Prediction of Environmental Impact of High-Energy Materials with Atomistic Computer Simulations

DTIC Science & Technology

2010-11-01

from a training set of compounds. Other methods include Quantitative Struc- ture-Activity Relationship ( QSAR ) and Quantitative Structure-Property...26 28 the development of QSPR/ QSAR models, in contrast to boiling points and critical parameters derived from empirical correlations, to improve...Quadratic Configuration Interaction Singles Doubles QSAR Quantitative Structure-Activity Relationship QSPR Quantitative Structure-Property

Arginine-based poly(ester amide) nanoparticle platform: From structure-property relationship to nucleic acid delivery.

PubMed

You, Xinru; Gu, Zhipeng; Huang, Jun; Kang, Yang; Chu, Chih-Chang; Wu, Jun

2018-05-25

Many different types of polycations have been vigorously studied for nucleic acid delivery, but a systematical investigation of the structure-property relationships of polycations for nucleic acid delivery is still lacking. In this study, a new library of biodegradable and biocompatible arginine-based poly(ester amide) (Arg-PEA) biomaterials was designed and synthesized with a tunable structure for such a comprehensive structure-property research. Nanoparticle (NP) complexes were formed through the electrostatic interactions between the polycationic Arg-PEAs and anionic nucleic acids. The following structure effects of the Arg-PEAs on the transfection efficiency of nucleic acids were investigated: 1) the linker/spacer length (length effect and odd-even effect); 2) salt type of arginine; 3) the side chain; 4) chain stiffness; 5) molecular weight (MW). The data obtained revealed that a slight change in the Arg-PEA structure could finely tune its physicochemical property such as hydrophobicity, and this could subsequently affect the nanoparticle size and zeta potential, which, in turn, regulate the transfection efficiency and silencing outcomes. A further study of the Arg-PEA/CpG oligodeoxynucleotide NP complexes indicated that the polymer structure could precisily regulate the immune response of CpG, thus providing a new potential nano-immunotherapy strategy. The in vitro data have further confirmed that the Arg-PEA NPs showed a satisfactory delivery performance for a variety of nucleic acids. Therefore, the data from the current study provide comprehensive information about the Arg-PEA structure-transfection property relationship; the tunable property of the library of Arg-PEA biomaterials can be one of the promising candidates for nucleic acid delivery and other biomedical applications. Polycations have being intensive utilized for nucleic acid delivery. However, there has not been elucidated about the relationship between polycation's structure and the physicochemical properties/biological function. In this timely report, an arginine based poly(ester amide) (Arg-PEA) library was prepared with finely tunable structure to systematically investigate the structure-property relationships of polycations for nucleic acid delivery. The results revealed that slight change of Arg-PEA structure could finely tune the physicochemical property (such as hydrophobicity), which subsequently affect the size and zeta potential of Arg-PEA/nucleic acid nanoparticles(NPs), and finally regulate the resulting transfection or silencing outcomes. Further study of Arg-PEA/CpG NPs indicated that the polymer structure could precisely regulate immuno response of CpG, providing new potential nano-immunotherapy strategy. In vitro evaluations confirmed that the NPs showed satisfied delivery performance for a variety types of nucleic acids. Therefore, these studies provide comprehensive information of Arg-PEA structure-property relationship, and the tunable properties of Arg-PEAs make them promising candidates for nucleic acid delivery and other biomedical applications. Overall, we have shown enough significance and novelty in terms of nucleic acid delivery, biomaterials, pharmaceutical science and nanomedicine. Copyright © 2018. Published by Elsevier Ltd.

Relationship between critical mechanical properties and age for structural lightweight concrete.

DOT National Transportation Integrated Search

1964-02-25

The necessity to use structural lightweight concrete has created : a need for investigations into its critical mechanical properties that : affect the design and performance of structures. The primary critical : properties were found to be direct ten...

Structure-function-property-design interplay in biopolymers: spider silk.

PubMed

Tokareva, Olena; Jacobsen, Matthew; Buehler, Markus; Wong, Joyce; Kaplan, David L

2014-04-01

Spider silks have been a focus of research for almost two decades due to their outstanding mechanical and biophysical properties. Recent advances in genetic engineering have led to the synthesis of recombinant spider silks, thus helping to unravel a fundamental understanding of structure-function-property relationships. The relationships between molecular composition, secondary structures and mechanical properties found in different types of spider silks are described, along with a discussion of artificial spinning of these proteins and their bioapplications, including the role of silks in biomineralization and fabrication of biomaterials with controlled properties. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A review of the structure-property relationships in lead-free piezoelectric (1−x)Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}–(x)BaTiO{sub 3}

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

McQuade, Ryan R.; Dolgos, Michelle R., E-mail: Michelle.Dolgos@oregonstate.edu

2016-10-15

Piezoelectric materials are increasingly being investigated for energy harvesting applications where (1−x)Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}–(x)BaTiO{sub 3} (NBT-BT) is an important lead-free piezoelectric material with potential to be used as an actuator in energy harvesting devices. Much effort has been put into modifying NBT-BT to tune the properties for specific applications, but there is currently no consensus regarding the structure-property relationships in this material, making targeted, rational design a major challenge. In this review, we will summarize the current body of knowledge of NBT-BT and discuss contradicting studies, unresolved problems, and future directions in the field. - Graphical abstract: This reviewmore » of (1−x)Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}–(x)BaTiO{sub 3} (NBT-BT) summarizes the large body of literature regarding the structure-property relationships of this complex material. We highlight structural studies of the average and local structures of both unpoled and poled samples of NBT-BT at its morphotropic phase boundary and discuss them in context of the observed piezoelectric properties. - Highlights: • Local and average structure of NBT-BT at morphotropic phase boundary is reviewed. • Average structure of poled and unpoled samples of NBT-BT is discussed. • Structure-property relationships in NBT-BT and future directions are summarized.« less

Quantitative description on structure-property relationships of Li-ion battery materials for high-throughput computations

NASA Astrophysics Data System (ADS)

Wang, Youwei; Zhang, Wenqing; Chen, Lidong; Shi, Siqi; Liu, Jianjun

2017-12-01

Li-ion batteries are a key technology for addressing the global challenge of clean renewable energy and environment pollution. Their contemporary applications, for portable electronic devices, electric vehicles, and large-scale power grids, stimulate the development of high-performance battery materials with high energy density, high power, good safety, and long lifetime. High-throughput calculations provide a practical strategy to discover new battery materials and optimize currently known material performances. Most cathode materials screened by the previous high-throughput calculations cannot meet the requirement of practical applications because only capacity, voltage and volume change of bulk were considered. It is important to include more structure-property relationships, such as point defects, surface and interface, doping and metal-mixture and nanosize effects, in high-throughput calculations. In this review, we established quantitative description of structure-property relationships in Li-ion battery materials by the intrinsic bulk parameters, which can be applied in future high-throughput calculations to screen Li-ion battery materials. Based on these parameterized structure-property relationships, a possible high-throughput computational screening flow path is proposed to obtain high-performance battery materials.

Quantitative description on structure-property relationships of Li-ion battery materials for high-throughput computations.

PubMed

Wang, Youwei; Zhang, Wenqing; Chen, Lidong; Shi, Siqi; Liu, Jianjun

2017-01-01

Li-ion batteries are a key technology for addressing the global challenge of clean renewable energy and environment pollution. Their contemporary applications, for portable electronic devices, electric vehicles, and large-scale power grids, stimulate the development of high-performance battery materials with high energy density, high power, good safety, and long lifetime. High-throughput calculations provide a practical strategy to discover new battery materials and optimize currently known material performances. Most cathode materials screened by the previous high-throughput calculations cannot meet the requirement of practical applications because only capacity, voltage and volume change of bulk were considered. It is important to include more structure-property relationships, such as point defects, surface and interface, doping and metal-mixture and nanosize effects, in high-throughput calculations. In this review, we established quantitative description of structure-property relationships in Li-ion battery materials by the intrinsic bulk parameters, which can be applied in future high-throughput calculations to screen Li-ion battery materials. Based on these parameterized structure-property relationships, a possible high-throughput computational screening flow path is proposed to obtain high-performance battery materials.

Rationalizing the photophysical properties of BODIPY laser dyes via aromaticity and electron-donor-based structural perturbations

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

Waddell, Paul G.; Liu, Xiaogang; Zhao, Teng

2015-05-01

The absorption and fluorescence properties of six boron dipyrromethene (BODIPY) laser dyes with simple non-aromatic substituents are rationalized by relating them to observable structural perturbations within the molecules of the dyes. An empirical relationship involving the structure and the optical properties is derived using a combination of single-crystal X-ray diffraction data, quantum chemical calculations and electronic constants: i.e. the tendency of the pyrrole bond lengths towards aromaticity and the UV-vis absorption and fluorescence wavelengths correlating with the electron-donor properties of the substituents. The effect of molecular conformation on the solid-state optical properties of the dyes is also discussed. The findingsmore » in this study also demonstrate the usefulness and limitations of using crystal structure data to develop structure-property relationships in this class of optical materials, contributing to the growing effort to design optoelectronic materials with tunable properties via molecular engineering.« less

Advanced thermally stable jet fuels. Technical progress report, January 1995--March 1995

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

Schobert, H.H.; Eser, S.; Song, C.

Quantitative structure-property relationships have been applied to study the thermal stability of pure hydrocarbons typical of jet fuel components. A simple method of chemical structure description in terms of Benson groups was tested in searching for structure-property relationships for the hydrocarbons tested experimentally in this program. Molecular connectivity as a structure-based approach to chemical structure-property relationship analysis was also tested. Further development of both the experimental data base and computational methods will be necessary. Thermal decomposition studies, using glass tube reactors, were extended to two additional model compounds: n-decane and n-dodecane. Efforts on refining the deposit growth measurement and characterizationmore » of suspended matter in stressed fuels have lead to improvements in the analysis of stressed fuels. Catalytic hydrogenation and dehydrogenation studies utilizing a molybdenum sulfide catalyst are also described.« less

Structure-Property-Function Relationship in Humic Substances to Explain the Biological Activity in Plants

PubMed Central

García, Andrés Calderín; de Souza, Luiz Gilberto Ambrosio; Pereira, Marcos Gervasio; Castro, Rosane Nora; García-Mina, José María; Zonta, Everaldo; Lisboa, Francy Junior Gonçalves; Berbara, Ricardo Luis Louro

2016-01-01

Knowledge of the structure-property-function relationship of humic substances (HSs) is key for understanding their role in soil. Despite progress, studies on this topic are still under discussion. We analyzed 37 humic fractions with respect to their isotopic composition, structural characteristics, and properties responsible for stimulating plant root parameters. We showed that regardless of the source of origin of the carbon (C3 or C4), soil-extracted HSs and humic acids (HAs) are structurally similar to each other. The more labile and functionalized HS fraction is responsible for root emission, whereas the more recalcitrant and less functionalized HA fraction is related to root growth. Labile structures promote root stimulation at lower concentrations, while recalcitrant structures require higher concentrations to promote a similar stimulus. These findings show that lability and recalcitrance, which are derived properties of humic fractions, are related to the type and intensity of their bioactivity. In summary, the comparison of humic fractions allowed a better understanding of the relationship between the source of origin of plant carbon and the structure, properties, and type and intensity of the bioactivity of HSs in plants. In this study, scientific concepts are unified and the basis for the agronomic use of HSs is established. PMID:26862010

Inherent structure length in metallic glasses: Simplicity behind complexity

DOE PAGES

Wu, Yuan; Wang, Hui; Cheng, Yongqiang; ...

2015-08-06

One of the central themes in materials science is the structure-property relationship. In conventional crystalline metals, their mechanical behaviour is often dictated by well-defined structural defects such as dislocations, impurities, and twins. However, the structure-property relationship in amorphous alloys is far from being understood, due to great difficulties in characterizing and describing the disordered atomic-level structure. Here, we report a universal, yet simple, correlation between the macroscopic mechanical properties (i.e., yield strength and shear modulus) and a unique characteristic structural length in metallic glasses (MGs). Lastly, our analysis indicates that this characteristic length can incorporate effects of both the inter-atomicmore » distance and valence electron density in MGs, and result in the observed universal correlation. The current findings shed lights on the basic understanding of mechanical properties of MGs from their disordered atomic structures.« less

Structure-to-property relationships in fuel cell catalyst supports: Correlation of surface chemistry and morphology with oxidation resistance of carbon blacks

NASA Astrophysics Data System (ADS)

Artyushkova, Kateryna; Pylypenko, Svitlana; Dowlapalli, Madhu; Atanassov, Plamen

2012-09-01

Linking durability of carbon blacks, expressed as their oxidation resistance, used in PEMFCs as catalyst supports, with their chemistry and morphology is an important task towards designing carbon blacks with desired properties. Structure-to-property relationship between surface chemistry determined by X-ray photoelectron spectroscopy (XPS), morphological structure determined by digital image processing of scanning electron microscopy (SEM) images, physical properties, and electrochemical corrosion behavior determined in an air-breathing gas-diffusion electrode is studied for several un-altered and several modified carbon blacks. We are showing that surface chemistry, graphitic content and certain physical characteristics such as Brunauer-Emmett-Teller (BET) surface area and pore volume, determined by nitrogen adsorptions are not sufficient to explain high corrosion instability of types of carbon blacks. Inclusion of morphological characteristics, such as roughness, texture and shape parameters provide for more inclusive description and therefore more complete structure-to-property correlations of corrosion behavior of carbon blacks. This paper presents the first direct statistically-derived structure-to-property relationship, developed by multivariate analysis (MVA) that links chemical and physical structural properties of the carbon blacks to their critical properties as supports for PEMFC catalysts. We have found that balance between electrocatalytic activity and high resistance towards oxidation and corrosion is achieved by balance between amount of graphitic content and surface oxide coverage, smaller overall roughness and, finally, larger amount of big elongated and loose, and, hypothetically, more hydrophobic pores.

Characterizing ceramics and the interfacial adhesion to resin: I - The relationship of microstructure, composition, properties and fractography.

PubMed

Della Bona, Alvaro

2005-03-01

The appeal of ceramics as structural dental materials is based on their light weight, high hardness values, chemical inertness, and anticipated unique tribological characteristics. A major goal of current ceramic research and development is to produce tough, strong ceramics that can provide reliable performance in dental applications. Quantifying microstructural parameters is important to develop structure/property relationships. Quantitative microstructural analysis provides an association among the constitution, physical properties, and structural characteristics of materials. Structural reliability of dental ceramics is a major factor in the clinical success of ceramic restorations. Complex stress distributions are present in most practical conditions and strength data alone cannot be directly extrapolated to predict structural performance.

System and method for generating and/or screening potential metal-organic frameworks

DOEpatents

Wilmer, Christopher E; Leaf, Michael; Snurr, Randall Q; Farha, Omar K; Hupp, Joseph T

2015-04-21

A system and method for systematically generating potential metal-organic framework (MOFs) structures given an input library of building blocks is provided herein. One or more material properties of the potential MOFs are evaluated using computational simulations. A range of material properties (surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, methane adsorption capability, and the like) can be estimated, and in doing so, illuminate unidentified structure-property relationships that may only have been recognized by taking a global view of MOF structures. In addition to identifying structure-property relationships, this systematic approach to identify the MOFs of interest is used to identify one or more MOFs that may be useful for high pressure methane storage.

System and method for generating and/or screening potential metal-organic frameworks

DOEpatents

Wilmer, Christopher E; Leaf, Michael; Snurr, Randall Q; Farha, Omar K; Hupp, Joseph T

2014-12-02

A system and method for systematically generating potential metal-organic framework (MOFs) structures given an input library of building blocks is provided herein. One or more material properties of the potential MOFs are evaluated using computational simulations. A range of material properties (surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, methane adsorption capability, and the like) can be estimated, and in doing so, illuminate unidentified structure-property relationships that may only have been recognized by taking a global view of MOF structures. In addition to identifying structure-property relationships, this systematic approach to identify the MOFs of interest is used to identify one or more MOFs that may be useful for high pressure methane storage.

THE USE OF STRUCTURE-ACTIVITY RELATIONSHIPS IN INTEGRATING THE CHEMISTRY AND TOXICOLOGY OF ENDOCRINE DISRUPTING CHEMICALS

EPA Science Inventory

Structure activity relationships (SARs) are based on the principle that structurally similar chemicals should have similar biological activity. SARs relate specifically-defined toxicological activity of chemicals to their molecular structure and physico-chemical properties. To de...

Efficiently mapping structure-property relationships of gas adsorption in porous materials: application to Xe adsorption.

PubMed

Kaija, A R; Wilmer, C E

2017-09-08

Designing better porous materials for gas storage or separations applications frequently leverages known structure-property relationships. Reliable structure-property relationships, however, only reveal themselves when adsorption data on many porous materials are aggregated and compared. Gathering enough data experimentally is prohibitively time consuming, and even approaches based on large-scale computer simulations face challenges. Brute force computational screening approaches that do not efficiently sample the space of porous materials may be ineffective when the number of possible materials is too large. Here we describe a general and efficient computational method for mapping structure-property spaces of porous materials that can be useful for adsorption related applications. We describe an algorithm that generates random porous "pseudomaterials", for which we calculate structural characteristics (e.g., surface area, pore size and void fraction) and also gas adsorption properties via molecular simulations. Here we chose to focus on void fraction and Xe adsorption at 1 bar, 5 bar, and 10 bar. The algorithm then identifies pseudomaterials with rare combinations of void fraction and Xe adsorption and mutates them to generate new pseudomaterials, thereby selectively adding data only to those parts of the structure-property map that are the least explored. Use of this method can help guide the design of new porous materials for gas storage and separations applications in the future.

Examining the Relationship Between Ballistic and Structural Properties of Lightweight Thermoplastic Unidirectional Composite Laminates

DTIC Science & Technology

2011-08-01

Kevlar KM2® Style 705 PVB phenolic woven aramid composite was included. A developmental unidirectional thermoplastic aramid fiber, Honeywell...Examining the Relationship Between Ballistic and Structural Properties of Lightweight Thermoplastic Unidirectional Composite Laminates by...Unidirectional Composite Laminates Lionel R. Vargas-Gonzalez, Shawn M. Walsh, and James C. Gurganus Weapons and Materials Research Directorate, ARL

Quantitative structure-property relationship modeling of Grätzel solar cell dyes.

PubMed

Venkatraman, Vishwesh; Åstrand, Per-Olof; Alsberg, Bjørn Kåre

2014-01-30

With fossil fuel reserves on the decline, there is increasing focus on the design and development of low-cost organic photovoltaic devices, in particular, dye-sensitized solar cells (DSSCs). The power conversion efficiency (PCE) of a DSSC is heavily influenced by the chemical structure of the dye. However, as far as we know, no predictive quantitative structure-property relationship models for DSSCs with PCE as one of the response variables have been reported. Thus, we report for the first time the successful application of comparative molecular field analysis (CoMFA) and vibrational frequency-based eigenvalue (EVA) descriptors to model molecular structure-photovoltaic performance relationships for a set of 40 coumarin derivatives. The results show that the models obtained provide statistically robust predictions of important photovoltaic parameters such as PCE, the open-circuit voltage (V(OC)), short-circuit current (J(SC)) and the peak absorption wavelength λ(max). Some of our findings based on the analysis of the models are in accordance with those reported in the literature. These structure-property relationships can be applied to the rational structural design and evaluation of new photovoltaic materials. Copyright © 2013 Wiley Periodicals, Inc.

Chemical Structure and Properties: A Modified Atoms-First, One-Semester Introductory Chemistry Course

ERIC Educational Resources Information Center

Schaller, Chris P.; Graham, Kate J.; Johnson, Brian J.; Jakubowski, Henry V.; McKenna, Anna G.; McIntee, Edward J.; Jones, T. Nicholas; Fazal, M. A.; Peterson, Alicia A.

2015-01-01

A one-semester, introductory chemistry course is described that develops a primarily qualitative understanding of structure-property relationships. Starting from an atoms-first approach, the course examines the properties and three-dimensional structure of metallic and ionic solids before expanding into a thorough investigation of molecules. In…

Nanoporous Cyanate Ester Resins: Structure-Gas Transport Property Relationships

NASA Astrophysics Data System (ADS)

Gusakova, Kristina; Fainleib, Alexander; Espuche, Eliane; Grigoryeva, Olga; Starostenko, Olga; Gouanve, Fabrice; Boiteux, Gisèle; Saiter, Jean-Marc; Grande, Daniel

2017-04-01

This contribution addresses the relationships between the structure and gas transport properties of nanoporous thermostable cyanate ester resins (CERs) derived from polycyclotrimerization of 1,1'-bis(4-cyanatophenyl)ethane in the presence of 30 or 50 wt% of inert high-boiling temperature porogens (i.e., dimethyl- or dibutyl phthalates), followed by their quantitative removal. The nanopores in the films obtained were generated via a chemically induced phase separation route with further porogen extraction from the densely crosslinked CERs. To ensure a total desorption of the porogen moieties from the networks, an additional short-term thermal annealing at 250 °C was performed. The structure and morphology of such nanoporous CER-based films were investigated by FTIR and SEM techniques, respectively. Further, the gas transport properties of CER films were analyzed after the different processing steps, and relationships between the material structure and the main gas transport parameters were established.

Influence of Molecular Conformations and Microstructure on the Optoelectronic Properties of Conjugated Polymers

PubMed Central

Botiz, Ioan; Stingelin, Natalie

2014-01-01

It is increasingly obvious that the molecular conformations and the long-range arrangement that conjugated polymers can adopt under various experimental conditions in bulk, solutions or thin films, significantly impact their resulting optoelectronic properties. As a consequence, the functionalities and efficiencies of resulting organic devices, such as field-effect transistors, light-emitting diodes, or photovoltaic cells, also dramatically change due to the close structure/property relationship. A range of structure/optoelectronic properties relationships have been investigated over the last few years using various experimental and theoretical methods, and, further, interesting correlations are continuously revealed by the scientific community. In this review, we discuss the latest findings related to the structure/optoelectronic properties interrelationships that exist in organic devices fabricated with conjugated polymers in terms of charge mobility, absorption, photoluminescence, as well as photovoltaic properties. PMID:28788568

Ring-Opening Copolymerization of Epoxides and Cyclic Anhydrides with Discrete Metal Complexes: Structure-Property Relationships.

PubMed

Longo, Julie M; Sanford, Maria J; Coates, Geoffrey W

2016-12-28

Polyesters synthesized through the alternating copolymerization of epoxides and cyclic anhydrides compose a growing class of polymers that exhibit an impressive array of chemical and physical properties. Because they are synthesized through the chain-growth polymerization of two variable monomers, their syntheses can be controlled by discrete metal complexes, and the resulting materials vary widely in their functionality and physical properties. This polymer-focused review gives a perspective on the current state of the field of epoxide/anhydride copolymerization mediated by discrete catalysts and the relationships between the structures and properties of these polyesters.

On the Development and Use of Large Chemical Similarity Networks, Informatics Best Practices and Novel Chemical Descriptors towards Materials Quantitative Structure Property Relationships

ERIC Educational Resources Information Center

Krein, Michael

2011-01-01

After decades of development and use in a variety of application areas, Quantitative Structure Property Relationships (QSPRs) and related descriptor-based statistical learning methods have achieved a level of infamy due to their misuse. The field is rife with past examples of overtrained models, overoptimistic performance assessment, and outright…

Data-driven multi-scale multi-physics models to derive process-structure-property relationships for additive manufacturing

NASA Astrophysics Data System (ADS)

Yan, Wentao; Lin, Stephen; Kafka, Orion L.; Lian, Yanping; Yu, Cheng; Liu, Zeliang; Yan, Jinhui; Wolff, Sarah; Wu, Hao; Ndip-Agbor, Ebot; Mozaffar, Mojtaba; Ehmann, Kornel; Cao, Jian; Wagner, Gregory J.; Liu, Wing Kam

2018-05-01

Additive manufacturing (AM) possesses appealing potential for manipulating material compositions, structures and properties in end-use products with arbitrary shapes without the need for specialized tooling. Since the physical process is difficult to experimentally measure, numerical modeling is a powerful tool to understand the underlying physical mechanisms. This paper presents our latest work in this regard based on comprehensive material modeling of process-structure-property relationships for AM materials. The numerous influencing factors that emerge from the AM process motivate the need for novel rapid design and optimization approaches. For this, we propose data-mining as an effective solution. Such methods—used in the process-structure, structure-properties and the design phase that connects them—would allow for a design loop for AM processing and materials. We hope this article will provide a road map to enable AM fundamental understanding for the monitoring and advanced diagnostics of AM processing.

Data-driven multi-scale multi-physics models to derive process-structure-property relationships for additive manufacturing

NASA Astrophysics Data System (ADS)

Yan, Wentao; Lin, Stephen; Kafka, Orion L.; Lian, Yanping; Yu, Cheng; Liu, Zeliang; Yan, Jinhui; Wolff, Sarah; Wu, Hao; Ndip-Agbor, Ebot; Mozaffar, Mojtaba; Ehmann, Kornel; Cao, Jian; Wagner, Gregory J.; Liu, Wing Kam

2018-01-01

Additive manufacturing (AM) possesses appealing potential for manipulating material compositions, structures and properties in end-use products with arbitrary shapes without the need for specialized tooling. Since the physical process is difficult to experimentally measure, numerical modeling is a powerful tool to understand the underlying physical mechanisms. This paper presents our latest work in this regard based on comprehensive material modeling of process-structure-property relationships for AM materials. The numerous influencing factors that emerge from the AM process motivate the need for novel rapid design and optimization approaches. For this, we propose data-mining as an effective solution. Such methods—used in the process-structure, structure-properties and the design phase that connects them—would allow for a design loop for AM processing and materials. We hope this article will provide a road map to enable AM fundamental understanding for the monitoring and advanced diagnostics of AM processing.

