the image contrast on defocus and specimen thickness has been observed. In thin areas, the projected crystal potential is basically imaged with either dark or bright contrast at two defocus values close to Scherzer defocus as confirmed by image simulations utilizing the principlemore » of reciprocity. Models for square-triangle tilings describing the arrangement of the basic clusters can be derived from such images. - Graphical abstract: PC-STEM image of a (Ta,V){sub 151}Te{sub 74} cluster. Highlights: Black-Right-Pointing-Pointer C{sub s}-corrected STEM is applied for the characterization of dodecagonal quasicrystals. Black-Right-Pointing-Pointer The projected potential of the structure is mirrored in the images. Black-Right-Pointing-Pointer Phase-contrast STEM imaging depends on defocus and thickness. Black-Right-Pointing-Pointer For simulations of phase-contrast STEM images, the reciprocity theorem is applicable.« less

A comprehensive investigation of structural, morphological, hydrogen absorption and magnetic properties of MmNi4.22Co0.48Mn0.15Al0.15 alloy

NASA Astrophysics Data System (ADS)

Zareii, Seyyed Mojtaba; Arabi, Hadi; Pourarian, Faiz

2014-05-01

A comprehensive study of structural, morphological, hydrogen absorption and magnetic properties of MmNi4.22 Co0.48Mn0.15Al0.15 alloy as a promising hydrogen storage media was investigated. The X-ray diffraction (XRD) profiles show that the alloy maintains its crystal structure (hexagonal LaNi5-type) even after 30 hydrogenation/dehydrogenation (H/D) cycles. However, the XRD peaks are found to be slightly broadened after cycling. SEM images reveal that particles size of the cycled sample decreases, with more uniform particle size distribution compared to noncycled ones. The pressure-composition (PC) isotherms and kinetics curves of hydrogen absorption reaction were obtained at different working temperatures by using a homemade Sievert apparatus. The enthalpy and entropy of hydride formation of the alloy were evaluated. Furthermore, the Jander diffusion and Johnson-Mehl-Avrami models as the fitting models were employed to study the kinetic mechanism of hydriding reaction and its activation energy. The room temperature magnetic measurements indicate that the milling and H/D cycling change the magnetic properties of the as-annealed alloy.

Structural properties and UV to NIR absorption spectra of metal-free phthalocyanine (H2Pc) thin films P. B. Thakor, P. N. Gajjar and A. R. Jani: Different reference systems in the study of structural properties of some simple liquid metals Shazia Bashir, M. S. Rafique, M. Khaleeq-ur-Rahman, Faizan-ul-Haq and B. R. Alvina: CO2 and Nd:YAG laser radiation induced damage in aluminium Smail Bougouffa: The study of atomic transitions by use of Numerov technique in schematic model

NASA Astrophysics Data System (ADS)

El-Nahass, M. M.; Farid, A. M.; Attia, A. A.; Ali, H. A. M.

The structural properties and absorption spectra of H2Pc thin films have been studied. The films used in these studies were thermally evaporated on glass/quartz substrates with thickness ranging from 60 to 460 nm. The XRD studies of H2Pc thin films showed that the as-deposited films have a-form with monoclinic system. The mean crystallite size (L), the dislocation density (d) and the strain (x) were evaluated. The molecular structure of H2Pc thin films is confirmed by analysis of (FTIR) spectra. The surface morphology of H2Pc thin films was examined by scanning electron microscope. The absorption spectra of H2Pc recorded in the UV - VIS - IR region for the as-deposited and the annealed thin films of different thickness have been analyzed. The spectra showed two absorption bands namely the Q-band and the Soret (B)-band. The Q-band shows its characteristic splitting (Davydove splitting) with DQ = 0.21 eV. Values of some important optical parameters, namely optical absorption coefficient (a¢), molar extinction coefficient (emolar), half-band-width (Dl), electronic dipole strength (q2) and oscillator strength (f) were calculated. The fundamental and the onset of the indirect energy gaps were also determined as 2.47 and 1.4 eV, respectively.

Structural distinction of diacyl-, alkylacyl, and alk-1-enylacyl glycerophosphocholines as [M - 15]⁻ ions by multiple-stage linear ion-trap mass spectrometry with electrospray ionization.

PubMed

Hsu, Fong-Fu; Lodhi, Irfan J; Turk, John; Semenkovich, Clay F

2014-08-01

We describe a linear ion-trap (LIT) multiple-stage (MS(n)) mass spectrometric approach towards differentiation of alkylacyl, alk-1-enylacyl- and diacyl-glycerophoscholines (PCs) as the [M - 15]⁻ ions desorbed by electrospray ionization (ESI) in the negative-ion mode. The MS⁴ mass spectra of the [M - 15 - R²'CH = CO]⁻ ions originated from the three PC subfamilies are readily distinguishable, resulting in unambiguous distinction of the lipid classes. This method is applied to two alkyl ether rich PC mixtures isolated from murine bone marrow neutrophils and kidney, respectively, to explore its utility in the characterization of complex PC mixture of biological origin, resulting in the realization of the detailed structures of the PC species, including various classes and many minor isobaric isomers.

3D Finite Element Analysis of Some Structural Modified PC Sleeper with the Vibration Characteristics between Sleeper and Ballast

NASA Astrophysics Data System (ADS)

Sakai, Hirotaka; Urakawa, Fumihiro; Aikawa, Akira; Namura, Akira

The vibration of concrete sleepers is an important factor engendering track deterioration. In this paper, we created a three-dimensional finite element model to reproduce a prestressed concrete (PC) sleeper in detail, expressing influence of ballast layers with a 3D spring series and dampers to reproduce their vibration and dynamic characteristics. Determination of these parameters bases on the experimental modal analysis using an impact excitation technique for PC sleepers by adjusting the accelerance between the analytical results and experimental results. Furthermore, we compared the difference of these characteristics between normal sleepers and those with some structural modifications. Analytical results clarified that such means as sleeper width extension and increased sleeper thickness will influence the reduction of ballasted track vibration as improvements of PC sleepers.

The Gould’s Belt Distances Survey (GOBELINS) II. Distances and Structure toward the Orion Molecular Clouds

NASA Astrophysics Data System (ADS)

Kounkel, Marina; Hartmann, Lee; Loinard, Laurent; Ortiz-León, Gisela N.; Mioduszewski, Amy J.; Rodríguez, Luis F.; Dzib, Sergio A.; Torres, Rosa M.; Pech, Gerardo; Galli, Phillip A. B.; Rivera, Juana L.; Boden, Andrew F.; Evans, Neal J., II; Briceño, Cesar; Tobin, John J.

2017-01-01

We present the results of the Gould’s Belt Distances Survey of young star-forming regions toward the Orion Molecular Cloud Complex. We detected 36 young stellar objects (YSOs) with the Very Large Baseline Array, 27 of which have been observed in at least three epochs over the course of two years. At least half of these YSOs belong to multiple systems. We obtained parallax and proper motions toward these stars to study the structure and kinematics of the Complex. We measured a distance of 388 ± 5 pc toward the Orion Nebula Cluster, 428 ± 10 pc toward the southern portion L1641, 388 ± 10 pc toward NGC 2068, and roughly ˜420 pc toward NGC 2024. Finally, we observed a strong degree of plasma radio scattering toward λ Ori.

Ionic network analysis of tectosilicates: the example of coesite at variable pressure.

PubMed

Reifenberg, Melina; Thomas, Noel W

2018-04-01

The method of ionic network analysis [Thomas (2017). Acta Cryst. B73, 74-86] is extended to tectosilicates through the example of coesite, the high-pressure polymorph of SiO 2 . The structural refinements of Černok et al. [Z. Kristallogr. (2014), 229, 761-773] are taken as the starting point for applying the method. Its purpose is to predict the unit-cell parameters and atomic coordinates at (p-T-X) values in-between those of diffraction experiments. The essential development step for tectosilicates is to define a pseudocubic parameterization of the O 4 cages of the SiO 4 tetrahedra. The six parameters a PC , b PC , c PC , α PC , β PC and γ PC allow a full quantification of the tetrahedral structure, i.e. distortion and enclosed volume. Structural predictions for coesite require that two separate quasi-planar networks are defined, one for the silicon ions and the other for the O 4 cage midpoints. A set of parametric curves is used to describe the evolution with pressure of these networks and the pseudocubic parameters. These are derived by fitting to the crystallographic data. Application of the method to monoclinic feldspars and to quartz and cristobalite is discussed. Further, a novel two-parameter quantification of the degree of tetrahedral distortion is described. At pressures in excess of ca 20.45 GPa it is not possible to find a self-consistent solution to the parametric curves for coesite, pointing to the likelihood of a phase transition.

[Study on discrimination of varieties of fire resistive coating for steel structure based on near-infrared spectroscopy].

PubMed

Xue, Gang; Song, Wen-qi; Li, Shu-chao

2015-01-01

In order to achieve the rapid identification of fire resistive coating for steel structure of different brands in circulating, a new method for the fast discrimination of varieties of fire resistive coating for steel structure by means of near infrared spectroscopy was proposed. The raster scanning near infrared spectroscopy instrument and near infrared diffuse reflectance spectroscopy were applied to collect the spectral curve of different brands of fire resistive coating for steel structure and the spectral data were preprocessed with standard normal variate transformation(standard normal variate transformation, SNV) and Norris second derivative. The principal component analysis (principal component analysis, PCA)was used to near infrared spectra for cluster analysis. The analysis results showed that the cumulate reliabilities of PC1 to PC5 were 99. 791%. The 3-dimentional plot was drawn with the scores of PC1, PC2 and PC3 X 10, which appeared to provide the best clustering of the varieties of fire resistive coating for steel structure. A total of 150 fire resistive coating samples were divided into calibration set and validation set randomly, the calibration set had 125 samples with 25 samples of each variety, and the validation set had 25 samples with 5 samples of each variety. According to the principal component scores of unknown samples, Mahalanobis distance values between each variety and unknown samples were calculated to realize the discrimination of different varieties. The qualitative analysis model for external verification of unknown samples is a 10% recognition ration. The results demonstrated that this identification method can be used as a rapid, accurate method to identify the classification of fire resistive coating for steel structure and provide technical reference for market regulation.

Genetic inactivation of prohormone convertase (PC1) causes a reduction in cholecystokinin (CCK) levels in the hippocampus, amygdala, pons and medulla in mouse brain that correlates with the degree of colocalization of PC1 and CCK mRNA in these structures in rat brain.

PubMed

Cain, B M; Connolly, K; Blum, A C; Vishnuvardhan, D; Marchand, J E; Zhu, X; Steiner, D F; Beinfeld, M C

2004-04-01

Prohormone convertase (PC1) is found in endocrine cell lines that express cholecystokinin (CCK) mRNA and process pro CCK to biologically active products. Other studies have demonstrated that PC1 may be a one of the enzymes responsible for the endoproteolytic cleavages that occur in pro CCK during its biosynthesis and processing. Prohormone convertase 1 (PC1) has a distribution that is similar to cholecystokinin (CCK) in rat brain. A moderate to high percentage of CCK mRNA-positive neurons express PC1 mRNA. CCK levels were measured in PC1 knockout and control mice to assess the degree to which loss of PC1 changed CCK content. CCK levels were decreased 62% in hippocampus, 53% in amygdala and 57% in pons-medulla in PC1 knockout mice as compared to controls. These results are highly correlated with the colocalization of CCK and PC1. The majority of CCK mRNA-positive neurons in the pyramidal cell layer of the hippocampus express PC1 mRNA and greater than 50% of CCK mRNA-positive neurons in several nuclei of the amygdala also express PC1. These results demonstrate that PC1 is important for CCK processing. PC2 and PC5 are also widely colocalized with CCK. It may be that PC2, PC5 or another non-PC enzyme are able to substitute for PC1 and sustain production of some amidated CCK. Together these enzymes may represent a redundant system to insure the production of CCK.

Colorimetric characterization models based on colorimetric characteristics evaluation for active matrix organic light emitting diode panels.

PubMed

Gong, Rui; Xu, Haisong; Tong, Qingfen

2012-10-20

The colorimetric characterization of active matrix organic light emitting diode (AMOLED) panels suffers from their poor channel independence. Based on the colorimetric characteristics evaluation of channel independence and chromaticity constancy, an accurate colorimetric characterization method, namely, the polynomial compensation model (PC model) considering channel interactions was proposed for AMOLED panels. In this model, polynomial expressions are employed to calculate the relationship between the prediction errors of XYZ tristimulus values and the digital inputs to compensate the XYZ prediction errors of the conventional piecewise linear interpolation assuming the variable chromaticity coordinates (PLVC) model. The experimental results indicated that the proposed PC model outperformed other typical characterization models for the two tested AMOLED smart-phone displays and for the professional liquid crystal display monitor as well.

Micro-Raman spectroscopy and chemometrical analysis for the distinction of copper phthalocyanine polymorphs in paint layers.

PubMed

Defeyt, C; Van Pevenage, J; Moens, L; Strivay, D; Vandenabeele, P

2013-11-01

In art analysis, copper phthalocyanine (CuPc) is often identified as an important pigment (PB15) in 20th century artworks. Raman spectroscopy is a very valuable technique for the detection of this pigment in paint systems. However, PB15 is used in different polymorphic forms and identification of the polymorph could retrieve information on the production process of the pigment at the moment. Raman spectroscopy, being a molecular spectroscopic method of analysis, is able to discriminate between polymorphs of crystals. However, in the case of PB15, spectral interpretation is not straightforward, and Raman data treatment requires some improvements concerning the PB15 polymorphic discrimination in paints. Here, Raman spectroscopy is combined with chemometrical analysis in order to develop a procedure allowing us to identify the PB15 crystalline structure in painted layers and in artworks. The results obtained by Linear Discriminant Analysis (LDA), using intensity ratios as variables, demonstrate the ability of this procedure to predict the crystalline structure of a PB15 pigment in unknown paint samples. Copyright © 2013 Elsevier B.V. All rights reserved.

From a novel HTS hit to potent, selective, and orally bioavailable KDM5 inhibitors.

PubMed

Liang, Jun; Labadie, Sharada; Zhang, Birong; Ortwine, Daniel F; Patel, Snahel; Vinogradova, Maia; Kiefer, James R; Mauer, Till; Gehling, Victor S; Harmange, Jean-Christophe; Cummings, Richard; Lai, Tommy; Liao, Jiangpeng; Zheng, Xiaoping; Liu, Yichin; Gustafson, Amy; Van der Porten, Erica; Mao, Weifeng; Liederer, Bianca M; Deshmukh, Gauri; An, Le; Ran, Yingqing; Classon, Marie; Trojer, Patrick; Dragovich, Peter S; Murray, Lesley

2017-07-01

A high-throughput screening (HTS) of the Genentech/Roche library identified a novel, uncharged scaffold as a KDM5A inhibitor. Lacking insight into the binding mode, initial attempts to improve inhibitor potency failed to improve potency, and synthesis of analogs was further hampered by the presence of a C-C bond between the pyrrolidine and pyridine. Replacing this with a C-N bond significantly simplified synthesis, yielding pyrazole analog 35, of which we obtained a co-crystal structure with KDM5A. Using structure-based design approach, we identified 50 with improved biochemical, cell potency and reduced MW and lower lipophilicity (LogD) compared with the original hit. Furthermore, 50 showed lower clearance than 9 in mice. In combination with its remarkably low plasma protein binding (PPB) in mice (40%), oral dosing of 50 at 5mg/kg resulted in unbound C max ∼2-fold of its cell potency (PC9 H3K4Me3 0.96μM), meeting our criteria for an in vivo tool compound from a new scaffold. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparing the validity of the payment card and structured haggling willingness to pay methods: The case of a diabetes prevention program in rural Kenya.

PubMed

Kangethe, Anne; Franic, Duska M; Corso, Phaedra S

2016-11-01

The objective of this study was to compare the theoretical validity of two willingness-to-pay (WTP) methods, the commonly used payment card (PC) and the recently developed structured haggling (SH), for estimating the potential benefits of a diabetes prevention program in rural Kenya. A convenience sample of adult residents from a rural county in Kenya (Kiambu), with no history of diabetes, was randomly assigned to one of two WTP methods, PC or SH, using structured face-to-face interviews from December 2011 to February 2012. A total of 376 respondents completed the interviews using PC (n = 185) or SH (n = 191). More than 95% of respondents were willing to pay something for program access. The study showed that both methods were feasible in rural Kenya. SH resulted in a higher annual mean WTP than PC, Ksh504.05 (US$7.25) versus Ksh619.95 (US$5.90), respectively (p < 0.01). Based on theory, it was hypothesized that certain predisposing factors would result in greater WTP. Greater socio-economic status (measured using income proxies) resulted in greater unconditional WTP for both the PC and SH groups (t-tests and bivariate correlations) and conditional WTP (GLM models). GLM for PC showed being male, employed and having distant relatives with diabetes were significant predictors for WTP, while for SH being educated, employed and owning a vehicle were significant predictors. Both PC and SH showed theoretical validity in rural Kenya. However, the use of SH over PC in rural Kenya may be the better choice given that SH more closely mirrors marketplace transactions in this setting and the use of SH resulted in more significant variables in the GLM models. Copyright © 2016 Elsevier Ltd. All rights reserved.

Disentangling the Circumnuclear Environs of Centaurus A. III. An Inner Molecular Ring, Nuclear Shocks, and the CO to Warm H{sub 2} Interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Espada, D.; Miura, R. E.; Iono, D.

2017-07-10

We present the distribution and kinematics of the molecular gas in the circumnuclear disk (CND; 400 pc × 200 pc) of Centaurus A with resolutions of ∼5 pc (0.″3) and shed light onto the mechanism feeding the active galactic nucleus (AGN) using CO(3–2), HCO{sup +}(4–3), HCN(4–3), and CO(6–5) observations obtained with ALMA. Multiple filaments or streamers of tens to a hundred parsec scale exist within the CND, which form a ring-like structure with an unprojected diameter of 9″ × 6″ (162 pc × 108 pc) and a position angle P.A. ≃ 155°. Inside the nuclear ring, there are two leadingmore » and straight filamentary structures with lengths of about 30–60 pc at P.A. ≃ 120° on opposite sides of the AGN, with a rotational symmetry of 180° and steeper position–velocity diagrams, which are interpreted as nuclear shocks due to non-circular motions. Along the filaments, and unlike other nearby AGNs, several dense molecular clumps present low HCN/HCO{sup +}(4–3) ratios (≲0.5). The filaments abruptly end in the probed transitions at r ≃ 20 pc from the AGN, but previous near-IR H{sub 2}( J = 1–0)S(1) maps show that they continue in an even warmer gas phase ( T ∼ 1000 K), winding up in the form of nuclear spirals, and forming an inner ring structure with another set of symmetric filaments along the N–S direction and within r ≃ 10 pc. The molecular gas is governed primarily by non-circular motions, being the successive shock fronts at different scales where loss of angular momentum occurs, a mechanism that may feed efficiently powerful radio galaxies down to parsec scales.« less

Polycomb group protein bodybuilding: working out the routines.

PubMed

Sievers, Cem; Paro, Renato

2013-09-30

Polycomb group (PcG) proteins regulate gene expression by modifying chemical and structural properties of chromatin. Isono et al. (2013) now report in Developmental Cell a polymerization-dependent mechanism used by PcG proteins to form higher-order chromatin structures, referred to as Polycomb bodies, and demonstrate its necessity for gene silencing. Copyright © 2013 Elsevier Inc. All rights reserved.

Frenkel-Charge-Transfer exciton intermixing theory for molecular crystals with two isolated Frenkel exciton states.

NASA Astrophysics Data System (ADS)

Bondarev, Igor; Popescu, Adrian

We develop an analytical theory for the intra-intermolecular exciton intermixing in periodic 1D chains of planar organic molecules with two isolated low-lying Frenkel exciton states, typical of copper phthalocyanine (CuPc) and other transition metal phthalocyanine molecules. We formulate the Hamiltonian and use the exact Bogoliubov diagonalization procedure to derive the eigen energy spectrum for the two lowest intramolecular Frenkel excitons coupled to the intermolecular charge transfer (CT) exciton state. By comparing our theoretical spectrum with available experimental CuPc absorption data, we obtain the parameters of the Frenkel-CT exciton intermixing in CuPc thin films. The two Frenkel exciton states here are spaced apart by 0.26 eV, and the charge transfer exciton state is 50 meV above the lowest Frenkel exciton. Both Frenkel excitons are strongly mixed with the CT exciton, showing the coupling constant 0.17 eV in agreement with earlier electron transport experiments. Our results can be used for the proper interpretation of the physical properties of crystalline phthalocyanines. DOE-DE-SC0007117 (I.B.), UNC-GA ROI Grant (A.P.).