Molecular Descriptors

NASA Astrophysics Data System (ADS)

Consonni, Viviana; Todeschini, Roberto

In the last decades, several scientific researches have been focused on studying how to encompass and convert - by a theoretical pathway - the information encoded in the molecular structure into one or more numbers used to establish quantitative relationships between structures and properties, biological activities, or other experimental properties. Molecular descriptors are formally mathematical representations of a molecule obtained by a well-specified algorithm applied to a defined molecular representation or a well-specified experimental procedure. They play a fundamental role in chemistry, pharmaceutical sciences, environmental protection policy, toxicology, ecotoxicology, health research, and quality control. Evidence of the interest of the scientific community in the molecular descriptors is provided by the huge number of descriptors proposed up today: more than 5000 descriptors derived from different theories and approaches are defined in the literature and most of them can be calculated by means of dedicated software applications. Molecular descriptors are of outstanding importance in the research fields of quantitative structure-activity relationships (QSARs) and quantitative structure-property relationships (QSPRs), where they are the independent chemical information used to predict the properties of interest. Along with the definition of appropriate molecular descriptors, the molecular structure representation and the mathematical tools for deriving and assessing models are other fundamental components of the QSAR/QSPR approach. The remarkable progress during the last few years in chemometrics and chemoinformatics has led to new strategies for finding mathematical meaningful relationships between the molecular structure and biological activities, physico-chemical, toxicological, and environmental properties of chemicals. Different approaches for deriving molecular descriptors here reviewed and some of the most relevant descriptors are presented in detail with numerical examples.

36 CFR 242.14 - Relationship to State procedures and regulations.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 36 Parks, Forests, and Public Property 2 2010-07-01 2010-07-01 false Relationship to State procedures and regulations. 242.14 Section 242.14 Parks, Forests, and Public Property FOREST SERVICE, DEPARTMENT OF AGRICULTURE SUBSISTENCE MANAGEMENT REGULATIONS FOR PUBLIC LANDS IN ALASKA Program Structure § 242.14 Relationship to State procedures and...

A Quantitative Structure-Property Relationship (QSPR) Study of Aliphatic Alcohols by the Method of Dividing the Molecular Structure into Substructure

PubMed Central

Liu, Fengping; Cao, Chenzhong; Cheng, Bin

2011-01-01

A quantitative structure–property relationship (QSPR) analysis of aliphatic alcohols is presented. Four physicochemical properties were studied: boiling point (BP), n-octanol–water partition coefficient (lg POW), water solubility (lg W) and the chromatographic retention indices (RI) on different polar stationary phases. In order to investigate the quantitative structure–property relationship of aliphatic alcohols, the molecular structure ROH is divided into two parts, R and OH to generate structural parameter. It was proposed that the property is affected by three main factors for aliphatic alcohols, alkyl group R, substituted group OH, and interaction between R and OH. On the basis of the polarizability effect index (PEI), previously developed by Cao, the novel molecular polarizability effect index (MPEI) combined with odd-even index (OEI), the sum eigenvalues of bond-connecting matrix (SX1CH) previously developed in our team, were used to predict the property of aliphatic alcohols. The sets of molecular descriptors were derived directly from the structure of the compounds based on graph theory. QSPR models were generated using only calculated descriptors and multiple linear regression techniques. These QSPR models showed high values of multiple correlation coefficient (R > 0.99) and Fisher-ratio statistics. The leave-one-out cross-validation demonstrated the final models to be statistically significant and reliable. PMID:21731451

Relationships between chemical structure, mechanical properties and materials processing in nanopatterned organosilicate fins.

PubMed

Stan, Gheorghe; Gates, Richard S; Hu, Qichi; Kjoller, Kevin; Prater, Craig; Jit Singh, Kanwal; Mays, Ebony; King, Sean W

2017-01-01

The exploitation of nanoscale size effects to create new nanostructured materials necessitates the development of an understanding of relationships between molecular structure, physical properties and material processing at the nanoscale. Numerous metrologies capable of thermal, mechanical, and electrical characterization at the nanoscale have been demonstrated over the past two decades. However, the ability to perform nanoscale molecular/chemical structure characterization has only been recently demonstrated with the advent of atomic-force-microscopy-based infrared spectroscopy (AFM-IR) and related techniques. Therefore, we have combined measurements of chemical structures with AFM-IR and of mechanical properties with contact resonance AFM (CR-AFM) to investigate the fabrication of 20-500 nm wide fin structures in a nanoporous organosilicate material. We show that by combining these two techniques, one can clearly observe variations of chemical structure and mechanical properties that correlate with the fabrication process and the feature size of the organosilicate fins. Specifically, we have observed an inverse correlation between the concentration of terminal organic groups and the stiffness of nanopatterned organosilicate fins. The selective removal of the organic component during etching results in a stiffness increase and reinsertion via chemical silylation results in a stiffness decrease. Examination of this effect as a function of fin width indicates that the loss of terminal organic groups and stiffness increase occur primarily at the exposed surfaces of the fins over a length scale of 10-20 nm. While the observed structure-property relationships are specific to organosilicates, we believe the combined demonstration of AFM-IR with CR-AFM should pave the way for a similar nanoscale characterization of other materials where the understanding of such relationships is essential.

Structure-Property Relationship in High Tg Thermosetting Polyimides

NASA Technical Reports Server (NTRS)

Chuang, Kathy C.; Meador, Mary Ann B.; HardyGreen, DeNise

2000-01-01

This viewgraph presentation gives an overview of the structure-property relationship in high glass transition temperatures (T(sub g)) thermosetting polyimides. The objectives of this work are to replace MDA in PMR-15 with 2,2-substituted benzidine and to evaluate the thermo-oxidative stability and mechanical properties of DMBZ-15 against PMR-15. Details are given on the T(sub g) of polyimide resins, the x-ray crystal structure of 2,2-Bis(trifluoro)benzidine (BFBZ), the isothermal aging of polyimide resins at 288 C under 1 atm of circulating air, the compressive strength of polyimide composites, and a gas evaluation profile of DMBZ-15 polyimide resins.

The Relationship of Physical Property Indicators and Clay Soil Structural Strength of Tomsk Oblast Territory

NASA Astrophysics Data System (ADS)

Kramarenko, V. V.; Nikitenkov, A. N.; Molokov, V. Y.; Matveenko, I. A.; Shramok, A. V.

2015-11-01

The article deals with the characteristic of initial condition in fine-grained soils - its structural strength - pstr. Estimation and measurement of this factor at soil testing are of primary importance for defining its physical and mechanical properties as well as for subsequent calculation of foundation settlements that is insufficiently covered in Code of practice, national standard and inefficiently applicable in practice of engineering geological investigations. The article reveals the relationship between soil physical property, its occurrence depth, which will make possible to forecast pstr over the given territory.

A primer on selecting grain boundary sets for comparison of interfacial fracture properties in molecular dynamics simulations

DOE PAGES

Dingreville, Remi; Aksoy, Doruk; Spearot, Douglas E.

2017-08-21

In this study, all grain boundaries are not equal in their predisposition for fracture due to the complex coupling between lattice geometry, interfacial structure, and mechanical properties. The ability to understand these relationships is crucial to engineer materials resilient to grain boundary fracture. Here, a methodology is presented to isolate the role of grain boundary structure on interfacial fracture properties, such as the tensile strength and work of separation, using atomistic simulations. Instead of constructing sets of grain boundary models within the misorientation/structure space by simply varying the misorientation angle around a fixed misorientation axis, the proposed method creates setsmore » of grain boundary models by means of isocurves associated with important fracture-related properties of the adjoining lattices. Such properties may include anisotropic elastic moduli, the Schmid factor for primary slip, and the propensity for simultaneous slip on multiple slip systems. This approach eliminates the effect of lattice properties from the comparative analysis of interfacial fracture properties and thus enables the identification of structure-property relationships for grain boundaries. As an example, this methodology is implemented to study crack propagation along Ni grain boundaries. Segregated H is used as a means to emphasize differences in the selected grain boundary structures while keeping lattice properties fixed.« less

A primer on selecting grain boundary sets for comparison of interfacial fracture properties in molecular dynamics simulations

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

Dingreville, Remi; Aksoy, Doruk; Spearot, Douglas E.

In this study, all grain boundaries are not equal in their predisposition for fracture due to the complex coupling between lattice geometry, interfacial structure, and mechanical properties. The ability to understand these relationships is crucial to engineer materials resilient to grain boundary fracture. Here, a methodology is presented to isolate the role of grain boundary structure on interfacial fracture properties, such as the tensile strength and work of separation, using atomistic simulations. Instead of constructing sets of grain boundary models within the misorientation/structure space by simply varying the misorientation angle around a fixed misorientation axis, the proposed method creates setsmore » of grain boundary models by means of isocurves associated with important fracture-related properties of the adjoining lattices. Such properties may include anisotropic elastic moduli, the Schmid factor for primary slip, and the propensity for simultaneous slip on multiple slip systems. This approach eliminates the effect of lattice properties from the comparative analysis of interfacial fracture properties and thus enables the identification of structure-property relationships for grain boundaries. As an example, this methodology is implemented to study crack propagation along Ni grain boundaries. Segregated H is used as a means to emphasize differences in the selected grain boundary structures while keeping lattice properties fixed.« less

Estimation of Melting Points of Organics.

PubMed

Yalkowsky, Samuel H; Alantary, Doaa

2018-05-01

Unified physicochemical property estimation relationships is a system of empirical and theoretical relationships that relate 20 physicochemical properties of organic molecules to each other and to chemical structure. Melting point is a key parameter in the unified physicochemical property estimation relationships scheme because it is a determinant of several other properties including vapor pressure, and solubility. This review describes the first-principals calculation of the melting points of organic compounds from structure. The calculation is based on the fact that the melting point, T m , is equal to the ratio of the heat of melting, ΔH m , to the entropy of melting, ΔS m . The heat of melting is shown to be an additive constitutive property. However, the entropy of melting is not entirely group additive. It is primarily dependent on molecular geometry, including parameters which reflect the degree of restriction of molecular motion in the crystal to that of the liquid. Symmetry, eccentricity, chirality, flexibility, and hydrogen bonding, each affect molecular freedom in different ways and thus make different contributions to the total entropy of fusion. The relationships of these entropy determining parameters to chemical structure are used to develop a reasonably accurate means of predicting the melting points over 2000 compounds. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Pressure-induced dramatic changes in organic–inorganic halide perovskites

PubMed Central

Yang, Wenge

2017-01-01

Organic–inorganic halide perovskites have emerged as a promising family of functional materials for advanced photovoltaic and optoelectronic applications with high performances and low costs. Various chemical methods and processing approaches have been employed to modify the compositions, structures, morphologies, and electronic properties of hybrid perovskites. However, challenges still remain in terms of their stability, the use of environmentally unfriendly chemicals, and the lack of an insightful understanding into structure–property relationships. Alternatively, pressure, a fundamental thermodynamic parameter that can significantly alter the atomic and electronic structures of functional materials, has been widely utilized to further our understanding of structure–property relationships, and also to enable emergent or enhanced properties of given materials. In this perspective, we describe the recent progress of high-pressure research on hybrid perovskites, particularly regarding pressure-induced novel phenomena and pressure-enhanced properties. We discuss the effect of pressure on structures and properties, their relationships and the underlying mechanisms. Finally, we give an outlook on future research avenues in which high pressure and related alternative methods such as chemical tailoring and interfacial engineering may lead to novel hybrid perovskites uniquely suited for high-performance energy applications. PMID:29147500

Modeling process-structure-property relationships for additive manufacturing

NASA Astrophysics Data System (ADS)

Yan, Wentao; Lin, Stephen; Kafka, Orion L.; Yu, Cheng; Liu, Zeliang; Lian, Yanping; Wolff, Sarah; Cao, Jian; Wagner, Gregory J.; Liu, Wing Kam

2018-02-01

This paper presents our latest work on comprehensive modeling of process-structure-property relationships for additive manufacturing (AM) materials, including using data-mining techniques to close the cycle of design-predict-optimize. To illustrate the processstructure relationship, the multi-scale multi-physics process modeling starts from the micro-scale to establish a mechanistic heat source model, to the meso-scale models of individual powder particle evolution, and finally to the macro-scale model to simulate the fabrication process of a complex product. To link structure and properties, a highefficiency mechanistic model, self-consistent clustering analyses, is developed to capture a variety of material response. The model incorporates factors such as voids, phase composition, inclusions, and grain structures, which are the differentiating features of AM metals. Furthermore, we propose data-mining as an effective solution for novel rapid design and optimization, which is motivated by the numerous influencing factors in the AM process. We believe this paper will provide a roadmap to advance AM fundamental understanding and guide the monitoring and advanced diagnostics of AM processing.

The structure-activity relationship of inhibitors of serotonin uptake and receptor binding

NASA Astrophysics Data System (ADS)

Hansch, Corwin; Caldwell, Jonathan

1991-10-01

An analysis of five different datasets of inhibitors of serotonin uptake has yielded quantitative structure/ activity relationships (QSARs) which delineate the role of steric and hydrophobic properties essential for inhibition by phenylethylamine-type analogues.

Grain Boundary Plane Orientation Fundamental Zones and Structure-Property Relationships

PubMed Central

Homer, Eric R.; Patala, Srikanth; Priedeman, Jonathan L.

2015-01-01

Grain boundary plane orientation is a profoundly important determinant of character in polycrystalline materials that is not well understood. This work demonstrates how boundary plane orientation fundamental zones, which capture the natural crystallographic symmetries of a grain boundary, can be used to establish structure-property relationships. Using the fundamental zone representation, trends in computed energy, excess volume at the grain boundary, and temperature-dependent mobility naturally emerge and show a strong dependence on the boundary plane orientation. Analysis of common misorientation axes even suggests broader trends of grain boundary energy as a function of misorientation angle and plane orientation. Due to the strong structure-property relationships that naturally emerge from this work, boundary plane fundamental zones are expected to simplify analysis of both computational and experimental data. This standardized representation has the potential to significantly accelerate research in the topologically complex and vast five-dimensional phase space of grain boundaries. PMID:26498715

Grain boundary plane orientation fundamental zones and structure-property relationships

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

Homer, Eric R.; Patala, Srikanth; Priedeman, Jonathan L.

2015-10-26

Grain boundary plane orientation is a profoundly important determinant of character in polycrystalline materials that is not well understood. This work demonstrates how boundary plane orientation fundamental zones, which capture the natural crystallographic symmetries of a grain boundary, can be used to establish structure-property relationships. Using the fundamental zone representation, trends in computed energy, excess volume at the grain boundary, and temperature-dependent mobility naturally emerge and show a strong dependence on the boundary plane orientation. Analysis of common misorientation axes even suggests broader trends of grain boundary energy as a function of misorientation angle and plane orientation. Due to themore » strong structure-property relationships that naturally emerge from this work, boundary plane fundamental zones are expected to simplify analysis of both computational and experimental data. This standardized representation has the potential to significantly accelerate research in the topologically complex and vast five-dimensional phase space of grain boundaries.« less

Chemical graphs, molecular matrices and topological indices in chemoinformatics and quantitative structure-activity relationships.

PubMed

Ivanciuc, Ovidiu

2013-06-01

Chemical and molecular graphs have fundamental applications in chemoinformatics, quantitative structureproperty relationships (QSPR), quantitative structure-activity relationships (QSAR), virtual screening of chemical libraries, and computational drug design. Chemoinformatics applications of graphs include chemical structure representation and coding, database search and retrieval, and physicochemical property prediction. QSPR, QSAR and virtual screening are based on the structure-property principle, which states that the physicochemical and biological properties of chemical compounds can be predicted from their chemical structure. Such structure-property correlations are usually developed from topological indices and fingerprints computed from the molecular graph and from molecular descriptors computed from the three-dimensional chemical structure. We present here a selection of the most important graph descriptors and topological indices, including molecular matrices, graph spectra, spectral moments, graph polynomials, and vertex topological indices. These graph descriptors are used to define several topological indices based on molecular connectivity, graph distance, reciprocal distance, distance-degree, distance-valency, spectra, polynomials, and information theory concepts. The molecular descriptors and topological indices can be developed with a more general approach, based on molecular graph operators, which define a family of graph indices related by a common formula. Graph descriptors and topological indices for molecules containing heteroatoms and multiple bonds are computed with weighting schemes based on atomic properties, such as the atomic number, covalent radius, or electronegativity. The correlation in QSPR and QSAR models can be improved by optimizing some parameters in the formula of topological indices, as demonstrated for structural descriptors based on atomic connectivity and graph distance.

Structure modification and functionality of whey proteins: quantitative structure-activity relationship approach.

PubMed

Nakai, S; Li-Chan, E

1985-10-01

According to the original idea of quantitative structure-activity relationship, electric, hydrophobic, and structural parameters should be taken into consideration for elucidating functionality. Changes in these parameters are reflected in the property of protein solubility upon modification of whey proteins by heating. Although solubility is itself a functional property, it has been utilized to explain other functionalities of proteins. However, better correlations were obtained when hydrophobic parameters of the proteins were used in conjunction with solubility. Various treatments reported in the literature were applied to whey protein concentrate in an attempt to obtain whipping and gelling properties similar to those of egg white. Mapping simplex optimization was used to search for the best results. Improvement in whipping properties by pepsin hydrolysis may have been due to higher protein solubility, and good gelling properties resulting from polyphosphate treatment may have been due to an increase in exposable hydrophobicity. However, the results of angel food cake making were still unsatisfactory.

Structure Property Relationships of Carboxylic Acid Isosteres.

PubMed

Lassalas, Pierrik; Gay, Bryant; Lasfargeas, Caroline; James, Michael J; Tran, Van; Vijayendran, Krishna G; Brunden, Kurt R; Kozlowski, Marisa C; Thomas, Craig J; Smith, Amos B; Huryn, Donna M; Ballatore, Carlo

2016-04-14

The replacement of a carboxylic acid with a surrogate structure, or (bio)-isostere, is a classical strategy in medicinal chemistry. The general underlying principle is that by maintaining the features of the carboxylic acid critical for biological activity, but appropriately modifying the physicochemical properties, improved analogs may result. In this context, a systematic assessment of the physicochemical properties of carboxylic acid isosteres would be desirable to enable more informed decisions of potential replacements to be used for analog design. Herein we report the structure-property relationships (SPR) of 35 phenylpropionic acid derivatives, in which the carboxylic acid moiety is replaced with a series of known isosteres. The data set generated provides an assessment of the relative impact on the physicochemical properties that these replacements may have compared to the carboxylic acid analog. As such, this study presents a framework for how to rationally apply isosteric replacements of the carboxylic acid functional group.

ESTIMATION OF CHEMICAL SPECIFIC PARAMETERS WITHIN PHYSIOLOGICALLY BASED PHARMACOKINETIC/PHARMACODYNAMIC MODELS

EPA Science Inventory

While relationships between chemical structure and observed properties or activities (QSAR - quantitative structure activity relationship) can be used to predict the behavior of unknown chemicals, this method is semiempirical in nature relying on high quality experimental data to...

Synthesis, quantitative structure-property relationship study of novel fluorescence active 2-pyrazolines and application.

PubMed

Girgis, Adel S; Basta, Altaf H; El-Saied, Houssni; Mohamed, Mohamed A; Bedair, Ahmad H; Salim, Ahmad S

2018-03-01

A variety of fluorescence-active fluorinated pyrazolines 13-33 was synthesized in good yields through cyclocondensation reaction of propenones 1-9 with aryl hydrazines 10-12 . Some of the synthesized compounds provided promising fluorescence properties with quantum yield ( Φ ) higher than that of quinine sulfate (standard reference). Quantitative structure-property relationship studies were undertaken supporting the exhibited fluorescence properties and estimating the parameters governing properties. Five synthesized fluorescence-active pyrazolines ( 13 , 15 , 18 , 19 and 23 ) with variable Φ were selected for treating two types of paper sheets (Fabriano and Bible paper). These investigated fluorescence compounds, especially compounds 19 and 23 , provide improvements in strength properties of paper sheets. Based on the observed performance they can be used as markers in security documents.

Synthesis, quantitative structure-property relationship study of novel fluorescence active 2-pyrazolines and application

NASA Astrophysics Data System (ADS)

Girgis, Adel S.; Basta, Altaf H.; El-Saied, Houssni; Mohamed, Mohamed A.; Bedair, Ahmad H.; Salim, Ahmad S.

2018-03-01

A variety of fluorescence-active fluorinated pyrazolines 13-33 was synthesized in good yields through cyclocondensation reaction of propenones 1-9 with aryl hydrazines 10-12. Some of the synthesized compounds provided promising fluorescence properties with quantum yield (Φ) higher than that of quinine sulfate (standard reference). Quantitative structure-property relationship studies were undertaken supporting the exhibited fluorescence properties and estimating the parameters governing properties. Five synthesized fluorescence-active pyrazolines (13, 15, 18, 19 and 23) with variable Φ were selected for treating two types of paper sheets (Fabriano and Bible paper). These investigated fluorescence compounds, especially compounds 19 and 23, provide improvements in strength properties of paper sheets. Based on the observed performance they can be used as markers in security documents.

A novel method for a multi-level hierarchical composite with brick-and-mortar structure

PubMed Central

Brandt, Kristina; Wolff, Michael F. H.; Salikov, Vitalij; Heinrich, Stefan; Schneider, Gerold A.

2013-01-01

The fascination for hierarchically structured hard tissues such as enamel or nacre arises from their unique structure-properties-relationship. During the last decades this numerously motivated the synthesis of composites, mimicking the brick-and-mortar structure of nacre. However, there is still a lack in synthetic engineering materials displaying a true hierarchical structure. Here, we present a novel multi-step processing route for anisotropic 2-level hierarchical composites by combining different coating techniques on different length scales. It comprises polymer-encapsulated ceramic particles as building blocks for the first level, followed by spouted bed spray granulation for a second level, and finally directional hot pressing to anisotropically consolidate the composite. The microstructure achieved reveals a brick-and-mortar hierarchical structure with distinct, however not yet optimized mechanical properties on each level. It opens up a completely new processing route for the synthesis of multi-level hierarchically structured composites, giving prospects to multi-functional structure-properties relationships. PMID:23900554

A novel method for a multi-level hierarchical composite with brick-and-mortar structure.

PubMed

Brandt, Kristina; Wolff, Michael F H; Salikov, Vitalij; Heinrich, Stefan; Schneider, Gerold A

2013-01-01

The fascination for hierarchically structured hard tissues such as enamel or nacre arises from their unique structure-properties-relationship. During the last decades this numerously motivated the synthesis of composites, mimicking the brick-and-mortar structure of nacre. However, there is still a lack in synthetic engineering materials displaying a true hierarchical structure. Here, we present a novel multi-step processing route for anisotropic 2-level hierarchical composites by combining different coating techniques on different length scales. It comprises polymer-encapsulated ceramic particles as building blocks for the first level, followed by spouted bed spray granulation for a second level, and finally directional hot pressing to anisotropically consolidate the composite. The microstructure achieved reveals a brick-and-mortar hierarchical structure with distinct, however not yet optimized mechanical properties on each level. It opens up a completely new processing route for the synthesis of multi-level hierarchically structured composites, giving prospects to multi-functional structure-properties relationships.

A novel method for a multi-level hierarchical composite with brick-and-mortar structure

NASA Astrophysics Data System (ADS)

Brandt, Kristina; Wolff, Michael F. H.; Salikov, Vitalij; Heinrich, Stefan; Schneider, Gerold A.

2013-07-01

The fascination for hierarchically structured hard tissues such as enamel or nacre arises from their unique structure-properties-relationship. During the last decades this numerously motivated the synthesis of composites, mimicking the brick-and-mortar structure of nacre. However, there is still a lack in synthetic engineering materials displaying a true hierarchical structure. Here, we present a novel multi-step processing route for anisotropic 2-level hierarchical composites by combining different coating techniques on different length scales. It comprises polymer-encapsulated ceramic particles as building blocks for the first level, followed by spouted bed spray granulation for a second level, and finally directional hot pressing to anisotropically consolidate the composite. The microstructure achieved reveals a brick-and-mortar hierarchical structure with distinct, however not yet optimized mechanical properties on each level. It opens up a completely new processing route for the synthesis of multi-level hierarchically structured composites, giving prospects to multi-functional structure-properties relationships.

Viscosity, conductivity, and electrochemical property of dicyanamide ionic liquids

NASA Astrophysics Data System (ADS)

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-03-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands.

Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids

PubMed Central

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-01-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous, and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes, and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands. PMID:29600245

Dissecting the relationship between protein structure and sequence variation

NASA Astrophysics Data System (ADS)

Shahmoradi, Amir; Wilke, Claus; Wilke Lab Team

2015-03-01

Over the past decade several independent works have shown that some structural properties of proteins are capable of predicting protein evolution. The strength and significance of these structure-sequence relations, however, appear to vary widely among different proteins, with absolute correlation strengths ranging from 0 . 1 to 0 . 8 . Here we present the results from a comprehensive search for the potential biophysical and structural determinants of protein evolution by studying more than 200 structural and evolutionary properties in a dataset of 209 monomeric enzymes. We discuss the main protein characteristics responsible for the general patterns of protein evolution, and identify sequence divergence as the main determinant of the strengths of virtually all structure-evolution relationships, explaining ~ 10 - 30 % of observed variation in sequence-structure relations. In addition to sequence divergence, we identify several protein structural properties that are moderately but significantly coupled with the strength of sequence-structure relations. In particular, proteins with more homogeneous back-bone hydrogen bond energies, large fractions of helical secondary structures and low fraction of beta sheets tend to have the strongest sequence-structure relation. BEACON-NSF center for the study of evolution in action.