Spin-orbit coupling and transport in strongly correlated two-dimensional systems

NASA Astrophysics Data System (ADS)

Huang, Jian; Pfeiffer, L. N.; West, K. W.

2017-05-01

Measuring the magnetoresistance (MR) of ultraclean GaAs two-dimensional holes for a large rs range of 20-50, two striking behaviors in relation to the spin-orbit coupling (SOC) emerge in response to strong electron-electron interaction. First, in exact correspondence to the zero-field metal-to-insulator transition (MIT), the sign of the MR switches from being positive in the metallic regime to being negative in the insulating regime when the carrier density crosses the critical density pc of MIT (rs˜39 ). Second, as the SOC-driven correction Δ ρ to the MR decreases with reducing carrier density (or the in-plane wave vector), it exhibits an upturn in the close proximity just above pc where rs is beyond 30, indicating a substantially enhanced SOC effect. This peculiar behavior echoes with a trend of delocalization long suspected for the SOC-interaction interplay. Meanwhile, for p 40 , in contrast to the common belief that a magnet field enhances Wigner crystallization, the negative MR is likely linked to enhanced interaction.

Effects of Solvent Composition on Liquid Range, Glass Transition, and Conductivity of Electrolytes of a (Li, Cs)PF 6 Salt in EC-PC-EMC Solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Michael S.; Li, Qiuyan; Li, Xing

Electrolytes of 1 M LiPF 6 (lithium hexafluorophosphate) and 0.05 M CsPF 6 (cesium hexafluorophosphate) in EC-PC-EMC (ethylene carbonate-propylene carbonate-ethyl methyl carbonate) solvents of varying solvent compositions were studied for the effects of solvent composition on the lower limit of liquid range, viscosity (as reflected by the glass transition temperature), and electrolytic conductivity. In addition, a ternary phase diagram of EC-PC-EMC was constructed and crystallization temperatures of EC and EMC were calculated to assist the interpretation and understanding of the change of liquid range with solvent composition. A function based on Vogel-Fulcher-Tammann equation was fitted to the conductivity data inmore » their entirety and plotted as conductivity surfaces in solvent composition space for more direct and clear comparisons and discussions. Changes of viscosity and dielectric constant of the solvents with their composition, in relation to those of the solvent components, were found to be underlying many of the processes studied.« less

Magnetic and Magnetocaloric Properties of Ca0.97La0.03MnO3 Manganites

NASA Astrophysics Data System (ADS)

Gong, G. D.; Hu, P. F.; Li, Y.; Kim, D. H.; Liu, C. L.; Phan, T. L.; Ho, T. A.; Yu, S. C.; Telegin, A.; Naumov, S. V.

2016-07-01

In spite of many previous studies on electron-doped CaMnO3 perovskite manganites, detailed investigations into the influence of low-doping concentrations on their magnetic and magnetocaloric (MC) properties have not been carried out yet. Additionally, there is still the lack of the comparison between single-crystal (SC) and polycrystalline (PC) materials. Dealing with these problems, we prepared orthorhombic Ca0.97La0.03MnO3 SC and PC samples. Magnetization measurements versus the temperature and magnetic field revealed remarkable differences in the magnetic property, particularly around the antiferromagnetic/ferromagnetic-paramagnetic phase-transition region. The analyses of the magnetization versus magnetic field, M( H), data indicated a weak MC effect with magnetic-entropy changes less than 0.1 J kg-1 K-1 for an applied field interval H = 10 kOe because ferromagnetic interactions between Mn3+ and Mn4+ ions are insignificant. The differences in the magnetic and MC properties of the SC and PC samples are ascribed to the effects of grain boundary, magnetic anisotropy, and nonstoichiometry in oxygen.

Divergent prion strain evolution driven by PrPC expression level in transgenic mice

PubMed Central

Le Dur, Annick; Laï, Thanh Lan; Stinnakre, Marie-George; Laisné, Aude; Chenais, Nathalie; Rakotobe, Sabine; Passet, Bruno; Reine, Fabienne; Soulier, Solange; Herzog, Laetitia; Tilly, Gaëlle; Rézaei, Human; Béringue, Vincent; Vilotte, Jean-Luc; Laude, Hubert

2017-01-01

Prions induce a fatal neurodegenerative disease in infected host brain based on the refolding and aggregation of the host-encoded prion protein PrPC into PrPSc. Structurally distinct PrPSc conformers can give rise to multiple prion strains. Constrained interactions between PrPC and different PrPSc strains can in turn lead to certain PrPSc (sub)populations being selected for cross-species transmission, or even produce mutation-like events. By contrast, prion strains are generally conserved when transmitted within the same species, or to transgenic mice expressing homologous PrPC. Here, we compare the strain properties of a representative sheep scrapie isolate transmitted to a panel of transgenic mouse lines expressing varying levels of homologous PrPC. While breeding true in mice expressing PrPC at near physiological levels, scrapie prions evolve consistently towards different strain components in mice beyond a certain threshold of PrPC overexpression. Our results support the view that PrPC gene dosage can influence prion evolution on homotypic transmission. PMID:28112164

Environmental stress cracking in gamma-irradiated polycarbonate - A diffusion approach

NASA Astrophysics Data System (ADS)

Silva, Pietro Paolo J. C. de O.; Araújo, Patricia L. B.; da Silveira, Leopoldo B. B.; Araújo, Elmo S.

2017-01-01

Polycarbonate (PC) is an engineering polymer which presents interesting properties. This material has been also used in medical devices, which is frequently exposed to gamma radiosterilization and to chemical agents. This may produce significant changes in polymer structure, leading to failure in service. The present work brings about a new approach on environmental stress cracking (ESC) processes elucidation in 100 kGy gamma-irradiated PC, by evaluating the diffusion process of methanol or 2-propanol in test specimens and determining the diffusion parameters on solvent-irradiated polymer systems. A comparison of diffusion parameters for both solvents indicated that methanol has a considerable ESC action on PC, with diffusion parameter of 7.5×10-14±1% m2 s-1 for non-irradiated PC and 7.8×10-14±2.8% m2 s-1 for PC irradiated at 100 kGy. In contrast, 2-propanol did not act as an ESC agent, as it did promote neither swelling nor cracks in the test specimens. These results were confirmed by visual analysis and optical microscopy. Unexpectedly, structural damages evidenced in tensile strength tests suggested that 2-propanol is as aggressive as methanol chemical for PC. Moreover, although some manufacturers indicate the use of 2-propanol as a cleaning product for PC artifacts, such use should be avoided in parts under mechanical stress.

Prion protein β2–α2 loop conformational landscape

PubMed Central

Caldarulo, Enrico; Wüthrich, Kurt; Parrinello, Michele

2017-01-01

In transmissible spongiform encephalopathies (TSEs), which are lethal neurodegenerative diseases that affect humans and a wide range of other mammalian species, the normal “cellular” prion protein (PrPC) is transformed into amyloid aggregates representing the “scrapie form” of the protein (PrPSc). Continued research on this system is of keen interest, since new information on the physiological function of PrPC in healthy organisms is emerging, as well as new data on the mechanism of the transformation of PrPC to PrPSc. In this paper we used two different approaches: a combination of the well-tempered ensemble (WTE) and parallel tempering (PT) schemes and metadynamics (MetaD) to characterize the conformational free-energy surface of PrPC. The focus of the data analysis was on an 11-residue polypeptide segment in mouse PrPC(121–231) that includes the β2–α2 loop of residues 167–170, for which a correlation between structure and susceptibility to prion disease has previously been described. This study includes wild-type mouse PrPC and a variant with the single-residue replacement Y169A. The resulting detailed conformational landscapes complement in an integrative manner the available experimental data on PrPC, providing quantitative insights into the nature of the structural transition-related function of the β2–α2 loop. PMID:28827331

Switchable multi-wavelength fiber ring laser based on a compact in-fiber Mach-Zehnder interferometer with photonic crystal fiber

NASA Astrophysics Data System (ADS)

Chen, W. G.; Lou, S. Q.; Feng, S. C.; Wang, L. W.; Li, H. L.; Guo, T. Y.; Jian, S. S.

2009-11-01

Switchable multi-wavelength fiber ring laser with an in-fiber Mach-Zehnder interferometer incorporated into the ring cavity serving as wavelength-selective filter at room temperature is demonstrated. The filter is formed by splicing a section of few-mode photonic crystal fiber (PCF) and two segments of single mode fiber (SMF) with the air-holes on the both sides of PCF intentionally collapsed in the vicinity of the splices. By adjusting the states of the polarization controller (PC) appropriately, the laser can be switched among the stable single-, dual- and triple-wavelength lasing operations by exploiting polarization hole burning (PHB) effect.

Switchable dual-wavelength erbium-doped fiber laser based on the photonic crystal fiber loop mirror and chirped fiber Bragg grating

NASA Astrophysics Data System (ADS)

Chen, Wei-Guo; Lou, Shu-Qin; Wang, Li-Wen; Li, Hong-Lei; Guo, Tieying; Jian, Shui-Sheng

2010-03-01

The switchable dual-wavelength erbium-doped fiber laser (EDFL) with a two-mode photonic crystal fiber (PCF) loop mirror and a chirped fiber Bragg grating (CFBG) at room temperature is proposed and experimentally demonstrated. The two-mode PCF loop mirror is formed by inserting a piece of two-mode PCF into a Sagnac loop mirror, with the air-holes of the PCF intentionally collapsing at the splices. By adjusting the state of the polarization controller (PC) appropriately, the laser can be switched between the stable single- and dual-wavelength operations by means of the polarization hole burning (PHB) and spectral hole burning (SHB) effects.

Fabrication of a Quartz-Crystal-Microbalance/Optical-Waveguide Hybrid Sensor and In situ Evaluation of Vacuum-Evaporated Lead Phthalocyanine Thin Film

NASA Astrophysics Data System (ADS)

Shinbo, Kazunari; Uno, Akihiro; Hirakawa, Ryo; Baba, Akira; Ohdaira, Yasuo; Kato, Keizo; Kaneko, Futao

2013-05-01

In this study, we fabricated a novel quartz-crystal-microbalance (QCM)/optical-waveguide hybrid sensor. An in situ observation of a lead phthalocyanine (PbPc) thin-film deposition was conducted during vacuum evaporation, and the effectiveness of the sensor was demonstrated. The film thickness was obtained from the QCM frequency, and the optical absorption of the film was observed by optical waveguide spectroscopy using part of the QCM substrate without the electrode. The film absorption depends on the polarization direction, substrate temperature and deposition rate, owing to aggregate formation. The thickness dependence of the absorption property was also investigated.

Using mass spectrometry and small molecule reagents to detect distinctive structural features of different prion conformations (strains)

USDA-ARS?s Scientific Manuscript database

A prion (PrPSc) is a conformer of a normal cellular prion protein (PrPC). Although they are isosequential, PrPSc is an infectious protein able to convert PrPC into the prion conformation and thereby propagate an infection. PrPC is monomeric while PrPSc is a multimer. PrPSc can adopt more than one co...

PC-based Multiple Information System Interface (PC/MISI) detailed design and implementation plan

NASA Technical Reports Server (NTRS)

Dominick, Wayne D. (Editor); Hall, Philip P.

1985-01-01

The design plan for the personal computer multiple information system interface (PC/MISI) project is discussed. The document is intended to be used as a blueprint for the implementation of the system. Each component is described in the detail necessary to allow programmers to implement the system. A description of the system data flow and system file structures is given.

Active site formation mechanism of carbon-based oxygen reduction catalysts derived from a hyperbranched iron phthalocyanine polymer.

PubMed

Hiraike, Yusuke; Saito, Makoto; Niwa, Hideharu; Kobayashi, Masaki; Harada, Yoshihisa; Oshima, Masaharu; Kim, Jaehong; Nabae, Yuta; Kakimoto, Masa-Aki

2015-01-01

Carbon-based cathode catalysts derived from a hyperbranched iron phthalocyanine polymer (HB-FePc) were characterized, and their active-site formation mechanism was studied by synchrotron-based spectroscopy. The properties of the HB-FePc catalyst are compared with those of a catalyst with high oxygen reduction reaction (ORR) activity synthesized from a mixture of iron phthalocyanine and phenolic resin (FePc/PhRs). Electrochemical measurements demonstrate that the HB-FePc catalyst does not lose its ORR activity up to 900°C, whereas that of the FePc/PhRs catalyst decreases above 700°C. Hard X-ray photoemission spectra reveal that the HB-FePc catalysts retain more nitrogen components than the FePc/PhRs catalysts between pyrolysis temperatures of 600°C and 800°C. This is because the linked structure of the HB-FePc precursor has high thermostability against nitrogen desorption. Consequently, effective doping of active nitrogen species into the sp (2) carbon network of the HB-FePc catalysts may occur up to 900°C.

Probing long-range structural order in SnPc/Ag(111) by umklapp process assisted low-energy angle-resolved photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Jauernik, Stephan; Hein, Petra; Gurgel, Max; Falke, Julian; Bauer, Michael

2018-03-01

Laser-based angle-resolved photoelectron spectroscopy is performed on tin-phthalocyanine (SnPc) adsorbed on silver Ag(111). Upon adsorption of SnPc, strongly dispersing bands are observed which are identified as secondary Mahan cones formed by surface umklapp processes acting on photoelectrons from the silver substrate as they transit through the ordered adsorbate layer. We show that the photoemission data carry quantitative structural information on the adsorbate layer similar to what can be obtained from a conventional low-energy electron diffraction (LEED) study. More specifically, we compare photoemission data and LEED data probing an incommensurate-to-commensurate structural phase transition of the adsorbate layer. Based on our results we propose that Mahan-cone spectroscopy operated in a pump-probe configuration can be used in the future to probe structural dynamics at surfaces with a temporal resolution in the sub-100-fs regime.

Mode control in photonic crystal surface emitting lasers (PCSELs) through in-plane feedback (Conference Presentation)

NASA Astrophysics Data System (ADS)

Taylor, Richard J. E.; Li, Guangrui; Ivanov, Pavlo; Childs, David T. D.; Stevens, Ben J.; Babazadeh, Nasser; Ignatova, Olesya; Hogg, Richard A.

2017-02-01

All-semiconductor photonic crystal surface-emitting lasers (PCSELs) operating in CW mode at room temperature and coherently coupled arrays of these lasers are reviewed. These PCSELs are grown via MOVPE on GaAs substrates and include QW active elements and GaAs/InGaP photonic crystal (PC) layer situated above this active zone. Atoms of triangular shapes have been shown to increase optical power from the PCSEL but are also shown to result in a competition between lasing modes. Simulation shows that the energy splitting of lasing modes is smaller for triangular atoms, than for circles making high power single-mode devices difficult to achieve. In this work we experimentally investigate the effect of lateral optical feedback introduced by a facet cleave along one or two perpendicular PCSEL edges. This cleavage plane is misaligned to the PC resulting in a periodic variation of facet phase along the side of the device. Results confirm that a single cleave selects the lowest threshold 2D lasing mode, resulting in a 20% reduction in threshold current and favours single-mode emission. The addition of a second cleave at right-angles to the first has no significant effect upon threshold current. The virgin device is shown to have a symmetric far-field (1 degree) whilst a single cleave produces a 1 degree divergence perpendicular to cleave and 5 degree parallel to cleave. The second orthogonal cleave results in the far field becoming symmetric again but with a divergence angle of 1 degree indicating that single-mode lasing is supported over a wider area.

Toward large-area roll-to-roll printed nanophotonic sensors

NASA Astrophysics Data System (ADS)

Karioja, Pentti; Hiltunen, Jussi; Aikio, Sanna M.; Alajoki, Teemu; Tuominen, Jarkko; Hiltunen, Marianne; Siitonen, Samuli; Kontturi, Ville; Böhlen, Karl; Hauser, Rene; Charlton, Martin; Boersma, Arjen; Lieberzeit, Peter; Felder, Thorsten; Eustace, David; Haskal, Eliav

2014-05-01

Polymers have become an important material group in fabricating discrete photonic components and integrated optical devices. This is due to their good properties: high optical transmittance, versatile processability at relative low temperatures and potential for low-cost production. Recently, nanoimprinting or nanoimprint lithography (NIL) has obtained a plenty of research interest. In NIL, a mould is pressed against a substrate coated with a moldable material. After deformation of the material, the mold is separated and a replica of the mold is formed. Compared with conventional lithographic methods, imprinting is simple to carry out, requires less-complicated equipment and can provide high-resolution with high throughput. Nanoimprint lithography has shown potential to become a method for low-cost and high-throughput fabrication of nanostructures. We show the development process of nano-structured, large-area multi-parameter sensors using Photonic Crystal (PC) and Surface Enhanced Raman Scattering (SERS) methodologies for environmental and pharmaceutical applications. We address these challenges by developing roll-to-roll (R2R) UV-nanoimprint fabrication methods. Our development steps are the following: Firstly, the proof of concept structures are fabricated by the use of wafer-level processes in Si-based materials. Secondly, the master molds of successful designs are fabricated, and they are used to transfer the nanophotonic structures into polymer materials using sheet-level UV-nanoimprinting. Thirdly, the sheet-level nanoimprinting processes are transferred to roll-to-roll fabrication. In order to enhance roll-to-roll manufacturing capabilities, silicone-based polymer material development was carried out. In the different development phases, Photonic Crystal and SERS sensor structures with increasing complexities were fabricated using polymer materials in order to enhance sheet-level and roll-to-roll manufacturing processes. In addition, chemical and molecular imprint (MIP) functionalization methods were applied in the sensor demonstrators. In this paper, the process flow in fabricating large-area nanophotonic structures by the use of sheet-level and roll-to-roll UV- nanoimprinting is reported.

Study of relation between Pc 3 micropulsations and magnetosheath fluctuations, and multisatellite investigation of earth's bow shock

NASA Technical Reports Server (NTRS)

Greenstadt, E. W.

1975-01-01

The validity is investigated of a suggested model according to which Pc 3 and/or Pc 4 micropulsations are excited by magnetosheath field (and plasma) fluctuations arising in the quasi-parallel structure of the subsolar bow shock. The influence of solar wind plasma parameters on local shock structure and on the configuration of the entire bow shock system is included. Simultaneous data from two or more spacecraft and from multiple diagnostics is used to evaluate the geometrical factor, field-to-shock normal angle, or its B-X equivalent, and the principal plasma parameters. Results are presented and discussed.

Correlations of OGO-V plasmapause crossing with observations of type Pi micropulsations on the ground.

NASA Technical Reports Server (NTRS)

Heacock, R. R.; Mullen, A. J.; Hessler, V. P.; Sucksdorff, C.; Kivinen, M.; Kataja, E.

1971-01-01

Comparison of plasmapause positions with Pi micropulsation events observed at College (L 5.4) or at Sodankyla (L 5.1), showing that in almost all cases the plasmapause was inside the field line of the observing site when the Pi event was recorded. Strong Pi events were seen at Nurmijaarvi (L 3.4) only when Kp was very high, when the plasmapause would be expected to be inside L 3.4. When Pi events and structure Pc 1 events were observed nearly simultaneously, the Pi activity was always more prominent at the poleward site. A demarcation line seems to exist, separating the Pi and structured Pc 1 source regions. This line may be the plasmapause, with structured Pc 1 inside and Pi outside.

Androgen Receptor-Targeted Treatments for Prostate Cancer: 35 Years' Progress with Antiandrogens.

PubMed

Crawford, E David; Schellhammer, Paul F; McLeod, David G; Moul, Judd W; Higano, Celestia S; Shore, Neal; Denis, Louis; Iversen, Peter; Eisenberger, Mario A; Labrie, Fernand

2018-05-03

Antiandrogens inhibit the androgen receptor (AR) and play an important role in the treatment of prostate cancer (PC). This review provides a historical perspective on the development and clinical benefit of antiandrogens in the treatment of PC. We searched PubMed ® for clinical trials with the search terms "antiandrogens" and "prostate cancer" combined with drug names for antiandrogens. This article represents a collaboration of clinical investigators who have made critical scientific contributions leading to the approval of antiandrogens for treating patients with PC. Antiandrogens differ in chemical structure and exert varying efficacy and safety profiles. The unfavorable therapeutic index of steroidal antiandrogens led to their replacement by safer nonsteroidal agents. Flutamide, nilutamide and bicalutamide, designed to target the AR, were developed primarily for use in combination with castration to provide "combined" androgen blockade. Modest clinical benefits were observed with the combination of first-generation antiandrogens and castration vs castration alone. With increased knowledge of the AR structure and its biological functions, a new generation of antiandrogens without agonist activity was designed to provide more potent inhibition of the AR. Randomized clinical trials in patients with metastatic castration-resistant PC exhibited significant survival benefits, which led to the approval, in August 2012, of enzalutamide. Apalutamide was recently approved, while darolutamide is not yet approved in the United States. These next-generation antiandrogens are being actively tested in earlier disease states such as nonmetastatic PC. Evolving knowledge of resistance mechanisms to AR-targeted treatments will stimulate research and drug discovery for additional compounds. Further testing in nonmetastatic castration-resistant PC as well as castration-sensitive disease states will hopefully augment our ability to treat a broader spectrum of PC patients. Antiandrogens have already provided important benefits for PC treatment. Greater knowledge about the structural and functional biology of the AR in PC will facilitate further discovery and development of further improved antiandrogens with enhanced clinical activity in patients with advanced metastatic disease. Testing of these new agents earlier in the course of a patient's PC may further improve the survival and quality of life of those with current local and/or systemic treatment modalities. Copyright © 2018 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Developing a palliative care service model for Muslim Middle Eastern countries.