Research on the relationship between the structural properties of bedding layer in spring mattress and sleep quality.

PubMed

Shen, Liming; Chen, Yu-xia; Guo, Yong; Zhong, ShiLu; Fang, Fei; Zhao, Jing; Hu, Tian-Yi

2012-01-01

Mattress, as a sleep platform, its types and physical properties has an important effect on sleep quality and rest efficiency. In this paper, by subjective evaluations, analysis of sleeping behaviors and tests of depth of sleep, the relationship between characteristics of the bedding materials, the structure of mattress, sleep quality and sleep behaviors were studied. The results showed that: (1) Characteristics of the bedding materials and structure of spring mattress had a remarkable effect on sleep behaviors and sleep quality. An optimum combination of the bedding materials, the structure of mattress and its core could improve the overall comfort of mattress, thereby improving the depth of sleep and sleep quality. (2) Sleep behaviors had a close relationship with sleeping postures and sleep habits. The characteristics of sleep behaviors vary from person to person.

Using Theoretical Descriptors in Structural Activity Relationships: 4. Molecular Orbital Basicity and Electrostatic Basicity

DTIC Science & Technology

1988-11-01

rates.6 The Hammet equation , also called the Linear Free Energy Relationship (LFER) because of the relationship of the Gibb’s Free Energy to the... equations for numerous biological and physicochemical properties. Linear Solvation Enery Relationship (LSER), a sub-set of QSAR have been used by...originates from thermodynamics, where Hammet recognized the relationship of structure to the Gibb’s Free Energy, and ultimately to equilibria and reaction

Structural evolution and electronic properties of n-type doped hydrogenated amorphous silicon thin films

NASA Astrophysics Data System (ADS)

He, Jian; Li, Wei; Xu, Rui; Qi, Kang-Cheng; Jiang, Ya-Dong

2011-12-01

The relationship between structure and electronic properties of n-type doped hydrogenated amorphous silicon (a-Si:H) thin films was investigated. Samples with different features were prepared by plasma enhanced chemical vapor deposition (PECVD) at various substrate temperatures. Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy were used to evaluate the structural evolution, meanwhile, electronic-spin resonance (ESR) and optical measurement were applied to explore the electronic properties of P-doped a-Si:H thin films. Results reveal that the changes in materials structure affect directly the electronic properties and the doping efficiency of dopant.

When Do Students Recognize Relationships between Molecular Structure and Properties? A Longitudinal Comparison of the Impact of Traditional and Transformed Curricula

ERIC Educational Resources Information Center

Underwood, Sonia M.; Reyes-Gastelum, David; Cooper, Melanie M.

2016-01-01

The ability to use a chemical structure to predict and explain phenomenon is essential to a robust understanding of chemistry; however, previous research has shown that students find it difficult to make the connection between structure and properties. In this study we examine how student recognition of the connections between structure and…

Data mining graphene: Correlative analysis of structure and electronic degrees of freedom in graphenic monolayers with defects

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

Ziatdinov, Maxim A.; Fujii, Shintaro; Kiguchi, Manabu

The link between changes in the material crystal structure and its mechanical, electronic, magnetic, and optical functionalities known as the structure-property relationship is the cornerstone of the contemporary materials science research. The recent advances in scanning transmission electron and scanning probe microscopies (STEM and SPM) have opened an unprecedented path towards examining the materials structure property relationships on the single-impurity and atomic-configuration levels. Lacking, however, are the statistics-based approaches for cross-correlation of structure and property variables obtained in different information channels of the STEM and SPM experiments. Here we have designed an approach based on a combination of sliding windowmore » Fast Fourier Transform, Pearson correlation matrix, linear and kernel canonical correlation, to study a relationship between lattice distortions and electron scattering from the SPM data on graphene with defects. Our analysis revealed that the strength of coupling to strain is altered between different scattering channels which can explain coexistence of several quasiparticle interference patterns in the nanoscale regions of interest. In addition, the application of the kernel functions allowed us extracting a non-linear component of the relationship between the lattice strain and scattering intensity in graphene. Lastly, the outlined approach can be further utilized to analyzing correlations in various multi-modal imaging techniques where the information of interest is spatially distributed and has usually a complex multidimensional nature.« less

Data mining graphene: Correlative analysis of structure and electronic degrees of freedom in graphenic monolayers with defects

DOE PAGES

Ziatdinov, Maxim A.; Fujii, Shintaro; Kiguchi, Manabu; ...

2016-11-09

The link between changes in the material crystal structure and its mechanical, electronic, magnetic, and optical functionalities known as the structure-property relationship is the cornerstone of the contemporary materials science research. The recent advances in scanning transmission electron and scanning probe microscopies (STEM and SPM) have opened an unprecedented path towards examining the materials structure property relationships on the single-impurity and atomic-configuration levels. Lacking, however, are the statistics-based approaches for cross-correlation of structure and property variables obtained in different information channels of the STEM and SPM experiments. Here we have designed an approach based on a combination of sliding windowmore » Fast Fourier Transform, Pearson correlation matrix, linear and kernel canonical correlation, to study a relationship between lattice distortions and electron scattering from the SPM data on graphene with defects. Our analysis revealed that the strength of coupling to strain is altered between different scattering channels which can explain coexistence of several quasiparticle interference patterns in the nanoscale regions of interest. In addition, the application of the kernel functions allowed us extracting a non-linear component of the relationship between the lattice strain and scattering intensity in graphene. Lastly, the outlined approach can be further utilized to analyzing correlations in various multi-modal imaging techniques where the information of interest is spatially distributed and has usually a complex multidimensional nature.« less

Synthesis, Spectra, and Theoretical Investigations of 1,3,5-Triazines Compounds as Ultraviolet Rays Absorber Based on Time-Dependent Density Functional Calculations and three-Dimensional Quantitative Structure-Property Relationship.

PubMed

Wang, Xueding; Xu, Yilian; Yang, Lu; Lu, Xiang; Zou, Hao; Yang, Weiqing; Zhang, Yuanyuan; Li, Zicheng; Ma, Menglin

2018-03-01

A series of 1,3,5-triazines were synthesized and their UV absorption properties were tested. The computational chemistry methods were used to construct quantitative structure-property relationship (QSPR), which was used to computer aided design of new 1,3,5-triazines ultraviolet rays absorber compounds. The experimental UV absorption data are in good agreement with those predicted data using the Time-dependent density functional theory (TD-DFT) [B3LYP/6-311 + G(d,p)]. A suitable forecasting model (R > 0.8, P < 0.0001) was revealed. Predictive three-dimensional quantitative structure-property relationship (3D-QSPR) model was established using multifit molecular alignment rule of Sybyl program, which conclusion is consistent with the TD-DFT calculation. The exceptional photostability mechanism of such ultraviolet rays absorber compounds was studied and confirmed as principally banked upon their ability to undergo excited-state deactivation via an ultrafast excited-state proton transfer (ESIPT). The intramolecular hydrogen bond (IMHB) of 1,3,5-triazines compounds is the basis for the excited state proton transfer, which was explored by IR spectroscopy, UV spectra, structural and energetic aspects of different conformers and frontier molecular orbitals analysis.

Flavonoid interactions during digestion, absorption, distribution and metabolism: a sequential structure-activity/property relationship-based approach in the study of bioavailability and bioactivity.

PubMed

Gonzales, Gerard Bryan; Smagghe, Guy; Grootaert, Charlotte; Zotti, Moises; Raes, Katleen; Van Camp, John

2015-05-01

Flavonoids are a group of polyphenols that provide health-promoting benefits upon consumption. However, poor bioavailability has been a major hurdle in their use as drugs or nutraceuticals. Low bioavailability has been associated with flavonoid interactions at various stages of the digestion, absorption and distribution process, which is strongly affected by their molecular structure. In this review, we use structure-activity/property relationship to discuss various flavonoid interactions with food matrices, digestive enzymes, intestinal transporters and blood proteins. This approach reveals specific bioactive properties of flavonoids in the gastrointestinal tract as well as various barriers for their bioavailability. In the last part of this review, we use these insights to determine the effect of different structural characteristics on the overall bioavailability of flavonoids. Such information is crucial when flavonoid or flavonoid derivatives are used as active ingredients in foods or drugs.

Structure-Property Relationships of Polymer Brushes in Restricted Geometries and their Utilization as Ultra-Low Lubricants

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

Kuhl, Tonya Lynn; Faller, Roland

2015-09-28

Though polymer films are widely used to modify or tailor the physical, chemical and mechanical properties of interfaces in both solid and liquid systems, the rational design of interface- or surface-active polymer modifiers has been hampered by a lack of information about the behavior and structure-property relationships of this class of molecules. This is especially true for systems in which the role of the polymer is to modify the interaction between two solid surfaces in intimate contact and under load, to cause them to be mechanically coupled (e.g. to promote adhesion and wetting) or to minimize their interaction (e.g. lubrication,more » colloidal stabilization, etc.). Detailed structural information on these systems has largely been precluded by the many difficulties and challenges associated with direct experimental measurements of polymer structure in these geometries. As a result, many practitioners have been forced to employ indirect measurements or rely wholly on theoretical modeling. This has resulted in an incomplete understanding of the structure-property relationships, which are relied upon for the rational design of improved polymer modifiers. Over the course of this current research program, we made direct measurements of the structure of polymers at the interface between two solid surfaces under confinement and elucidated the fundamental physics behind these phenomena using atomistic and coarse grained simulations. The research has potential to lead to new lubricants and wear reducing agents to improve efficiency.« less

Structure—activity relationships for insecticidal carbamates*

PubMed Central

Metcalf, Robert L.

1971-01-01

Carbamate insecticides are biologically active because of their structural complementarity to the active site of acetylcholinesterase (AChE) and their consequent action as substrates with very low turnover numbers. Carbamates behave as synthetic neurohormones that produce their toxic action by interrupting the normal action of AChE so that acetylcholine accumulates at synaptic junctions. The necessary properties for a suitable insecticidal carbamate are lipid solubility, suitable structural complementarity to AChE, and sufficient stability to multifunction-oxidase detoxification. The relationships between the structure and the activity of a large number of synthetic carbamates are analysed in detail, with particular attention to the second of these properties. PMID:5315358

Observations on the relationship of structure to the mechanical properties of thin TD-NiCr sheet

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.

1976-01-01

A study of the relationship between structure and mechanical properties of thin TD-NiCr sheet indicated that the elevated temperature tensile, stress-rupture, and creep strength properties are dependent on grain aspect ratio and sheet thickness. In general, the strength properties increase with increasing grain aspect ratio and sheet thickness. Tensile testing revealed an absence of ductility at elevated temperatures (not less than 1144 K). Significant creep damage as determined by subsequent tensile testing at room temperature occurs after very small amounts (less than 0.1%) of prior creep deformation over the temperature range 1144-1477 K. A threshold stress for creep appears to exist. Creep exposure below the threshold stress at T not less than 1366 K results in almost full retention of room temperature tensile properties.

Effect of processing on Polymer/Composite structure and properties

NASA Technical Reports Server (NTRS)

1982-01-01

Advances in the vitality and economic health of the field of polymer forecasting are discussed. A consistent and rational point of view which considers processing as a participant in the underlying triad of relationships which comprise materials science and engineering is outlined. This triad includes processing as it influences material structure, and ultimately properties. Methods in processing structure properties, polymer science and engineering, polymer chemistry and synthesis, structure and modification and optimization through processing, and methods of melt flow modeling in processing structure property relations of polymer were developed. Mechanical properties of composites are considered, and biomedical materials research to include polymer processing effects are studied. An analysis of the design technology of advances graphite/epoxy composites is also reported.

The relationship between dermal papillary structure and skin surface properties, color, and elasticity.

PubMed

Mizukoshi, K; Nakamura, T; Oba, A

2016-08-01

The skin contains an undulating structure called the dermal papillary structure between the border of the epidermis and dermis. The physiological importance of the dermal papillary structures has been discussed, however, the dermal papillary structures have never been evaluated for their contribution to skin appearance. In this study, we investigated the correlation between the dermal papillary structure and skin color and elasticity. In addition, the relationship was validated with skin model experiments. The dermal papillary structures in the skin of the female cheek were quantitatively measured by in vivo confocal laser scanning microscopy images. In addition, the skin color and elasticity were measured at the same site. A skin model with dermal papilla-like structures was created by referring to the optical and shape properties of the skin using agar gel and a scattering sheet. Correlations were found between the dermal papillary structures and skin color irregularity and skin elasticity. These relationships were verified by the experiments employing a skin model. The results of this study indicated that the dermal papillary structure is also an important factor for skin appearance such as color and elasticity. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Investigating structure–property relationships of biomineralized calcium phosphate compounds as fluorescent quenching–recovery platform

PubMed Central

Wang, Liuzheng; He, Xiang; Zhang, Wei; Liu, Yong; Zhang, Ying

2018-01-01

The structure–property relationship between biomineralized calcium phosphate compounds upon a fluorescent quenching–recovery platform and their distinct crystalline structure and surficial functional groups are investigated. A fluorescence-based sensing platform is shown to be viable for the sensing of 8-hydroxy-2-deoxy-guanosine in simulated systems. PMID:29515827

Synthesis, structure-activity relationships, and in vivo evaluation of N3-phenylpyrazinones as novel corticotropin-releasing factor-1 (CRF1) receptor antagonists.

PubMed

Hartz, Richard A; Ahuja, Vijay T; Arvanitis, Argyrios G; Rafalski, Maria; Yue, Eddy W; Denhart, Derek J; Schmitz, William D; Ditta, Jonathan L; Deskus, Jeffrey A; Brenner, Allison B; Hobbs, Frank W; Payne, Joseph; Lelas, Snjezana; Li, Yu-Wen; Molski, Thaddeus F; Mattson, Gail K; Peng, Yong; Wong, Harvey; Grace, James E; Lentz, Kimberley A; Qian-Cutrone, Jingfang; Zhuo, Xiaoliang; Shu, Yue-Zhong; Lodge, Nicholas J; Zaczek, Robert; Combs, Andrew P; Olson, Richard E; Bronson, Joanne J; Mattson, Ronald J; Macor, John E

2009-07-23

Evidence suggests that corticotropin-releasing factor-1 (CRF(1)) receptor antagonists may offer therapeutic potential for the treatment of diseases associated with elevated levels of CRF such as anxiety and depression. A pyrazinone-based chemotype of CRF(1) receptor antagonists was discovered. Structure-activity relationship studies led to the identification of numerous potent analogues including 12p, a highly potent and selective CRF(1) receptor antagonist with an IC(50) value of 0.26 nM. The pharmacokinetic properties of 12p were assessed in rats and Cynomolgus monkeys. Compound 12p was efficacious in the defensive withdrawal test (an animal model of anxiety) in rats. The synthesis, structure-activity relationships and in vivo properties of compounds within the pyrazinone chemotype are described.

Quantitative structure-property relationships for prediction of boiling point, vapor pressure, and melting point.

PubMed

Dearden, John C

2003-08-01

Boiling point, vapor pressure, and melting point are important physicochemical properties in the modeling of the distribution and fate of chemicals in the environment. However, such data often are not available, and therefore must be estimated. Over the years, many attempts have been made to calculate boiling points, vapor pressures, and melting points by using quantitative structure-property relationships, and this review examines and discusses the work published in this area, and concentrates particularly on recent studies. A number of software programs are commercially available for the calculation of boiling point, vapor pressure, and melting point, and these have been tested for their predictive ability with a test set of 100 organic chemicals.

In silico designing of power conversion efficient organic lead dyes for solar cells using todays innovative approaches to assure renewable energy for future

NASA Astrophysics Data System (ADS)

Kar, Supratik; Roy, Juganta K.; Leszczynski, Jerzy

2017-06-01

Advances in solar cell technology require designing of new organic dye sensitizers for dye-sensitized solar cells with high power conversion efficiency to circumvent the disadvantages of silicon-based solar cells. In silico studies including quantitative structure-property relationship analysis combined with quantum chemical analysis were employed to understand the primary electron transfer mechanism and photo-physical properties of 273 arylamine organic dyes from 11 diverse chemical families explicit to iodine electrolyte. The direct quantitative structure-property relationship models enable identification of the essential electronic and structural attributes necessary for quantifying the molecular prerequisites of 11 classes of arylamine organic dyes, responsible for high power conversion efficiency of dye-sensitized solar cells. Tetrahydroquinoline, N,N'-dialkylaniline and indoline have been least explored classes under arylamine organic dyes for dye-sensitized solar cells. Therefore, the identified properties from the corresponding quantitative structure-property relationship models of the mentioned classes were employed in designing of "lead dyes". Followed by, a series of electrochemical and photo-physical parameters were computed for designed dyes to check the required variables for electron flow of dye-sensitized solar cells. The combined computational techniques yielded seven promising lead dyes each for all three chemical classes considered. Significant (130, 183, and 46%) increment in predicted %power conversion efficiency was observed comparing with the existing dye with highest experimental %power conversion efficiency value for tetrahydroquinoline, N,N'-dialkylaniline and indoline, respectively maintaining required electrochemical parameters.

Age Related Changes in Topological Properties of Brain Functional Network and Structural Connectivity.

PubMed

Shah, Chandan; Liu, Jia; Lv, Peilin; Sun, Huaiqiang; Xiao, Yuan; Liu, Jieke; Zhao, Youjin; Zhang, Wenjing; Yao, Li; Gong, Qiyong; Lui, Su

2018-01-01

Introduction: There are still uncertainties about the true nature of age related changes in topological properties of the brain functional network and its structural connectivity during various developmental stages. In this cross- sectional study, we investigated the effects of age and its relationship with regional nodal properties of the functional brain network and white matter integrity. Method: DTI and fMRI data were acquired from 458 healthy Chinese participants ranging from age 8 to 81 years. Tractography was conducted on the DTI data using FSL. Graph Theory analyses were conducted on the functional data yielding topological properties of the functional network using SPM and GRETNA toolbox. Two multiple regressions were performed to investigate the effects of age on nodal topological properties of the functional brain network and white matter integrity. Result: For the functional studies, we observed that regional nodal characteristics such as node betweenness were decreased while node degree and node efficiency was increased in relation to increasing age. Perversely, we observed that the relationship between nodal topological properties and fasciculus structures were primarily positive for nodal betweenness but negative for nodal degree and nodal efficiency. Decrease in functional nodal betweenness was primarily located in superior frontal lobe, right occipital lobe and the global hubs. These brain regions also had both direct and indirect anatomical relationships with the 14 fiber bundles. A linear age related decreases in the Fractional anisotropy (FA) value was found in the callosum forceps minor. Conclusion: These results suggests that age related differences were more pronounced in the functional than in structural measure indicating these measures do not have direct one-to-one mapping. Our study also indicates that the fiber bundles with longer fibers exhibited a more pronounced effect on the properties of functional network.

Relationship between Fiber Furnish and the Structural Performance of MDF

Treesearch

Leslie H. Groom; Laurence Mott; Stephen Shaler

1999-01-01

The structural performance of medium density fiberboard (MDF) is attributable to three primary variables which are: physical and mechanical properties of individual wood fibers; fiber-to-fiber stress transfer; and fiber orientation. These origins of fiber properties and stress transfer can be traced to the fiber generation method wherein fiber orientation is associated...

Looking beyond Lewis Structures: A General Chemistry Molecular Modeling Experiment Focusing on Physical Properties and Geometry

ERIC Educational Resources Information Center

Linenberger, Kimberly J.; Cole, Renee S.; Sarkar, Somnath

2011-01-01

We present a guided-inquiry experiment using Spartan Student Version, ready to be adapted and implemented into a general chemistry laboratory course. The experiment provides students an experience with Spartan Molecular Modeling software while discovering the relationships between the structure and properties of molecules. Topics discussed within…

Failure Analysis in Platelet Molded Composite Systems

NASA Astrophysics Data System (ADS)

Kravchenko, Sergii G.

Long-fiber discontinuous composite systems in the form of chopped prepreg tapes provide an advanced, structural grade, molding compound allowing for fabrication of complex three-dimensional components. Understanding of process-structure-property relationship is essential for application of prerpeg platelet molded components, especially because of their possible irregular disordered heterogeneous morphology. Herein, a structure-property relationship was analyzed in the composite systems of many platelets. Regular and irregular morphologies were considered. Platelet-based systems with more ordered morphology possess superior mechanical performance. While regular morphologies allow for a careful inspection of failure mechanisms derived from the morphological characteristics, irregular morphologies are representative of the composite architectures resulting from uncontrolled deposition and molding with chopped prerpegs. Progressive failure analysis (PFA) was used to study the damaged deformation up to ultimate failure in a platelet-based composite system. Computational damage mechanics approaches were utilized to conduct the PFA. The developed computational models granted understanding of how the composite structure details, meaning the platelet geometry and system morphology (geometrical arrangement and orientation distribution of platelets), define the effective mechanical properties of a platelet-molded composite system, its stiffness, strength and variability in properties.

Electrical conduction in polymer dielectrics

NASA Technical Reports Server (NTRS)

Cotts, D. B.

1985-01-01

The use of polymer dielectrics with moderate resistivities could reduce or eliminate problems associated with spacecraft charging. The processes responsible for conduction and the properties of electroactive polymers are reviewed, and correlations drawn between molecular structure and electrical conductivity. These structure-property relationships led to the development of several new electroactive polymer compositions and the identification of several systems that have the requisite thermal, mechanical, environmental and electrical properties for use in spacecraft.

Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions.

PubMed

Bedford, Nicholas M; Hughes, Zak E; Tang, Zhenghua; Li, Yue; Briggs, Beverly D; Ren, Yang; Swihart, Mark T; Petkov, Valeri G; Naik, Rajesh R; Knecht, Marc R; Walsh, Tiffany R

2016-01-20

Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction data and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.

Using Theoretical Descriptions in Structure Activity Relations. 3. Electronic Descriptors

DTIC Science & Technology

1988-08-01

Activity Relationships (QSAR) have been used successfully in the past to develop predictive equations for several biological and physical properties...Linear Free Energy Relationships (,FF.3) and is based on work by Hammet in which he derived electronic descriptors for the dissociation of substituted...structure of a compound and its activity in a system. Several different structural descriptors have been used in QSAR equations . These range from

Structure-Property Relationships of Organic Electrolytes and Their Effects on Li/S Battery Performance.

PubMed

Kaiser, Mohammad Rejaul; Chou, Shulei; Liu, Hua-Kun; Dou, Shi-Xue; Wang, Chunsheng; Wang, Jiazhao

2017-12-01

Electrolytes, which are a key component in electrochemical devices, transport ions between the sulfur/carbon composite cathode and the lithium anode in lithium-sulfur batteries (LSBs). The performance of a LSB mostly depends on the electrolyte due to the dissolution of polysulfides into the electrolyte, along with the formation of a solid-electrolyte interphase. The selection of the electrolyte and its functionality during charging and discharging is intricate and involves multiple reactions and processes. The selection of the proper electrolyte, including solvents and salts, for LSBs strongly depends on its physical and chemical properties, which is heavily controlled by its molecular structure. In this review, the fundamental properties of organic electrolytes for LSBs are presented, and an attempt is made to determine the relationship between the molecular structure and the properties of common organic electrolytes, along with their effects on the LSB performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chalcones: structural requirements for antioxidant, estrogenic and antiproliferative activities.

PubMed

Calliste, C A; Le Bail, J C; Trouillas, P; Pouget, C; Habrioux, G; Chulia, A J; Duroux, J L

2001-01-01

Flavonoids are largely studied for their biological properties and particularly for their scavenging and antioxidant activities. In the present study, we first evaluated the antioxidant and the estrogenic actions of chalcones, then we tested their effects on MCF-7 cell proliferation. Chalcones are unique in the flavonoids family in lacking a heterocyclic C ring. We tested substituted chalcones with different numbers and different positions of the hydroxy groups: 2'-hydroxychalcone, 4'-hydroxychalcone, 4-hydroxychalcone, 2',4-dihydroxychalcone, isoliquiritigenin, 2',4'-dihydroxychalcone, phloretin and naringenin chalcone. For the antioxidant tests we established the importance of the alpha-beta double bond and the 6'-hydroxy group. The establishment of the structure-activity relationship for the estrogenic properties showed a correlation between the antioxidant and the estrogenic properties. The importance of conformation and hydroxy group positions observed for chalcones, having antioxidant and estrogenic properties, was also observed on MCF-7 cell growth with the same structure-activity relationship. The role of electron and hydrogen transfer in the correlation between these three biological activities was discussed.

Processing, structure, property and performance relationships for the thermal spray of the internal surface of aluminum cylinders

NASA Astrophysics Data System (ADS)

Cook, David James

The increased need for automotive weight reduction has necessitated the use of aluminum for engine blocks. Conventional aluminum alloys cannot survive the constant wear from a piston ring reciprocating on the surface. However, a wear resistant thermal spray coating can be applied on the internal surface of the cylinder bore, which has significant advantages over other available options. Thermal spray is a well-established process for depositing molten, semi-molten, or solid particles onto a substrate to form a protective coating. For this application, the two main challenges were obtaining good wear resistance, and achieving good adhesion. To design a system capable of producing a well-adhered, wear resistant coating for this high volume application it is necessary to identify the overall processing, structure, properties, and performance relationships. The results will demonstrate that very important relationships exist among particle characteristics, substrate conditions, and the properties of the final coating. However, it is the scientific studies to understand some of the process physics in these relationships that allow recognition of the critical processing conditions that need to be controlled to ensure a consistent, reliable thermal spray coating. In this investigation, it will be shown that the critical microstructural aspect of the coating that produced the required tribological properties was the presence of wuestite (FeO). It was found that by using a low carbon steel material with compressed air atomizing gas, it was possible to create an Fe/FeO structure that exhibited excellent tribological properties. This study will also show that traditional thermal spray surface preparation techniques were not ideal for this application, therefore a novel alternative approach was developed. The application of a flux to the aluminum surface prior to thermal spray promotes excellent bond strengths to non-roughened aluminum. Analysis will show that this flux strips the oxide from the aluminum and allows for chemical bonding of the NiAl coating to the aluminum via the formation of intermetallics. By developing processing, structure, property, and performance relationships for the full process, it was possible to design a complete coating process to succeed in this application. The determination of these relationships and the underlying process physics improves reliability and instills confidence in the process.

Uncovering the structure-function relationship in spider silk

NASA Astrophysics Data System (ADS)

Yarger, Jeffery L.; Cherry, Brian R.; van der Vaart, Arjan

2018-03-01

All spiders produce protein-based biopolymer fibres that we call silk. The most studied of these silks is spider dragline silk, which is very tough and relatively abundant compared with other types of spider silks. Considerable research has been devoted to understanding the relationship between the molecular structure and mechanical properties of spider dragline silks. In this Review, we overview experimental and computational studies that have provided a wealth of detail at the molecular level on the highly conserved repetitive core and terminal regions of spider dragline silk. We also discuss the role of the nanocrystalline β-sheets and amorphous regions in determining the properties of spider silk fibres, endowing them with strength and elasticity. Additionally, we outline imaging techniques and modelling studies that elucidate the importance of the hierarchical structure of silk fibres at the molecular level. These insights into structure-function relationships can guide the reverse engineering of spider silk to enable the production of superior synthetic fibres.

Hybrid Mixed Media Nonwovens: An Investigation of Structure-Property Relationships

NASA Astrophysics Data System (ADS)

Hollowell, Kendall Birckhead

There have been myriad studies on utilizing bicomponent splittables produced through spunbond/spunlace processes. These production methods have proven to yield microfibers which increase the surface area of the nonwoven structures. There has been recent focus on studying the microfibers within these nonwoven structures as well as using a multiplicity of deniers of fibers within the nonwoven. There have also been studies on producing nonwovens with fibers of differing cross-sectional shapes and diameters. The purpose of this study is to examine the properties of a nonwoven structure, marrying the concepts of multi-denier fibers with multi-shaped fibers in two configurations: three-layer and alternating. The basis for this study will be US Patent 6,964,931 B2 "Method of making Continuous Filament Web with Statistical Filament Distribution" as well as US Patent 7,981,336 B2 "Process of Making Mixed Fibers and Nonwoven Fabrics". This study addresses the melt-spinning and hydroentanglement of nonwoven webs made from bicomponent fibers in three-layer and alternating configurations. The bicomponent cross-sections that will be used include 16-segmented pie and 7-islands-in-the-sea. In this study the establishment of the utility of mixed media nonwovens will take place through property and structure analysis in order to determine the inherent properties of the mixed media structures as well as the structure-property relationships of the nonwoven fabric. Property and structure analysis will also take place on mixed media structures containing poly(lactic acid) as a sacrificial component in the bicomponent fiber after optimizing the removal conditions of the poly(lactic acid) in a sodium hydroxide (NaOH) bath.

Quantitative structure-property relationship (QSPR) modeling of drug-loaded polymeric micelles via genetic function approximation.

PubMed

Wu, Wensheng; Zhang, Canyang; Lin, Wenjing; Chen, Quan; Guo, Xindong; Qian, Yu; Zhang, Lijuan

2015-01-01

Self-assembled nano-micelles of amphiphilic polymers represent a novel anticancer drug delivery system. However, their full clinical utilization remains challenging because the quantitative structure-property relationship (QSPR) between the polymer structure and the efficacy of micelles as a drug carrier is poorly understood. Here, we developed a series of QSPR models to account for the drug loading capacity of polymeric micelles using the genetic function approximation (GFA) algorithm. These models were further evaluated by internal and external validation and a Y-randomization test in terms of stability and generalization, yielding an optimization model that is applicable to an expanded materials regime. As confirmed by experimental data, the relationship between microstructure and drug loading capacity can be well-simulated, suggesting that our models are readily applicable to the quantitative evaluation of the drug-loading capacity of polymeric micelles. Our work may offer a pathway to the design of formulation experiments.

Quantitative Structure-Property Relationship (QSPR) Modeling of Drug-Loaded Polymeric Micelles via Genetic Function Approximation

PubMed Central

Lin, Wenjing; Chen, Quan; Guo, Xindong; Qian, Yu; Zhang, Lijuan

2015-01-01

Self-assembled nano-micelles of amphiphilic polymers represent a novel anticancer drug delivery system. However, their full clinical utilization remains challenging because the quantitative structure-property relationship (QSPR) between the polymer structure and the efficacy of micelles as a drug carrier is poorly understood. Here, we developed a series of QSPR models to account for the drug loading capacity of polymeric micelles using the genetic function approximation (GFA) algorithm. These models were further evaluated by internal and external validation and a Y-randomization test in terms of stability and generalization, yielding an optimization model that is applicable to an expanded materials regime. As confirmed by experimental data, the relationship between microstructure and drug loading capacity can be well-simulated, suggesting that our models are readily applicable to the quantitative evaluation of the drug-loading capacity of polymeric micelles. Our work may offer a pathway to the design of formulation experiments. PMID:25780923

Crystal structure of Au25(SePh)18 nanoclusters and insights into their electronic, optical and catalytic properties

NASA Astrophysics Data System (ADS)

Song, Yongbo; Zhong, Juan; Yang, Sha; Wang, Shuxin; Cao, Tiantian; Zhang, Jun; Li, Peng; Hu, Daqiao; Pei, Yong; Zhu, Manzhou

2014-10-01

The crystal structure of selenolate-capped Au25(SePh)18- nanoclusters has been unambiguously determined for the first time, and provides a solid basis for a deeper understanding of the structure-property relationships. The selenolate-capped Au25 cluster shows noticeable differences from the previously reported Au25(SCH2CH2Ph)18- counterpart, albeit both share the icosahedral Au13 core and semi-ring Au2(SeR)3 or Au2(SR)3 motifs. Distinct differences in the electronic structure and optical, catalytic and electrochemical properties are revealed by the coupling experiments with density functional theory (TD-DFT) calculations. Overall, the successful determination of the Au25(SePh)18- structure removes any ambiguity about its structure, and comparison with the thiolated Au25 counterpart helps us to further understand how the ligands affect the properties of the nanocluster.The crystal structure of selenolate-capped Au25(SePh)18- nanoclusters has been unambiguously determined for the first time, and provides a solid basis for a deeper understanding of the structure-property relationships. The selenolate-capped Au25 cluster shows noticeable differences from the previously reported Au25(SCH2CH2Ph)18- counterpart, albeit both share the icosahedral Au13 core and semi-ring Au2(SeR)3 or Au2(SR)3 motifs. Distinct differences in the electronic structure and optical, catalytic and electrochemical properties are revealed by the coupling experiments with density functional theory (TD-DFT) calculations. Overall, the successful determination of the Au25(SePh)18- structure removes any ambiguity about its structure, and comparison with the thiolated Au25 counterpart helps us to further understand how the ligands affect the properties of the nanocluster. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04631e

Synthetic study on the relationship between structure and sweet taste properties of steviol glycosides.

PubMed

Upreti, Mani; Dubois, Grant; Prakash, Indra

2012-04-05

The structure activity relationship between the C₁₆-C₁₇ methylene double bond on the aglycone of steviol glycosides and the corresponding impact on their sweet taste has been reported here for the first time. It has been observed that converting stevioside and rebaudioside A to their corresponding ketones by switching the doubly bonded methylene on C-17 for a ketone group actually removes the sweet taste properties of these molecules completely. Regenerating the original molecules tends to restore the sweet taste of both the steviol glycosides. Thus this C₁₆-C₁₇ methylene double bond in rebaudioside A and stevioside can be regarded as a pharmacophore essential for the sweetness property of these molecules.

Atomic force microscopy study of the structure function relationships of the biofilm-forming bacterium Streptococcus mutans

NASA Astrophysics Data System (ADS)

Cross, Sarah E.; Kreth, Jens; Zhu, Lin; Qi, Fengxia; Pelling, Andrew E.; Shi, Wenyuan; Gimzewski, James K.

2006-02-01

Atomic force microscopy (AFM) has garnered much interest in recent years for its ability to probe the structure, function and cellular nanomechanics inherent to specific biological cells. In particular, we have used AFM to probe the important structure-function relationships of the bacterium Streptococcus mutans. S. mutans is the primary aetiological agent in human dental caries (tooth decay), and is of medical importance due to the virulence properties of these cells in biofilm initiation and formation, leading to increased tolerance to antibiotics. We have used AFM to characterize the unique surface structures of distinct mutants of S. mutans. These mutations are located in specific genes that encode surface proteins, thus using AFM we have resolved characteristic surface features for mutant strains compared to the wild type. Ultimately, our characterization of surface morphology has shown distinct differences in the local properties displayed by various S. mutans strains on the nanoscale, which is imperative for understanding the collective properties of these cells in biofilm formation.

Oxide Thermoelectric Materials: A Structure-Property Relationship

NASA Astrophysics Data System (ADS)

Nag, Abanti; Shubha, V.

2014-04-01

Recent demand for thermoelectric materials for power harvesting from automobile and industrial waste heat requires oxide materials because of their potential advantages over intermetallic alloys in terms of chemical and thermal stability at high temperatures. Achievement of thermoelectric figure of merit equivalent to unity ( ZT ≈ 1) for transition-metal oxides necessitates a second look at the fundamental theory on the basis of the structure-property relationship giving rise to electron correlation accompanied by spin fluctuation. Promising transition-metal oxides based on wide-bandgap semiconductors, perovskite and layered oxides have been studied as potential candidate n- and p-type materials. This paper reviews the correlation between the crystal structure and thermoelectric properties of transition-metal oxides. The crystal-site-dependent electronic configuration and spin degeneracy to control the thermopower and electron-phonon interaction leading to polaron hopping to control electrical conductivity is discussed. Crystal structure tailoring leading to phonon scattering at interfaces and nanograin domains to achieve low thermal conductivity is also highlighted.

Structure-activity relationships for novel drug precursor N-substituted-6-acylbenzothiazolon derivatives: A theoretical approach

NASA Astrophysics Data System (ADS)

Sıdır, Yadigar Gülseven; Sıdır, İsa

2013-08-01

In this study, the twelve new modeled N-substituted-6-acylbenzothiazolon derivatives having analgesic analog structure have been investigated by quantum chemical methods using a lot of electronic parameters and structure-activity properties; such as molecular polarizability (α), dipole moment (μ), EHOMO, ELUMO, q-, qH+, molecular volume (Vm), ionization potential (IP), electron affinity (EA), electronegativity (χ), molecular hardness (η), molecular softness (S), electrophilic index (ω), heat of formation (HOF), molar refractivity (MR), octanol-water partition coefficient (log P), thermochemical properties (entropy (S), capacity of heat (Cv)); as to investigate activity relationships with molecular structure. The correlations of log P with Vm, MR, ω, EA, EHOMO - ELUMO (ΔE), HOF in aqueous phase, χ, μ, S, η parameters, respectively are obtained, while the linear relation of log P with IP, Cv, HOF in gas phase are not observed. The log P parameter is obtained to be depending on different properties of compounds due to their complexity.

Infrared and Ultraviolet Spectroscopy of Gas-Phase Imidazolium and Pyridinium Ionic Liquids.

NASA Astrophysics Data System (ADS)

Young, Justin W.; Booth, Ryan S.; Annesley, Christopher; Stearns, Jaime A.

2015-06-01

Ionic liquids (ILs) are a highly variable and potentially game-changing class of molecules for a number of Air Force applications such as satellite propulsion, but the complex nature of IL structure and intermolecular interactions makes it difficult to adequately predict structure-property relationships in order to make new IL-based technology a reality. For example, methylation of imidazolium ionic liquids leads to a substantial increase in viscosity but the underlying physical mechanism is not understood. In addition, the role of hydrogen bonding in ILs, and especially its relationship to macroscopic properties, is a matter of ongoing research. Here we describe the gas-phase spectroscopy of a series of imidazolium- and pyridinium-based ILs, using a combination of infrared spectroscopy and density functional theory to establish the intermolecular interactions present in various ILs, to assess how well they are described by theory, and to relate microscopic structure to macroscopic properties.

Machine learning of molecular electronic properties in chemical compound space

NASA Astrophysics Data System (ADS)

Montavon, Grégoire; Rupp, Matthias; Gobre, Vivekanand; Vazquez-Mayagoitia, Alvaro; Hansen, Katja; Tkatchenko, Alexandre; Müller, Klaus-Robert; Anatole von Lilienfeld, O.

2013-09-01

The combination of modern scientific computing with electronic structure theory can lead to an unprecedented amount of data amenable to intelligent data analysis for the identification of meaningful, novel and predictive structure-property relationships. Such relationships enable high-throughput screening for relevant properties in an exponentially growing pool of virtual compounds that are synthetically accessible. Here, we present a machine learning model, trained on a database of ab initio calculation results for thousands of organic molecules, that simultaneously predicts multiple electronic ground- and excited-state properties. The properties include atomization energy, polarizability, frontier orbital eigenvalues, ionization potential, electron affinity and excitation energies. The machine learning model is based on a deep multi-task artificial neural network, exploiting the underlying correlations between various molecular properties. The input is identical to ab initio methods, i.e. nuclear charges and Cartesian coordinates of all atoms. For small organic molecules, the accuracy of such a ‘quantum machine’ is similar, and sometimes superior, to modern quantum-chemical methods—at negligible computational cost.

Thermomechanical Formation–Structure–Property Relationships in Photopolymerized Copper-Catalyzed Azide–Alkyne (CuAAC) Networks

PubMed Central

Baranek, Austin; Song, Han Byul; McBride, Mathew; Finnegan, Patricia; Bowman, Christopher N.

2016-01-01

Bulk photopolymerization of a library of synthesized multifunctional azides and alkynes was carried out toward developing structure–property relationships for CuAAC-based polymer networks. Multifunctional azides and alkynes were formulated with a copper catalyst and a photoinitiator, cured, and analyzed for their mechanical properties. Material properties such as the glass transition temperatures (Tg) show a strong dependence on monomer structure with Tg values ranging from 41 to 90 °C for the series of CuAAC monomers synthesized in this study. Compared to the triazoles, analogous thioether-based polymer networks exhibit a 45–49 °C lower Tg whereas analogous monomers composed of ethers in place of carbamates exhibit a 40 °C lower Tg. Here, the formation of the triazole moiety during the polymerization represents a critical component in dictating the material properties of the ultimate polymer network where material properties such as the rubbery modulus, cross-link density, and Tg all exhibit strong dependence on polymerization conversion, monomer composition, and structure postgelation. PMID:27867223

Mapping in vitro local material properties of intact and disrupted virions at high resolution using multi-harmonic atomic force microscopy.

PubMed

Cartagena, Alexander; Hernando-Pérez, Mercedes; Carrascosa, José L; de Pablo, Pedro J; Raman, Arvind

2013-06-07

Understanding the relationships between viral material properties (stiffness, strength, charge density, adhesion, hydration, viscosity, etc.), structure (protein sub-units, genome, surface receptors, appendages), and functions (self-assembly, stability, disassembly, infection) is of significant importance in physical virology and nanomedicine. Conventional Atomic Force Microscopy (AFM) methods have measured a single physical property such as the stiffness of the entire virus from nano-indentation at a few points which severely limits the study of structure-property-function relationships. We present an in vitro dynamic AFM technique operating in the intermittent contact regime which synthesizes anharmonic Lorentz-force excited AFM cantilevers to map quantitatively at nanometer resolution the local electro-mechanical force gradient, adhesion, and hydration layer viscosity within individual φ29 virions. Furthermore, the changes in material properties over the entire φ29 virion provoked by the local disruption of its shell are studied, providing evidence of bacteriophage depressurization. The technique significantly generalizes recent multi-harmonic theory (A. Raman, et al., Nat. Nanotechnol., 2011, 6, 809-814) and enables high-resolution in vitro quantitative mapping of multiple material properties within weakly bonded viruses and nanoparticles with complex structure that otherwise cannot be observed using standard AFM techniques.

Effect of Carbon Doping on the Electronic Structure and Elastic Properties of Boron Suboxide

DTIC Science & Technology

2015-06-01

harden or soften B6O. The hardening or softening depends on the location and the type of a dopant . When the doping creates a B4C-like local...Lett. 2005;86:041911. 9. Nifise E. Study of sintering and structure property relationships in boron suboxide – alkaline earth metal oxide, cobalt

Synthesis-Structure-Activity Relationships in Co3O4 Catalyzed CO Oxidation

NASA Astrophysics Data System (ADS)

Mingle, Kathleen; Lauterbach, Jochen

2018-05-01

In this work, a statistical design and analysis platform was used to develop cobalt oxide based oxidation catalysts prepared via one pot metal salt reduction. An emphasis was placed upon understanding the effects of synthesis conditions, such as heating regimen and Co2+ concentration on the metal salt reduction mechanism, the resultant nanomaterial properties (i.e. size, crystal structure, and crystal faceting), and the catalytic activity in CO oxidation. This was accomplished by carrying out XRD, TEM, and FTIR studies on synthesis intermediates and products. Additionally, high-throughput experimentation was employed to study the performance of Co3O4 oxidation catalysts over a wide range of reaction conditions using a 16-channel fixed bed reactor equipped with a parallel infrared imaging system. Specifically, Co3O4 nanomaterials of varying properties were evaluated for their performance as CO oxidation catalysts. Figure-of-merits including light-off temperatures and activation energies were measured and mapped back to the catalyst properties and synthesis conditions. Statistical analysis methods were used to elucidate significant property-activity relationships as well as the design rules relevant in the synthesis of active catalysts. It was found that CO oxidation light off temperatures could be decreased to <90°C by utilizing the discovered synthesis-structure-activity relationships.

Machine learning for quantum dynamics: deep learning of excitation energy transfer properties

DOE PAGES

Häse, Florian; Kreisbeck, Christoph; Aspuru-Guzik, Alán

2017-01-01

Understanding the relationship between the structure of light-harvesting systems and their excitation energy transfer properties is of fundamental importance in many applications including the development of next generation photovoltaics.

PREDICTING THE ADSORPTION CAPACITY OF ACTIVATED CARBON FOR ORGANIC CONTAMINANTS FROM ADSORBENT AND ADSORBATE PROPERTIES

EPA Science Inventory

A quantitative structure-property relationship (QSPR) was developed and combined with the Polanyi-Dubinin-Manes model to predict adsorption isotherms of emerging contaminants on activated carbons with a wide range of physico-chemical properties. Affinity coefficients (β_l

On the design of wave digital filters with low sensitivity properties.

NASA Technical Reports Server (NTRS)

Renner, K.; Gupta, S. C.

1973-01-01

The wave digital filter patterned after doubly terminated maximum available power (MAP) networks by means of the Richard's transformation has been shown to have low-coefficient-sensitivity properties. This paper examines the exact nature of the relationship between the wave-digital-filter structure and the MAP networks and how the sensitivity property arises, which permits implementation of the digital structure with a lower coefficient word length than that possible with the conventional structures. The proper design procedure is specified and the nature of the unique complementary outputs is discussed. Finally, an example is considered which illustrates the design, the conversion techniques, and the low sensitivity properties.

Thienoacene-based organic semiconductors.

PubMed

Takimiya, Kazuo; Shinamura, Shoji; Osaka, Itaru; Miyazaki, Eigo

2011-10-11

Thienoacenes consist of fused thiophene rings in a ladder-type molecular structure and have been intensively studied as potential organic semiconductors for organic field-effect transistors (OFETs) in the last decade. They are reviewed here. Despite their simple and similar molecular structures, the hitherto reported properties of thienoacene-based OFETs are rather diverse. This Review focuses on four classes of thienoacenes, which are classified in terms of their chemical structures, and elucidates the molecular electronic structure of each class. The packing structures of thienoacenes and the thus-estimated solid-state electronic structures are correlated to their carrier transport properties in OFET devices. With this perspective of the molecular structures of thienoacenes and their carrier transport properties in OFET devices, the structure-property relationships in thienoacene-based organic semiconductors are discussed. The discussion provides insight into new molecular design strategies for the development of superior organic semiconductors. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On a relationship between molecular polarizability and partial molar volume in water.

PubMed

Ratkova, Ekaterina L; Fedorov, Maxim V

2011-12-28

We reveal a universal relationship between molecular polarizability (a single-molecule property) and partial molar volume in water that is an ensemble property characterizing solute-solvent systems. Since both of these quantities are of the key importance to describe solvation behavior of dissolved molecular species in aqueous solutions, the obtained relationship should have a high impact in chemistry, pharmaceutical, and life sciences as well as in environments. We demonstrated that the obtained relationship between the partial molar volume in water and the molecular polarizability has in general a non-homogeneous character. We performed a detailed analysis of this relationship on a set of ~200 organic molecules from various chemical classes and revealed its fine well-organized structure. We found that this structure strongly depends on the chemical nature of the solutes and can be rationalized in terms of specific solute-solvent interactions. Efficiency and universality of the proposed approach was demonstrated on an external test set containing several dozens of polyfunctional and druglike molecules.

Relationship between unit cell type and porosity and the fatigue behavior of selective laser melted meta-biomaterials.

PubMed

Amin Yavari, S; Ahmadi, S M; Wauthle, R; Pouran, B; Schrooten, J; Weinans, H; Zadpoor, A A

2015-03-01

Meta-materials are structures when their small-scale properties are considered, but behave as materials when their homogenized macroscopic properties are studied. There is an intimate relationship between the design of the small-scale structure and the homogenized properties of such materials. In this article, we studied that relationship for meta-biomaterials that are aimed for biomedical applications, otherwise known as meta-biomaterials. Selective laser melted porous titanium (Ti6Al4V ELI) structures were manufactured based on three different types of repeating unit cells, namely cube, diamond, and truncated cuboctahedron, and with different porosities. The morphological features, static mechanical properties, and fatigue behavior of the porous biomaterials were studied with a focus on their fatigue behavior. It was observed that, in addition to static mechanical properties, the fatigue properties of the porous biomaterials are highly dependent on the type of unit cell as well as on porosity. None of the porous structures based on the cube unit cell failed after 10(6) loading cycles even when the applied stress reached 80% of their yield strengths. For both other unit cells, higher porosities resulted in shorter fatigue lives for the same level of applied stress. When normalized with respect to their yield stresses, the S-N data points of structures with different porosities very well (R(2)>0.8) conformed to one single power law specific to the type of the unit cell. For the same level of normalized applied stress, the truncated cuboctahedron unit cell resulted in a longer fatigue life as compared to the diamond unit cell. In a similar comparison, the fatigue lives of the porous structures based on both truncated cuboctahedron and diamond unit cells were longer than that of the porous structures based on the rhombic dodecahedron unit cell (determined in a previous study). The data presented in this study could serve as a basis for design of porous biomaterials as well as for corroboration of relevant analytical and computational models. Copyright © 2014 Elsevier Ltd. All rights reserved.

Relationships for electron-vibrational coupling in conjugated π organic systems

NASA Astrophysics Data System (ADS)

O'Neill, L.; Lynch, P.; McNamara, M.; Byrne, H. J.

2005-06-01

A series of π conjugated systems were studied by absorption, photoluminescence and vibrational spectroscopy. As is common for these systems, a linear relationship between the positioning of the absorption and photoluminescence maxima plotted against inverse conjugation length is observed. The relationships are in good agreement with the simple particle in a box method, one of the earliest descriptions of the properties of one-dimensional organic molecules. In addition to the electronic transition energies, it was observed that the Stokes shift also exhibited a well-defined relationship with increasing conjugation length, implying a correlation between the electron-vibrational coupling and chain length. This correlation is further examined using Raman spectroscopy, whereby the integrated Raman scattering is seen to behave superlinearly with chain length. There is a clear indication that the vibrational activity and thus nonradiative decay processes are controllable through molecular structure. The correlations between the Stokes energies and the vibrational structure are also observed in a selection of PPV based polymers and a clear trend of increasing luminescence efficiency with decreasing vibrational activity and Stokes shift is observable. The implications of such structure property relationships in terms of materials design are discussed.

Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions

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

Bedford, Nicholas M.; Hughes, Zak E.; Tang, Zhenghua

Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction datamore » and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.« less

Structural phylogeny by profile extraction and multiple superimposition using electrostatic congruence as a discriminator

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

Chakraborty, Sandeep; Rao, Basuthkar J.; Baker, Nathan A.