PubMed

Al-Awamer, Ahmed; Downar, James

2014-12-01

Palliative Care (PC) was first introduced to Muslim Middle Eastern (MME) countries in 1992, but growth of PC has been slow and access to PC is still limited in the region. While most PC models have been developed in Western countries, MME societies have different cultural and religious values that are not incorporated in Western models. We conducted a qualitative study to look at these differences, in order to inform a culturally acceptable model of PC that meets the needs of MME patients and their families. We conducted semi-structured interviews of PC physicians and nurses with experience in both Western and MME countries. Participants were identified by snowball sampling. Interviews were transcribed and analyzed using a modified grounded-theory approach. We achieved conceptual saturation after 13 interviews. Participants identified four differences between PC practice in Western and MME countries including: cultural differences, legal and policy differences, stances on PC philosophy, and the availability of resources and support for PC. Participants identified five barriers to advancing PC in the MME: shortage of resources, unclear laws and policies, healthcare system barriers, unfamiliarity with the role and benefits of PC, and cultural barriers. Respondents suggested many facilitators at the institutional, regional, and societal levels. We identified a number of important differences in PC practice, as well as common barriers and facilitators for developing PC services in MME countries. This information can help clinicians who are developing PC services in a MME country.

Transannular sulfur-nitrogen interaction in 1,5-thiazocine derivatives: an X-ray study

NASA Astrophysics Data System (ADS)

Kuti, M.; Rábai, J.; Kapovits, I.; Jalsovszky, I.; Argay, Gy.; Kálmán, A.; Párkányi, L.

1996-08-01

7-Acetylbenzo[ b]naphtho[1,8- f, g]thiazocin-8(7 H)-onesulfide- N-acetyllactam 3) and its 13-oxide (sulfoxide- N-acetyl-lactam 4, exhibiting polymorphy, 4a and 4b) have been prepared and their structures established by X-ray crystallography from diffractometer data. Compound 3 (C 19H 13NO 2S) crystallizes in the monoclinic space group {P2 1}/{c} with a = 10.716(3), b = 9.222(2), c = 16.077(5) Å, β = 106.68(2)°, V = 1521.9(7) Å3, Z = 4, Dc = 1.394 g cm -3 and μ(Mo K α) = 0.22 mm -1. Compound 4a (C 19H 13NO 3S) crystallizes in the monoclinic space group Pc with a = 7.821(1), b = 24.795(6), c = 8.342(1) Å, β = 101.15(1)°, V = 1587.2(4) Å3, Z = 4 (two molecules, 4a' and 4a″, in the asymmetric unit), Dc = 1.40 g cm -3 and μ(Mo K α) = 0.21 mm -1. Compound 4b also crystallizes in the monoclinic space group {P2 1}/{c} with a = 11.791(1), b = 10.719(1), c = 25.193(2) Å, β = 96.02(1)°, V = 3166.4(4) Å3, Z = 8 (two molecules, 4b' and 4b″ in the asymmetric unit), Dc = 1.394 g cm -3 and μ(Cu K α) = 1.92 mm -1. The crystal structures were solved by direct methods and refined to R = 0.052 for 3, R = 0.088 for 4a, and R = 0.048 for 4b, by using 9413, 4759 and 5195 reflections, respectively. Owing to the cis-amide structure, compounds 3 and 4 assume a boat-like conformation with transannular sulfur-nitrogen close contact; r( S…N) = 2.968(1) Å for 3 and 2.753(3)-2.832(2) Å for 4a' and 4b″. The out-of-ring position of the sulfinyl oxygen leads to a sulfurane-like trigonal bipyramidal geometry about sulfur in in 4a' and 4b″; θ(OS…N) = 175.8(3)-178.7(2)°. The interatomic distances r( SO) = 1.483(2)-1.498(3) Å and r( OS…N) = 4.245-4.314 Å are in agreement with an SO double bond and S…N close contact rather than with an OSN type molecular structure observed in spirosulfuranes. The stereochemistries of 1,5-thiazocine and 1,5-thiazonine rings are compared.

Effects of Phase Separation Behavior on Morphology and Performance of Polycarbonate Membranes.

PubMed

Idris, Alamin; Man, Zakaria; Maulud, Abdulhalim S; Khan, Muhammad Saad

2017-04-05

The phase separation behavior of bisphenol-A-polycarbonate (PC), dissolved in N -methyl-2-pyrrolidone and dichloromethane solvents in coagulant water, was studied by the cloud point method. The respective cloud point data were determined by titration against water at room temperature and the characteristic binodal curves for the ternary systems were plotted. Further, the physical properties such as viscosity, refractive index, and density of the solution were measured. The critical polymer concentrations were determined from the viscosity measurements. PC/NMP and PC/DCM membranes were fabricated by the dry-wet phase inversion technique and characterized for their morphology, structure, and thermal stability using field emission scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis, respectively. The membranes' performances were tested for their permeance to CO₂, CH₄, and N₂ gases at 24 ± 0.5 °C with varying feed pressures from 2 to 10 bar. The PC/DCM membranes appeared to be asymmetric dense membrane types with appreciable thermal stability, whereas the PC/NMP membranes were observed to be asymmetric with porous structures exhibiting 4.18% and 9.17% decrease in the initial and maximum degradation temperatures, respectively. The ideal CO₂/N₂ and CO₂/CH₄ selectivities of the PC/NMP membrane decreased with the increase in feed pressures, while for the PC/DCM membrane, the average ideal CO₂/N₂ and CO₂/CH₄ selectivities were found to be 25.1 ± 0.8 and 21.1 ± 0.6, respectively. Therefore, the PC/DCM membranes with dense morphologies are appropriate for gas separation applications.

Structural characteristics of phosphorus-doped C60 thin film prepared by radio frequency-plasma assisted thermal evaporation technique.

PubMed

Arie, Arenst Andreas; Lee, Joong Kee

2012-02-01

Phosphorus doped C60 (P:C60) thin films were prepared by a radio frequency plasma assisted thermal evaporation technique using C60 powder as a carbon source and a mixture of argon and phosphine (PH3) gas as a dopant precursor. The effects of the plasma power on the structural characteristics of the as-prepared films were then studied using Raman spectroscopy, Auger electron spectroscopy (AES) and X-ray photo-electrons spectroscopy (XPS). XPS and Auger analysis indicated that the films were mainly composed of C and P and that the concentration of P was proportional to the plasma power. The Raman results implied that the doped films contained a more disordered carbon structure than the un-doped samples. The P:C60 films were then used as a coating layer for the Si anodes of lithium ion secondary batteries. The cyclic voltammetry (CV) analysis of the P:C60 coated Si electrodes demonstrated that the P:C60 coating layer might be used to improve the transport of Li-ions at the electrode/electrolyte interface.

Energetic and Informative Interaction of Microwaves with Neurons and Enzymes

NASA Astrophysics Data System (ADS)

Maharramov, A. A.; Babazade, S. N.; Yusifov, E. Yu.; Gajiyev, A. M.

2007-04-01

Besides Purkinje Cells (PC) in cat cerebellum, experiments on Microwave-Living System interaction have been performed on some antioxidant enzymes - Super oxide dismutase (SOD), Catalase (C) and Glutathione peroxidase (GP) in the eye structures (pigment epithelium and neuronal structure - retina) in frogs, and on Glucose-6-Phosphatedehydrogenase (GPD) and Pyruvate-kinase (PK) in different organs - cerebellum, hypothalamus, liver and erythrocytes - of wistar albino rats. Exposure parameters of Microwaves of decimetre range (DRM) - total exposure, λ=65 cm, duration of exposition 10-20 minutes. According to the data obtained it may be concluded that, PC increasing their impulse activity irregularity, may react to the energetic (thermal) component of DRM action, whereas the result of informative (subtle) interaction between DRM and PC leads to the increase of regularity in electrophysiological activity of the latter. In the case of enzymes, in identification of the character of interactions, the type of the enzymes, the structure where an enzyme activity is studied and the physiological conditions related to such a factor as hunger, for example, take places. In this paper the effects of DRM on PC, G6PD and PK have been presented.

CuPc/Au(1 1 0): Determination of the azimuthal alignment by a combination of angle-resolved photoemission and density functional theory

PubMed Central

Lüftner, Daniel; Milko, Matus; Huppmann, Sophia; Scholz, Markus; Ngyuen, Nam; Wießner, Michael; Schöll, Achim; Reinert, Friedrich; Puschnig, Peter

2014-01-01

Here we report on a combined experimental and theoretical study on the structural and electronic properties of a monolayer of Copper-Phthalocyanine (CuPc) on the Au(1 1 0) surface. Low-energy electron diffraction reveals a commensurate overlayer unit cell containing one adsorbate species. The azimuthal alignment of the CuPc molecule is revealed by comparing experimental constant binding energy (kxky)-maps using angle-resolved photoelectron spectroscopy with theoretical momentum maps of the free molecule's highest occupied molecular orbital (HOMO). This structural information is confirmed by total energy calculations within the framework of van-der-Waals corrected density functional theory. The electronic structure is further analyzed by computing the molecule-projected density of states, using both a semi-local and a hybrid exchange-correlation functional. In agreement with experiment, the HOMO is located about 1.2 eV below the Fermi-level, while there is no significant charge transfer into the molecule and the CuPc LUMO remains unoccupied on the Au(1 1 0) surface. PMID:25284953

THE GOULD’S BELT DISTANCES SURVEY (GOBELINS). II. DISTANCES AND STRUCTURE TOWARD THE ORION MOLECULAR CLOUDS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kounkel, Marina; Hartmann, Lee; Loinard, Laurent

We present the results of the Gould’s Belt Distances Survey of young star-forming regions toward the Orion Molecular Cloud Complex. We detected 36 young stellar objects (YSOs) with the Very Large Baseline Array, 27 of which have been observed in at least three epochs over the course of two years. At least half of these YSOs belong to multiple systems. We obtained parallax and proper motions toward these stars to study the structure and kinematics of the Complex. We measured a distance of 388 ± 5 pc toward the Orion Nebula Cluster, 428 ± 10 pc toward the southern portion L1641, 388 ± 10 pc towardmore » NGC 2068, and roughly ∼420 pc toward NGC 2024. Finally, we observed a strong degree of plasma radio scattering toward λ Ori.« less

Design and synthesis of formononetin-dithiocarbamate hybrids that inhibit growth and migration of PC-3 cells via MAPK/Wnt signaling pathways

PubMed Central

Fu, Dong-Jun; Zhang, Li; Song, Jian; Mao, Ruo-Wang; Zhao, Ruo-Han; Liu, Ying-Chao; Hou, Yu-Hui; Li, Jia-Huan; Yang, Jia-Jia; Jin, Cheng-Yun; Li, Ping; Zi, Xiao-Lin; Liu, Hong-Min; Zhang, Sai-Yang; Zhang, Yan-Bing

2017-01-01

A series of novel formononetin-dithiocarbamate derivatives were designed, synthesized and evaluated for antiproliferative activity against three selected cancer cell line (MGC-803, EC-109, PC-3). The first structure-activity relationship (SAR) for this formononetin-dithiocarbamate scaffold is explored in this report with evaluation of 14 variants of the structural class. Among these analogues, tert-butyl 4-(((3-((3-(4-methoxyphenyl)-4-oxo-4H–chromen-7-yl)oxy)propyl)thio)carbonothioyl)piperazine-1-carboxylate (8i) showed the best inhibitory activity against PC-3 cells (IC50 = 1. 97 µM). Cellular mechanism studies elucidated 8i arrests cell cycle at G1 phase and regulates the expression of G1 checkpoint-related proteins in concentration-dependent manners. Furthermore, 8i could inhibit cell growth via MAPK signaling pathway and inhibit migration via Wnt pathway in PC-3 cells. PMID:28038329

Designer Disordered Complex Media: Hyperuniform Photonic and Phononic Band Gap Materials

NASA Astrophysics Data System (ADS)

Amoah, Timothy

In this thesis we investigate designer disordered complex media for photonics and phononics applications. Initially we focus on the photonic properties and we analyse hyperuniform disordered structures (HUDS) using numerical simulations. Photonic HUDS are a new class of photonic solids, which display large, isotropic photonic band gaps (PBG) comparable in size to the ones found in photonic crystals (PC). We review their complex interference properties, including the origin of PBGs and potential applications. HUDS combine advantages of both isotropy due to disorder (absence of long-range order) and controlled scattering properties from uniform local topology due to hyperuniformity (constrained disorder). The existence of large band gaps in HUDS contradicts the longstanding intuition that Bragg scattering and long-range translational order is required in PBG formation, and demonstrates that interactions between Mie-like local resonances and multiple scattering can induce on their own PBGs. The discussion is extended to finite height effects of planar architectures such as pseudo-band-gaps in photonic slabs as well as the vertical confinement in the presence of disorder. The particular case of a silicon-on-insulator compatible hyperuniform disordered network structure is considered for TE polarised light. We address technologically realisable designs of HUDS including localisation of light in point-defect-like optical cavities and the guiding of light in freeform PC waveguide analogues. Using finite-difference time domain and band structure computer simulations, we show that it is possible to construct optical cavities in planar hyperuniform disordered solids with isotropic band gaps that effciently confine TE polarised radiation. We thus demonstrate that HUDS are a promising general-purpose design platform for integrated optical micro-circuitry. After analysing HUDS for photonic applications we investigate them in the context of elastic waves towards phononics applications. We demonstrate the first phononic band gaps (PnBG) for HUDS. We find that PnBGs in phononic HUDS can confine and guide elastic waves similar to photonic HUDS for EM radiation.

[Synthesis of a supermolecular nanoparticle γ-hy-PC/Ada-Dox and its antitumor activity].

PubMed

Li, Yong-bin; Wang, Kai; Hu, Tian-nan; Wang, Qi-wen; Hu, Qi-da; Zhou, Jun; Hu, Xiu-rong; Tang, Gu-ping

2012-11-01

To synthesize a (2-Hydroxypropyl)-γ-cyclodextrin-polyethylenimine/adamantane-conjugated doxorubicin (γ-hy-PC/Ada-Dox) based supramolecular nanoparticle with host-guest interaction and to identify its physicochemical characterizations and antitumor effect. A novel non-viral gene delivery vector γ-hy-PC/Ada-Dox was synthesized based on host-guest interaction. 1H-NMR, NOESY, UV-Vis, XRD and TGA were used to confirm the structure of the vector. The DNA condensing ability of complexes was investigated by particle size, zeta potential and gel retardation assay. Cytotoxicity of complexes was determined by MTT assay in BEL-7402 and SMMC-7721 cells. Cell wound healing assay was performed in HEK293 and BEL-7404 cells. The transfection efficiency was investigated in HEK293 cells. H/E staining and cell uptake assay was performed in BEL-7402 cells. The structure of γ-hy-PC/Ada-Dox was characterized by 1H-NMR, NOESY, UV-Vis, XRD, TGA. The drug loading was 0.5% and 5.5%. Gel retardation assay showed that γ-hy-PC was able to completely condense DNA at N/P ratio of 2; 0.5% and 5.5% γ-hy-PC/Ada-Dox was able to completely condense DNA at N/P ratio of 3 and 4,respectively. The cytotoxicity of polymers was lower than that of PEI25KDa. The transfection efficiency of γ-hy-PC was higher than that of γ-hy-PC/Ada-Dox at N/P ratio of 30 in HEK293 cells; and the transfection efficiency was decreasing when Ada-Dox loading was increasing. Cell uptake assay showed that γ-hy-PC/Ada-Dox was able to carry drug and FAM-siRNA into cells. The novel vector γ-hy-PC/Ada-Dox has been developed successfully, which has certain transfection efficiency and antitumor activity.

Controlling insulin release from reverse hexagonal (HII) liquid crystalline mesophase by enzymatic lipolysis.

PubMed

Mishraki-Berkowitz, Tehila; Cohen, Guy; Aserin, Abraham; Garti, Nissim

2018-01-01

In the present study we aimed to control insulin release from the reverse hexagonal (H II ) mesophase using Thermomyces lanuginosa lipase (TLL) in the environment (outer TLL) or within the H II cylinders (inner TLL). Two insulin-loaded systems differing by the presence (or absence) of phosphatidylcholine (PC) were examined. In general, incorporation of PC into the H II interface (without TLL) increased insulin release, as a more cooperative system was formed. Addition of TLL to the systems' environments resulted in lipolysis of the H II structure. In the absence of PC, the lipolysis was more dominant and led to a significant increase in insulin release (50% after 8h). However, the presence of PC stabilized the interface, hindering the lipolysis, and therefore no impact on the release profile was detected during the first 8h. Entrapment of TLL within the H II cylinders (with and without PC) drastically increased insulin release in both systems up to 100%. In the presence of PC insulin released faster and the structure was more stable. Consequently, the presence of lipases (inner or outer) both enhanced the destruction of the carrier, and provided sustained release of the entrapped insulin. Copyright © 2017 Elsevier B.V. All rights reserved.

Impact-induced fracture mechanisms of immiscible PC/ABS (50/50) blends

NASA Astrophysics Data System (ADS)

Machmud, M. N.; Omiya, M.; Inoue, H.; Kishimoto, K.

2018-03-01

This paper presents a study on fracture mechanisms of polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) (50/50) blends with different ABS types under a drop weight impact test (DWIT) using a circular sheet specimen. Formation of secondary crack indicated by a stress-whitening layer on the mid-plane of scattered specimens and secondary surface of fracture perpendicular to primary fracture surface were captured under scanning electron microscope (SEM). Although the both blends finally failed in brittle modes, SEM observation showed that their secondary fracture mechanisms were completely different. Observation through the thickness of the etched PC/ABS specimen samples using SEM also clearly showed that PC and ABS were immiscible. The immiscibility between PC and ABS was indicated by presence of their layer structures through the thickness of the blends. It was revealed that layer of ABS structure was influenced by size of rubber particle and this latter parameter then affected microstructure and fracture mechanisms of the blends. Impact-induced fracture mechanisms of the blends due to such microstructures are discussed in this paper. It was also pointed out that the secondary cracking was likely caused by interface delamination between PC and ABS layers in the core due to transverse shear stress generated during the impact test.

Can your software engineer program your PLC?

NASA Astrophysics Data System (ADS)

Borrowman, Alastair J.; Taylor, Philip

2016-07-01

The use of Programmable Logic Controllers (PLCs) in the control of large physics experiments is ubiquitous1, 2, 3. The programming of these controllers is normally the domain of engineers with a background in electronics, this paper introduces PLC program development from the software engineer's perspective. PLC programs provide the link between control software running on PC architecture systems and physical hardware controlled and monitored by digital and analog signals. The higher-level software running on the PC is typically responsible for accepting operator input and from this deciding when and how hardware connected to the PLC is controlled. The PLC accepts demands from the PC, considers the current state of its connected hardware and if correct to do so (based upon interlocks or other constraints) adjusts its hardware output signals appropriately for the PC's demands. A published ICD (Interface Control Document) defines the PLC memory locations available to be written and read by the PC to control and monitor the hardware. Historically the method of programming PLCs has been ladder diagrams that closely resemble circuit diagrams, however, PLC manufacturers nowadays also provide, and promote, the use of higher-level programming languages4. Based on techniques used in the development of high-level PC software to control PLCs for multiple telescopes, this paper examines the development of PLC programs to operate the hardware of a medical cyclotron beamline controlled from a PC using the Experimental Physics and Industrial Control System (EPICS), which is also widely used in telescope control5, 6, 7. The PLC used is the new generation Siemens S7-1200 programmed using Siemens Pascal based Structured Control Language (SCL), which is their implementation of Structured Text (ST). The approach described is that from a software engineer's perspective, utilising Siemens Totally Integrated Automation (TIA) Portal integrated development environment (IDE) to create modular PLC programs based upon reusable functions capable of being unit tested without the PLC connected to hardware. Emphasis has been placed on designing an interface between EPICS and SCL that enforces correct operation of hardware through stringent separation of PC accessible PLC memory and hardware I/O addresses used only by the PLC. The paper also introduces the method used to automate the creation, from the same source document, the PLC memory structure (tag) definitions (defining memory used to access hardware I/O and that accessed by the PC) and creation of the PC program data structures (EPICS database records) used to access the permitted PLC addresses. From direct experience this paper demonstrates the advantages of PLC program development being shared between electronic and software engineers, to enable use of the most appropriate processes from both the perspective of the hardware and the higher-level software used to control it.