2013-04-01

Phylogenetic analysis of proteins using multiple sequence alignment (MSA) assumes an underlying evolutionary relationship in these proteins which occasionally remains undetected due to considerable sequence divergence. Structural alignment programs have been developed to unravel such fuzzy relationships. However, none of these structure based methods have used electrostatic properties to discriminate between spatially equivalent residues. We present a methodology for MSA of a set of related proteins with known structures using electrostatic properties as an additional discriminator (STEEP). STEEP first extracts a profile, then generates a multiple structural superimposition providing a consolidated spatial framework for comparing residues and finally emits themore » MSA. Residues that are aligned differently by including or excluding electrostatic properties can be targeted by directed evolution experiments to transform the enzymatic properties of one protein into another. We have compared STEEP results to those obtained from a MSA program (ClustalW) and a structural alignment method (MUSTANG) for chymotrypsin serine proteases. Subsequently, we used PhyML to generate phylogenetic trees for the serine and metallo-β-lactamase superfamilies from the STEEP generated MSA, and corroborated the accepted relationships in these superfamilies. We have observed that STEEP acts as a functional classifier when electrostatic congruence is used as a discriminator, and thus identifies potential targets for directed evolution experiments. In summary, STEEP is unique among phylogenetic methods for its ability to use electrostatic congruence to specify mutations that might be the source of the functional divergence in a protein family. Based on our results, we also hypothesize that the active site and its close vicinity contains enough information to infer the correct phylogeny for related proteins.« less

The structural, connectomic and network covariance of the human brain.

PubMed

Irimia, Andrei; Van Horn, John D

2013-02-01

Though it is widely appreciated that complex structural, functional and morphological relationships exist between distinct areas of the human cerebral cortex, the extent to which such relationships coincide remains insufficiently appreciated. Here we determine the extent to which correlations between brain regions are modulated by either structural, connectomic or network-theoretic properties using a structural neuroimaging data set of magnetic resonance imaging (MRI) and diffusion tensor imaging (DTI) volumes acquired from N=110 healthy human adults. To identify the linear relationships between all available pairs of regions, we use canonical correlation analysis to test whether a statistically significant correlation exists between each pair of cortical parcels as quantified via structural, connectomic or network-theoretic measures. In addition to this, we investigate (1) how each group of canonical variables (whether structural, connectomic or network-theoretic) contributes to the overall correlation and, additionally, (2) whether each individual variable makes a significant contribution to the test of the omnibus null hypothesis according to which no correlation between regions exists across subjects. We find that, although region-to-region correlations are extensively modulated by structural and connectomic measures, there are appreciable differences in how these two groups of measures drive inter-regional correlation patterns. Additionally, our results indicate that the network-theoretic properties of the cortex are strong modulators of region-to-region covariance. Our findings are useful for understanding the structural and connectomic relationship between various parts of the brain, and can inform theoretical and computational models of cortical information processing. Published by Elsevier Inc.

Quantitative structure property relationships for the adsorption of pharmaceuticals onto activated carbon.

PubMed

Dickenson, E R V; Drewes, J E

2010-01-01

Isotherms were determined for the adsorption of five pharmaceutical residues, primidone, carbamazepine, ibuprofen, naproxen and diclofenac, to Calgon Filtrasorb 300 powdered activated carbon (PAC). The sorption behavior was examined in ultra-pure and wastewater effluent organic matter (EfOM) matrices, where more sorption was observed in the ultra-pure water for PAC doses greater than 10 mg/L suggesting the presence of EfOM hinders the sorption of the pharmaceuticals to the PAC. Adsorption behaviors were described by the Freundlich isotherm model. Quantitative structure property relationships (QSPRs) in the form of polyparameter linear solvation energy relationships were developed for simulating the Freundlich adsorption capacity in both ultra-pure and EfOM matrices. The significant 3D-based descriptors for the QSPRs were the molar volume, polarizability and hydrogen-bond donor parameters.

Effect of Material Ion Exchanges on the Mechanical Stiffness Properties and Shear Deformation of Hydrated Cement Material Chemistry Structure C-S-H Jennit - A Computational Modeling Study

DTIC Science & Technology

2014-01-01

Study Material properties and performance are governed by material molecular chemistry structures and molecular level interactions. Methods to...understand relationships between the material properties and performance and their correlation to the molecular level chemistry and morphology, and thus...find ways of manipulating and adjusting matters at the atomistic level in order to improve material performance are required. A computational material

Relationships among the structural topology, bond strength, and mechanical properties of single-walled aluminosilicate nanotubes.

PubMed

Liou, Kai-Hsin; Tsou, Nien-Ti; Kang, Dun-Yen

2015-10-21

Carbon nanotubes (CNTs) are regarded as small but strong due to their nanoscale microstructure and high mechanical strength (Young's modulus exceeds 1000 GPa). A longstanding question has been whether there exist other nanotube materials with mechanical properties as good as those of CNTs. In this study, we investigated the mechanical properties of single-walled aluminosilicate nanotubes (AlSiNTs) using a multiscale computational method and then conducted a comparison with single-walled carbon nanotubes (SWCNTs). By comparing the potential energy estimated from molecular and macroscopic material mechanics, we were able to model the chemical bonds as beam elements for the nanoscale continuum modeling. This method allowed for simulated mechanical tests (tensile, bending, and torsion) with minimum computational resources for deducing their Young's modulus and shear modulus. The proposed approach also enabled the creation of hypothetical nanotubes to elucidate the relative contributions of bond strength and nanotube structural topology to overall nanotube mechanical strength. Our results indicated that it is the structural topology rather than bond strength that dominates the mechanical properties of the nanotubes. Finally, we investigated the relationship between the structural topology and the mechanical properties by analyzing the von Mises stress distribution in the nanotubes. The proposed methodology proved effective in rationalizing differences in the mechanical properties of AlSiNTs and SWCNTs. Furthermore, this approach could be applied to the exploration of new high-strength nanotube materials.

PREDICTING THE ADSORPTION CAPACITY OF ACTIVATED CARBON FOR EMERGING ORGANIC CONTAMINANTS FROM FUNDAMENTAL ADSORBENT AND ADSORBATE PROPERTIES - PRESENTATION

EPA Science Inventory

A quantitative structure-property relationship (QSPR) was developed and combined with the Polanyi-Dubinin-Manes model to predict adsorption isotherms of emerging contaminants on activated carbons with a wide range of physico-chemical properties. Affinity coefficients (β_l

Mechanical properties and the electronic structure of transition of metal alloys

NASA Technical Reports Server (NTRS)

Arsenault, R. J.; Drew, H. D.

1977-01-01

This interdiscipline research program was undertaken in an effort to investigate the relationship between the mechanical strength of Mo based alloys with their electronic structure. Electronic properties of these alloys were examined through optical studies, and the classical solid solution strengthening mechanisms were considered, based on size and molecular differences to determine if these mechanisms could explain the hardness data.

Doping effect in layer structured SrBi2Nb2O9 ferroelectrics

NASA Astrophysics Data System (ADS)

Wu, Yun; Forbess, Mike J.; Seraji, Seana; Limmer, Steven J.; Chou, Tammy P.; Nguyen, Carolyn; Cao, Guozhong

2001-11-01

This article reports a systematic study of doping effects on the crystal structure, microstructure, dielectric, and electrical properties of layer-structured strontium bismuth niobate, SrBi2Nb2O9 (SBN), ferroelectrics. Substitution in both the A site (Sr2+ by Ca2+ and Ba2+) and B site (Nb5+ by V5+) up to 30 at % were studied. It was found that crystal lattice constant, dielectric, and electrical properties of SBN ferroelectrics varied appreciably with the type and amount of dopants. The relationships among the ionic radii, structural constraint imposed by [Bi2O2]2+ interlayers, and properties were discussed.

Atomically-thick two-dimensional crystals: electronic structure regulation and energy device construction.

PubMed

Sun, Yongfu; Gao, Shan; Xie, Yi

2014-01-21

Atomically-thick two-dimensional crystals can provide promising opportunities to satisfy people's requirement of next-generation flexible and transparent nanodevices. However, the characterization of these low-dimensional structures and the understanding of their clear structure-property relationship encounter many great difficulties, owing to the lack of long-range order in the third dimensionality. In this review, we survey the recent progress in fine structure characterization by X-ray absorption fine structure spectroscopy and also overview electronic structure modulation by density-functional calculations in the ultrathin two-dimensional crystals. In addition, we highlight their structure-property relationship, transparent and flexible device construction as well as wide applications in photoelectrochemical water splitting, photodetectors, thermoelectric conversion, touchless moisture sensing, supercapacitors and lithium ion batteries. Finally, we outline the major challenges and opportunities that face the atomically-thick two-dimensional crystals. It is anticipated that the present review will deepen people's understanding of this field and hence contribute to guide the future design of high-efficiency energy-related devices.

A polymer dataset for accelerated property prediction and design.

PubMed

Huan, Tran Doan; Mannodi-Kanakkithodi, Arun; Kim, Chiho; Sharma, Vinit; Pilania, Ghanshyam; Ramprasad, Rampi

2016-03-01

Emerging computation- and data-driven approaches are particularly useful for rationally designing materials with targeted properties. Generally, these approaches rely on identifying structure-property relationships by learning from a dataset of sufficiently large number of relevant materials. The learned information can then be used to predict the properties of materials not already in the dataset, thus accelerating the materials design. Herein, we develop a dataset of 1,073 polymers and related materials and make it available at http://khazana.uconn.edu/. This dataset is uniformly prepared using first-principles calculations with structures obtained either from other sources or by using structure search methods. Because the immediate target of this work is to assist the design of high dielectric constant polymers, it is initially designed to include the optimized structures, atomization energies, band gaps, and dielectric constants. It will be progressively expanded by accumulating new materials and including additional properties calculated for the optimized structures provided.

Some pungent arguments against the physico-chemical theories of the origin of the genetic code and corroborating the coevolution theory.

PubMed

Di Giulio, Massimo

2017-02-07

Whereas it is extremely easy to prove that "if the biosynthetic relationships between amino acids were fundamental in the structuring of the genetic code, then their physico-chemical properties might also be revealed in the genetic code table"; it is, on the contrary, impossible to prove that "if the physico-chemical properties of amino acids were fundamental in the structuring of the genetic code, then the presence of the biosynthetic relationships between amino acids should not be revealed in the genetic code". And, given that in the genetic code table are mirrored both the biosynthetic relationships between amino acids and their physico-chemical properties, all this would be a test that would falsify the physico-chemical theories of the origin of the genetic code. That is to say, if the physico-chemical properties of amino acids had a fundamental role in organizing the genetic code, then we would not have duly revealed the presence - in the genetic code - of the biosynthetic relationships between amino acids, and on the contrary this has been observed. Therefore, this falsifies the physico-chemical theories of genetic code origin. Whereas, the coevolution theory of the origin of the genetic code would be corroborated by this analysis, because it would be able to give a description of evolution of the genetic code more coherent with the indisputable empirical observations that link both the biosynthetic relationships of amino acids and their physico-chemical properties to the evolutionary organization of the genetic code. Copyright © 2016 Elsevier Ltd. All rights reserved.

Joint two-dimensional inversion of magnetotelluric and gravity data using correspondence maps

NASA Astrophysics Data System (ADS)

Carrillo, Jonathan; Gallardo, Luis A.

2018-05-01

An accurate characterization of subsurface targets relies on the interpretation of multiple geophysical properties and their relationships. There are mainly two links to jointly invert different geophysical parameters: structural and petrophysical relationships. Structural approaches aim at minimizing topological differences and are widely popular since they need only a few assumptions about models. Conversely, methods based on petrophysical links rely mostly on the property values themselves and can provide a strong coupling between models, but they need to be treated carefully because specific direct relationship must be known or assumed. While some petrophysical relationships are widely accepted, it remains the question whether we may be able to detect them directly from the geophysical data. Currently, there is no reported development that takes full advantage of the flexibility of jointly estimating in-situ empirical relationships and geophysical models for a given geological scenario. We thus developed an algorithm for the two dimensional joint inversion of gravity and magnetotelluric data that seeks simultaneously for a density-resistivity relationship optimal for each studied site described trough a polynomial function. The iterative two-dimensional scheme is tested using synthetic and field data from Cerro Prieto, Mexico. The resulting models show an enhanced resolution with an increased structural and petrophysical correlation. We show that by fitting a functional relationship we increased significantly the coupled geological sense of the models at a little cost in terms of data misfit.

Decoupling Polymer Properties to Elucidate Mechanisms Governing Cell Behavior

PubMed Central

Wang, Xintong; Boire, Timothy C.; Bronikowski, Christine; Zachman, Angela L.; Crowder, Spencer W.

2012-01-01

Determining how a biomaterial interacts with cells (“structure-function relationship”) reflects its eventual clinical applicability. Therefore, a fundamental understanding of how individual material properties modulate cell-biomaterial interactions is pivotal to improving the efficacy and safety of clinically translatable biomaterial systems. However, due to the coupled nature of material properties, their individual effects on cellular responses are difficult to understand. Structure-function relationships can be more clearly understood by the effective decoupling of each individual parameter. In this article, we discuss three basic decoupling strategies: (1) surface modification, (2) cross-linking, and (3) combinatorial approaches (i.e., copolymerization and polymer blending). Relevant examples of coupled material properties are briefly reviewed in each section to highlight the need for improved decoupling methods. This follows with examples of more effective decoupling techniques, mainly from the perspective of three primary classes of synthetic materials: polyesters, polyethylene glycol, and polyacrylamide. Recent strides in decoupling methodologies, especially surface-patterning and combinatorial techniques, offer much promise in further understanding the structure-function relationships that largely govern the success of future advancements in biomaterials, tissue engineering, and drug delivery. PMID:22536977

Prediction of Solvent Physical Properties using the Hierarchical Clustering Method

EPA Science Inventory

Recently a QSAR (Quantitative Structure Activity Relationship) method, the hierarchical clustering method, was developed to estimate acute toxicity values for large, diverse datasets. This methodology has now been applied to the estimate solvent physical properties including sur...

Theoretical framework for analyzing structural compliance properties of proteins.

PubMed

Arikawa, Keisuke

2018-01-01

We propose methods for directly analyzing structural compliance (SC) properties of elastic network models of proteins, and we also propose methods for extracting information about motion properties from the SC properties. The analysis of SC properties involves describing the relationships between the applied forces and the deformations. When decomposing the motion according to the magnitude of SC (SC mode decomposition), we can obtain information about the motion properties under the assumption that the lower SC mode motions or the softer motions occur easily. For practical applications, the methods are formulated in a general form. The parts where forces are applied and those where deformations are evaluated are separated from each other for enabling the analyses of allosteric interactions between the specified parts. The parts are specified not only by the points but also by the groups of points (the groups are treated as flexible bodies). In addition, we propose methods for quantitatively evaluating the properties based on the screw theory and the considerations of the algebraic structures of the basic equations expressing the SC properties. These methods enable quantitative discussions about the relationships between the SC mode motions and the motions estimated from two different conformations; they also help identify the key parts that play important roles for the motions by comparing the SC properties with those of partially constrained models. As application examples, lactoferrin and ATCase are analyzed. The results show that we can understand their motion properties through their lower SC mode motions or the softer motions.

Theoretical framework for analyzing structural compliance properties of proteins

PubMed Central

2018-01-01

We propose methods for directly analyzing structural compliance (SC) properties of elastic network models of proteins, and we also propose methods for extracting information about motion properties from the SC properties. The analysis of SC properties involves describing the relationships between the applied forces and the deformations. When decomposing the motion according to the magnitude of SC (SC mode decomposition), we can obtain information about the motion properties under the assumption that the lower SC mode motions or the softer motions occur easily. For practical applications, the methods are formulated in a general form. The parts where forces are applied and those where deformations are evaluated are separated from each other for enabling the analyses of allosteric interactions between the specified parts. The parts are specified not only by the points but also by the groups of points (the groups are treated as flexible bodies). In addition, we propose methods for quantitatively evaluating the properties based on the screw theory and the considerations of the algebraic structures of the basic equations expressing the SC properties. These methods enable quantitative discussions about the relationships between the SC mode motions and the motions estimated from two different conformations; they also help identify the key parts that play important roles for the motions by comparing the SC properties with those of partially constrained models. As application examples, lactoferrin and ATCase are analyzed. The results show that we can understand their motion properties through their lower SC mode motions or the softer motions. PMID:29607281

Structure-property relationships in low-temperature adhesives. [for inflatable structures

NASA Technical Reports Server (NTRS)

Schoff, C. K.; Udipi, K.; Gillham, J. K.

1977-01-01

Adhesive materials of aliphatic polyester, linear hydroxyl end-capped polybutadienes, or SBS block copolymers are studied with the objective to replace conventional partially aromatic end-reactive polyester-isocyanate adhesives that have shown embrittlement

Food structure: Its formation and relationships with other properties.

PubMed

Joardder, Mohammad U H; Kumar, Chandan; Karim, M A

2017-04-13

Food materials are complex in nature as it has heterogeneous, amorphous, hygroscopic and porous properties. During processing, microstructure of food materials changes which significantly affects other properties of food. An appropriate understanding of the microstructure of the raw food material and its evolution during processing is critical in order to understand and accurately describe dehydration processes and quality anticipation. This review critically assesses the factors that influence the modification of microstructure in the course of drying of fruits and vegetables. The effect of simultaneous heat and mass transfer on microstructure in various drying methods is investigated. Effects of changes in microstructure on other functional properties of dried foods are discussed. After an extensive review of the literature, it is found that development of food structure significantly depends on fresh food properties and process parameters. Also, modification of microstructure influences the other properties of final product. An enhanced understanding of the relationships between food microstructure, drying process parameters and final product quality will facilitate the energy efficient optimum design of the food processor in order to achieve high-quality food.

Second-Order Nonlinear Optical Dendrimers and Dendronized Hyperbranched Polymers.

PubMed

Tang, Runli; Li, Zhen

2017-01-01

Second-order nonlinear optical (NLO) dendrimers with a special topological structure were regarded as the most promising candidates for practical applications in the field of optoelectronic materials. Dendronized hyperbranched polymers (DHPs), a new type of polymers with dendritic structures, proposed and named by us recently, demonstrated interesting properties and some advantages over other polymers. Some of our work concerning these two types of polymers are presented herein, especially focusing on the design idea and structure-property relationship. To enhance their comprehensive NLO performance, dendrimers were designed and synthesized by adjusting their isolation mode, increasing the number of the dendritic generation, modifying their topological structure, introducing isolation chromophores, and utilizing the Ar-Ar F self-assembly effect. To make full use of the advantages of both the structural integrity of dendrimers and the convenient one-pot synthesis of hyperbranched polymers, DHPs were explored by utilizing low-generation dendrons as big monomers to construct hyperbranched polymers. These selected works could provide valuable information to deeply understand the relationship between the structure and properties of functional polymers with dendritic structures, but not only limited to the NLO ones, and might contribute much to the further development of functional polymers with rational design. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Updating CMAQ secondary organic aerosol properties relevant for aerosol water interactions

EPA Science Inventory

Properties of secondary organic aerosol (SOA) compounds in CMAQ are updated with state-of-the-science estimates from structure activity relationships to provide consistency among volatility, molecular weight, degree of oxygenation, and solubility/hygroscopicity. These updated pro...

3-D Structure of Molecules of Biological Significance

ERIC Educational Resources Information Center

Bennett, Alice S.; Schwenk, Karl

1974-01-01

Describes how to use the distinctive properties of osazone formation in conjunction with molecular model construction to demonstrate the relationship between the three-dimensional structures of simple sugars and the shapes of crystals they form. (BR)

(The relationship between microstructure and magnetic properties in high-energy permanent magnets characterized by polytwinned structures)

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

Not Available

1992-01-01

This report summarizes the results of a study of the relationship between microstructure and magnetic properties in a unique genre of ferromagnetic material characterized by a polysynthetically twinned structure which arises during solid state transformation. These results stem from the work over a period of approximately 27 months of a nominal 3 year grant period. The report also contains a proposal to extend the research project for an additional 3 years. The polytwinned structures produce an inhomogeneous magnetic medium in which the easy axis of magnetization varies quasi-periodically giving rise to special domain configurations which are expected to markedly influencemore » the mechanism of magnetization reversal and hysteresis behavior of these materials in bulk or thin films. The extraordinary permanent magnet properties exhibited by the well-known Co-Pt alloys as well as the Fe-Pt and Fe-Pd systems near the equiatomic composition derive from the formation of a polytwinned microstructure.« less

[The relationship between microstructure and magnetic properties in high-energy permanent magnets characterized by polytwinned structures

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

Not Available

1992-07-01

This report summarizes the results of a study of the relationship between microstructure and magnetic properties in a unique genre of ferromagnetic material characterized by a polysynthetically twinned structure which arises during solid state transformation. These results stem from the work over a period of approximately 27 months of a nominal 3 year grant period. The report also contains a proposal to extend the research project for an additional 3 years. The polytwinned structures produce an inhomogeneous magnetic medium in which the easy axis of magnetization varies quasi-periodically giving rise to special domain configurations which are expected to markedly influencemore » the mechanism of magnetization reversal and hysteresis behavior of these materials in bulk or thin films. The extraordinary permanent magnet properties exhibited by the well-known Co-Pt alloys as well as the Fe-Pt and Fe-Pd systems near the equiatomic composition derive from the formation of a polytwinned microstructure.« less

The relationship between microstructure and magnetic properties in high-energy permanent magnets characterized by polytwinned structures

NASA Astrophysics Data System (ADS)

This report summarizes the results of a study of the relationship between microstructure and magnetic properties in a unique genre of ferromagnetic material characterized by a polysynthetically twinned structure which arises during solid state transformation. These results stem from the work over a period of approximately 27 months of a nominal 3 year grant period. The report also contains a proposal to extend the research project for an additional 3 years. The polytwinned structures produce an inhomogeneous magnetic medium in which the easy axis of magnetization varies quasi-periodically giving rise to special domain configurations which are expected to markedly influence the mechanism of magnetization reversal and hysteresis behavior of these materials in bulk or thin films. The extraordinary permanent magnet properties exhibited by the well-known Co-Pt alloys as well as the Fe-Pt and Fe-Pd systems near the equiatomic composition derive from the formation of a polytwinned microstructure.

Boiling points of halogenated aliphatic compounds: a quantitative structure-property relationship for prediction and validation.

PubMed

Oberg, Tomas

2004-01-01

Halogenated aliphatic compounds have many technical uses, but substances within this group are also ubiquitous environmental pollutants that can affect the ozone layer and contribute to global warming. The establishment of quantitative structure-property relationships is of interest not only to fill in gaps in the available database but also to validate experimental data already acquired. The three-dimensional structures of 240 compounds were modeled with molecular mechanics prior to the generation of empirical descriptors. Two bilinear projection methods, principal component analysis (PCA) and partial-least-squares regression (PLSR), were used to identify outliers. PLSR was subsequently used to build a multivariate calibration model by extracting the latent variables that describe most of the covariation between the molecular structure and the boiling point. Boiling points were also estimated with an extension of the group contribution method of Stein and Brown.

Using FT-IR Spectroscopy to Elucidate the Structures of Ablative Polymers

NASA Technical Reports Server (NTRS)

Fan, Wendy

2011-01-01

The composition and structure of an ablative polymer has a multifaceted influence on its thermal, mechanical and ablative properties. Understanding the molecular level information is critical to the optimization of material performance because it helps to establish correlations with the macroscopic properties of the material, the so-called structure-property relationship. Moreover, accurate information of molecular structures is also essential to predict the thermal decomposition pathways as well as to identify decomposition species that are fundamentally important to modeling work. In this presentation, I will describe the use of infrared transmission spectroscopy (FT-IR) as a convenient tool to aid the discovery and development of thermal protection system materials.

H/C atomic ratio as a smart linkage between pyrolytic temperatures, aromatic clusters and sorption properties of biochars derived from diverse precursory materials

PubMed Central

Xiao, Xin; Chen, Zaiming; Chen, Baoliang

2016-01-01

Biochar is increasingly gaining attention due to multifunctional roles in soil amelioration, pollution mitigation and carbon sequestration. It is a significant challenge to compare the reported results from world-wide labs regarding the structure and sorption of biochars derived from various precursors under different pyrolytic conditions due to a lack of a simple linkage. By combining the published works on various biochars, we established a quantitative relationship between H/C atomic ratio and pyrolytic temperature (T), aromatic structure, and sorption properties for naphthalene and phenanthrene. A reverse sigmoid shape between T and the H/C ratio was observed, which was independent of the precursors of biochars, including the ash contents. Linear correlations of Freundlich parameters (N, log Kf) and sorption amount (log Qe, log QA) with H/C ratios were found. A rectangle-like model was proposed to predict the aromatic cluster sizes of biochars from their H/C ratios, and then a good structure-sorption relationship was derived. These quantitative relationships indicate that the H/C atomic ratio is a universal linkage to predict pyrolytic temperatures, aromatic cluster sizes, and sorption characteristics. This study would guide the global study of biochars toward being comparable, and then the development of the structure-sorption relationships will benefit the structural design and environmental application of biochars. PMID:26940984

Anisotropic properties of periodically polarity-inverted zinc oxide structures

NASA Astrophysics Data System (ADS)

Park, J. S.; Minegishi, T.; Lee, J. W.; Hong, S. K.; Song, J. H.; Lee, J. Y.; Yoon, E.; Yao, T.

2010-06-01

We report on the anisotropic structural properties of periodically polarity-inverted (PPI) ZnO structures grown on patterned templates. The etching and growth rates along ⟨112¯0⟩ direction of ZnO structures are higher than those of ⟨101¯0⟩ direction of ZnO films. From the strain evaluation by Raman spectroscopy, compressive strains are observed in all PPI ZnO samples with different stripe pattern size and the smaller pattern size is more effective to residual stress relaxation. The detailed structures at transition region show relationship with the anisotropic crystal quality.

Role of Sequence and Structural Polymorphism on the Mechanical Properties of Amyloid Fibrils

PubMed Central

Kim, Jae In; Na, Sungsoo; Eom, Kilho

2014-01-01

Amyloid fibrils playing a critical role in disease expression, have recently been found to exhibit the excellent mechanical properties such as elastic modulus in the order of 10 GPa, which is comparable to that of other mechanical proteins such as microtubule, actin filament, and spider silk. These remarkable mechanical properties of amyloid fibrils are correlated with their functional role in disease expression. This suggests the importance in understanding how these excellent mechanical properties are originated through self-assembly process that may depend on the amino acid sequence. However, the sequence-structure-property relationship of amyloid fibrils has not been fully understood yet. In this work, we characterize the mechanical properties of human islet amyloid polypeptide (hIAPP) fibrils with respect to their molecular structures as well as their amino acid sequence by using all-atom explicit water molecular dynamics (MD) simulation. The simulation result suggests that the remarkable bending rigidity of amyloid fibrils can be achieved through a specific self-aggregation pattern such as antiparallel stacking of β strands (peptide chain). Moreover, we have shown that a single point mutation of hIAPP chain constituting a hIAPP fibril significantly affects the thermodynamic stability of hIAPP fibril formed by parallel stacking of peptide chain, and that a single point mutation results in a significant change in the bending rigidity of hIAPP fibrils formed by antiparallel stacking of β strands. This clearly elucidates the role of amino acid sequence on not only the equilibrium conformations of amyloid fibrils but also their mechanical properties. Our study sheds light on sequence-structure-property relationships of amyloid fibrils, which suggests that the mechanical properties of amyloid fibrils are encoded in their sequence-dependent molecular architecture. PMID:24551113

Effect of High-Pressure Treatment on Catalytic and Physicochemical Properties of Pepsin.

PubMed

Wang, Jianan; Bai, Tenghui; Ma, Yaping; Ma, Hanjun

2017-10-11

For a long time, high-pressure treatment has been used to destroy the compact structures of natural proteins in order to promote subsequent enzymatic hydrolysis. However, there are few reports evaluating the feasibility of directly improving the catalytic capability of proteases by using high-pressure treatments. In this study, the effects of high-pressure treatment on the catalytic capacity and structure of pepsin were investigated, and the relationship between its catalytic properties and changes in its physicochemical properties was explored. It was found that high-pressure treatment could lead to changes of the sulfhydryl group/disulfide bond content, hydrophobicity, hydrodynamic radius, intrinsic viscosity, and subunit composition of pepsin, and the conformational change of pepsin resulted in improvement to its enzymatic activity and hydrolysis efficiency, which had an obvious relationship with the high-pressure treatment conditions.

Comments on the use of network structures to analyse commercial companies’ evolution and their impact on economic behaviour

NASA Astrophysics Data System (ADS)

Costea, Carmen

2006-10-01

Network analysis studies the development of the social structure of relationships around a group or an institutional body, and how it affects beliefs and behaviours. Causal constraints require a special and deeper attention to the social structure. The purpose of this paper is to give a new approach to the idea that this reality should be primarily conceived and investigated from the perspective of the properties of relations between and within units, instead of the properties of these units themselves. The relationship may refer to the exchange of products, labour, information and money. By mapping these relationships, network analysis can help to uncover the emergent and informal communication patterns of commercial companies that may be compared to the formal communication structures. These emergent patterns can be used to explain institutional and individuals’ behaviours. Network analysis techniques focus on the communication structure of an organization that can be subdivided and handled with different approaches. Structural features that can be analysed through the use of network analysis techniques are, for example, the (formal and informal) communication patterns in an organization or the identification of specific groups within an organization. Special attention may be given to specific aspects of communication patterns.

Design, Fabrication, Characterization and Modeling of Integrated Functional Materials

DTIC Science & Technology

2010-10-19

ribbons: A relationship between the soft magnetic properties and GMI effect has been established in Co69Fe4.5R1.5Si10B15 (R = Ni, Al , Cr) amorphous... deposition . A strain compression-relaxation mechanism has been proposed in order to explain the structure- property relationships in the CFO-PZT bilayer...being pursued. The new Laser Assisted Spray process chamber for co- deposition of QDs and polymer films is shown in Fig. 55. Fig. 55

Operational Determination of Physical and Mechanical Properties of Cast Samples of High-Strength Iron by Means of a Magnetic-Mechanical Method

NASA Astrophysics Data System (ADS)

Slyusarev, Yu. K.; Braga, A. V.; Slyusarev, I. Yu.

2017-09-01

The effect of the chemical composition of high-strength cast iron VCh35 on the content, shape and diameter of graphite inclusions and on the presence of structurally-free cementite and defects is studied. A relationship is determined between the structure and metallurgical defects and characteristics of the mechanical and magnetic rigidity of cast samples. Relationships are established in a group of factors and property characteristics: chemical composition - microstructure - mechanical rigidity - magnetic stiffness. The basis of a method is established making it possible to perform operative non-destructive monitoring of the melt quality preparation for high-strength iron casting.

Geophysics applications in critical zone science: emerging topics

USDA-ARS?s Scientific Manuscript database

Geophysical studies have resulted in remarkable advances in characterization of critical zone. The geophysics applications uncover the relationships between structure and function in subsurface as they seek to define subsurface structural units with individual properties of retention and trans...

First-principle calculations of crystal structures, electronic structures, and optical properties of RETaO4 (RE = Y, La, Sm, Eu, Dy, Er)

NASA Astrophysics Data System (ADS)

Ma, Zhuang; Zheng, Jiayi; Wang, Song; Gao, Lihong

2018-01-01

It is an effective method to protect components from high power laser damage using high reflective materials. The rare earth tantalates RETaO4 with high dielectric constant suggests that they may have very high reflectivity, according to the relationship between dielectric constant and reflectivity. The crystal structures, electronic structures, and optical properties of RETaO4 (RE=Y, La, Sm, Eu, Dy, Er) have been studied by first-principle calculations. With the increasing atomic number of RE (i.e., the number of 4f electrons), a 4f electron shell moves from the bottom of conduction band to the forbidden gap and then to the valence band. The relationship between the electronic structures and optical properties is explored. The electron transitions among O 2p states, RE 4f states, and Ta 5d states have a key effect on optical properties such as dielectric function, absorption coefficient, and reflectivity. For the series of RETaO4, the appearance of the 4f electronic states will obviously promote the improvement of reflectivity. When the 4f states appear at the middle of the forbidden gap, the reflectivity reaches the maximum. The reflectivity of EuTaO4 at 1064 nm is up to 93.47%, indicating that it has potential applications in the antilaser radiation area.

Relationship between nano/micro structure and physical properties of TiO2-sodium caseinate composite films.

PubMed

Montes-de-Oca-Ávalos, Juan Manuel; Altamura, Davide; Candal, Roberto Jorge; Scattarella, Francesco; Siliqi, Dritan; Giannini, Cinzia; Herrera, María Lidia

2018-03-01

Films obtained by casting, starting from conventional emulsions (CE), nanoemulsions (NE) or their gels, which led to different structures, with the aim of explore the relationship between structure and physical properties, were prepared. Sodium caseinate was used as the matrix, glycerol as plasticizer, glucono-delta-lactone as acidulant to form the gels, and TiO 2 nanoparticles as reinforcement to improve physical behavior. Structural characterization was performed by SAXS and WAXS (Small and Wide Angle X-ray Scattering, respectively), combined with confocal and scanning electron microscopy. The results demonstrate that the incorporation of the lipid phase does not notably modify the mechanical properties of the films compared to solution films. Films from NE were more stable against oil release than those from CE. Incorporation of TiO 2 improved mechanical properties as measured by dynamical mechanical analysis (DMA) and uniaxial tensile tests. TiO 2 macroscopic spatial distribution homogeneity and the nanostructure character of NE films were confirmed by mapping the q-dependent scattering intensity in scanning SAXS experiments. SAXS microscopies indicated a higher intrinsic homogeneity of NE films compared to CE films, independently of the TiO 2 load. NE-films containing structures with smaller and more homogeneously distributed building blocks showed greater potential for food applications than the films prepared from sodium caseinate solutions, which are the best known films. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Formation, Transport Properties and Microstructure of 45 Degrees (001) Tilt Grain Boundaries in Yttrium BARIUM(2) COPPER(3) OXYGEN(7-X) Thin Films

NASA Astrophysics Data System (ADS)

Vuchic, Boris Vukan

1995-01-01

Most high angle grain boundaries in high-T _{c} superconductors exhibit weak link behavior. The Josephson-like properties of these grain boundaries can be used for many device applications such as superconducting quantum interference devices (SQUIDs). The structure-property relationship of different types of 45 ^circ (001) YBa_2 Cu_3O_{7-x} thin film grain boundary junctions are examined to study their weak link nature. A technique, termed sputter-induced epitaxy, is developed to form 45^circ (001) tilt grain boundaries in YBa_2Cu _3O_{7-x} thin films on (100) MgO substrates. A low voltage ion bombardment pre-growth substrate treatment is used to modify the epitaxial orientation relationship between the thin film and the substrate in selected regions. By modifying the orientation of the thin film, grain boundary junctions can be placed in any configuration on the substrate. A variety of pre-growth sputtering conditions in conjunction with atomic force microscopy and Rutherford backscatter spectrometry are used to determine the role of the ions in modifying the substrate surface. Sputter-induced epitaxy is extended to a multilayer MgO/LaAlO_3 substrate, allowing integration of the sputter -induced epitaxy junctions into multilayer structures. The low temperature transport properties of the sputter-induced epitaxy junctions and a set of bi-epitaxial grain boundaries are studied. Individual grain boundaries are isolated and characterized for resistance vs. temperature, current vs. voltage as a function of temperature and magnetic field behavior. Resistive and superconducting grain boundaries are compared. Microstructural analysis is performed using scanning electron microscopy, transmission electron microscopy and high resolution electron microscopy (HREM). Marked differences are observed in the microstructure of resistive and superconducting grain boundaries. HREM studies suggest the importance of the local atomic scale structure of the grain boundary in transport properties. A phenomenological grain boundary model is proposed to describe the structure -property relationship of the boundaries.

Creating 3D Physical Models to Probe Student Understanding of Macromolecular Structure

ERIC Educational Resources Information Center

Cooper, A. Kat; Oliver-Hoyo, M. T.

2017-01-01

The high degree of complexity of macromolecular structure is extremely difficult for students to process. Students struggle to translate the simplified two-dimensional representations commonly used in biochemistry instruction to three-dimensional aspects crucial in understanding structure-property relationships. We designed four different physical…

Evaluating the effect of tillage on soil structural properties using the pedostructure concept

USDA-ARS?s Scientific Manuscript database

The pedostructure (PS) concept is a physically-based method of soil characterization that defines a soil based on its structure and the relationship between structure and soil water behavior. There are fifteen unique pedostructure parameters that define the macropore and micropore soil water behavio...

High-throughput determination of structural phase diagram and constituent phases using GRENDEL

NASA Astrophysics Data System (ADS)

Kusne, A. G.; Keller, D.; Anderson, A.; Zaban, A.; Takeuchi, I.

2015-11-01

Advances in high-throughput materials fabrication and characterization techniques have resulted in faster rates of data collection and rapidly growing volumes of experimental data. To convert this mass of information into actionable knowledge of material process-structure-property relationships requires high-throughput data analysis techniques. This work explores the use of the Graph-based endmember extraction and labeling (GRENDEL) algorithm as a high-throughput method for analyzing structural data from combinatorial libraries, specifically, to determine phase diagrams and constituent phases from both x-ray diffraction and Raman spectral data. The GRENDEL algorithm utilizes a set of physical constraints to optimize results and provides a framework by which additional physics-based constraints can be easily incorporated. GRENDEL also permits the integration of database data as shown by the use of critically evaluated data from the Inorganic Crystal Structure Database in the x-ray diffraction data analysis. Also the Sunburst radial tree map is demonstrated as a tool to visualize material structure-property relationships found through graph based analysis.

Polychlorinated Biphenyls

ERIC Educational Resources Information Center

Peakall, David B.; Lincer, Jeffrey L.

1970-01-01

Describes structure, use, analysis, and toxicological properties of polychlorinated biphenyls. Provides data on occurrence and biological magnification in ecosystems. Significance, and synergistic relationships with DDT summarized. (AL)

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

Theoretical study on surface plasmon properties of gold nanostars

NASA Astrophysics Data System (ADS)

Shan, Feng; Zhang, Tong

2018-03-01

With the rapid development of nanotechnology, the surface plasmon properties of metal nanostructures have become the focus of research. In this paper, a multi-tip gold nanostars (GNSs) structure is designed theoretically, and its surface plasmon properties are simulated by using the finite element method (FEM), which is practical and versatile. Compared with the traditional spherical and triangular plate particles, the results show that the tip structure of the GNSs has a stronger hot spots effect, resulting in greater local field enhancement properties. The relationship between the structure parameters of GNSs and their resonance peaks was also studied. The results indicate that the resonance peaks of GNSs depend strongly on the size, spacing between two GNSs, quantity and refractive index of the GNSs.

Validating the German Version of the Quality of Relationship Inventory: Confirming the Three-Factor Structure and Report of Psychometric Properties

PubMed Central

Reiner, Iris; Beutel, Manfred; Skaletz, Christian; Brähler, Elmar; Stöbel-Richter, Yve

2012-01-01

Research on psychosocial influences such as relationship characteristics has received increased attention in the clinical as well as social-psychological field. Several studies demonstrated that the quality of relationships, in particular with respect to the perceived support within intimate relationships, profoundly affects individuals' mental and physical health. There is, however, a limited choice of valid and internationally known assessments of relationship quality in Germany. We report the validation of the German version of the Quality of Relationships Inventory (QRI). First, we evaluated its factor structure in a representative German sample of 1.494 participants by means of confirmatory factor analysis. Our findings support the previously proposed three-factor structure. Second, importance and satisfaction with different relationship domains (family/children and relationship/sexuality) were linked with the QRI scales, demonstrating high construct validity. Finally, we report sex and age differences regarding the perceived relationship support, conflict and depth in our German sample. In conclusion, the QRI is a reliable and valid measurement to assess social support in romantic relationships in the German population. PMID:22662151

Three-dimensional quantitative structure-property relationship (3D-QSPR) models for prediction of thermodynamic properties of polychlorinated biphenyls (PCBs): enthalpy of vaporization.

PubMed

Puri, Swati; Chickos, James S; Welsh, William J

2002-01-01

Three-dimensional Quantitative Structure-Property Relationship (QSPR) models have been derived using Comparative Molecular Field Analysis (CoMFA) to correlate the vaporization enthalpies of a representative set of polychlorinated biphenyls (PCBs) at 298.15 K with their CoMFA-calculated physicochemical properties. Various alignment schemes, such as inertial, as is, and atom fit, were employed in this study. The CoMFA models were also developed using different partial charge formalisms, namely, electrostatic potential (ESP) charges and Gasteiger-Marsili (GM) charges. The most predictive model for vaporization enthalpy (Delta(vap)H(m)(298.15 K)), with atom fit alignment and Gasteiger-Marsili charges, yielded r2 values 0.852 (cross-validated) and 0.996 (conventional). The vaporization enthalpies of PCBs increased with the number of chlorine atoms and were found to be larger for the meta- and para-substituted isomers. This model was used to predict Delta(vap)H(m)(298.15 K) of the entire set of 209 PCB congeners.

Molecular basis of quantitative structure-properties relationships (QSPR): a quantum similarity approach.

PubMed

Ponec, R; Amat, L; Carbó-Dorca, R

1999-05-01

Since the dawn of quantitative structure-properties relationships (QSPR), empirical parameters related to structural, electronic and hydrophobic molecular properties have been used as molecular descriptors to determine such relationships. Among all these parameters, Hammett sigma constants and the logarithm of the octanol-water partition coefficient, log P, have been massively employed in QSPR studies. In the present paper, a new molecular descriptor, based on quantum similarity measures (QSM), is proposed as a general substitute of these empirical parameters. This work continues previous analyses related to the use of QSM to QSPR, introducing molecular quantum self-similarity measures (MQS-SM) as a single working parameter in some cases. The use of MQS-SM as a molecular descriptor is first confirmed from the correlation with the aforementioned empirical parameters. The Hammett equation has been examined using MQS-SM for a series of substituted carboxylic acids. Then, for a series of aliphatic alcohols and acetic acid esters, log P values have been correlated with the self-similarity measure between density functions in water and octanol of a given molecule. And finally, some examples and applications of MQS-SM to determine QSAR are presented. In all studied cases MQS-SM appeared to be excellent molecular descriptors usable in general QSPR applications of chemical interest.

Molecular basis of quantitative structure-properties relationships (QSPR): A quantum similarity approach

NASA Astrophysics Data System (ADS)

Ponec, Robert; Amat, Lluís; Carbó-dorca, Ramon

1999-05-01

Since the dawn of quantitative structure-properties relationships (QSPR), empirical parameters related to structural, electronic and hydrophobic molecular properties have been used as molecular descriptors to determine such relationships. Among all these parameters, Hammett σ constants and the logarithm of the octanol- water partition coefficient, log P, have been massively employed in QSPR studies. In the present paper, a new molecular descriptor, based on quantum similarity measures (QSM), is proposed as a general substitute of these empirical parameters. This work continues previous analyses related to the use of QSM to QSPR, introducing molecular quantum self-similarity measures (MQS-SM) as a single working parameter in some cases. The use of MQS-SM as a molecular descriptor is first confirmed from the correlation with the aforementioned empirical parameters. The Hammett equation has been examined using MQS-SM for a series of substituted carboxylic acids. Then, for a series of aliphatic alcohols and acetic acid esters, log P values have been correlated with the self-similarity measure between density functions in water and octanol of a given molecule. And finally, some examples and applications of MQS-SM to determine QSAR are presented. In all studied cases MQS-SM appeared to be excellent molecular descriptors usable in general QSPR applications of chemical interest.

A polymer dataset for accelerated property prediction and design

DOE PAGES

Huan, Tran Doan; Mannodi-Kanakkithodi, Arun; Kim, Chiho; ...

2016-03-01

Emerging computation- and data-driven approaches are particularly useful for rationally designing materials with targeted properties. Generally, these approaches rely on identifying structure-property relationships by learning from a dataset of sufficiently large number of relevant materials. The learned information can then be used to predict the properties of materials not already in the dataset, thus accelerating the materials design. Herein, we develop a dataset of 1,073 polymers and related materials and make it available at http://khazana.uconn.edu/. This dataset is uniformly prepared using first-principles calculations with structures obtained either from other sources or by using structure search methods. Because the immediate targetmore » of this work is to assist the design of high dielectric constant polymers, it is initially designed to include the optimized structures, atomization energies, band gaps, and dielectric constants. As a result, it will be progressively expanded by accumulating new materials and including additional properties calculated for the optimized structures provided.« less

Structure/property relationships in polymer membranes for water purification and energy applications

NASA Astrophysics Data System (ADS)

Geise, Geoffrey

Providing sustainable supplies of purified water and energy is a critical global challenge for the future, and polymer membranes will play a key role in addressing these clear and pressing global needs for water and energy. Polymer membrane-based processes dominate the desalination market, and polymer membranes are crucial components in several rapidly developing power generation and storage applications that rely on membranes to control rates of water and/or ion transport. Much remains unknown about the influence of polymer structure on intrinsic water and ion transport properties, and these relationships must be developed to design next generation polymer membrane materials. For desalination applications, polymers with simultaneously high water permeability and low salt permeability are desirable in order to prepare selective membranes that can efficiently desalinate water, and a tradeoff relationship between water/salt selectivity and water permeability suggests that attempts to prepare such materials should rely on approaches that do more than simply vary polymer free volume. One strategy is to functionalize hydrocarbon polymers with fixed charge groups that can ionize upon exposure to water, and the presence of charged groups in the polymer influences transport properties. Additionally, in many emerging energy applications, charged polymers are exposed to ions that are very different from sodium and chloride. Specific ion effects have been observed in charged polymers, and these effects must be understood to prepare charged polymers that will enable emerging energy technologies. This presentation discusses research aimed at further understanding fundamental structure/property relationships that govern water and ion transport in charged polymer films considered for desalination and electric potential field-driven applications that can help address global needs for clean water and energy.

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga2O3 nanocrystalline films

NASA Astrophysics Data System (ADS)

Battu, Anil K.; Manandhar, S.; Shutthanandan, V.; Ramana, C. V.

2017-09-01

An approach is presented to design refractory-metal incorporated Ga2O3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga2O3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga2O3), higher Mo-content results in amorphization. Chemically-induced band gap variability (Eg ∼ 1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality and performance of Ga-Mo-O films is possible by tuning the Mo-content.

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga 2 O 3 nanocrystalline films

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

Battu, Anil K.; Manandhar, S.; Shutthanandan, V.

An approach is presented to design refractory-metal incorporated Ga2O3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga2O3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga2O3), higher Mo-content results in amorphization. Chemically-induced band gap variability (Eg~1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality and performance of Ga-Mo-O films is possible by tuning the Mo-content.

The brief family relationship scale: a brief measure of the relationship dimension in family functioning.

PubMed

Fok, Carlotta Ching Ting; Allen, James; Henry, David

2014-02-01

The Relationship dimension of the Family Environment Scale, which consists of the Cohesion, Expressiveness, and Conflict subscales, measures a person's perception of the quality of his or her family relationship functioning. This study investigates an adaptation of the Relationship dimension of the Family Environment Scale for Alaska Native youth. The authors tested the adapted measure, the Brief Family Relationship Scale, for psychometric properties and internal structure with 284 12- to 18-year-old predominately Yup'ik Eskimo Alaska Native adolescents from rural, remote communities. This non-Western cultural group is hypothesized to display higher levels of collectivism traditionally organized around an extended kinship family structure. Results demonstrate a subset of the adapted items function satisfactorily, a three-response alternative format provided meaningful information, and the subscale's underlying structure is best described through three distinct first-order factors, organized under one higher order factor. Convergent and discriminant validity of the Brief Family Relationship Scale was assessed through correlational analysis.

Dehalogenation of persistent halogenated organic compounds: A review of computational studies and quantitative structure-property relationships.

PubMed

Luo, Jin; Hu, Jiwei; Wei, Xionghui; Fu, Liya; Li, Lingyun

2015-07-01

Dehalogenation is one of the highly important degradation reactions for halogenated organic compounds (HOCs) in the environment, which is also being developed as a potential type of the remediation technologies. In combination with the experimental results, intensive efforts have recently been devoted to the development of efficient theoretical methodologies (e.g. multi-scale simulation) to investigate the mechanisms for dehalogenation of HOCs. This review summarizes the structural characteristics of neutral molecules, anionic species and excited states of HOCs as well as their adsorption behavior on the surface of graphene and the Fe cluster. It discusses the key physiochemical properties (e.g. frontier orbital energies and thermodynamic properties) calculated at various levels of theory (e.g. semiempirical, ab initio, density functional theory (DFT) and the periodic DFT) as well as their connections to the reactivity and reaction pathway for the dehalogenation. This paper also reviews the advances in the linear and nonlinear quantitative structure-property relationship models for the dehalogenation kinetics of HOCs and in the mathematical modeling of the dehalogenation processes. Furthermore, prospects of further expansion and exploration of the current research fields are described in this article. Published by Elsevier Ltd.

Additively Manufactured Open-Cell Porous Biomaterials Made from Six Different Space-Filling Unit Cells: The Mechanical and Morphological Properties

PubMed Central

Ahmadi, Seyed Mohammad; Amin Yavari, Saber; Wauthle, Ruebn; Pouran, Behdad; Schrooten, Jan; Weinans, Harrie; Zadpoor, Amir A.

2015-01-01

It is known that the mechanical properties of bone-mimicking porous biomaterials are a function of the morphological properties of the porous structure, including the configuration and size of the repeating unit cell from which they are made. However, the literature on this topic is limited, primarily because of the challenge in fabricating porous biomaterials with arbitrarily complex morphological designs. In the present work, we studied the relationship between relative density (RD) of porous Ti6Al4V EFI alloy and five compressive properties of the material, namely elastic gradient or modulus (Es20–70), first maximum stress, plateau stress, yield stress, and energy absorption. Porous structures with different RD and six different unit cell configurations (cubic (C), diamond (D), truncated cube (TC), truncated cuboctahedron (TCO), rhombic dodecahedron (RD), and rhombicuboctahedron (RCO)) were fabricated using selective laser melting. Each of the compressive properties increased with increase in RD, the relationship being of a power law type. Clear trends were seen in the influence of unit cell configuration and porosity on each of the compressive properties. For example, in terms of Es20–70, the structures may be divided into two groups: those that are stiff (comprising those made using C, TC, TCO, and RCO unit cell) and those that are compliant (comprising those made using D and RD unit cell). PMID:28788037

Additively Manufactured Open-Cell Porous Biomaterials Made from Six Different Space-Filling Unit Cells: The Mechanical and Morphological Properties.

PubMed

Ahmadi, Seyed Mohammad; Yavari, Saber Amin; Wauthle, Ruebn; Pouran, Behdad; Schrooten, Jan; Weinans, Harrie; Zadpoor, Amir A

2015-04-21

It is known that the mechanical properties of bone-mimicking porous biomaterials are a function of the morphological properties of the porous structure, including the configuration and size of the repeating unit cell from which they are made. However, the literature on this topic is limited, primarily because of the challenge in fabricating porous biomaterials with arbitrarily complex morphological designs. In the present work, we studied the relationship between relative density (RD) of porous Ti6Al4V EFI alloy and five compressive properties of the material, namely elastic gradient or modulus (E s20 -70 ), first maximum stress, plateau stress, yield stress, and energy absorption. Porous structures with different RD and six different unit cell configurations (cubic (C), diamond (D), truncated cube (TC), truncated cuboctahedron (TCO), rhombic dodecahedron (RD), and rhombicuboctahedron (RCO)) were fabricated using selective laser melting. Each of the compressive properties increased with increase in RD, the relationship being of a power law type. Clear trends were seen in the influence of unit cell configuration and porosity on each of the compressive properties. For example, in terms of E s20 -70 , the structures may be divided into two groups: those that are stiff (comprising those made using C, TC, TCO, and RCO unit cell) and those that are compliant (comprising those made using D and RD unit cell).