Structure-activity relationships of aminocoumarin-type gyrase and topoisomerase IV inhibitors obtained by combinatorial biosynthesis.

PubMed

Flatman, Ruth H; Eustaquio, Alessandra; Li, Shu-Ming; Heide, Lutz; Maxwell, Anthony

2006-04-01

Novobiocin and clorobiocin are gyrase inhibitors produced by Streptomyces strains. Structurally, the two compounds differ only by substitution at two positions: CH3 versus Cl at position 8' of the aminocoumarin ring and carbamoyl versus 5-methyl-pyrrol-2-carbonyl (MePC) at the 3"-OH of noviose. Using genetic engineering, we generated a series of analogs carrying H, CH3, or Cl at 8' and H, carbamoyl, or MePC at 3"-OH. Comparison of the gyrase inhibitory activities of all nine structural permutations confirmed that acylation of 3"-OH is essential for activity, with MePC being more effective than carbamoyl. Substitution at 8' further enhanced activity, but the effect of CH3 or Cl depended on the nature of the acyl group at 3": in the presence of carbamoyl at 3", CH3 resulted in higher activity; in the presence of MePC at 3", Cl resulted in higher activity. This suggests that the structures of both natural compounds are highly evolved for optimal interaction with gyrase. In a second series of experiments, clorobiocin derivatives with and without the methyl group at 4"-OH of noviose, and with different positions of the MePC group of noviose, were tested. Again clorobiocin was superior to all of its analogs. The activities of all compounds were also tested against topoisomerase IV (topo IV). Clorobiocin stood out as a remarkably effective topo IV inhibitor. The relative activities of the different compounds toward topo IV showed a pattern similar to that of the relative gyrase-inhibitory activities. This is the first report of a systematic evaluation of a series of aminocoumarins against both gyrase and topo IV. The results give further insight into the structure-activity relationships of aminocoumarin antibiotics.

Structure-Activity Relationships of Aminocoumarin-Type Gyrase and Topoisomerase IV Inhibitors Obtained by Combinatorial Biosynthesis

PubMed Central

Flatman, Ruth H.; Eustaquio, Alessandra; Li, Shu-Ming; Heide, Lutz; Maxwell, Anthony

2006-01-01

Novobiocin and clorobiocin are gyrase inhibitors produced by Streptomyces strains. Structurally, the two compounds differ only by substitution at two positions: CH3 versus Cl at position 8′ of the aminocoumarin ring and carbamoyl versus 5-methyl-pyrrol-2-carbonyl (MePC) at the 3"-OH of noviose. Using genetic engineering, we generated a series of analogs carrying H, CH3, or Cl at 8′ and H, carbamoyl, or MePC at 3"-OH. Comparison of the gyrase inhibitory activities of all nine structural permutations confirmed that acylation of 3"-OH is essential for activity, with MePC being more effective than carbamoyl. Substitution at 8′ further enhanced activity, but the effect of CH3 or Cl depended on the nature of the acyl group at 3": in the presence of carbamoyl at 3", CH3 resulted in higher activity; in the presence of MePC at 3", Cl resulted in higher activity. This suggests that the structures of both natural compounds are highly evolved for optimal interaction with gyrase. In a second series of experiments, clorobiocin derivatives with and without the methyl group at 4"-OH of noviose, and with different positions of the MePC group of noviose, were tested. Again clorobiocin was superior to all of its analogs. The activities of all compounds were also tested against topoisomerase IV (topo IV). Clorobiocin stood out as a remarkably effective topo IV inhibitor. The relative activities of the different compounds toward topo IV showed a pattern similar to that of the relative gyrase-inhibitory activities. This is the first report of a systematic evaluation of a series of aminocoumarins against both gyrase and topo IV. The results give further insight into the structure-activity relationships of aminocoumarin antibiotics. PMID:16569821

Improving Fatigue Strength of polymer concrete using nanomaterials.

DOT National Transportation Integrated Search

2016-11-30

Polymer concrete (PC) is that type of concrete where the cement binder is replaced with polymer. PC is often used to improve friction and protect structural substrates in reinforced concrete and orthotropic steel bridges. However, its low fatigue per...

Adaptive non-local means on local principle neighborhood for noise/artifacts reduction in low-dose CT images.

PubMed

Zhang, Yuanke; Lu, Hongbing; Rong, Junyan; Meng, Jing; Shang, Junliang; Ren, Pinghong; Zhang, Junying

2017-09-01

Low-dose CT (LDCT) technique can reduce the x-ray radiation exposure to patients at the cost of degraded images with severe noise and artifacts. Non-local means (NLM) filtering has shown its potential in improving LDCT image quality. However, currently most NLM-based approaches employ a weighted average operation directly on all neighbor pixels with a fixed filtering parameter throughout the NLM filtering process, ignoring the non-stationary noise nature of LDCT images. In this paper, an adaptive NLM filtering scheme on local principle neighborhoods (PC-NLM) is proposed for structure-preserving noise/artifacts reduction in LDCT images. Instead of using neighboring patches directly, in the PC-NLM scheme, the principle component analysis (PCA) is first applied on local neighboring patches of the target patch to decompose the local patches into uncorrelated principle components (PCs), then a NLM filtering is used to regularize each PC of the target patch and finally the regularized components is transformed to get the target patch in image domain. Especially, in the NLM scheme, the filtering parameter is estimated adaptively from local noise level of the neighborhood as well as the signal-to-noise ratio (SNR) of the corresponding PC, which guarantees a "weaker" NLM filtering on PCs with higher SNR and a "stronger" filtering on PCs with lower SNR. The PC-NLM procedure is iteratively performed several times for better removal of the noise and artifacts, and an adaptive iteration strategy is developed to reduce the computational load by determining whether a patch should be processed or not in next round of the PC-NLM filtering. The effectiveness of the presented PC-NLM algorithm is validated by experimental phantom studies and clinical studies. The results show that it can achieve promising gain over some state-of-the-art methods in terms of artifact suppression and structure preservation. With the use of PCA on local neighborhoods to extract principal structural components, as well as adaptive NLM filtering on PCs of the target patch using filtering parameter estimated based on the local noise level and corresponding SNR, the proposed PC-NLM method shows its efficacy in preserving fine anatomical structures and suppressing noise/artifacts in LDCT images. © 2017 American Association of Physicists in Medicine.

Evaluation of aluminum phthalocyanine chloride and DNA interactions for the design of an advanced drug delivery system in photodynamic therapy.

PubMed

Jayme, Cristiano Ceron; Calori, Italo Rodrigo; Cunha, Elise Marques Freire; Tedesco, Antonio Claudio

2018-08-05

The aim of this study was to evaluate the interaction of aluminum phthalocyanine chloride (AlClPc) with double-stranded DNA. Absorption and fluorescence spectra, resonance light scattering, and circular dichroism were evaluated in water and water/ethanol mixtures with different concentrations of DNA or AlClPc. AlClPc showed a high ability to bind to DNA in both water and 4/6 water/ethanol mixture (v/v), with a majority of monomeric and aggregated initial forms of AlClPc, respectively. In this interaction, AlClPc bound preferentially to the grooves of DNA. The monomeric/aggregate state of AlClPc in DNA was dependent on the AlClPc/DNA ratio. At low concentrations of AlClPc, the interaction of AlClPc with few DNA sites caused a curvature in the DNA structure that provided a favorable environment for the intercalation of AlClPc aggregates. Increase in AlClPc concentration induced interactions with a high number of binding sites on DNA, which prevented bending and therefore aggregation of AlClPc molecules throughout the double-stranded DNA. These results are relevant to the understanding of the behavior and interaction of AlClPc with double-stranded DNA in the design of novel drug delivery systems for clinical application in photodynamic therapy as a new approach to treat skin or oral cancer, scars, or wound healing. Copyright © 2018 Elsevier B.V. All rights reserved.

Nanoscale Morphology of PTB7 Based Organic Photovoltaics as a Function of Fullerene Size

DOE PAGES

Roehling, John D.; Baran, Derya; Sit, Joseph; ...

2016-08-08

High efficiency polymer:fullerene photovoltaic device layers self-assemble with hierarchical features from ångströms to 100’s of nanometers. The feature size, shape, composition, orientation, and order all contribute to device efficiency and are simultaneously difficult to study due to poor contrast between carbon based materials. This study seeks to increase device efficiency and simplify morphology measurements by replacing the typical fullerene acceptor with endohedral fullerene Lu 3N@PC 80BEH. The metal atoms give excellent scattering contrast for electron beam and x-ray experiments. Additionally, Lu 3N@PC 80BEH has a lower electron affinity than standard fullerenes, which can raise the open circuit voltage of photovoltaicmore » devices. Electron microscopy techniques are used to produce a detailed account of morphology evolution in mixtures of Lu 3N@PC 80BEH with the record breaking donor polymer, PTB7 and coated using solvent mixtures. We demonstrate that common solvent additives like 1,8-diiodooctane or chloronapthalene do not improve the morphology of endohedral fullerene devices as expected. The poor device performance is attributed to the lack of mutual miscibility between this particular polymer:fullerene combination and to co-crystallization of Lu 3N@PC 80BEH with 1,8-diiodooctane. This negative result explains why solvent additives mixtures are not necessarily a morphology cure-all.« less

Nanoscale Morphology of PTB7 Based Organic Photovoltaics as a Function of Fullerene Size

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roehling, John D.; Baran, Derya; Sit, Joseph

High efficiency polymer:fullerene photovoltaic device layers self-assemble with hierarchical features from ångströms to 100’s of nanometers. The feature size, shape, composition, orientation, and order all contribute to device efficiency and are simultaneously difficult to study due to poor contrast between carbon based materials. This study seeks to increase device efficiency and simplify morphology measurements by replacing the typical fullerene acceptor with endohedral fullerene Lu 3N@PC 80BEH. The metal atoms give excellent scattering contrast for electron beam and x-ray experiments. Additionally, Lu 3N@PC 80BEH has a lower electron affinity than standard fullerenes, which can raise the open circuit voltage of photovoltaicmore » devices. Electron microscopy techniques are used to produce a detailed account of morphology evolution in mixtures of Lu 3N@PC 80BEH with the record breaking donor polymer, PTB7 and coated using solvent mixtures. We demonstrate that common solvent additives like 1,8-diiodooctane or chloronapthalene do not improve the morphology of endohedral fullerene devices as expected. The poor device performance is attributed to the lack of mutual miscibility between this particular polymer:fullerene combination and to co-crystallization of Lu 3N@PC 80BEH with 1,8-diiodooctane. This negative result explains why solvent additives mixtures are not necessarily a morphology cure-all.« less

Hydrothermal synthesis, crystal structure, and catalytic potential of a one-dimensional molybdenum oxide/bipyridinedicarboxylate hybrid.

PubMed

Amarante, Tatiana R; Neves, Patrícia; Valente, Anabela A; Paz, Filipe A Almeida; Fitch, Andrew N; Pillinger, Martyn; Gonçalves, Isabel S

2013-04-15

The reaction of MoO3, 2,2'-bipyridine-5,5-dicarboxylic acid (H2bpdc), water, and dimethylformamide in the mole ratio 1:1:1730:130 at 150 °C for 3 days in a rotating Teflon-lined digestion bomb leads to the isolation of the molybdenum oxide/bipyridinedicarboxylate hybrid material (DMA)[MoO3(Hbpdc)]·nH2O (1) (DMA = dimethylammonium). Compound 1 was characterized by scanning electron microscopy, FT-IR and (13)C{(1)H} CP MAS NMR spectroscopies, and elemental and thermogravimetric analyses. The solid state structure of 1 was solved and refined through Rietveld analysis of high resolution synchrotron X-ray powder diffraction data in conjunction with information derived from the above techniques. The material, crystallizing in the noncentrosymmetric monoclinic space group Pc, is composed of an anionic one-dimensional organic-inorganic hybrid polymer, ∞(1)[MoO3(Hbpdc)](-), formed by corner-sharing distorted {MoO4N2} octahedra, which cocrystallizes with charge-balancing DMA(+) cations and one water molecule per metal center. In the crystal structure of 1, the close packing of individual anionic polymers, DMA(+) cations, and water molecules is mediated by a series of supramolecular contacts, namely strong (O-H···O, N(+)-H···O(-)) and weak (C-H···O) hydrogen bonding interactions, and π-π contacts involving adjacent coordinated Hbpdc(-) ligands. The catalytic potential of 1 was investigated in the epoxidation reactions of the bioderived olefins methyl oleate (Ole) and DL-limonene (Lim) using tert-butylhydroperoxide (TBHP) as the oxygen donor and 1,2-dichloroethane (DCE) or (trifluoromethyl)benzene (BTF) as cosolvent, at 55 or 75 °C. Under these conditions, 1 acts as a source of active soluble species, leading to epoxide yields of up to 98% for methyl 9,10-epoxystearate (BTF, 75 °C, 100% conversion of Ole) and 89% for 1,2-epoxy-p-menth-8-ene (DCE, 55 °C, 95% conversion of Lim). Catalytic systems employing the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide as solvent could be effectively recycled.

Carrier induced magnetic coupling transitions in phthalocyanine-based organometallic sheet.

PubMed

Zhou, Jian; Sun, Qiang

2014-01-07

A two-dimensional sheet with long range ferromagnetic (FM) order has been hotly pursued currently. The recent success in synthesizing polymerized Fe-phthalocyanine (poly-FePc) porous sheets paves a possible way to achieve this goal. However, the poly-FePc and its analog poly-CrPc structure are intrinsically antiferromagnetic (AFM). Using first principles combined with Monte-Carlo simulations, we study systematically the carrier-induced magnetic coupling transitions in poly-CrPc and poly-FePc sheets. We show that electron doping can induce stable FM states with Curie temperatures of 130-140 K, while hole doping will enhance the stability of the AFM states. Such changes in magnetic couplings depend on the balance of AFM superexchange and FM p-d exchange.

Preliminary Procedure for Structural Design of Pervious Concrete Pavements

DOT National Transportation Integrated Search

2017-11-01

Pervious concrete (PC) is a pavement material that provides a porous medium to facilitate the infiltration of stormwater to the underlayers. With the increasing use of PC pavement nationwide, the mechanical properties of the material need to be estab...

Effect of thermal annealing on the structural, optical and dielectrical properties of P3HT:PC{sub 70}BM nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aloui, Walid, E-mail: alouiwalid26@yahoo.fr; Adhikari, Tham; Nunzi, Jean-Michel

2016-06-15

Highlights: • A typical structure of ITO/PEDOT: PSS/P3HT: PC{sub 70}BM/Al was fabricated. • Charge carrier diffusion and recombination have been calculated. • AFM and optical results show that thermal annealing promotes the phase separation. • The annealing process improves the transport of charges. - Abstract: The effect of thermal annealing on the optical, structural and the dielectric properties of P3HT:PC{sub 70}BM blended films were investigated. By means of atomic force microscopy, we observed the morphology evolution of the annealed P3HT:PC{sub 70}BM nanocomposites. Raman spectroscopy showed a substantial ordering in the polymer film after annealing. The absorption spectra of the annealedmore » P3HT:PC{sub 70}BM films were improved and red shifted than un-annealed samples. The results indicate that the P3HT in the nanocomposite becomes an ordered structure with annealing. The ordered P3HT facilitates the charge transport. From the photoluminescence measurements, the formation of polymer crystallites was observed upon annealing. Thus, the device efficiency reaches 2.2% after annealing at 150 °C. Impedance spectroscopy shows the classical complex plan curves; the low frequency is related to the effective lifetime of charge carriers and the high frequency corresponds to the diffusion time of these carriers. Global mobilities are in the range 3.8–4.6 × 10{sup −3} cm{sup 2} V{sup −1} s{sup −1}.« less

Texturing of sodium bismuth titanate-barium titanate ceramics by templated grain growth

NASA Astrophysics Data System (ADS)

Yilmaz, Huseyin

2002-01-01

Sodium bismuth titanate modified with barium titanate, (Na1/2Bi 1/2)TiO3-BaTiO3 (NBT-BT), is a candidate lead-free piezoelectric material which has been shown to have comparatively high piezoelectric response. In this work, textured (Na1/2Bi1/2)TiO 3-BaTiO3 (5.5mol% BaTiO3) ceramics with <100> pc (where pc denotes the pseudocubic perovskite cell) orientation were fabricated by Templated Grain Growth (TGG) or Reactive Templated Grain Growth (RTGG) using anisotropically shaped template particles. In the case of TGG, molten salt synthesized SrTiO3 platelets were tape cast with a (Na1/2Bi1/2)TiO3-5.5mol%BaTiO3 powder and sintered at 1200°C for up to 12 hours. For the RTGG approach, Bi4Ti3O12 (BiT) platelets were tape cast with a Na2CO3, Bi2O3, TiO 2, and BaCO3 powder mixture and reactively sintered. The TGG approach using SrTiO3 templates gave stronger texture along [001] compared to the RTGG approach using BiT templates. The textured ceramics were characterized by X-ray and electron backscatter diffraction for the quality of texture. The texture function was quantified by the Lotgering factor, rocking curve, pole figures, inverse pole figures, and orientation imaging microscopy. Electrical and electromechanical property characterization of randomly oriented and <001>pc textured (Na1/2Bi1/2)TiO 3-5.5 mol% BaTiO3 rhombohedral ceramics showed 0.26% strain at 70 kV/cm, d33 coefficients over 500 pC/N have been obtained for highly textured samples (f ˜ 90%). The piezoelectric coefficient from Berlincourt was d33 ˜ 200 pC/N. The materials show considerable hysteresis. The presence of hysteresis in the unipolar-electric field curve is probably linked to the ferroelastic phase transition seen in the (Na 1/2Bi1/2)TiO3 system on cooling from high temperature at ˜520°C. The macroscopic physical properties (remanent polarization, dielectric constant, and piezoelectric coefficient) of random and textured ([001] pc) rhombohedral perovskites were estimated by linear averaging of single crystal data. However, the complete polarization, dielectric, and piezoelectric tensors are not available for NBT-BT single crystals. Therefore, the properties of lead based (PZT, 52/48) rhombohedral ferroelectric single domain-single crystals, whose properties (polarization, dielectric and piezoelectric) were computed using Landau-Ginsburg-Devonshire phenomenological theory (by Haun et. al.), were used in the calculations for random and textured cases. (Abstract shortened by UMI.)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Wenjie; Zhang, Honghu; Feng, Shuren

Surface-sensitive X-ray scattering and spectroscopy techniques reveal significant adsorption of iron ions and iron-hydroxide (Fe(III)) complexes to a charge-neutral zwitterionic template of phosphatidylcholine (PC). The PC template is formed by a Langmuir monolayer of dipalmitoyl-PC (DPPC) that is spread on the surface of 2 to 40 μM FeCl 3 solutions at physiological levels of KCl (100 mM). At 40 μM of Fe(III) as many as ~3 iron atoms are associated with each PC group. Grazing incidence X-ray diffraction measurements indicate a significant disruption in the in-plane ordering of DPPC molecules upon iron adsorption. The binding of iron-hydroxide complexes to amore » neutral PC surface is yet another example of nonelectrostatic, presumably covalent bonding to a charge-neutral organic template. Furthermore, the strong binding and the disruption of in-plane lipid structure has biological implications on the integrity of PC-derived lipid membranes, including those based on sphingomyelin.« less

Observations of explosion generated PcP spectra at near-normal incidence

NASA Astrophysics Data System (ADS)

Niazi, Mansour; McLaughlin, Keith L.

1987-10-01

Short period recordings of PcP at the SRO station ANTO have been observed at epicentral distance of 13.5° from presumed underground explosions in western Kazahk, USSR. The core reflections are narrow band (0.6 to 2.4 Hz), short duration (3 sec) signals. Comparison of these near normally incident reflections to P waveforms observed at greater distances reveals that the PcP spectra are peaked with respect to the more representative P-wave spectra. The 1.2 Hz spectral peak is also observed for PcP waves recorded at 50 degrees. Corrections for frequency independent mantle Q attnuation models only increase the high frequency deficiency of the PcP spectra at frequencies above 1.2 Hz. A plausible explanation calls for finer structural features of core-mantle boundary (CMB) than hitherto suggested. The influence of small scale lateral heterogeneities, however, cannot be completely ruled out. (Mantle-core boundary, near normal PcP reflection.)

Solvothermal preparation of phthalocyanine nanorod/rGO composites and their application to visible-light-responsive photocatalysts

NASA Astrophysics Data System (ADS)

Zhang, Shuai; Lu, Yongting; Zhang, Fan; Qu, Jie; Lin, Bencai; Yuan, Ningyi; Fang, Bijun; Ding, Jian-Ning

2016-09-01

Phthalocyanine (Pc) nanorod/reduced graphene oxide (rGO) composites were prepared by a simple solvothermal method, in which Pc nanosheet and graphene oxide (GO) suspensions were mixed in methanol. As characterized by scanning electron microscopy, transmission electron microscopy, and selected area electron diffraction, Pc nanorods with an amorphous structure and an average diameter of 250nm are partially covered by rGO sheets. In the photodegradation experiments, all the composites with different rGO content show enhanced photocatalytic activity for Rhodamine B decomposition under visible-light compared to pure Pc nanorods or rGO sheets. The enhanced photocatalytic activity shall be ascribed to the large surface area offered by rGO and the charge-transfer from Pc to rGO as indicated by the photoluminescence measurement, in which fluorescence intensity of the composites is much weaker than that of Pc nanorods.

Effects of Phase Separation Behavior on Morphology and Performance of Polycarbonate Membranes

PubMed Central

Idris, Alamin; Man, Zakaria; Maulud, Abdulhalim S.; Khan, Muhammad Saad

2017-01-01

The phase separation behavior of bisphenol-A-polycarbonate (PC), dissolved in N-methyl-2-pyrrolidone and dichloromethane solvents in coagulant water, was studied by the cloud point method. The respective cloud point data were determined by titration against water at room temperature and the characteristic binodal curves for the ternary systems were plotted. Further, the physical properties such as viscosity, refractive index, and density of the solution were measured. The critical polymer concentrations were determined from the viscosity measurements. PC/NMP and PC/DCM membranes were fabricated by the dry-wet phase inversion technique and characterized for their morphology, structure, and thermal stability using field emission scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis, respectively. The membranes’ performances were tested for their permeance to CO2, CH4, and N2 gases at 24 ± 0.5 °C with varying feed pressures from 2 to 10 bar. The PC/DCM membranes appeared to be asymmetric dense membrane types with appreciable thermal stability, whereas the PC/NMP membranes were observed to be asymmetric with porous structures exhibiting 4.18% and 9.17% decrease in the initial and maximum degradation temperatures, respectively. The ideal CO2/N2 and CO2/CH4 selectivities of the PC/NMP membrane decreased with the increase in feed pressures, while for the PC/DCM membrane, the average ideal CO2/N2 and CO2/CH4 selectivities were found to be 25.1 ± 0.8 and 21.1 ± 0.6, respectively. Therefore, the PC/DCM membranes with dense morphologies are appropriate for gas separation applications. PMID:28379173

Assessing cancer-specific anxiety in Chinese men with prostate cancer: psychometric evaluation of the Chinese version of the Memorial Anxiety Scale for Prostate Cancer (MAX-PC).

PubMed

Huang, Qingmei; Jiang, Ping; Zhang, Zijun; Luo, Jie; Dai, Yun; Zheng, Li; Wang, Wei

2017-12-01

The Memorial Anxiety Scale for Prostate Cancer (MAX-PC) was developed to identify and assess cancer-specific anxiety among men with prostate cancer (PCa); however, there is no Chinese version. The aim of our study was to translate the English version of MAX-PC into Chinese and evaluate the psychometric properties of it. The study cohort comprised 254 participants. Internal consistency including the Cronbach's alpha coefficient and item-total correlations were used to measure the reliability of the scale. Factor structure was analyzed by exploratory factor analysis and concurrent validity by comparing MAX-PC scores with anxiety subscale scores of the Hospital Anxiety and Depression Scale (HADS). Divergent validity was assessed by correlating MAX-PC with HADS depression subscale, while discriminant ability by comparing differences in MAX-PC scores between different patient groups. The Chinese version of MAX-PC demonstrated good reliability; the Cronbach's alpha coefficient for the total and three subscales (prostate cancer anxiety, PSA anxiety, and fear of recurrence) being 0.94, 0.93, 0.82, and 0.85, respectively. Exploratory factor analysis supported the three-factor structure of the scale established in the original version. Despite the somewhat underperformed divergent validity, the scale demonstrated good concurrent validity with a strong correlation with the HADS anxiety subscale (r = 0.71, p < 0.01). Moreover, discriminant ability was demonstrated by ability to differentiate between disease stages. The MAX-PC Chinese version was confirmed to be a valid, reliable instrument and is thus appropriate for identifying and quantifying cancer-specific anxiety in Chinese PCa patients.

Lipid structure does not modify incorporation of EPA and DHA into blood lipids in healthy adults: a randomised-controlled trial.

PubMed

West, Annette L; Burdge, Graham C; Calder, Philip C

2016-09-01

Dietary supplementation is an effective means to improve EPA and DHA status. However, it is unclear whether lipid structure affects EPA+DHA bioavailability. We determined the effect of consuming different EPA and DHA lipid structures on their concentrations in blood during the postprandial period and during dietary supplementation compared with unmodified fish oil TAG (uTAG). In a postprandial cross-over study, healthy men (n 9) consumed in random order test meals containing 1·1 g EPA+0·37 g DHA as either uTAG, re-esterified TAG, free fatty acids (FFA) or ethyl esters (EE). In a parallel design supplementation study, healthy men and women (n 10/sex per supplement) consumed one supplement type for 12 weeks. Fatty acid composition was determined by GC. EPA incorporation over 6 h into TAG or phosphatidylcholine (PC) did not differ between lipid structures. EPA enrichment in NEFA was lower from EE than from uTAG (P=0·01). Plasma TAG, PC or NEFA DHA incorporation did not differ between lipid structures. Lipid structure did not affect TAG or NEFA EPA incorporation and PC or NEFA DHA incorporation following dietary supplementation. Plasma TAG peak DHA incorporation was greater (P=0·02) and time to peak shorter (P=0·02) from FFA than from uTAG in men. In both studies, the order of EPA and DHA incorporation was PC>TAG>NEFA. In conclusion, EPA and DHA lipid structure may not be an important consideration in dietary interventions.

Compact Mach-Zehnder interferometer based on photonic crystal fiber and its application in switchable multi-wavelength fiber laser

NASA Astrophysics Data System (ADS)

Chen, Weiguo; Lou, Shuqin; Wang, Liwen; Li, Honglei; Guo, Tieying; Jian, Shuisheng

2009-08-01

The compact Mach-Zehnder interferometer is proposed by splicing a section of photonic crystal fiber (PCF) and two pieces of single mode fiber (SMF) with the air-holes of PCF intentionally collapsed in the vicinity of the splices. The depedence of the fringe spacing on the length of PCF is investigated. Based on the Mach-Zehnder interferometer as wavelength-selective filter, a switchable dual-wavelength fiber ring laser is demonstrated with a homemade erbiumdoped fiber amplifier (EDFA) as the gain medium at room temperature. By adjusting the states of the polarization controller (PC) appropriately, the laser can be switched among the stable single-and dual -wavelength lasing operations by exploiting polarization hole burning (PHB) effect.

Motion and properties of nuclear radio components in Seyfert galaxies seen with VLBI

NASA Astrophysics Data System (ADS)

Middelberg, E.; Roy, A. L.; Nagar, N. M.; Krichbaum, T. P.; Norris, R. P.; Wilson, A. S.; Falcke, H.; Colbert, E. J. M.; Witzel, A.; Fricke, K. J.

2004-04-01

We report EVN, MERLIN and VLBA observations at 18 cm, 6 cm and 3.6 cm of the Seyfert galaxies NGC 7674, NGC 5506, NGC 2110 and Mrk 1210 to study their structure and proper motions on pc scales and to add some constraints on the many possible causes of the radio-quietness of Seyferts. The component configurations in NGC 7674 and NGC 2110 are simple, linear structures, whereas the configurations in NGC 5506 and Mrk 1210 have multiple components with no clear axis of symmetry. We suggest that NGC 7674 is a low-luminosity compact symmetric object. Comparing the images at different epochs, we find a proper motion in NGC 7674 of (0.92±0.07) c between the two central components separated by 282 pc and, in NGC 5506, we find a 3 σ upper limit of 0.50 c for the components separated by 3.8 pc. Our results confirm and extend earlier work showing that the outward motion of radio components in Seyfert galaxies is non-relativistic on pc scales. We briefly discuss whether this non-relativistic motion is intrinsic to the jet-formation process or results from deceleration of an initially relativistic jet by interaction with the pc or sub-pc scale interstellar medium. We combined our sample with a list compiled from the literature of VLBI observations made of Seyfert galaxies, and found that most Seyfert nuclei have at least one flat-spectrum component on the VLBI scale, which was not seen in the spectral indices measured at arcsec resolution. We found also that the bimodal alignment of pc and kpc radio structures displayed by radio galaxies and quasars is not displayed by this sample of Seyferts, which shows a uniform distribution of misalignment between 0° and 90°. The frequent misalignment could result from jet precession or from deflection of the jet by interaction with gas in the interstellar medium.

Well-aligned Vertically Oriented ZnO Nanorod Arrays and their Application in Inverted Small Molecule Solar Cells.

PubMed

Lin, Ming-Yi; Wu, Shang-Hsuan; Hsiao, Li-Jen; Budiawan, Widhya; Chen, Shih-Lun; Tu, Wei-Chen; Lee, Chia-Yen; Chang, Yia-Chung; Chu, Chih-Wei

2018-04-25

This manuscript describes how to design and fabricate efficient inverted solar cells, which are based on a two-dimensional conjugated small molecule (SMPV1) and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), by utilizing ZnO nanorods (NRs) grown on a high quality Al-doped ZnO (AZO) seed layer. The inverted SMPV1:PC71BM solar cells with ZnO NRs that grew on both a sputtered and sol-gel processed AZO seed layer are fabricated. Compared with the AZO thin film prepared by the sol-gel method, the sputtered AZO thin film exhibits better crystallization and lower surface roughness, according to X-ray diffraction (XRD) and atomic force microscope (AFM) measurements. The orientation of the ZnO NRs grown on a sputtered AZO seed layer shows better vertical alignment, which is beneficial for the deposition of the subsequent active layer, forming better surface morphologies. Generally, the surface morphology of the active layer mainly dominates the fill factor (FF) of the devices. Consequently, the well-aligned ZnO NRs can be used to improve the carrier collection of the active layer and to increase the FF of the solar cells. Moreover, as an anti-reflection structure, it can also be utilized to enhance the light harvesting of the absorption layer, with the power conversion efficiency (PCE) of solar cells reaching 6.01%, higher than the sol-gel based solar cells with an efficiency of 4.74%.

Circumnuclear Structures in Megamaser Host Galaxies

NASA Astrophysics Data System (ADS)

Pjanka, Patryk; Greene, Jenny E.; Seth, Anil C.; Braatz, James A.; Henkel, Christian; Lo, Fred K. Y.; Läsker, Ronald

2017-08-01

Using the Hubble Space Telescope, we identify circumnuclear (100-500 pc scale) structures in nine new H2O megamaser host galaxies to understand the flow of matter from kpc-scale galactic structures down to the supermassive black holes (SMBHs) at galactic centers. We double the sample analyzed in a similar way by Greene et al. and consider the properties of the combined sample of 18 sources. We find that disk-like structure is virtually ubiquitous when we can resolve <200 pc scales, in support of the notion that non-axisymmetries on these scales are a necessary condition for SMBH fueling. We perform an analysis of the orientation of our identified nuclear regions and compare it with the orientation of megamaser disks and the kpc-scale disks of the hosts. We find marginal evidence that the disk-like nuclear structures show increasing misalignment from the kpc-scale host galaxy disk as the scale of the structure decreases. In turn, we find that the orientation of both the ˜100 pc scale nuclear structures and their host galaxy large-scale disks is consistent with random with respect to the orientation of their respective megamaser disks.

Preliminary results of human PrPC protein studied by spectroscopic techniques

NASA Astrophysics Data System (ADS)

Nowakowski, Michał; Czapla-Masztafiak, Joanna; Kozak, Maciej; Zhukov, Igor; Zhukova, Lilia; Szlachetko, Jakub; Kwiatek, Wojciech M.

2017-11-01

Neurodegenerative diseases are one of the malfunctions of human nervous system, being a class of complex and prominent pathologies. The human prion Protease Resistant Protein (PrP) is protein regulating copper metabolism in mammalian cells through binding of Cu(II) ions to specific fragments. Nowadays misfolding of this protein is associated with development of prion diseases. Therefore, it is crucial to obtain structural information about coordination of Cu(II) by PrP protein. Herein, we report X-ray absorption spectroscopy (XAS) measurements, carried out on SuperXAS beamline (SLS, PSI Villigen) on PrPC-Cu(II) complexes. Obtained results were compared with theoretical predictions done by FEFF 9.6 software. Complementary to XAS data, Atomic Force Microscopy (AFM) measurements were conducted to obtain low resolution structural information about prepared sample that allow to develop protocol of fixing PrPC molecules on solid substrate used for further experiments. It has been established that folded C-terminal domain of PrPC protein has around 5 nm in diameter. Presented results showed that both XAS and AFM methods are useful tools in detailed examination of complexes of human PrPC either with Cu(II) or with other divalent metal ions.

Comparison of factor-analytic and reduced rank models for test-day milk yield in Gyr dairy cattle (Bos indicus).

PubMed

Pereira, R J; Ayres, D R; El Faro, L; Verneque, R S; Vercesi Filho, A E; Albuquerque, L G

2013-09-27

We analyzed 46,161 monthly test-day records of milk production from 7453 first lactations of crossbred dairy Gyr (Bos indicus) x Holstein cows. The following seven models were compared: standard multivariate model (M10), three reduced rank models fitting the first 2, 3, or 4 genetic principal components, and three models considering a 2-, 3-, or 4-factor structure for the genetic covariance matrix. Full rank residual covariance matrices were considered for all models. The model fitting the first two principal components (PC2) was the best according to the model selection criteria. Similar phenotypic, genetic, and residual variances were obtained with models M10 and PC2. The heritability estimates ranged from 0.14 to 0.21 and from 0.13 to 0.21 for models M10 and PC2, respectively. The genetic correlations obtained with model PC2 were slightly higher than those estimated with model M10. PC2 markedly reduced the number of parameters estimated and the time spent to reach convergence. We concluded that two principal components are sufficient to model the structure of genetic covariances between test-day milk yields.

LANL seismic screening method for existing buildings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dickson, S.L.; Feller, K.C.; Fritz de la Orta, G.O.

1997-01-01

The purpose of the Los Alamos National Laboratory (LANL) Seismic Screening Method is to provide a comprehensive, rational, and inexpensive method for evaluating the relative seismic integrity of a large building inventory using substantial life-safety as the minimum goal. The substantial life-safety goal is deemed to be satisfied if the extent of structural damage or nonstructural component damage does not pose a significant risk to human life. The screening is limited to Performance Category (PC) -0, -1, and -2 buildings and structures. Because of their higher performance objectives, PC-3 and PC-4 buildings automatically fail the LANL Seismic Screening Method andmore » will be subject to a more detailed seismic analysis. The Laboratory has also designated that PC-0, PC-1, and PC-2 unreinforced masonry bearing wall and masonry infill shear wall buildings fail the LANL Seismic Screening Method because of their historically poor seismic performance or complex behavior. These building types are also recommended for a more detailed seismic analysis. The results of the LANL Seismic Screening Method are expressed in terms of separate scores for potential configuration or physical hazards (Phase One) and calculated capacity/demand ratios (Phase Two). This two-phase method allows the user to quickly identify buildings that have adequate seismic characteristics and structural capacity and screen them out from further evaluation. The resulting scores also provide a ranking of those buildings found to be inadequate. Thus, buildings not passing the screening can be rationally prioritized for further evaluation. For the purpose of complying with Executive Order 12941, the buildings failing the LANL Seismic Screening Method are deemed to have seismic deficiencies, and cost estimates for mitigation must be prepared. Mitigation techniques and cost-estimate guidelines are not included in the LANL Seismic Screening Method.« less

Slingshot mechanism for clusters: Gas density regulates star density in the Orion Nebula Cluster (M42)

NASA Astrophysics Data System (ADS)

Stutz, Amelia M.

2018-02-01

We characterize the stellar and gas volume density, potential, and gravitational field profiles in the central ∼0.5 pc of the Orion Nebula Cluster (ONC), the nearest embedded star cluster (or rather, protocluster) hosting massive star formation available for detailed observational scrutiny. We find that the stellar volume density is well characterized by a Plummer profile ρstars(r) = 5755 M⊙ pc- 3 (1 + (r/a)2)- 5/2, where a = 0.36 pc. The gas density follows a cylindrical power law ρgas(R) = 25.9 M⊙ pc- 3 (R/pc)- 1.775. The stellar density profile dominates over the gas density profile inside r ∼ 1 pc. The gravitational field is gas-dominated at all radii, but the contribution to the total field by the stars is nearly equal to that of the gas at r ∼ a. This fact alone demonstrates that the protocluster cannot be considered a gas-free system or a virialized system dominated by its own gravity. The stellar protocluster core is dynamically young, with an age of ∼2-3 Myr, a 1D velocity dispersion of σobs = 2.6 km s-1, and a crossing time of ∼0.55 Myr. This time-scale is almost identical to the gas filament oscillation time-scale estimated recently by Stutz & Gould. This provides strong evidence that the protocluster structure is regulated by the gas filament. The protocluster structure may be set by tidal forces due to the oscillating filamentary gas potential. Such forces could naturally suppress low density stellar structures on scales ≳ a. The analysis presented here leads to a new suggestion that clusters form by an analogue of the 'slingshot mechanism' previously proposed for stars.

Electrical conductivity and total dissolved solids in urine.

PubMed

Fazil Marickar, Y M

2010-08-01

The objective of this paper is to study the relevance of electrical conductivity (EC) and total dissolved solids (TDS) in early morning and random samples of urine of urinary stone patients; 2,000 urine samples were studied. The two parameters were correlated with the extent of various urinary concrements. The early morning urine (EMU) and random samples of the patients who attended the urinary stone clinic were analysed routinely. The pH, specific gravity, EC, TDS, redox potential, albumin, sugar and microscopic study of the urinary sediments including red blood cells (RBC), pus cells (PC), crystals, namely calcium oxalate monohydrate (COM), calcium oxalate dihydrate (COD), uric acid (UA), and phosphates and epithelial cells were assessed. The extent of RBC, PC, COM, COD, UA and phosphates was correlated with EC and TDS. The values of EC ranged from 1.1 to 33.9 mS, the mean value being 21.5 mS. TDS ranged from 3,028 to 18,480 ppm, the mean value being 7,012 ppm. The TDS levels corresponded with EC of urine. Both values were significantly higher (P < 0.05) in the EMU samples than the random samples. There was a statistically significant correlation between the level of abnormality in the urinary deposits (r = +0.27, P < 0.05). In samples, where the TDS were more than 12,000 ppm, there were more crystals than those samples containing TDS less than 12,000 ppm. However, there were certain urine samples, where the TDS were over 12,000, which did not contain any urinary crystals. It is concluded that the value of TDS has relevance in the process of stone formation.

Spectroscopic study of 3-Hydroxyflavone - protein interaction in lipidic bi-layers immobilized on silver nanoparticles

NASA Astrophysics Data System (ADS)

Voicescu, Mariana; Ionescu, Sorana; Nistor, Cristina L.

2017-01-01

The interaction of 3-Hydroxyflavone with serum proteins (BSA and HSA) in lecithin lipidic bi-layers (PC) immobilized on silver nanoparticles (SNPs), was studied by fluorescence and Raman spectroscopy. BSA secondary structure was quantified with a deconvolution algorithm, showing a decrease in α-helix structure when lipids were added to the solution. The effect of temperature on the rate of the excited-state intra-molecular proton transfer and on the dual fluorescence emission of 3-HF in the HSA/PC/SNPs systems was discussed. Evaluation of the antioxidant activity of 3-HF in HSA/PC/SNPs systems was also studied. The antioxidant activity of 3-HF decreased in the presence of SNPs. The results are discussed with relevance to the secondary structure of proteins and of the 3-HF based nano-systems to a topical formulation useful in the oxidative stress process.

Three-dimensional structure of the Upper Scorpius association with the Gaia first data release

NASA Astrophysics Data System (ADS)

Galli, Phillip A. B.; Joncour, Isabelle; Moraux, Estelle

2018-06-01

Using new proper motion data from recently published catalogues, we revisit the membership of previously identified members of the Upper Scorpius association. We confirmed 750 of them as cluster members based on the convergent point method, compute their kinematic parallaxes, and combined them with Gaia parallaxes to investigate the 3D structure and geometry of the association using a robust covariance method. We find a mean distance of 146 ± 3 ± 6 pc and show that the morphology of the association defined by the brightest (and most massive) stars yields a prolate ellipsoid with dimensions of 74 × 38 × 32 pc3, while the faintest cluster members define a more elongated structure with dimensions of 98 × 24 × 18 pc3. We suggest that the different properties of both populations are an imprint of the star formation history in this region.

Structural Characterization of Unsaturated Phosphatidylcholines Using Traveling Wave Ion Mobility Spectrometry

PubMed Central

Kim, Hugh I.; Kim, Hyungjun; Pang, Eric S.; Ryu, Ernest K.; Beegle, Luther W.; Loo, Joseph A.; Goddard, William A.; Kanik, Isik

2009-01-01

A number of phosphatidylcholine (PC) cations spanning a mass range of 400 to 1000 Da are investigated using electrospray ionization mass spectrometry coupled with traveling wave ion mobility spectrometry (TWIMS). A high correlation between mass and mobility is demonstrated with saturated phosphatidylcholine cations in N2. A significant deviation from this mass-mobility correlation line is observed for the unsaturated PC cation. We found that the double bond in the acyl chain causes a 5% reduction in drift time. The drift time is reduced at a rate of ~1% for each additional double bond. Theoretical collision cross sections of PC cations exhibit good agreement with experimentally evaluated values. Collision cross sections are determined using the recently derived relationship between mobility and drift time in TWIMS stacked ring ion guide (SRIG) and compared to estimate collision cross-sections using empiric calibration method. Computational analysis was performed using the modified trajectory (TJ) method with nonspherical N2 molecules as the drift gas. The difference between estimated collision cross-sections and theoretical collision cross-sections of PC cations is related to the sensitivity of the PC cation collision cross-sections to the details of the ion-neutral interactions. The origin of the observed correlation and deviation between mass and mobility of PC cations is discussed in terms of the structural rigidity of these molecules using molecular dynamic simulations. PMID:19764704

Predictive model of complexity in early palliative care: a cohort of advanced cancer patients (PALCOM study).

PubMed

Tuca, Albert; Gómez-Martínez, Mónica; Prat, Aleix

2018-01-01

Model of early palliative care (PC) integrated in oncology is based on shared care from the diagnosis to the end of life and is mainly focused on patients with greater complexity. However, there is no definition or tools to evaluate PC complexity. The objectives of the study were to identify the factors influencing level determination of complexity, propose predictive models, and build a complexity scale of PC. We performed a prospective, observational, multicenter study in a cohort of advanced cancer patients with an estimated prognosis ≤ 6 months. An ad hoc structured evaluation including socio-demographic and clinical data, symptom burden, functional and cognitive status, psychosocial problems, and existential-ethic dilemmas was recorded systematically. According to this multidimensional evaluation, investigator classified patients as high, medium, or low palliative complexity, associated to need of basic or specialized PC. Logistic regression was used to identify the variables influencing determination of level of PC complexity and explore predictive models. We included 324 patients; 41% were classified as having high PC complexity and 42.9% as medium, both levels being associated with specialized PC. Variables influencing determination of PC complexity were as follows: high symptom burden (OR 3.19 95%CI: 1.72-6.17), difficult pain (OR 2.81 95%CI:1.64-4.9), functional status (OR 0.99 95%CI:0.98-0.9), and social-ethical existential risk factors (OR 3.11 95%CI:1.73-5.77). Logistic analysis of variables allowed construct a complexity model and structured scales (PALCOM 1 and 2) with high predictive value (AUC ROC 76%). This study provides a new model and tools to assess complexity in palliative care, which may be very useful to manage referral to specialized PC services, and agree intensity of their intervention in a model of early-shared care integrated in oncology.

A carboxylated Zn-phthalocyanine inhibits fibril formation of Alzheimer's amyloid β peptide.

PubMed

Tabassum, Shatera; Sheikh, Abdullah M; Yano, Shozo; Ikeue, Takafumi; Handa, Makoto; Nagai, Atsushi

2015-02-01

Amyloid β (Aβ), a 39-42 amino acid peptide derived from amyloid precursor protein, is deposited as fibrils in Alzheimer's disease brains, and is considered to play a major role in the pathogenesis of the disease. We have investigated the effects of a water-soluble Zn-phthalocyanine, ZnPc(COONa)₈, a macrocyclic compound with near-infrared optical properties, on Aβ fibril formation in vitro. A thioflavin T fluorescence assay showed that ZnPc(COONa)₈ significantly inhibited Aβ fibril formation, increasing the lag time and dose-dependently decreasing the plateau level of fibril formation. Moreover, it destabilized pre-formed Aβ fibrils, resulting in an increase in low-molecular-weight species. After fibril formation in the presence of ZnPc(COONa)₈, immunoprecipitation of Aβ₁₋₄₂ using Aβ-specific antibody followed by near-infrared scanning demonstrated binding of ZnPc(COONa)₈ to Aβ₁₋₄₂. A study using the hydrophobic fluorescent probe 8-anilino-1-naphthalenesulfonic acid showed that ZnPc(COONa)8 decreased the hydrophobicity during Aβ₁₋₄₂ fibril formation. CD spectroscopy showed an increase in the α helix structure and a decrease in the β sheet structure of Aβ₁₋₄₀ in fibril-forming buffer containing ZnPc(COONa)₈. SDS/PAGE and a dot-blot immunoassay showed that ZnPc(COONa)₈ delayed the disappearance of low-molecular-weight species and the appearance of higher-molecular-weight oligomeric species of Aβ₁₋₄₂. A cell viability assay showed that ZnPc(COONa)₈ was not toxic to a neuronal cell line (A1), but instead protected A1 cells against Aβ₁₋₄₂-induced toxicity. Overall, our results indicate that ZnPc(COONa)₈ binds to Aβ and decreases the hydrophobicity, and this change is unfavorable for Aβ oligomerization and fibril formation. © 2014 FEBS.

Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions. A Combined EPR and DFT Study

DOE PAGES

Mardis, Kristy L.; Webb, J.; Holloway, Tarita; ...

2015-12-03

Organic photovoltaic (OPV) devices are a promising alternative energy source. Attempts to improve their performance have focused on the optimization of electron-donating polymers, while electron-accepting fullerenes have received less attention. Here, we report an electronic structure study of the widely used soluble fullerene derivatives PC61BM and PC71BM in their singly reduced state, that are generated in the polymer:fullerene blends upon light-induced charge separation. Density functional theory (DFT) calculations characterize the electronic structures of the fullerene radical anions through spin density distributions and magnetic resonance parameters. The good agreement of the calculated magnetic resonance parameters with those determined experimentally by advancedmore » electron paramagnetic resonance (EPR) allows the validation of the DFT calculations. Thus, for the first time, the complete set of magnetic resonance parameters including directions of the principal g-tensor axes were determined. For both molecules, no spin density is present on the PCBM side chain, and the axis of the largest g-value lies along the PCBM molecular axis. While the spin density distribution is largely uniform for PC61BM, it is not evenly distributed for PC71BM.« less

Biological applications of phase-contrast electron microscopy.

PubMed

Nagayama, Kuniaki

2014-01-01

Here, I review the principles and applications of phase-contrast electron microscopy using phase plates. First, I develop the principle of phase contrast based on a minimal model of microscopy, introducing a double Fourier-transform process to mathematically formulate the image formation. Next, I explain four phase-contrast (PC) schemes, defocus PC, Zernike PC, Hilbert differential contrast, and schlieren optics, as image-filtering processes in the context of the minimal model, with particular emphases on the Zernike PC and corresponding Zernike phase plates. Finally, I review applications of Zernike PC cryo-electron microscopy to biological systems such as protein molecules, virus particles, and cells, including single-particle analysis to delineate three-dimensional (3D) structures of protein and virus particles and cryo-electron tomography to reconstruct 3D images of complex protein systems and cells.

Chemical pressure tuning of URu2Si2 via isoelectronic substitution of Ru with Fe

NASA Astrophysics Data System (ADS)

Das, Pinaki; Kanchanavatee, N.; Helton, J. S.; Huang, K.; Baumbach, R. E.; Bauer, E. D.; White, B. D.; Burnett, V. W.; Maple, M. B.; Lynn, J. W.; Janoschek, M.

2015-02-01

We have used specific heat and neutron diffraction measurements on single crystals of URu2 -xFexSi2 for Fe concentrations x ≤0.7 to establish that chemical substitution of Ru with Fe acts as "chemical pressure" Pc h as previously proposed by Kanchanavatee et al. [Phys. Rev. B 84, 245122 (2011), 10.1103/PhysRevB.84.245122] based on bulk measurements on polycrystalline samples. Notably, neutron diffraction reveals a sharp increase of the uranium magnetic moment at x =0.1 , reminiscent of the behavior at the "hidden order" to large-moment-antiferromagnetic phase transition observed at a pressure Px≈0.5 -0.7 GPa in URu2Si2 . Using the unit-cell volume determined from our measurements and an isothermal compressibility κT=5.2 ×10-3 GPa-1 for URu2Si2 , we determine the chemical pressure Pc h in URu2 -xFexSi2 as a function of x . The resulting temperature (T )-chemical pressure (Pc h) phase diagram for URu2 -xFexSi2 is in agreement with the established temperature (T )-external pressure (P ) phase diagram of URu2Si2 .

Electronic Structure of C60/Zinc Phthalocyanine/V₂O₅ Interfaces Studied Using Photoemission Spectroscopy for Organic Photovoltaic Applications.

PubMed

Lim, Chang Jin; Park, Min Gyu; Kim, Min Su; Han, Jeong Hwa; Cho, Soohaeng; Cho, Mann-Ho; Yi, Yeonjin; Lee, Hyunbok; Cho, Sang Wan

2018-02-18

The interfacial electronic structures of a bilayer of fullerene (C 60 ) and zinc phthalocyanine (ZnPc) grown on vanadium pentoxide (V₂O₅) thin films deposited using radio frequency sputtering under various conditions were studied using X-ray and ultraviolet photoelectron spectroscopy. The energy difference between the highest occupied molecular orbital (HOMO) level of the ZnPc layer and the lowest unoccupied molecular orbital (LUMO) level of the C 60 layer was determined and compared with that grown on an indium tin oxide (ITO) substrate. The energy difference of a heterojunction on all V₂O₅ was found to be 1.3~1.4 eV, while that on ITO was 1.1 eV. This difference could be due to the higher binding energy of the HOMO of ZnPc on V₂O₅ than that on ITO regardless of work functions of the substrates. We also determined the complete energy level diagrams of C 60 /ZnPc on V₂O₅ and ITO.

Interaction of cationic phthalocyanines with DNA. Importance of the structure of the substituents.

PubMed

López Zeballos, N C; Gauna, G A; García Vior, M C; Awruch, J; Dicelio, L E

2014-07-05

The interaction of novel zinc (II) cationic phthalocyanines with CT-DNA was studied using absorption and fluorescence spectroscopy, as well as thermal denaturation profiles. Results showed an electrostatic interaction between the phthalocyanines and CT-DNA. The properties of these phthalocyanines were compared taking the structure of the macrocycle peripheral substituents into account. 2,9(10),16(17),23(24)-tetrakis[(N-butyl-N-methylammonium)ethylsulfanyl]phthalocyaninatozinc(II) tetraiodide (Pc6) had a greater affinity for the CT-DNA helix than its bioisoster 2,9(10),16(17),23(24)-tetrakis[(N-dibutyl-N-methylammonium)ethoxy]phthalocyaninatozinc(II) tetraiodide (Pc7). 2,9(10),16(17),23(24)-tetrakis[(2-trimethylammonium)ethyl-sulfanyl]phthalocyaninatozinc(II) tetraiodide (Pc13) also carried a sulfur atom like Pc6, but linked to bulky substituents such as trimethylammonium groups. The planar aromatic region of the cationic phthalocyanines in this study appears to be unable to facilitate their intercalation with CT-DNA. Copyright © 2014 Elsevier B.V. All rights reserved.

Structure-activity relationships of neoechinulin A analogues with cytoprotection against peroxynitrite-induced PC12 cell death.

PubMed

Kimoto, Kuniaki; Aoki, Toshiaki; Shibata, Yasushi; Kamisuki, Shinji; Sugawara, Fumio; Kuramochi, Kouji; Nakazaki, Atsuo; Kobayashi, Susumu; Kuroiwa, Kenji; Watanabe, Nobuo; Arai, Takao

2007-10-01

Neoechinulin A, an alkaloid from Eurotium rubrum Hiji025, protected neuronal PC12 cells against cell death induced by peroxynitrite derived from SIN-1 (3-(4-morpholinyl)sydnonimine hydrochloride). In this study, we investigated the structure-activity relationships of neoechinulin A and a set of its analogues by using assays to measure anti-nitration and antioxidant activities and cytoprotection against SIN-1-induced PC12 cell death. The presence of the diketopiperazine ring was essential for both the antioxidant and anti-nitration activities of neoechinulin A derivatives. Nevertheless, a derivative lacking the diketopiperazine ring could still protect PC12 cells against SIN-1 cytotoxicity. An acyclic analogue completely lost the cytoprotective effect while retaining its antioxidant/anti-nitration activities. Pre-incubation of the cells with neoechinulin A for at least 12 hours was essential for the cells to gain SIN-1 resistance. These results suggest that neoechinulin A endows the cells with cytoprotection through a biological effect different from the apparent antioxidant/anti-nitration activities.

Design and synthesis of formononetin-dithiocarbamate hybrids that inhibit growth and migration of PC-3 cells via MAPK/Wnt signaling pathways.

PubMed

Fu, Dong-Jun; Zhang, Li; Song, Jian; Mao, Ruo-Wang; Zhao, Ruo-Han; Liu, Ying-Chao; Hou, Yu-Hui; Li, Jia-Huan; Yang, Jia-Jia; Jin, Cheng-Yun; Li, Ping; Zi, Xiao-Lin; Liu, Hong-Min; Zhang, Sai-Yang; Zhang, Yan-Bing

2017-02-15

A series of novel formononetin-dithiocarbamate derivatives were designed, synthesized and evaluated for antiproliferative activity against three selected cancer cell line (MGC-803, EC-109, PC-3). The first structure-activity relationship (SAR) for this formononetin-dithiocarbamate scaffold is explored in this report with evaluation of 14 variants of the structural class. Among these analogues, tert-butyl 4-(((3-((3-(4-methoxyphenyl)-4-oxo-4H-chromen-7-yl)oxy)propyl)thio)carbonothioyl)piperazine-1-carboxylate (8i) showed the best inhibitory activity against PC-3 cells (IC 50  = 1.97 μM). Cellular mechanism studies elucidated 8i arrests cell cycle at G1 phase and regulates the expression of G1 checkpoint-related proteins in concentration-dependent manners. Furthermore, 8i could inhibit cell growth via MAPK signaling pathway and inhibit migration via Wnt pathway in PC-3 cells. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Micro hot embossing for high-aspect-ratio structure with materials flow enhancement by polymer sheet

NASA Astrophysics Data System (ADS)

Murakoshi, Yoichi; Shan, Xue-Chuan; Sano, Toshio; Takahashi, Masaharu; Maeda, Ryutaro

2004-04-01

Nano imprinting or Nano embossing process have been introduced to fabricate semiconductor, optical device and Micro Electro Mechanical Systems (MEMS) and the Nano Electro Mechanical Systems (NEMS) to reduce the fabrication cost. In our previous paper, micro hot embossing of Polycarbonate (PC) and Polyetheretherketone (PEEK) for optical switch with 8x8 mirrors was reported. The PC and PEEK sheets were embossed at elevated temperature with an embossing machine designed for the MEMS. In the application, the mirrors on the optical switch had some defects, such as slump, sticking and step at side of the mirror, due to embossing process and process conditions. These defects are attributed to the poor materials flow of plastics into the e Ni mold cavity of complicate shape with different aspect ratio. Therefore, the micro hot embossing is optimized in this paper with PTFE sheet to enhance the materials flow. In this paper, the PC and the PEEK sheets, thickness of 300um, are embossed at elevated temperature with the hot embossing machine with a Nickel mold. To control material flow of the PC or the PEEK sheets, Polytetrafluoroethylene (PTFE) sheet, the thickness of 100um, is placed on the PC or the PEEK sheets at elevated temperature. Mirror shape was transferred with better fidelity on the PC and PEEK sheet, and the thickness of cantilever became thinner than previous embossed structure without the PTFE. Especially, the mirror height and the thickness of cantilever on the PC have been improved at lower embossing temperature.

Coordination chemistry of 2,2'-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu

DOE PAGES

Macor, Joseph A.; Brown, Jessie L.; Cross, Justin Neil; ...

2015-01-01

New members of the dithiophosphinic acid family of potential actinide extractants were prepared: heterocyclic 2,2'-biphenylenedithiophosphinic acids of stoichiometry HS 2P(R 2C 12H 6) (R = H or tBu). The time- and atom-efficient syntheses afforded multigram quantities of pure HS 2P(R 2C 12H 6) in reasonable yields (~60%). These compounds differed from other diaryldithiophosphinic acid extractants in that the two aryl groups were connected to one another at the ortho positions to form a 5-membered dibenzophosphole ring. These 2,2'-biphenylenedithiophosphinic acids were readily deprotonated to form S 2P(R 2C 12H 6) 1- anions, which were crystallized as salts with tetraphenylpnictonium cations (ZPhmore » 4 1+; Z = P or As). Coordination chemistry between [S 2P( tBu 2C 12H 6)] 1- and [S 2P(C 6H 5)2] 1- with U, Np, and Pu was comparatively investigated. The results showed that dithiophosphinate complexes of UIV and NpIV were redox stable relative to those of UIII, whereas reactions involving PuIV gave intractable material. For instance, reactions involving UIV and NpIV generated An[S 2P( tBu 2C 12H 6)] 4 and An[S 2P(C 6H 5) 2] 4 whereas reactions between PuIV and [S 2P(C 6H 5) 2] 1- generated a mixture of products from which we postulated a transient PuIII species based on UV-Vis spectroscopy. However, the trivalent Pu[S 2P(C 6H 5) 2] 3(NC 5H 5) 2 compound is stable and could be isolated from reactions between [S 2P(C 6H 5) 2] 1- and the trivalent PuI 3(NC 5H 5) 4 starting material. Attempts to synthesize analogous trivalent compounds with UIII provided the tetravalent U[S 2P(C 6H 5 )2] 4 oxidation product.« less

On the Structure and Function of the Phytoene Desaturase CRTI from Pantoea ananatis, a Membrane-Peripheral and FAD-Dependent Oxidase/Isomerase

PubMed Central

Gemmecker, Sandra; Poussin-Courmontagne, Pierre; Mailliot, Justine; McEwen, Alastair G.; Ghisla, Sandro; Al-Babili, Salim; Cavarelli, Jean; Beyer, Peter

2012-01-01

CRTI-type phytoene desaturases prevailing in bacteria and fungi can form lycopene directly from phytoene while plants employ two distinct desaturases and two cis-tans isomerases for the same purpose. This property renders CRTI a valuable gene to engineer provitamin A-formation to help combat vitamin A malnutrition, such as with Golden Rice. To understand the biochemical processes involved, recombinant CRTI was produced and obtained in homogeneous form that shows high enzymatic activity with the lipophilic substrate phytoene contained in phosphatidyl-choline (PC) liposome membranes. The first crystal structure of apo-CRTI reveals that CRTI belongs to the flavoprotein superfamily comprising protoporphyrinogen IX oxidoreductase and monoamine oxidase. CRTI is a membrane-peripheral oxidoreductase which utilizes FAD as the sole redox-active cofactor. Oxygen, replaceable by quinones in its absence, is needed as the terminal electron acceptor. FAD, besides its catalytic role also displays a structural function by enabling the formation of enzymatically active CRTI membrane associates. Under anaerobic conditions the enzyme can act as a carotene cis-trans isomerase. In silico-docking experiments yielded information on substrate binding sites, potential catalytic residues and is in favor of single half-site recognition of the symmetrical C40 hydrocarbon substrate. PMID:22745782

Diet, Lifestyles, Family History, and Prostate Cancer Incidence in an East Algerian Patient Group

PubMed Central

Lassed, Somia; Deus, Cláudia M.; Lourenço, Nuno; Dahdouh, Abderrezak

2016-01-01

Prostate cancer (PC) is the fourth most common cancer in men and the sixth leading cause of death in Algeria. To examine the relationship between lifestyle factors, including diet, and family history and PC risk, a case-control study was performed in an eastern Algerian population, comprising 90 patients with histologically confirmed PC and 190 controls. Data collection was carried out through a structured questionnaire and statistical analysis was performed to evaluate the different variables. The data showed that consumption of lamb and beef meat and high intake of animal fat and dairy products increased PC risk. Seven to thirteen vegetables servings per week and fourteen or more servings decreased PC risk by 62% and 96%, respectively. Seven to fourteen fruit servings per week decrease PC risk by 98%. Green tea consumption reduced the risk of PC but the results were statistically borderline. Increased risk was observed for individuals with family history of PC in first and in second degree. A positive strong association was also found for alcohol and smoking intake and a dose-response relationship existed for quantity and history of smoking. This study suggests that dietary habits, lifestyle factors, and family history have influence on the development of PC in Algerian population. PMID:27975054

Diet, Lifestyles, Family History, and Prostate Cancer Incidence in an East Algerian Patient Group.

PubMed

Lassed, Somia; Deus, Cláudia M; Lourenço, Nuno; Dahdouh, Abderrezak; Rizvanov, Albert A; Oliveira, Paulo J; Zama, Djamila

2016-01-01

Prostate cancer (PC) is the fourth most common cancer in men and the sixth leading cause of death in Algeria. To examine the relationship between lifestyle factors, including diet, and family history and PC risk, a case-control study was performed in an eastern Algerian population, comprising 90 patients with histologically confirmed PC and 190 controls. Data collection was carried out through a structured questionnaire and statistical analysis was performed to evaluate the different variables. The data showed that consumption of lamb and beef meat and high intake of animal fat and dairy products increased PC risk. Seven to thirteen vegetables servings per week and fourteen or more servings decreased PC risk by 62% and 96%, respectively. Seven to fourteen fruit servings per week decrease PC risk by 98%. Green tea consumption reduced the risk of PC but the results were statistically borderline. Increased risk was observed for individuals with family history of PC in first and in second degree. A positive strong association was also found for alcohol and smoking intake and a dose-response relationship existed for quantity and history of smoking. This study suggests that dietary habits, lifestyle factors, and family history have influence on the development of PC in Algerian population.

Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion

DOE PAGES

Chaudhari, Mangesh I.; Nair, Jijeesh R.; Pratt, Lawrence R.; ...

2016-10-21

Lithium-ion solvation and diffusion properties in ethylene carbonate (EC) and propylene carbonate (PC) were studied by molecular simulation, experiments, and electronic structure calculations. Studies carried out in water provide a reference for interpretation. Classical molecular dynamics simulation results are compared to ab initio molecular dynamics to assess nonpolarizable force field parameters for solvation structure of the carbonate solvents. Quasi-chemical theory (QCT) was adapted to take advantage of fourfold occupancy of the near-neighbor solvation structure observed in simulations and used to calculate solvation free energies. The computed free energy for transfer of Li + to PC from water, based on electronicmore » structure calculations with cluster-QCT, agrees with the experimental value. The simulation-based direct-QCT results with scaled partial charges agree with the electronic structure-based QCT values. The computed Li +/PF 6 - transference numbers of 0.35/0.65 (EC) and 0.31/0.69 (PC) agree well with NMR experimental values of 0.31/0.69 (EC) and 0.34/0.66 (PC) and similar values obtained here with impedance spectroscopy. These combined results demonstrate that solvent partial charges can be scaled in systems dominated by strong electrostatic interactions to achieve trends in ion solvation and transport properties that are comparable to ab initio and experimental results. Thus, the results support the use of scaled partial charges in simple, nonpolarizable force fields in future studies of these electrolyte solutions.« less

Interband Photoconductivity of Metamorphic InAs/InGaAs Quantum Dots in the 1.3-1.55-μm Window

NASA Astrophysics Data System (ADS)

Golovynskyi, Sergii; Datsenko, Oleksandr I.; Seravalli, Luca; Trevisi, Giovanna; Frigeri, Paola; Babichuk, Ivan S.; Golovynska, Iuliia; Qu, Junle

2018-04-01

Photoelectric properties of the metamorphic InAs/In x Ga1 - x As quantum dot (QD) nanostructures were studied at room temperature, employing photoconductivity (PC) and photoluminescence spectroscopies, electrical measurements, and theoretical modeling. Four samples with different stoichiometry of In x Ga1 - x As cladding layer have been grown: indium content x was 0.15, 0.24, 0.28, and 0.31. InAs/In0.15Ga0.85As QD structure was found to be photosensitive in the telecom range at 1.3 μm. As x increases, a redshift was observed for all the samples, the structure with x = 0.31 was found to be sensitive near 1.55 μm, i.e., at the third telecommunication window. Simultaneously, only a slight decrease in the QD PC was recorded for increasing x, thus confirming a good photoresponse comparable with the one of In0.15Ga0.75As structures and of GaAs-based QD nanostructures. Also, the PC reduction correlate with the similar reduction of photoluminescence intensity. By simulating theoretically the quantum energy system and carrier localization in QDs, we gained insight into the PC mechanism and were able to suggest reasons for the photocurrent reduction, by associating them with peculiar behavior of defects in such a type of structures. All this implies that metamorphic QDs with a high x are valid structures for optoelectronic infrared light-sensitive devices.

Inferring functional connectivity in MRI using Bayesian network structure learning with a modified PC algorithm

PubMed Central

Iyer, Swathi; Shafran, Izhak; Grayson, David; Gates, Kathleen; Nigg, Joel; Fair, Damien

2013-01-01

Resting state functional connectivity MRI (rs-fcMRI) is a popular technique used to gauge the functional relatedness between regions in the brain for typical and special populations. Most of the work to date determines this relationship by using Pearson's correlation on BOLD fMRI timeseries. However, it has been recognized that there are at least two key limitations to this method. First, it is not possible to resolve the direct and indirect connections/influences. Second, the direction of information flow between the regions cannot be differentiated. In the current paper, we follow-up on recent work by Smith et al (2011), and apply a Bayesian approach called the PC algorithm to both simulated data and empirical data to determine whether these two factors can be discerned with group average, as opposed to single subject, functional connectivity data. When applied on simulated individual subjects, the algorithm performs well determining indirect and direct connection but fails in determining directionality. However, when applied at group level, PC algorithm gives strong results for both indirect and direct connections and the direction of information flow. Applying the algorithm on empirical data, using a diffusion-weighted imaging (DWI) structural connectivity matrix as the baseline, the PC algorithm outperformed the direct correlations. We conclude that, under certain conditions, the PC algorithm leads to an improved estimate of brain network structure compared to the traditional connectivity analysis based on correlations. PMID:23501054

Gene organization and alternative splicing of human prohormone convertase PC8.

PubMed Central

Goodge, K A; Thomas, R J; Martin, T J; Gillespie, M T

1998-01-01

The mammalian Ca2+-dependent serine protease prohormone convertase PC8 is expressed ubiquitously, being transcribed as 3.5, 4.3 and 6.0 kb mRNA isoforms in various tissues. To determine the origin of these various mRNA isoforms we report the characterization of the human PC8 gene, which has been previously localized to chromosome 11q23-24. Consisting of 16 exons, the human PC8 gene spans approx. 27 kb. A comparison of the position of intron-exon junctions of the human PC8 gene with the gene structures of previously reported prohormone convertase genes demonstrated a divergence of the human PC8 from the highly conserved nature of the gene organization of this enzyme family. The nucleotide sequence of the 5'-flanking region of the human PC8 is reported and possesses putative promoter elements characteristic of a GC-rich promoter. Further supporting the potential role of a GC-rich promoter element, multiple transcriptional initiation sites within a 200 bp region were demonstrated. We propose that the various mRNA isoforms of PC8 result from the inclusion of intronic sequences within transcripts. PMID:9820811

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Kee Sung; Rajput, Nav Nidhi; Persson, Kristin A.

Ferrocene (Fc) and N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethyl-sulfonimide (Fc1N112-TFSI) were dissolved in carbonate solvents and self-diffusion coefficients (D) of solutes and solvents were measured by {sup 1}H and {sup 19}F pulsed field gradient nuclear magnetic resonance (NMR) spectroscopy. The organic solvents were propylene carbonate (PC), ethyl methyl carbonate (EMC), and a ternary mixture that also includes ethylene carbonate (EC). Results from NMR studies over the temperature range of 0–50 °C and for various concentrations (0.25–1.7 M) of Fc1N112-TFSI are compared to values of D simulated with classical molecular dynamics (MD). The measured self-diffusion coefficients gradually decreased as the Fc1N112-TFSI concentration increased in allmore » solvents. Since TFSI{sup −} has fluoromethyl groups (CF{sub 3}), D{sub TFSI} could be measured separately and the values found are larger than those for D{sub Fc1N112} in all samples measured. The EC, PC, and EMC have the same D in the neat solvent mixture and when Fc is dissolved in EC/PC/EMC at a concentration of 0.2 M, probably due to the interactions between common carbonyl structures within EC, PC, and EMC. A difference in D (D{sub PC} < D{sub EC} < D{sub EMC}), and both a higher E{sub a} for translational motion and higher effective viscosity for PC in the mixture containing Fc1N112-TFSI reflect the interaction between PC and Fc1N112{sup +}, which is a relatively stronger interaction than that between Fc1N112{sup +} and other solvent species. In the EC/PC/EMC solution that is saturated with Fc1N112-TFSI, we find that D{sub PC} = D{sub EC} = D{sub EMC} and Fc1N112{sup +} and all components of the EC/PC/EMC solution have the same E{sub a} for translational motion, while the ratio D{sub EC/PC/EMC}/D{sub Fc1N112} is approximately 3. These results reflect the lack of available free volume for independent diffusion in the saturated solution. The Fc1N112{sup +} transference numbers lie around 0.4 and increase slightly as the temperature is increased in the PC and EMC solvents. The trends observed for D from simulations are in good agreement with experimental results and provide molecular level understanding of the solvation structure of Fc1N112-TFSI dissolved in EC/PC/EMC.« less

Legionella dumoffii Utilizes Exogenous Choline for Phosphatidylcholine Synthesis

PubMed Central

Palusinska-Szysz, Marta; Szuster-Ciesielska, Agnieszka; Kania, Magdalena; Janczarek, Monika; Chmiel, Elżbieta; Danikiewicz, Witold

2014-01-01

Phosphatidycholine (PC) is the major membrane-forming phospholipid in eukaryotes but it has been found in only a limited number of prokaryotes. Bacteria synthesize PC via the phospholipid N-methylation pathway (Pmt) or via the phosphatidylcholine synthase pathway (Pcs) or both. Here, we demonstrated that Legionella dumoffii has the ability to utilize exogenous choline for phosphatidylcholine (PC) synthesis when bacteria grow in the presence of choline. The Pcs seems to be a primary pathway for synthesis of this phospholipid in L. dumoffii. Structurally different PC species were distributed in the outer and inner membranes. As shown by the LC/ESI-MS analyses, PC15:0/15:0, PC16:0/15:0, and PC17:0/17:1 were identified in the outer membrane and PC14:0/16:0, PC16:0/17:1, and PC20:0/15:0 in the inner membrane. L. dumoffii pcsA gene encoding phosphatidylcholine synthase revealed the highest sequence identity to pcsA of L. bozemanae (82%) and L. longbeachae (81%) and lower identity to pcsA of L. drancourtii (78%) and L. pneumophila (71%). The level of TNF-α in THP1-differentiated cells induced by live and temperature-killed L. dumoffii cultured on a medium supplemented with choline was assessed. Live L. dumoffii bacteria cultured on the choline-supplemented medium induced TNF-α three-fold less efficiently than cells grown on the non-supplemented medium. There is an evident effect of PC modification, which impairs the macrophage inflammatory response. PMID:24821544

Structural Factors and Mechanisms Underlying the Improved Photodynamic Cell Killing with Silicon Phthalocyanine Photosensitizers Directed to Lysosomes Versus Mitochondria

PubMed Central

Rodriguez, Myriam E.; Zhang, Ping; Azizuddin, Kashif; Delos Santos, Grace B.; Chiu, Song-mao; Xue, Liang-yan; Berlin, Jeffery C.; Peng, Xinzhan; Wu, Hongqiao; Lam, Minh; Nieminen, Anna-Liisa; Kenney, Malcolm E.; Oleinick, Nancy L.

2012-01-01

The phthalocyanine photosensitizer Pc 4 has been shown to bind preferentially to mitochondrial and endoplasmic reticulum membranes. Upon photoirradiation of Pc 4-loaded cells, membrane components, especially Bcl-2, are photodamaged and apoptosis, as indicated by activation of caspase-3 and cleavage of poly(ADP-ribose) polymerase, is triggered. A series of analogs of Pc 4 were synthesized, and the results demonstrate that Pcs with the aminopropylsiloxy ligand of Pc 4 or a similar one on one side of the Pc ring and a second large axial ligand on the other side of the ring have unexpected properties, including enhanced cell uptake, greater monomerization resulting in greater intracellular fluorescence and three-fold higher affinity constants for liposomes. The hydroxyl-bearing axial ligands tend to reduce aggregation of the Pc and direct it to lysosomes, resulting in four to six times more killing of cells, as defined by loss of clonogenicity, than with Pc 4. Whereas Pc 4-PDT photodamages Bcl-2 and Bcl-xL, Pc 181-PDT causes much less photodamage to Bcl-2 over the same dose–response range relative to cell killing, with earlier cleavage of Bid and slower caspase-3-dependent apoptosis. Therefore, within this series of photosensitizers, these hydroxyl-bearing axial ligands are less aggregated than is Pc 4, tend to localize to lysosomes and are more effective in overall cell killing than is Pc 4, but induce apoptosis more slowly and by a modified pathway. PMID:19508642

Evaluating organizational change in health care: the patient-centered hospital model.

PubMed

Fiorio, Carlo V; Gorli, Mara; Verzillo, Stefano

2018-02-08

An increasing number of hospitals react to recent demographic, epidemiological and managerial challenges moving from a traditional organizational model to a Patient-Centered (PC) hospital model. Although the theoretical managerial literature on the PC hospital model is vast, quantitative evaluations of the performance of hospitals that moved from the traditional to the PC organizational structure is scarce. However, quantitative analysis of effects of managerial changes is important and can provide additional argument in support of innovation. We take advantage of a quasi-experimental setting and of a unique administrative data set on the population of hospital discharge charts (HDCs) over a period of 9 years of Lombardy, the richest and one of the most populated region of Italy. During this period three important hospitals switched to the PC model in 2010, whereas all the others remained with the functional organizational model. This allowed us to develop a difference-in-difference analysis of some selected measures of efficiency and effectiveness for PC hospitals focusing on the "between-variability" of the 25 major diagnostic categories (MDCs) in each hospital and estimating a difference-in-difference model. We contribute to the literature that addresses the evaluation of healthcare and hospital change by providing a quantitative estimation of efficiency and effectiveness changes following to the implementation of the PC hospital model. Results show that both efficiency and effectiveness have significantly increased in the average MDC of PC hospitals, thus confirming the need for policy makers to invest in new organizational models close to the principles of PC hospital structures. Although an organizational change towards the PC model can be a costly process, implying a rebalancing of responsibilities and power among hospital personnel (e.g. medical and nursing staff), our results suggest that changing towards a PC model can be worthwhile in terms of both efficacy and efficiency. This evidence can be used to inform and sustain hospital managers and policy makers in their hospital design efforts and to communicate the innovation advantages within the hospital organizations, among the personnel and in the public debate.

[Spectrum characterization and fine structure of copper phthalocyanine-doped TiO2 microcavities].

PubMed

Liu, Cheng-lin; Zhang, Xin-yi; Zhong, Ju-hua; Zhu, Yi-hua; He, Bo; Wei, Shi-qiang

2007-10-01

Copper phthalocyanine-doped TiO2 microcavities were fabricated by chemistry method. Their spectrum characterization was studied by Fourier transform infrared (FTIR) and Raman spectroscopy, and their fine structure was analyzed by X-ray absorption fine structure (XAFS). The results show that there is interaction of copper phthalocyanine (CuPc) and TiO2 microcavities after TiO2 microcavities was doped with CuPc. For example, there is absorption at 900.76 cm(-1) in FTIR spectra, and the "red shift" of both OH vibration at 3392.75 cm(-1) and CH vibration at 2848.83 cm(-1). There exist definite peak shifts and intensity changes in infrared absorption in the C-C or C-N vibration in the planar phthalocyanine ring, the winding vibration of C-H inside and C-N outside plane of benzene ring. In Raman spectrum, there are 403.4, 592.1 and 679.1 cm(-1) characterized peaks of TiO2 in CuPc-doped TiO2 microcavities, but their wave-numbers show shifts to anatase TiO2. The vibration peaks at 1586.8 and 1525.6 cm(-1) show that there exists the composite material of CuPc and TiO2. These changes are related to the plane tropism of the molecule structure of copper phthalocyanine. XAFS showed tetrahedron TiO4 structure of Ti in TiO2 microcavities doped with copper phthalocyanine, and the changes of inner "medial distances" and the surface structure of TiO2 microcavities.

Hardware, software, and scanning issues encountered during small animal imaging of photodynamic therapy in the athymic nude rat

NASA Astrophysics Data System (ADS)

Cross, Nathan; Sharma, Rahul; Varghai, Davood; Spring-Robinson, Chandra; Oleinick, Nancy L.; Muzic, Raymond F., Jr.; Dean, David

2007-02-01

Small animal imaging devices are now commonly used to study gene activation and model the effects of potential therapies. We are attempting to develop a protocol that non-invasively tracks the affect of Pc 4-mediated photodynamic therapy (PDT) in a human glioma model using structural image data from micro-CT and/or micro-MR scanning and functional data from 18F-fluorodeoxy-glucose (18F-FDG) micro-PET imaging. Methods: Athymic nude rat U87-derived glioma was imaged by micro-PET and either micro-CT or micro-MR prior to Pc 4-PDT. Difficulty insuring animal anesthesia and anatomic position during the micro-PET, micro-CT, and micro-MR scans required adaptation of the scanning bed hardware. Following Pc 4-PDT the animals were again 18F-FDG micro-PET scanned, euthanized one day later, and their brains were explanted and prepared for H&E histology. Histology provided the gold standard for tumor location and necrosis. The tumor and surrounding brain functional and structural image data were then isolated and coregistered. Results: Surprisingly, both the non-PDT and PDT groups showed an increase in tumor functional activity when we expected this signal to disappear in the group receiving PDT. Co-registration of the functional and structural image data was done manually. Discussion: As expected, micro-MR imaging provided better structural discrimination of the brain tumor than micro-CT. Contrary to expectations, in our preliminary analysis 18F-FDG micro-PET imaging does not readily discriminate the U87 tumors that received Pc 4-PDT. We continue to investigate the utility of micro-PET and other methods of functional imaging to remotely detect the specificity and sensitivity of Pc 4-PDT in deeply placed tumors.

Cryo-EM near-atomic structure of a dsRNA fungal virus shows ancient structural motifs preserved in the dsRNA viral lineage

PubMed Central

Luque, Daniel; Gómez-Blanco, Josué; Garriga, Damiá; Brilot, Axel F.; González, José M.; Havens, Wendy M.; Carrascosa, José L.; Trus, Benes L.; Verdaguer, Nuria; Ghabrial, Said A.; Castón, José R.

2014-01-01

Viruses evolve so rapidly that sequence-based comparison is not suitable for detecting relatedness among distant viruses. Structure-based comparisons suggest that evolution led to a small number of viral classes or lineages that can be grouped by capsid protein (CP) folds. Here, we report that the CP structure of the fungal dsRNA Penicillium chrysogenum virus (PcV) shows the progenitor fold of the dsRNA virus lineage and suggests a relationship between lineages. Cryo-EM structure at near-atomic resolution showed that the 982-aa PcV CP is formed by a repeated α-helical core, indicative of gene duplication despite lack of sequence similarity between the two halves. Superimposition of secondary structure elements identified a single “hotspot” at which variation is introduced by insertion of peptide segments. Structural comparison of PcV and other distantly related dsRNA viruses detected preferential insertion sites at which the complexity of the conserved α-helical core, made up of ancestral structural motifs that have acted as a skeleton, might have increased, leading to evolution of the highly varied current structures. Analyses of structural motifs only apparent after systematic structural comparisons indicated that the hallmark fold preserved in the dsRNA virus lineage shares a long (spinal) α-helix tangential to the capsid surface with the head-tailed phage and herpesvirus viral lineage. PMID:24821769

Fast data transmission from serial data acquisition for the GEM detector system

NASA Astrophysics Data System (ADS)

Kolasinski, Piotr; Pozniak, Krzysztof T.; Czarski, Tomasz; Byszuk, Adrian; Chernyshova, Maryna; Kasprowicz, Grzegorz; Krawczyk, Rafal D.; Wojenski, Andrzej; Zabolotny, Wojciech

2015-09-01

This article proposes new method of storing data and transferring it to PC in the X-ray GEM detector system. The whole process is performed by FPGA chips (Spartan-6 series from Xilinx). Comparing to previous methods, new approach allows to store much more data in the system. New, improved implementation of the communication algorithm significantly increases transfer rate between system and PC. In PC data is merged and processed by MATLAB. The structure of firmware implemented in the FPGAs is described.

Study of the relation between Pc 3 micropulsations and magnetosheath fluctuations and of the multisatellite, multimeasurement investigation of the earth's bow shock

NASA Technical Reports Server (NTRS)

1976-01-01

The structure and direction of bow shock waves and the occurence of Pc 3, 4 micropulsations were investigated. An observational description is given of a quasi-parallel structure in a plasma parameter regime. The use of approximation to estimate the thickness of thin, nearly perpendicular bow shocks at supralaminar Mach numbers is discussed. The pattern of energies of backstreaming protons in the foreshock are predicted.

Structure-function relationships between aldolase C/zebrin II expression and complex spike synchrony in the cerebellum.

PubMed

Tsutsumi, Shinichiro; Yamazaki, Maya; Miyazaki, Taisuke; Watanabe, Masahiko; Sakimura, Kenji; Kano, Masanobu; Kitamura, Kazuo

2015-01-14

Simple and regular anatomical structure is a hallmark of the cerebellar cortex. Parasagittally arrayed alternate expression of aldolase C/zebrin II in Purkinje cells (PCs) has been extensively studied, but surprisingly little is known about its functional significance. Here we found a precise structure-function relationship between aldolase C expression and synchrony of PC complex spike activities that reflect climbing fiber inputs to PCs. We performed two-photon calcium imaging in transgenic mice in which aldolase C compartments can be visualized in vivo, and identified highly synchronous complex spike activities among aldolase C-positive or aldolase C-negative PCs, but not across these populations. The boundary of aldolase C compartments corresponded to that of complex spike synchrony at single-cell resolution. Sensory stimulation evoked aldolase C compartment-specific complex spike responses and synchrony. This result further revealed the structure-function segregation. In awake animals, complex spike synchrony both within and between PC populations across the aldolase C boundary were enhanced in response to sensory stimuli, in a way that two functionally distinct PC ensembles are coactivated. These results suggest that PC populations characterized by aldolase C expression precisely represent distinct functional units of the cerebellar cortex, and these functional units can cooperate to process sensory information in awake animals. Copyright © 2015 the authors 0270-6474/15/350843-10$15.00/0.

Internal high-reflectivity omni-directional reflectors

NASA Astrophysics Data System (ADS)

Xi, J.-Q.; Ojha, Manas; Plawsky, J. L.; Gill, W. N.; Kim, Jong Kyu; Schubert, E. F.

2005-07-01

An internal high-reflectivity omni-directional reflector (ODR) for the visible spectrum is realized by the combination of total internal reflection using a low-refractive-index (low-n) material and reflection from a one-dimensional photonic crystal (1D PC). The low-n layer limits the range of angles in the 1D PC to values below the Brewster angle, thereby enabling high reflectivity and omni-directionality. This ODR is demonstrated using GaP as ambient, nanoporous SiO2 with a very low refractive index (n=1.10), and a four-pair TiO2/SiO2 multilayer stack. The results indicate a two orders of magnitude lower angle-integrated transverse-electric-transverse-magnetic polarization averaged mirror loss of the ODR compared with conventional distributed Bragg reflectors and metal reflectors. This indicates the high potential of the internal ODRs for optoelectronic semiconductor devices, e.g., light-emitting diodes.

Nanoantenna-Microcavity Hybrids with Highly Cooperative Plasmonic-Photonic Coupling

NASA Astrophysics Data System (ADS)

Liu, Jui-Nung; Huang, Qinglan; Liu, Keng-Ku; Singamaneni, Srikanth; Cunningham, Brian T.

2017-12-01

Nanoantennas concentrate electromagnetic energy into deep-subwavelength volumes (hotspot), which benefits a wide range of applications such as spontaneous emission enhancement, nonlinear optics, nanolaser, and surface-enhanced Raman scattering (SERS). To increase hotspot intensity, methods for sculpting individual nanoantenna resonance have been previously explored. Here, we study a nanoantenna-microcavity hybrid approach for highly cooperative hotspot enhancement, combining gold nanorods (AuNRs) for nanometer-scale light concentration and a resonant photonic crystal (PC) slab for efficient near-field excitation and optical feedback. We experimentally validate the predicted synergistic hybrid enhancement with SERS, and demonstrate that coupling to the modest-Q PC guided resonance (PCGR) boosts the hotspot intensity of the AuNR by at least one order of magnitude in comparison to the Fabry-Perot cavity enhanced (~5X) AuNR. These results exhibit a dissimilar hybrid cooperativity versus previously reported nanoantenna-cavity systems, and pave the new way to further facilitate light-nanoantenna interaction for many applications.

A Tool for Medical Research

NASA Technical Reports Server (NTRS)

1992-01-01

California Measurements, Inc.'s PC-2 Aerosol Particle Analyzer, developed by William Chiang, a former Jet Propulsion Laboratory (JPL) engineer, was used in a study to measure the size of particles in the medical environment. Chiang has a NASA license for the JPL crystal oscillator technology and originally built the instrument for atmospheric research. In the operating room, it enabled researchers from the University of California to obtain multiple sets of data repeatedly and accurately. The study concluded that significant amounts of aerosols are generated during surgery when power tools are employed, and most of these are in the respirable size. Almost all contain blood and are small enough to pass through surgical masks. Research on the presence of blood aerosols during oral surgery had similar results. Further studies are planned to determine the possibility of HIV transmission during surgery, and the PC-2H will be used to quantify blood aerosols.

High-performance polymer/layered silicate nanocomposites

NASA Astrophysics Data System (ADS)

Heidecker, Matthew J.

High-performance layered-silicate nanocomposites of Polycarbonate (PC), poly(ethylene terephthalate) (PET), and their blends were produced via conventional melt-blending techniques. The focus of this thesis was on the fundamentals of dispersion, control of thermal stability, maintenance of melt-blending processing conditions, and on optimization of the composites' mechanical properties via the design of controlled and thermodynamically favorable nano-filler dispersions within the polymer matrices. PET and PC require high temperatures for melt-processing, rendering impractical the use of conventional/commercial organically-modified layered-silicates, since the thermal degradation temperatures of their ammonium surfactants lies below the typical processing temperatures. Thus, different surfactant chemistries must be employed in order to develop melt-processable nanocomposites, also accounting for polymer matrix degradation due to water (PET) or amine compounds (PC). Novel high thermal-stability surfactants were developed and employed in montmorillonite nanocomposites of PET, PC, and PC/PET blends, and were compared to the respective nanocomposites based on conventional quaternary-ammonium modified montmorillonites. Favorable dispersion was achieved in all cases, however, the overall material behavior -- i.e., the combination of crystallization, mechanical properties, and thermal degradation -- was better for the nanocomposites based on the thermally-stable surfactant fillers. Studies were also done to trace, and ultimately limit, the matrix degradation of Polycarbonate/montmorillonite nanocomposites, through varying the montmorillonite surfactant chemistry, processing conditions, and processing additives. Molecular weight degradation was, maybe surprisingly, better controlled in the conventional quaternary ammonium based nanocomposites -- even though the thermal stability of the organically modified montmorillonites was in most cases the lowest. Dependence of the resultant nanocomposites' mechanical properties on the preferential alignment of the montmorillonite nano-platelet was also evaluated. Highly aligned filler platelets did not result in an additional enhancement in mechanical properties. PC/PET blends and their respective PC/PET/montmorillonite nanocomposites were synthesized and compared. The dispersion of the organically modified nano-fillers in the PC/PET blends was controlled via thermodynamic considerations, realized through proper surfactant choice: Nanocomposites in which the layered silicate was preferentially sequestered in the PET phase were designed and synthesized. This preferential dispersion of the nano-filler in the PET phase of the PC/PET blend was insensitive to processing conditions, including approaches employing a master-batch (filler concentrate); regardless of the master-batch matrix, both PC and PET were employed, thermodynamics drove the layered silicate to preferentially migrate to the PET phase of the PC/PET blend. In a second approach, the development of a nanocomposite with controlled PC/PET compatibilization near the montmorillonite platelets, in absence of appreciable transesterification reactions, led to the formation of very high performance nanocomposites. These latter systems, point to an exciting new avenue of future considerations for nanocomposite blends with selective nano-filler dispersions, where performance can be tailored via the controlled preferential dispersion of nano-fillers in one phase, or by filler-induced polymer compatibilization.

Sensing specific adhesion of liposomal and micellar systems with attached carbohydrate recognition structures at lectin surfaces.

PubMed

Hildebrand, Annegret; Schaedlich, Anita; Rothe, Ulrich; Neubert, Reinhard H H

2002-05-15

A quartz crystal microbalance was used to investigate the adsorption behavior of liposomes and mixed micelles with attached carbohydrate recognition structures at lectin-coated quartz plates. With a self-assembly technique, the quartz was coated with the lectin Concanavalin A. In a first attempt, liposomes of natural soybean PC as well as synthetic POPC, containing 10% reactive N-Glut-PE each, were decorated with a mannopyranoside recognition structure to investigate the specific adsorption at the lectin-coated quartz surface in dependence on the concentration. In a second model, the bile salt sodium cholate was introduced to solubilize the mannopyranoside-modified liposomes and to transform them into mannopyranoside-modified binary mixed micelles. The adsorption of these micelles was further investigated. In a third approach, the adsorption behavior of mannopyranoside-modified ternary mixed bile salt-phosphatidylcholine-fatty acid micelles was characterized with sodium laurate, palmitate, and oleate as fatty acids. The micelles with oleate showed only a small frequency decrease, whereas the micelles with laurate and palmitate induced higher frequency changes. A dependence on the alkyl chain length could be detected. While the adsorption of liposomes containing recognition structures at QCM surfaces is nowadays well-established, the QCM detection of the adsorption of mixed bile salt micelles, transformed from these liposomes by solubilization, is a novel and very promising field for the development of innovative colloidal drug delivery systems.

Revisiting the blind tests in crystal structure prediction: accurate energy ranking of molecular crystals.

PubMed

Asmadi, Aldi; Neumann, Marcus A; Kendrick, John; Girard, Pascale; Perrin, Marc-Antoine; Leusen, Frank J J

2009-12-24

In the 2007 blind test of crystal structure prediction hosted by the Cambridge Crystallographic Data Centre (CCDC), a hybrid DFT/MM method correctly ranked each of the four experimental structures as having the lowest lattice energy of all the crystal structures predicted for each molecule. The work presented here further validates this hybrid method by optimizing the crystal structures (experimental and submitted) of the first three CCDC blind tests held in 1999, 2001, and 2004. Except for the crystal structures of compound IX, all structures were reminimized and ranked according to their lattice energies. The hybrid method computes the lattice energy of a crystal structure as the sum of the DFT total energy and a van der Waals (dispersion) energy correction. Considering all four blind tests, the crystal structure with the lowest lattice energy corresponds to the experimentally observed structure for 12 out of 14 molecules. Moreover, good geometrical agreement is observed between the structures determined by the hybrid method and those measured experimentally. In comparison with the correct submissions made by the blind test participants, all hybrid optimized crystal structures (apart from compound II) have the smallest calculated root mean squared deviations from the experimentally observed structures. It is predicted that a new polymorph of compound V exists under pressure.

Application of photonic crystal defects in constructing all-optical switches, optical delay lines and low-cross-talk waveguide intersections for ultrashort optical pulses

NASA Astrophysics Data System (ADS)

Lan, Sheng; Sugimoto, Yoshimasa; Nishikawa, Satoshi; Ikeda, Naoki; Yang, Tao; Kanamoto, Kozyo; Ishikawa, Hiroshi; Asakawa, Kiyoshi

2002-07-01

We present a systematic study of coupled defects in photonic crystals (PCs) and explore their applications in constructing optical components and devices for ultrafast all-optical signal processing. First, we find that very deep band gaps can be generated in the impurity bands of coupled cavity waveguides (CCWs) by a small periodic modulation of defect modes. This phenomenon implies a high-efficiency all-optical switching mechanism. The switching mechanism can be easily extended from one-dimensional (1D) to two-dimensional and three-dimensional PC structures by utilizing the coupling of defect pairs which are generally present in PCs. Second, we suggest that CCWs with quasiflat and narrow impurity bands can be employed as efficient delay lines for ultrashort pulses. Criteria for designing such kind of CCWs have been derived from the analysis of defect coupling and the investigation of pulse transmission through various CCWs. It is found that the availability of quasiflat impurity bands depends not only on the intrinsic properties of the constituting defects but also on the detailed configuration of CCWs. In experiments, optical delay lines based on 1D monorail CCWs have been successfully fabricated and characterized. Finally, we have proposed a new mechanism for constructing waveguide intersections with broad bandwidth and low cross-talk.

Nanostructured Surfaces and Detection Instrumentation for Photonic Crystal Enhanced Fluorescence

PubMed Central

Chaudhery, Vikram; George, Sherine; Lu, Meng; Pokhriyal, Anusha; Cunningham, Brian T.

2013-01-01

Photonic crystal (PC) surfaces have been demonstrated as a compelling platform for improving the sensitivity of surface-based fluorescent assays used in disease diagnostics and life science research. PCs can be engineered to support optical resonances at specific wavelengths at which strong electromagnetic fields are utilized to enhance the intensity of surface-bound fluorophore excitation. Meanwhile, the leaky resonant modes of PCs can be used to direct emitted photons within a narrow range of angles for more efficient collection by a fluorescence detection system. The multiplicative effects of enhanced excitation combined with enhanced photon extraction combine to provide improved signal-to-noise ratios for detection of fluorescent emitters, which in turn can be used to reduce the limits of detection of low concentration analytes, such as disease biomarker proteins. Fabrication of PCs using inexpensive manufacturing methods and materials that include replica molding on plastic, nano-imprint lithography on quartz substrates result in devices that are practical for single-use disposable applications. In this review, we will describe the motivation for implementing high-sensitivity fluorescence detection in the context of molecular diagnosis and gene expression analysis though the use of PC surfaces. Recent efforts to improve the design and fabrication of PCs and their associated detection instrumentation are summarized, including the use of PCs coupled with Fabry-Perot cavities and external cavity lasers. PMID:23624689

Exquisite Enzyme-Fenton Biomimetic Catalysts for Hydroxyl Radical Production by Mimicking an Enzyme Cascade.

PubMed

Zhang, Qi; Chen, Shuo; Wang, Hua; Yu, Hongtao

2018-03-14

Hydrogen peroxide (H 2 O 2 ) is a key reactant in the Fenton process. As a byproduct of enzymatic reaction, H 2 O 2 can be obtained via catalytical oxidation of glucose using glucose oxidase in the presence of O 2 . Another oxidation product (gluconic acid) can suitably adjust the microenvironmental pH contributing to the Fe 3+ /Fe 2+ cycle in the Fenton reaction. Enzymes are extremely efficient at catalyzing a variety of reactions with high catalytic activity, substrate specificity, and yields in living organisms. Inspired by the multiple functions of natural multienzyme systems, an exquisite nanozyme-modified α-FeOOH/porous carbon (PC) biomimetic catalyst constructed by in situ growth of glucose oxidase-mimicking Au nanoparticles and crystallization of adsorbed ferric ions within carboxyl into hierarchically PC is developed as an efficient enzyme-Fenton catalyst. The products (H 2 O 2 , ∼4.07 mmol·L -1 ) of the first enzymatic reaction are immediately used as substrates for the second Fenton-like reaction to generate the valuable • OH (∼96.84 μmol·L -1 ), thus mimicking an enzyme cascade pathway. α-FeOOH nanocrystals, attached by C-O-Fe bondings, are encapsulated into the mesoporous PC frameworks, facilitating the electron transfer between α-FeOOH and the PC support and greatly suppressing iron leaching. This study paves a new avenue for designing biomimetic enzyme-based Fenton catalysts mimicking a natural system for • OH production.

Stereoscopic-3D display design: a new paradigm with Intel Adaptive Stable Image Technology [IA-SIT

NASA Astrophysics Data System (ADS)

Jain, Sunil

2012-03-01

Stereoscopic-3D (S3D) proliferation on personal computers (PC) is mired by several technical and business challenges: a) viewing discomfort due to cross-talk amongst stereo images; b) high system cost; and c) restricted content availability. Users expect S3D visual quality to be better than, or at least equal to, what they are used to enjoying on 2D in terms of resolution, pixel density, color, and interactivity. Intel Adaptive Stable Image Technology (IA-SIT) is a foundational technology, successfully developed to resolve S3D system design challenges and deliver high quality 3D visualization at PC price points. Optimizations in display driver, panel timing firmware, backlight hardware, eyewear optical stack, and synch mechanism combined can help accomplish this goal. Agnostic to refresh rate, IA-SIT will scale with shrinking of display transistors and improvements in liquid crystal and LED materials. Industry could profusely benefit from the following calls to action:- 1) Adopt 'IA-SIT S3D Mode' in panel specs (via VESA) to help panel makers monetize S3D; 2) Adopt 'IA-SIT Eyewear Universal Optical Stack' and algorithm (via CEA) to help PC peripheral makers develop stylish glasses; 3) Adopt 'IA-SIT Real Time Profile' for sub-100uS latency control (via BT Sig) to extend BT into S3D; and 4) Adopt 'IA-SIT Architecture' for Monitors and TVs to monetize via PC attach.

Neutron structure and inelastic-neutron-scattering and theoretical studies of Mo(CO)(H[sub 2])[(C[sub 6]D[sub 5])[sub 2]PC[sub 2]H[sub 4]P(C[sub 6]D[sub 5])[sub 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kubas, G.J.; Burns, C.J.; Eckert, J.

1993-01-27

The synthesis and characterization of derivatives of Mo(CO)(R[sub 2]PC[sub 2]H[sub 4]PR[sub 2])[sub 2] (R = Et, i-Bu, Ph, Et-Ph) and their reactions with H[sub 2], N[sub 2], and SO[sub 2] are reported. For R = Et and i-Bu, the H[sub 2] oxidatively adds to give dihydrides, but for R = Ph, a [eta][sup 2]-H[sub 2] complex is formed. Single-crystal neutron diffraction of Mo(CO)(H[sub 2])(Ph[sub 2]PC[sub 2]H[sub 4]PPh[sub 2])[sub 2] (as a 4.5-benzene solvate with all Ph groups deuterated) at 12 K showed the H-H bond to be oriented trans to the CO and parallel to a P-Mo-P axis, with amore » length close to that of free H[sub 2] (0.74 [Angstrom]). However, the thermal ellipsoids were very large, and inelastic neutron scattering showed that the barrier to rotation of the H[sub 2] is the lowest yet measured, ca. 0.7 kcal/mol. These observations indicate that librational motion of the H[sub 2] is artificially foreshortening the H-H bond length. Application of a correction procedure gave a distance of 0.80-0.85 [Angstrom] as being more likely. Extended Huckel calculations successfully modeled the H[sub 2] coordination and also showed a low rotational barrier (1.4 kcal/mol). Theoretical considerations suggest that the degree of distortion of the MP[sub 4] skeleton is largely responsible for the ability of the complex to bind molecular hydrogen and controls the amount of back-bonding from the metal d-orbital to H[sub 2] [sigma][sup *]. The lack of an elongated H-H bond length or equilibrium with a dihydride tautomer, despite the apparent nearness of the H[sub 2] to cleavage, leads to the conclusion that the reaction coordinate for oxidative addition of H[sub 2] is rather flat until relatively precipitous cleavage of the H[sub 2]. Mo(CO)(H[sub 2])[(C[sub 6]D[sub 5])[sub 2]PC[sub 2]H[sub 4]P(C[sub 6]D[sub 5])[sub 2

Mapping Flexibility and the Assembly Switch of Cell Division Protein FtsZ by Computational and Mutational Approaches*♦

PubMed Central

Martín-Galiano, Antonio J.; Buey, Rubén M.; Cabezas, Marta; Andreu, José M.

2010-01-01

The molecular switch for nucleotide-regulated assembly and disassembly of the main prokaryotic cell division protein FtsZ is unknown despite the numerous crystal structures that are available. We have characterized the functional motions in FtsZ with a computational consensus of essential dynamics, structural comparisons, sequence conservation, and networks of co-evolving residues. Employing this information, we have constructed 17 mutants, which alter the FtsZ functional cycle at different stages, to modify FtsZ flexibility. The mutant phenotypes ranged from benign to total inactivation and included increased GTPase, reduced assembly, and stabilized assembly. Six mutations clustering at the long cleft between the C-terminal β-sheet and core helix H7 deviated FtsZ assembly into curved filaments with inhibited GTPase, which still polymerize cooperatively. These mutations may perturb the predicted closure of the C-terminal domain onto H7 required for switching between curved and straight association modes and for GTPase activation. By mapping the FtsZ assembly switch, this work also gives insight into FtsZ druggability because the curved mutations delineate the putative binding site of the promising antibacterial FtsZ inhibitor PC190723. PMID:20472561