Relationship between microstructural and magnetic properties of PrCo-based films prepared by the vacuum evaporation method

NASA Astrophysics Data System (ADS)

Fersi, R.; Bouzidi, W.; Bezergheanu, A.; Cizmas, C. B.; Bessais, L.; Mliki, N.

2018-04-01

In this work, Ce2Ni7 type structural PrCo-based films were deposited on Si(1 0 0) substrate by ultra-high (UHV) vacuum evaporation process. The structural and magnetic properties of these films have been performed using X-ray diffraction (XRD), atomic force microscopy (AFM), vibrating sample magnetometer (VSM) and magnetic force microscopy (MFM) techniques. Two effects on structural and magnetic properties of PrCo films have been investigated: the effect of the annealing temperature (Ta) and the effect of the variation of the magnetic X-layer thickness. The as deposited PrCo films have a magnetic coercivity (Hc) of about 40-100 Oe. But after annealing at 600 °C, Hc has increased hight about 9.5 kOe for PrCo(X = 20 nm) and 10.2 kOe for PrCo(X = 50 nm) were observed. The magnetic properties were affected by the thickness due to the morphology, also the relationship between the intergrain exchange coupling (IEC), the size and quantity of the PrCo grains. The hight extrinsic properties of Hc = 10.2 kOe, maximum energy product (BH)max of 5.12 MGOe and remanence ratio Mr /Ms = 0.53 are reported for the PrCo(X = 50 nm) films. These properties are highly desirable for extremely high-density magnetic recording media applications.

Structure/Property Relationships of Siloxane-Based Liquid Crystalline Materials

DTIC Science & Technology

1992-05-01

482 (1989). (�) Gierlotka, S., Przedmojski, J., and Pura, B ., Liq. Cryst.,, 1989). 45 (101) Leadbetter, A.i., Gaughan, J.P., Kelly, B ., Gray. G.W...FUNDING NUMBERSSTRUCTURE/PROPERTY RELATIONSHIPS OF SILOXANE-BASED P: 612 LIQUID CRYSTALLINE MATERIALS PR: 624022 TA: 04 6 AUTHOR(S) W: 0 B unning, T.J...Klei, H.E.; Koberstein, J.T.; W. 0 Samulski, E.T.; Adams, 51.1.; Crane, R.L. 7i PERFORMINGT ORGANIZATION NAME(S) AND ADDRESS(ES) B PERFORMING

Structure property relationships in gallium oxide thin films grown by pulsed laser deposition [Structure property relationships in Ga 2O 3 thin films grown by pulsed laser deposition

DOE PAGES

Garten, Lauren M.; Zakutayev, Andriy; Perkins, John D.; ...

2016-11-21

Beta-gallium oxide (β-Ga 2O 3) is of increasing interest to the optoelectronic community for transparent conductor and power electronic applications. Considerable variability exists in the literature on the growth and doping of Ga 2O 3 films, especially as a function of growth approach, temperature, and oxygen partial pressure. Here pulsed laser deposition (PLD) was used to grow high-quality β-Ga 2O 3 films on (0001) sapphire and (–201) Ga 2O 3 single crystals and to explore the growth, stability, and dopability of these films as function of temperature and oxygen partial pressure. As a result, there is a strong temperature dependencemore » to the phase formation, morphology, and electronic properties of β-Ga 2O 3 from 350 to 550 °C.« less

Quantitative structure-property relationships for chemical functional use and weight fractions in consumer articles

EPA Science Inventory

Chemical functional use -- the functional role a chemical plays in processes or products -- may be a useful heuristic for predicting human exposure potential in that it comprises information about the compound's likely physical properties and the product formulations or articles ...

Structure-activity relationships in beta-defensin peptides.

PubMed

Taylor, Karen; Barran, Perdita E; Dorin, Julia R

2008-01-01

The beta-defensins comprise a large family of small cationic antimicrobial peptides widely distributed in plants, mammals and insects. These cysteine rich peptides display multifunctional properties with implications as potential therapeutic agents. Recent research has highlighted their role in both the innate and adaptive immune systems as well as being novel melanocortin ligands. Studies investigating structure and function provide an insight into the molecular basis of their immunological properties. (c) 2007 Wiley Periodicals, Inc.

RaptorX-Property: a web server for protein structure property prediction.

PubMed

Wang, Sheng; Li, Wei; Liu, Shiwang; Xu, Jinbo

2016-07-08

RaptorX Property (http://raptorx2.uchicago.edu/StructurePropertyPred/predict/) is a web server predicting structure property of a protein sequence without using any templates. It outperforms other servers, especially for proteins without close homologs in PDB or with very sparse sequence profile (i.e. carries little evolutionary information). This server employs a powerful in-house deep learning model DeepCNF (Deep Convolutional Neural Fields) to predict secondary structure (SS), solvent accessibility (ACC) and disorder regions (DISO). DeepCNF not only models complex sequence-structure relationship by a deep hierarchical architecture, but also interdependency between adjacent property labels. Our experimental results show that, tested on CASP10, CASP11 and the other benchmarks, this server can obtain ∼84% Q3 accuracy for 3-state SS, ∼72% Q8 accuracy for 8-state SS, ∼66% Q3 accuracy for 3-state solvent accessibility, and ∼0.89 area under the ROC curve (AUC) for disorder prediction. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

Comparative study of metallic silicide-germanide orthorhombic MnP systems.

PubMed

Connétable, Damien; Thomas, Olivier

2013-09-04

We present a comparative study of the structural, energetic, electronic and elastic properties of MX type MnP systems (where X=Si or Ge, and M=Pt, Pd or Ni) using first-principles calculations. The optimized ground state properties of these systems are in excellent agreement with the experimental values. A detailed comparative study of the elastic properties of polycrystalline structures is also presented. We analyze the relationship between the composition and the properties of the systems. Finally, we present the properties of NiSi1-xGex alloys. We show that these properties depend linearly on the Ge content of the alloy. This work has important consequences for semiconductor devices in which silicides, germanides and alloys thereof are used as contact materials.

Influence of Fe/Co ratio on structural and magnetic properties of (Fe100-xCox)84.5Nb5B8.5P2 alloy

NASA Astrophysics Data System (ADS)

Gehlot, K.; Kane, S. N.; Sinha, A. K.; Ghodke, N.; Varga, L. K.

2018-05-01

Structural and magnetic properties of a series of (Fe100-xCox)84.5Nb5B8.5P2 (x = 20, 40, 60) have been investigated respectively by using synchrotron x-ray diffraction and magnetic measurements. Results show that Fe/Co ratio: i) affects stability of the alloy against crystallization, ii) shows evidence for ordering, which has considerable effect on magnetic properties, iii) influences the grain diameter and volume fraction of the formed nano-grains range between 4.8 - 9.5 nm and 1.5 - 9 %, affects magnetic properties considerably. An empirical relation is obtained, which shows linear relationship between interatomic distances for 1st, 2nd co-ordination shell, suggests strong correlation between structural, magnetic properties.

CALCULATING PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS FOR ENVIRONMENTAL MODELING FROM MOLECULAR STRUCTURE

EPA Science Inventory

Mathematical models for predicting the transport and fate of pollutants in the environment require reactivity parameter values-- that is value of the physical and chemical constants that govern reactivity. Although empirical structure activity relationships have been developed t...

Characterizing Interaction with Visual Mathematical Representations

ERIC Educational Resources Information Center

Sedig, Kamran; Sumner, Mark

2006-01-01

This paper presents a characterization of computer-based interactions by which learners can explore and investigate visual mathematical representations (VMRs). VMRs (e.g., geometric structures, graphs, and diagrams) refer to graphical representations that visually encode properties and relationships of mathematical structures and concepts.…

Communication of Geometrical Structure and Its Relationship to Student Mathematical Achievement.

ERIC Educational Resources Information Center

Norrie, Alexander L.

The purpose of this study was to examine whether the mathematical structures inherent in grade 7 geometry curriculum objectives can be used to improve the communication of the objectives to students. Teacher inservice based upon geometrical properties and structures was combined with student teaching materials to try to improve student achievement…

Teaching Structure-Property Relationships: Investigating Molecular Structure and Boiling Point

ERIC Educational Resources Information Center

Murphy, Peter M.

2007-01-01

A concise, well-organized table of the boiling points of 392 organic compounds has facilitated inquiry-based instruction in multiple scientific principles. Many individual or group learning activities can be derived from the tabulated data of molecular structure and boiling point based on the instructor's education objectives and the students'…

Structural Equation Modeling in Assessing Students' Understanding of the State Changes of Matter

ERIC Educational Resources Information Center

Stamovlasis, Dimitrios; Tsitsipis, Georgios; Papageorgiou, George

2012-01-01

In this study, structural equation modeling (SEM) is applied to an instrument assessing students' understanding of the particulate nature of matter, the collective properties and physical changes, such as melting, evaporation, boiling and condensation. The structural relationships among particular groups of items were investigated. In addition,…

Crystal chemistry of M{sup II}M′{sup IV}(PO{sub 4}){sub 2} double monophosphates

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

Bregiroux, Damien, E-mail: damien.bregiroux@upmc.fr; Popa, Karin; Wallez, Gilles

2015-10-15

M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds have been extensively studied for several decades for their potential applications in the field of several domains such as matrices for actinides conditioning, phosphors etc. In this paper, the relationships between composition and crystal structure of these compounds are established. A review of the various processes used for the synthesis of these compounds is also proposed, as well as their most reported properties. M{sup II}M′{sup IV}(PO{sub 4}){sub 2} structures stem from two different archetypes: the cheralite and the yavapaiite structures, with some exceptions that are also described in this article. The ratio of themore » cations radii appears to be the most relevant parameter. The high ratio between the ionic radii of the divalent and tetravalent cations in yavapaiite derivates results in the ordering of these cations into well-differentiated polyhedra whereas cheralite is the only non-ordered structure encountered for M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds. - Graphical abstract: In this paper, the relationships between composition and crystal structure of M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds are established. A review of the various processes used for the synthesis of these compounds is also proposed, as well as their most reported properties. - Highlights: • Crystal structure–composition relationships of MIIM′IV(PO4)2 compounds. • Review of the various processes used for the synthesis of these compounds. • Their most reported properties are described and discussed.« less

Structural elements and organization of the ancestral translational machinery

NASA Technical Reports Server (NTRS)

Rein, R.; Srinivasan, S.; Mcdonald, J.; Raghunathan, G.; Shibata, M.

1987-01-01

The molecular mechanisms of the primitive translational apparatus are discussed in the framework of present-day protein biosynthesis. The structural necessities of an early adaptor and the multipoint recognition properties of such an adaptor are investigated on the basis of structure/function relationships found in a contemporary system and a molecular model of the contemporary transpeptidation complex. A model of the tRNA(Tyr)-tyrosyl tRNA synthetase complex including the positioning of the disordered region is proposed; the model is used to illustrate the required recognition properties of the ancestor aminoacyl synthetase.

Synthesis, crystal structure and redox properties of dihydropyrazole-bridged ferrocene-based derivatives

NASA Astrophysics Data System (ADS)

Li, Heng-Dong; Ma, Zai-He; Yang, Kun; Xie, Li-Li; Yuan, Yao-Feng

2012-09-01

Dihydropyrazole-bridged ferrocene-based derivatives were prepared by corresponding chalcones with hydrazine hydrate, then acylation with 3-(ethoxycarbonyl)propionyl chloride directly in high yields and purity. All of these compounds were characterized by MS, IR, 1H NMR, 13C NMR and elemental analysis. The relationship between the structure and redox properties was investigated based on the results of single crystal X-ray structure determinations and cyclic voltammetry. The mechanism of the electron transfer for representative compound 4b was verified by density functional theory (DFT) calculations.

Machine learnt bond order potential to model metal-organic (Co-C) heterostructures.

PubMed

Narayanan, Badri; Chan, Henry; Kinaci, Alper; Sen, Fatih G; Gray, Stephen K; Chan, Maria K Y; Sankaranarayanan, Subramanian K R S

2017-11-30

A fundamental understanding of the inter-relationships between structure, morphology, atomic scale dynamics, chemistry, and physical properties of mixed metallic-covalent systems is essential to design novel functional materials for applications in flexible nano-electronics, energy storage and catalysis. To achieve such knowledge, it is imperative to develop robust and computationally efficient atomistic models that describe atomic interactions accurately within a single framework. Here, we present a unified Tersoff-Brenner type bond order potential (BOP) for a Co-C system, trained against lattice parameters, cohesive energies, equation of state, and elastic constants of different crystalline phases of cobalt as well as orthorhombic Co 2 C derived from density functional theory (DFT) calculations. The independent BOP parameters are determined using a combination of supervised machine learning (genetic algorithms) and local minimization via the simplex method. Our newly developed BOP accurately describes the structural, thermodynamic, mechanical, and surface properties of both the elemental components as well as the carbide phases, in excellent accordance with DFT calculations and experiments. Using our machine-learnt BOP potential, we performed large-scale molecular dynamics simulations to investigate the effect of metal/carbon concentration on the structure and mechanical properties of porous architectures obtained via self-assembly of cobalt nanoparticles and fullerene molecules. Such porous structures have implications in flexible electronics, where materials with high electrical conductivity and low elastic stiffness are desired. Using unsupervised machine learning (clustering), we identify the pore structure, pore-distribution, and metallic conduction pathways in self-assembled structures at different C/Co ratios. We find that as the C/Co ratio increases, the connectivity between the Co nanoparticles becomes limited, likely resulting in low electrical conductivity; on the other hand, such C-rich hybrid structures are highly flexible (i.e., low stiffness). The BOP model developed in this work is a valuable tool to investigate atomic scale processes, structure-property relationships, and temperature/pressure response of Co-C systems, as well as design organic-inorganic hybrid structures with a desired set of properties.

In silico quantitative structure-toxicity relationship study of aromatic nitro compounds.

PubMed

Pasha, Farhan Ahmad; Neaz, Mohammad Morshed; Cho, Seung Joo; Ansari, Mohiuddin; Mishra, Sunil Kumar; Tiwari, Sharvan

2009-05-01

Small molecules often have toxicities that are a function of molecular structural features. Minor variations in structural features can make large difference in such toxicity. Consequently, in silico techniques may be used to correlate such molecular toxicities with their structural features. Relative to nine different sets of aromatic nitro compounds having known observed toxicities against different targets, we developed ligand-based 2D quantitative structure-toxicity relationship models using 20 selected topological descriptors. The topological descriptors have several advantages such as conformational independency, facile and less time-consuming computation to yield good results. Multiple linear regression analysis was used to correlate variations of toxicity with molecular properties. The information index on molecular size, lopping centric index and Kier flexibility index were identified as fundamental descriptors for different kinds of toxicity, and further showed that molecular size, branching and molecular flexibility might be particularly important factors in quantitative structure-toxicity relationship analysis. This study revealed that topological descriptor-guided quantitative structure-toxicity relationship provided a very useful, cost and time-efficient, in silico tool for describing small-molecule toxicities.

Breaking the limits of structural and mechanical imaging of the heterogeneous structure of coal macerals

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

Collins, L.; Tselev, A.; Jesse, S.

The correlation between local mechanical (elasto-plastic) and structural (composition) properties of coal presents significant fundamental and practical interest for coal processing and the development of rheological models of coal to coke transformations and for advancing novel approaches. Here, we explore the relationship between the local structural, chemical composition and mechanical properties of coal using a combination of confocal micro-Raman imaging and band excitation atomic force acoustic microscopy (BE-AFAM) for a bituminous coal. This allows high resolution imaging (10s of nm) of mechanical properties of the heterogeneous (banded) architecture of coal and correlating them to the optical gap, average crystallite size,more » the bond-bending disorder of sp2 aromatic double bonds and the defect density. This methodology hence allows the structural and mechanical properties of coal components (lithotypes, microlithotypes, and macerals) to be understood, and related to local chemical structure, potentially allowing for knowledge-based modelling and optimization of coal utilization processes.« less

Discovering charge density functionals and structure-property relationships with PROPhet: A general framework for coupling machine learning and first-principles methods

DOE PAGES

Kolb, Brian; Lentz, Levi C.; Kolpak, Alexie M.

2017-04-26

Modern ab initio methods have rapidly increased our understanding of solid state materials properties, chemical reactions, and the quantum interactions between atoms. However, poor scaling often renders direct ab initio calculations intractable for large or complex systems. There are two obvious avenues through which to remedy this problem: (i) develop new, less expensive methods to calculate system properties, or (ii) make existing methods faster. This paper describes an open source framework designed to pursue both of these avenues. PROPhet (short for PROPerty Prophet) utilizes machine learning techniques to find complex, non-linear mappings between sets of material or system properties. Themore » result is a single code capable of learning analytical potentials, non-linear density functionals, and other structure-property or property-property relationships. These capabilities enable highly accurate mesoscopic simulations, facilitate computation of expensive properties, and enable the development of predictive models for systematic materials design and optimization. Here, this work explores the coupling of machine learning to ab initio methods through means both familiar (e.g., the creation of various potentials and energy functionals) and less familiar (e.g., the creation of density functionals for arbitrary properties), serving both to demonstrate PROPhet’s ability to create exciting post-processing analysis tools and to open the door to improving ab initio methods themselves with these powerful machine learning techniques.« less

Discovering charge density functionals and structure-property relationships with PROPhet: A general framework for coupling machine learning and first-principles methods

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

Kolb, Brian; Lentz, Levi C.; Kolpak, Alexie M.

Modern ab initio methods have rapidly increased our understanding of solid state materials properties, chemical reactions, and the quantum interactions between atoms. However, poor scaling often renders direct ab initio calculations intractable for large or complex systems. There are two obvious avenues through which to remedy this problem: (i) develop new, less expensive methods to calculate system properties, or (ii) make existing methods faster. This paper describes an open source framework designed to pursue both of these avenues. PROPhet (short for PROPerty Prophet) utilizes machine learning techniques to find complex, non-linear mappings between sets of material or system properties. Themore » result is a single code capable of learning analytical potentials, non-linear density functionals, and other structure-property or property-property relationships. These capabilities enable highly accurate mesoscopic simulations, facilitate computation of expensive properties, and enable the development of predictive models for systematic materials design and optimization. Here, this work explores the coupling of machine learning to ab initio methods through means both familiar (e.g., the creation of various potentials and energy functionals) and less familiar (e.g., the creation of density functionals for arbitrary properties), serving both to demonstrate PROPhet’s ability to create exciting post-processing analysis tools and to open the door to improving ab initio methods themselves with these powerful machine learning techniques.« less

Quantitative structure-permeability relationships at various pH values for acidic and basic drugs and drug-like compounds.

PubMed

Oja, M; Maran, U

2015-01-01

Absorption in gastrointestinal tract compartments varies and is largely influenced by pH. Therefore, considering pH in studies and analyses of membrane permeability provides an opportunity to gain a better understanding of the behaviour of compounds and to obtain good permeability estimates for prediction purposes. This study concentrates on relationships between the chemical structure and membrane permeability of acidic and basic drugs and drug-like compounds. The membrane permeability of 36 acidic and 61 basic compounds was measured using the parallel artificial membrane permeability assay (PAMPA) at pH 3, 5, 7.4 and 9. Descriptive and/or predictive single-parameter quantitative structure-permeability relationships were derived for all pH values. For acidic compounds, membrane permeability is mainly influenced by hydrogen bond donor properties, as revealed by models with r(2) > 0.8 for pH 3 and pH 5. For basic compounds, the best (r(2) > 0.7) structure-permeability relationships are obtained with the octanol-water distribution coefficient for pH 7.4 and pH 9, indicating the importance of partition properties. In addition to the validation set, the prediction quality of the developed models was tested with folic acid and astemizole, showing good matches between experimental and calculated membrane permeabilities at key pHs. Selected QSAR models are available at the QsarDB repository ( http://dx.doi.org/10.15152/QDB.166 ).

Mechanistic Insights into the Specificity of Human Cytosolic Sulfotransferase 2A1 (hSULT2A1) for Hydroxylated Polychlorinated Biphenyls Through the Use of Fluoro-tagged Probes

PubMed Central

Ekuase, E.J.; van ’t Erve, T.J.; Rahaman, A.; Robertson, L.W.; Duffel, M.W.; Luthe, G.

2015-01-01

Determining the relationships between the structures of substrates and inhibitors and their interactions with drug-metabolizing enzymes is of prime importance in predicting the toxic potential of new and legacy xenobiotics. Traditionally, quantitative structure activity relationship (QSAR) studies are performed with many distinct compounds. Based on the chemical properties of the tested compounds, complex relationships can be established so that models can be developed to predict toxicity of novel compounds. In this study, the use of fluorinated analogues as supplemental QSAR compounds was investigated. Substituting fluorine induces changes in electronic and steric properties of the substrate without substantially changing the chemical backbone of the substrate. In vitro assays were performed using purified human cytosolic sulfotransferase hSULT2A1 as a model enzyme. A mono-hydroxylated polychlorinated biphenyl (4-OH PCB 14) and its four possible mono-fluoro analogues were used as test compounds. Remarkable similarities were found between this approach and previously published QSAR studies for hSULT2A1. Both studies implicate the importance of dipole moment and dihedral angle as being important to PCB structure in respect to being substrates for hSULT2A1. We conclude that mono-fluorinated analogues of a target substrate can be a useful tool to study the structure activity relationships for enzyme specificity. PMID:26165989

The relationship between bond ionicity, lattice energy, coefficient of thermal expansion and microwave dielectric properties of Nd(Nb(1-x)Sb(x))O4 ceramics.

PubMed

Zhang, Ping; Zhao, Yonggui; Wang, Xiuyu

2015-06-28

The crystalline structure refinement, chemical bond ionicity, lattice energy and coefficient of thermal expansion were carried out for Nd(Nb(1-x)Sb(x))O4 ceramics with a monoclinic fergusonite structure to investigate the correlations between the crystalline structure, phase stability, bond ionicity, lattice energy, coefficient of thermal expansion, and microwave dielectric properties. The bond ionicity, lattice energy, and coefficient of thermal expansion of Nd(Nb(1-x)Sb(x))O4 ceramics were calculated using a semiempirical method based on the complex bond theory. The phase structure stability varied with the lattice energy which was resulted by the substitution constant of Sb(5+). With the increasing of the Sb(5+) contents, the decrease of Nb/Sb-O bond ionicity was observed, which could be contributed to the electric polarization. The ε(r) had a close relationship with the Nb/Sb-O bond ionicity. The increase of the Q×f and |τ(f)| values could be attributed to the lattice energy and the coefficient of thermal expansion. The microwave dielectric properties of Nd(Nb(1-x)Sb(x))O4 ceramics with the monoclinic fergusonite structure were strongly dependent on the chemical bond ionicity, lattice energy and coefficient of thermal expansion.

Transport properties of electrons in fractal magnetic-barrier structures

NASA Astrophysics Data System (ADS)

Sun, Lifeng; Fang, Chao; Guo, Yong

2010-09-01

Quantum transport properties in fractal magnetically modulated structures are studied by the transfer-matrix method. It is found that the transmission spectra depend sensitively not only on the incident energy and the direction of the wave vector but also on the stage of the fractal structures. Resonance splitting, enhancement, and position shift of the resonance peaks under different magnetic modulation are observed at four different fractal stages, and the relationship between the conductance in the fractal structure and magnetic modulation is also revealed. The results indicate the spectra of the transmission can be considered as fingerprints for the fractal structures, which show the subtle correspondence between magnetic structures and transport behaviors.

Silicon-containing polymer-derived ceramic nanocomposites (PDC-NCs): preparative approaches and properties.

PubMed

Ionescu, Emanuel; Kleebe, Hans-Joachim; Riedel, Ralf

2012-08-07

Composites consist by definition of at least two materials (Gibbsian phases) with rather different properties. They exhibit a heterogeneous microstructure and possess improved properties with respect to their components. Furthermore, the design of their microstructure allows for tailoring their overall properties. In the last decades, intense work was performed on the synthesis of nanocomposites, which have the feature that at least one of their components is nanoscaled. However, the microstructure-property relationship of nanocomposite materials is still a challenging topic. This tutorial review paper deals with a special class of nanocomposites, i.e. polymer-derived ceramic nanocomposites (PDC-NCs), which have been shown to be promising materials for various structural and functional applications. Within this context, different preparative approaches for PDC-NCs as well as some of their properties will be presented and discussed. Furthermore, recent results concerning the relationship between the nano/microstructure of PDC-NCs and their properties will be highlighted.

Fluid Absorption and Release of Nonwovens and their Response to Compression

NASA Astrophysics Data System (ADS)

Bateny, Fatemeh

Fluid handling is a key property in one of the major nonwoven applications in absorbent product such as wipes, hygiene products, and baby diapers. These products are subjected to various levels of compression in real-use. The aim of this study was to investigate the liquid absorption and release properties of nonwovens to establish the absorption structure-property relationship at various compression levels. A comprehensive methodology, considering various flow directions, was employed to establish the relationship by decoupling the effect of structural parameters and material properties in two phases of this study respectively. In the first phase, the mechanism of absorption by pore structure was investigated through considering various fiber cross-sectional size and shape, as well as heterogeneous layered structures having a pore size reduction and expansion. In the second phase, the mechanism of absorption by fiber and consequent swelling was evaluated in view of fluid diffusion into the rayon fibers in samples having different percentages of PET fiber (non-absorbent) and rayon fiber (absorbent). The analysis of absorption and release properties through the entire dissertation was based on the pore characteristics of the nonwovens by measuring the average pore sizes, pore size distribution, and solidity. The investigation revealed that the absorption and release properties of nonwovens are governed by their pore characteristics. In homogeneous non-layered nonwoven fabrics, maximum absorption is mainly governed by the available pore volume. Absorbency rate is determined according to pore size and the maximum rate of absorption is achieved at a specific range of pore sizes. This indicates that an in-depth understanding of the absorption and release properties brings about valuable information for the absorbent product engineering.

Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

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

Ligare, Marshall R.; Baker, Erin S.; Laskin, Julia

Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

Personality Inventory for DSM-5-Short Form (PID-5-SF): Reliability, Factorial Structure, and Relationship With Functional Impairment in Dual Diagnosis Patients.

PubMed

Díaz-Batanero, Carmen; Ramírez-López, Juan; Domínguez-Salas, Sara; Fernández-Calderón, Fermín; Lozano, Óscar M

2017-11-01

Section III of the Diagnostic and Statistical Manual of Mental Disorders-Fifth edition ( DSM-5) has generated a personality paradigm consisting of 25 personality facets identified in five domains. The developed assessment instrument Personality Inventory for DSM-5 (PID-5) has showed good psychometric properties, but the potential for certain improvements still remain. In this article, a sample of 282 dual diagnosis patients is used to provide evidence of the psychometric properties of the PID-5-Short Form. The mean value of Cronbach's alpha coefficients reached .73 on the facets and .84 for domains and test-retest values ranged between .57 to .83 for facets and .70 to .87 for the domains. Confirmatory factor analyses conducted showed good fit on both models tested: the five correlated factor structure and hierarchical structure of personality traits. The WHODAS 2.0 domains of understanding and communicating, and participating in society, appear to show the strongest relationship with personality facets. In general, the PID-5-Short Form shows adequate psychometric properties for use in dual diagnosis patients.

Analytical relationships for prediction of the mechanical properties of additively manufactured porous biomaterials

PubMed Central

Hedayati, Reza

2016-01-01

Abstract Recent developments in additive manufacturing techniques have motivated an increasing number of researchers to study regular porous biomaterials that are based on repeating unit cells. The physical and mechanical properties of such porous biomaterials have therefore received increasing attention during recent years. One of the areas that have revived is analytical study of the mechanical behavior of regular porous biomaterials with the aim of deriving analytical relationships that could predict the relative density and mechanical properties of porous biomaterials, given the design and dimensions of their repeating unit cells. In this article, we review the analytical relationships that have been presented in the literature for predicting the relative density, elastic modulus, Poisson's ratio, yield stress, and buckling limit of regular porous structures based on various types of unit cells. The reviewed analytical relationships are used to compare the mechanical properties of porous biomaterials based on different types of unit cells. The major areas where the analytical relationships have improved during the recent years are discussed and suggestions are made for future research directions. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 3164–3174, 2016. PMID:27502358

Structure-property study of keto-ether polyimides

NASA Technical Reports Server (NTRS)

Dezern, James F.; Croall, Catharine I.

1991-01-01

As part of an on-going effort to develop an understanding of how changes in the chemical structure affect polymer properties, an empirical study was performed on polyimides containing only ether and/or carbonyl connecting groups in the polymer backbone. During the past two decades the structure-property relationships in linear aromatic polyimides have been extensively investigated. More recently, work has been performed to study the effect of isomeric attachment of keto-ether polyimides on properties such as glass transition temperature and solubility. However, little work has been reported on the relation of polyimide structure to mechanical properties. The purpose of this study was to determine the effect of structural changes in the backbone of keto-ether polyimides on their mechanical properties, specifically, unoriented thin film tensile properties. This study was conducted in two stages. The purpose of the initial stage was to examine the physical and mechanical properties of a representative group (four) of polyimide systems to determine the optimum solvent and cure cycle requirements. These optimum conditions were then utilized in the second stage to prepare films of keto-ether polyimides which were evaluated for mechanical and physical properties. All of the polyimides were prepared using isomers of oxydianiline (ODA) and diaminobenzophenone (DABP) in combination with 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4'-oxydiphthalic anhydride (ODPA).

Structure - Property Relationships of Furanyl Thermosetting Polymer Materials Derived from Biobased Feedstocks

NASA Astrophysics Data System (ADS)

Hu, Fengshuo

Biobased thermosetting polymers have drawn significant attention due to their potential positive economic and ecological impacts. New materials should mimic the rigid, phenylic structures of incumbent petroleum-based thermosetting monomers and possess superior thermal and mechanical properties. Furans and triglycerides derived from cellulose, hemicellulose and plant oils are promising candidates for preparing such thermosetting materials. In this work, furanyl diepoxies, diamines and di-vinyl esters were synthesized using biobased furanyl materials, and their thermal and mechanical properties were investigated using multiple techniques. The structure versus property relationship showed that, compared with the prepared phenylic analogues, biobased furanyl thermosetting materials possess improved glassy storage modulus (E '), advanced fracture toughness, superior high-temperature char yield and comparable glass transition temperature (Tg) properties. An additive molar function analysis of the furanyl building block to the physical properties, such as Tg and density, of thermosetting polymers was performed. The molar glass transition function value (Yg) and molar volume increment value (Va,i) of the furanyl building block were obtained. Biobased epoxidized soybean oil (ESO) was modified using different fatty acids at varying molar ratios, and these prepared materials dramatically improved the critical strain energy release rate (G1c) and the critical stress intensity factor (K1c) values of commercial phenylic epoxy resins, without impairing their Tg and E ' properties. Overall, it was demonstrated that biobased furans and triglycerides possess promising potential for use in preparing high-performance thermosetting materials, and the established methodologies in this work can be utilized to direct the preparation of thermosetting materials with thermal and mechanical properties desired for practical applications.

Quinone Photoreactivity: An Undergraduate Experiment in Photochemistry

ERIC Educational Resources Information Center

Vaughan, Pamela P.; Cochran, Michael; Haubrich, Nicole

2010-01-01

An experiment exploring the photochemical properties of quinones was developed. Their unique photochemistry and highly reactive nature make them an ideal class of compounds for examining structure-activity relationships. For several substituted quinones, photochemical reactivity was related to structure and ultimately to the Gibbs energy for…

Processing-Structure-Property Relationships for Lignin-Based Carbonaceous Materials Used in Energy-Storage Applications

DOE PAGES

García-Negrón, Valerie; Phillip, Nathan D.; Li, Jianlin; ...

2016-11-18

Lignin, an abundant organic polymer and a byproduct of pulp and biofuel production, has potential applications owing to its high carbon content and aromatic structure. Processing structure relationships are difficult to predict because of the heterogeneity of lignin. Here, this work discusses the roles of unit operations in the carbonization process of softwood lignin, and their resulting impacts on the material structure and electrochemical properties in application as the anode in lithium-ion cells. The processing variables include the lignin source, temperature, and duration of thermal stabilization, pyrolysis, and reduction. Materials are characterized at the atomic and microscales. High-temperature carbonization, atmore » 2000 °C, produces larger graphitic domains than at 1050 °C, but results in a reduced capacity. Coulombic efficiencies over 98 % are achieved for extended galvanostatic cycling. Consequently, a properly designed carbonization process for lignin is well suited for the generation of low-cost, high-efficiency electrodes.« less

Structural characterization/correlation of calorimetric properties of coal fluids: Final report, September 1, 1985--August 31, 1988

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

Starling, K.E.; Mallinson, R.G.; Li, M.H.

The objective of this research is to examine the relationship between the calorimetric properties of coal fluids and their molecular functional group composition. Coal fluid samples which have had their calorimetric properties measured are characterized using proton NMR, IR, and elemental analysis. These characterizations are then used in a chemical structural model to determine the composition of the coal fluid in terms of the important molecular functional groups. These functional groups are particularly important in determining the intramolecular based properties of a fluid, such as ideal gas heat capacities. Correlational frameworks for ideal gas heat capacities are then examined withinmore » an existing equation of state methodology to determine an optimal correlation. The optimal correlation for obtaining the characterization/chemical structure information and the sensitivity of the correlation to the characterization and structural model is examined. 8 refs.« less

Structural characterization/correlation of calorimetric properties of coal fluids: Second annual report, September 1, 1986-August 31, 1987

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

Starling, K.E.; Mallinson, R.G.; Li, M.H.

The objective of this research is to examine the relationship between the calorimetric properties of coal fluids and their molecular functional group composition. Coal fluid samples which have had their calorimetric properties measured are characterized using proton NMR, ir, and elemental analysis. These characterizations are then used in a chemical structural model to determine the composition of the coal fluid in terms of the important molecular functional groups. These functional groups are particularly important in determining the intramolecular based properties of a fluid, such as ideal gas heat capacities. Correlational frameworks for ideal gas heat capacities are then examined withinmore » an existing equation of state methodology to determine an optimal correlation. The optimal correlation for obtaining the characterization/chemical structure information and the sensitivity of the correlation to the characterization and structural model is examined.« less

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga 2O 3 nanocrystalline films

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

Battu, Anil K.; Manandhar, S.; Shutthanandan, V.

Here, an approach is presented to design refractory-metal incorporated Ga 2O 3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga 2O 3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga 2O 3), higher Mo-content results in amorphization. Chemically-induced band gap variability (E g ~ 1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality andmore » performance of Ga-Mo-O films is possible by tuning the Mo-content.« less

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga 2O 3 nanocrystalline films

DOE PAGES

Battu, Anil K.; Manandhar, S.; Shutthanandan, V.; ...

2017-07-01

Here, an approach is presented to design refractory-metal incorporated Ga 2O 3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga 2O 3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga 2O 3), higher Mo-content results in amorphization. Chemically-induced band gap variability (E g ~ 1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality andmore » performance of Ga-Mo-O films is possible by tuning the Mo-content.« less

Structural characterization/correlation of calorimetric properties of coal fluids. First annual report, September 1, 1985-August 31, 1986

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

Starling, K.E.; Mallinson, R.G.; Li, M.H.

The objective of this research is to examine the relationship between the calorimetric properties of coal liquids and their molecular functional group composition. Coal liquid samples which have had their calorimetric properties measured are characterized using proton NMR, ir and elemental analysis. These characterizations are then used in a chemical structural model to determine the composition of the coal liquid in terms of the important molecular functional groups. These functional groups are particularly important in determining the intramolecular based properties of a fluid, such as ideal gas heat capacities. Correlational frameworks for heat capacities will then be examined within anmore » existing equation of state methodology to determine an optimal correlation. Also, the optimal recipe for obtaining the characterization/chemical structure information and the sensitivity of the correlation to the characterization and structural model will be examined and determined. 7 refs.« less

Atomic force microscopy for two-dimensional materials: A tutorial review

NASA Astrophysics Data System (ADS)

Zhang, Hang; Huang, Junxiang; Wang, Yongwei; Liu, Rui; Huai, Xiulan; Jiang, Jingjing; Anfuso, Chantelle

2018-01-01

Low dimensional materials exhibit distinct properties compared to their bulk counterparts. A plethora of examples have been demonstrated in two-dimensional (2-D) materials, including graphene and transition metal dichalcogenides (TMDCs). These novel and intriguing properties at the nano-, molecular- and even monatomic scales have triggered tremendous interest and research, from fundamental studies to practical applications and even device fabrication. The unique behaviors of 2-D materials result from the special structure-property relationships that exist between surface topographical variations and mechanical responses, electronic structures, optical characteristics, and electrochemical properties. These relationships are generally convoluted and sensitive to ambient and external perturbations. Characterizing these systems thus requires techniques capable of providing multidimensional information under controlled environments, such as atomic force microscopy (AFM). Today, AFM plays a key role in exploring the basic principles underlying the functionality of 2-D materials. In this tutorial review, we provide a brief introduction to some of the unique properties of 2-D materials, followed by a summary of the basic principles of AFM and the various AFM modes most appropriate for studying these systems. Following that, we will focus on five important properties of 2-D materials and their characterization in more detail, including recent literature examples. These properties include nanomechanics, nanoelectromechanics, nanoelectrics, nanospectroscopy, and nanoelectrochemistry.

Structure-property relationship of supramolecular ferroelectric [H-66dmbp][Hca] accompanied by high polarization, competing structural phases, and polymorphs.

PubMed

Kobayashi, Kensuke; Horiuchi, Sachio; Ishibashi, Shoji; Kagawa, Fumitaka; Murakami, Youichi; Kumai, Reiji

2014-12-22

Three polymorphic forms of 6,6'-dimethyl-2,2'-bipyridinium chloranilate crystals were characterized to understand the origin of polarization properties and the thermal stability of ferroelectricity. According to the temperature-dependent permittivity, differential scanning calorimetry, and X-ray diffraction, structural phase transitions were found in all polymorphs. Notably, the ferroelectric α-form crystal, which has the longest hydrogen bond (2.95 Å) among the organic acid/base-type supramolecular ferroelectrics, transformed from a polar structure (space group, P21) into an anti-polar structure (space group, P21/c) at 378 K. The non-ferroelectric β- and γ-form crystals also exhibited structural rearrangements around hydrogen bonds. The hydrogen-bonded geometry and ferroelectric properties were compared with other supramolecular ferroelectrics. A positive relationship between the phase-transition temperature (TC ) and hydrogen-bond length () was observed, and was attributed to the potential barrier height for proton off-centering or order/disorder phenomena. The optimized spontaneous polarization (Ps ) agreed well with the results of the first-principles calculations, and could be amplified by separating the two equilibrium positions of protons with increasing . These data consistently demonstrated that stretching is a promising way to enhance the polarization performance and thermal stability of hydrogen-bonded organic ferroelectrics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomistic investigation of the structural, transport, and mechanical properties of Cu-Zr metallic glasses

NASA Astrophysics Data System (ADS)

Kumar, Mohit

The unique set of mechanical and magnetic properties possessed by metallic glasses has attracted a lot of recent scientific and technological interest. The development of new metallic glass alloys with improved manufacturability, enhanced properties and higher ductility relies on the fundamental understanding of the interconnections between their atomic structure, glass forming ability (GFA), transport properties, and elastic and plastic deformation mechanisms. This thesis is focused on finding these atomic structure-property relationships in Cu-Zr BMGs using molecular dynamics simulations. In the first study described herein, molecular dynamics simulations of the rapid solidification process over the Cu-Zr compositional domain were conducted to explore inter-dependencies of atomic transport and fragility, elasticity and structural ordering, and GFA. The second study investigated the atomic origins of serration events, which is the characteristic plastic deformation behaviour in BMGs. The combined results of this work suggest that GFA and ductility of metallic glasses could be compositionally tuned.

Low-loss Ca{sub 5-x}Sr{sub x}A{sub 2}TiO{sub 12} [A=Nb,Ta] ceramics: Microwave dielectric properties and vibrational spectroscopic analysis

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

Bijumon, Pazhoor Varghese; Sebastian, Mailadil Thomas; Dias, Anderson

2005-05-15

Complex perovskite-type Ca{sub 5-x}Sr{sub x}A{sub 2}TiO{sub 12} [A=Nb,Ta] (0{<=}x{<=}5) ceramics were prepared by conventional solid-state ceramic route. The crystal structure, microwave dielectric properties, and vibrational spectroscopic characteristics of these materials are reported. The structure and microstructure were investigated by x-ray diffraction and scanning electron microscopy techniques. The microwave dielectric properties were measured in the 3-5-GHz frequency range by the resonance method. Structural evolutions from orthorhombic to an averaged pseudocubic phase, with associated changes in dielectric properties, were observed as a function of composition. The structure-property relationships in these ceramics were established using Raman and Fourier transform infrared spectroscopic techniques. Ramanmore » analysis showed characteristic bands of ordered perovskite materials, with variation in both intensity and frequency as a function of composition.« less

QSAR modeling of cumulative environmental end-points for the prioritization of hazardous chemicals.

PubMed

Gramatica, Paola; Papa, Ester; Sangion, Alessandro

2018-01-24

The hazard of chemicals in the environment is inherently related to the molecular structure and derives simultaneously from various chemical properties/activities/reactivities. Models based on Quantitative Structure Activity Relationships (QSARs) are useful to screen, rank and prioritize chemicals that may have an adverse impact on humans and the environment. This paper reviews a selection of QSAR models (based on theoretical molecular descriptors) developed for cumulative multivariate endpoints, which were derived by mathematical combination of multiple effects and properties. The cumulative end-points provide an integrated holistic point of view to address environmentally relevant properties of chemicals.

Assessment of Romantic Perfectionism: Psychometric Properties of the Romantic Relationship Perfectionism Scale

ERIC Educational Resources Information Center

Matte, Melody; Lafontaine, Marie-France

2012-01-01

The objective of the present study was to provide validity evidence for the scores from the Romantic Relationship Perfectionism Scale. Results indicate a two-factor structure, adequate reliability, and overall good convergent, concurrent, discriminant, and incremental validity evidence. The strengths and limitations of this measure are discussed.…

Heterocyclic cationic gemini surfactants: a comparative overview of their synthesis, self-assembling, physicochemical, and biological properties.

PubMed

Sharma, Vishnu Dutt; Ilies, Marc A

2014-01-01

Gemini surfactants (GS) are presently receiving substantial attention due to their special self-assembling properties and unique interfacial activity. This comprehensive review is focused on positively charged heterocyclic GS, presenting their major synthetic access routes and examining the impact of structural elements on physicochemical and aggregation properties of this class of amphiphiles. Interaction of geminis surfactants with cells and their biological properties as novel transfection agents are emphasized through a detailed structure-activity relationship analysis. Throughout the review we have also presented the properties of selected ammonium GS, simple surfactants and lipid congeners, in order to emphasize the advantages conferred by using heterocyclic polar heads in GS design. © 2012 Wiley Periodicals, Inc.

Achilles tendons from decorin- and biglycan-null mouse models have inferior mechanical and structural properties predicted by an image-based empirical damage model

PubMed Central

Gordon, J.A.; Freedman, B.R.; Zuskov, A.; Iozzo, R.V.; Birk, D.E.; Soslowsky, L.J.

2015-01-01

Achilles tendons are a common source of pain and injury, and their pathology may originate from aberrant structure function relationships. Small leucine rich proteoglycans (SLRPs) influence mechanical and structural properties in a tendon-specific manner. However, their roles in the Achilles tendon have not been defined. The objective of this study was to evaluate the mechanical and structural differences observed in mouse Achilles tendons lacking class I SLRPs; either decorin or biglycan. In addition, empirical modeling techniques based on mechanical and image-based measures were employed. Achilles tendons from decorin-null (Dcn−/−) and biglycan-null (Bgn−/−) C57BL/6 female mice (N=102) were used. Each tendon underwent a dynamic mechanical testing protocol including simultaneous polarized light image capture to evaluate both structural and mechanical properties of each Achilles tendon. An empirical damage model was adapted for application to genetic variation and for use with image based structural properties to predict tendon dynamic mechanical properties. We found that Achilles tendons lacking decorin and biglycan had inferior mechanical and structural properties that were age dependent; and that simple empirical models, based on previously described damage models, were predictive of Achilles tendon dynamic modulus in both decorin- and biglycan-null mice. PMID:25888014

Achilles tendons from decorin- and biglycan-null mouse models have inferior mechanical and structural properties predicted by an image-based empirical damage model.

PubMed

Gordon, J A; Freedman, B R; Zuskov, A; Iozzo, R V; Birk, D E; Soslowsky, L J

2015-07-16

Achilles tendons are a common source of pain and injury, and their pathology may originate from aberrant structure function relationships. Small leucine rich proteoglycans (SLRPs) influence mechanical and structural properties in a tendon-specific manner. However, their roles in the Achilles tendon have not been defined. The objective of this study was to evaluate the mechanical and structural differences observed in mouse Achilles tendons lacking class I SLRPs; either decorin or biglycan. In addition, empirical modeling techniques based on mechanical and image-based measures were employed. Achilles tendons from decorin-null (Dcn(-/-)) and biglycan-null (Bgn(-/-)) C57BL/6 female mice (N=102) were used. Each tendon underwent a dynamic mechanical testing protocol including simultaneous polarized light image capture to evaluate both structural and mechanical properties of each Achilles tendon. An empirical damage model was adapted for application to genetic variation and for use with image based structural properties to predict tendon dynamic mechanical properties. We found that Achilles tendons lacking decorin and biglycan had inferior mechanical and structural properties that were age dependent; and that simple empirical models, based on previously described damage models, were predictive of Achilles tendon dynamic modulus in both decorin- and biglycan-null mice. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

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

Lin, Qisheng; Miller, Gordon J.

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e –/atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Furthermore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

DOE PAGES

Lin, Qisheng; Miller, Gordon J.

2017-12-18

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e –/atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Furthermore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate.

Adsorption properties for urokinase on local diatomite surface

NASA Astrophysics Data System (ADS)

Yang, Yuxiang; Zhang, Jianbo; Yang, Weimin; Wu, Jieda; Chen, Rongsan

2003-02-01

In this paper, adsorption isotherm of urokinase on two typical local diatomites were determined at 25 °C and their surface electrical potentials (ζ), isoelectrical point values (IEP) were determined. The properties of diatomites, the relationship among diatomite structure, pore-size distribution, surface ζ and adsorption isotherm were discussed. The adsorption equation of urokinase was calculated from the adsorption isotherm. The adsorption mode of urokinase on diatomite surface was judged by the configuration function α. The relationship between the amount of adsorbed urokinase and IEP value was also discussed.

Synthesis and characterization of antifouling poly(N-acryloylaminoethoxyethanol) with ultralow protein adsorption and cell attachment.

PubMed

Chen, Hong; Zhang, Mingzhen; Yang, Jintao; Zhao, Chao; Hu, Rundong; Chen, Qiang; Chang, Yung; Zheng, Jie

2014-09-02

Rational design of effective antifouling polymers is challenging but important for many fundamental and applied applications. Herein we synthesize and characterize an N-acryloylaminoethoxyethanol (AAEE) monomer, which integrates three hydrophilic groups of hydroxyl, amide, and ethylene glycol in the same material. AAEE monomers were further grafted and polymerized on gold substrates to form polyAAEE brushes with well-controlled thickness via surface-initiated atomic transfer radical polymerization (SI-ATRP), with particular attention to a better understanding of the molecular structure-antifouling property relationship of hydroxyl-acrylic-based polymers. The surface hydrophilicity and antifouling properties of polyAAEE brushes as a function of film thickness are studied by combined experimental and computational methods including surface plasmon resonance (SPR) sensors, atomic force microscopy (AFM), cell adhesion assay, and molecular dynamics (MD) simulations. With the optimal polymer film thicknesses (∼10-40 nm), polyAAEE-grafted surfaces can effectively resist protein adsorption from single-protein solutions and undiluted human blood plasma and serum to a nonfouling level (i.e., <0.3 ng/cm(2)). The polyAAEE brushes also highly resist mammalian cell attachment up to 3 days. MD simulations confirm that the integration of three hydrophilic groups induce a stronger and closer hydration layer around polyAAEE, revealing a positive relationship between surface hydration and antifouling properties. The molecular structure-antifouling properties relationship of a series of hydroxyl-acrylic-based polymers is also discussed. This work hopefully provides a promising structural motif for the design of new effective antifouling materials beyond traditional ethylene glycol-based antifouling materials.

THREE-DIMENSIONAL QUANTITATIVE STRUCTURE-PROPERTY RELATIONSHIP (3D-QSPR) MODELS FOR PREDICTION OF THERMODYNAMIC PROPERTIES OF POLYCHLORINATED BIPHENYLS (PCBS): ENTHALPY OF VAPORIZATION. (R826133)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Relationship between surface property and catalytic application of amorphous NiP/Hβ catalyst for n-hexane isomerization

NASA Astrophysics Data System (ADS)

Chen, Jinshe; Duan, Zunbin; Song, Zhaoyang; Zhu, Lijun; Zhou, Yulu; Xiang, Yuzhi; Xia, Daohong

2017-12-01

The amorphous NiP nanoparticles were synthesized and a novel amorphous NiP/Hβ catalyst was prepared successfully further. Due to the superior surface property of amorphous NiP/Hβ catalyst, it exhibited good catalytic application for n-hexane isomerization. The catalytic activity of amorphous NiP/Hβ catalyst was close to that of the prepared Pt/Hβ sample, and better than that of commercial catalyst and crystalline Ni2P/Hβ catalyst. What's more, the amorphous NiP/Hβ catalyst shows high resistance to different sulfur compounds and water on account of its unique surface property. The effect of loading amounts on surface property and catalytic performance was investigated, and the structure-function relationship among them was studied ulteriorly. The results demonstrate that loading amounts have effect on textural property and surface acid property, which further affect the catalytic performance. The 10 wt.% NiP/Hβ sample has appropriate pore structure and acid property with uniformly dispersed NiP nanoparticles on surface, which is helpful for providing suitable synergistic effect. The effects of reaction conditions on surface reactions and the mechanism for n-hexane isomerization were investigated further. Based on these results, the amorphous NiP/Hβ catalyst with superior surface property probably pavesa way to overcome the drawbacks of traditional noble metal catalyst, which shows good catalytic application prospects.

The past, present, and future of hockey-stick-shaped liquid crystals

NASA Astrophysics Data System (ADS)

Choi, E.-Joon

2014-02-01

Recently, the liquid crystalline materials with a bent-core mesogen have attracted attentions because their interesting properties such as polarity and biaxiality of the mesophase. There are several types of bent-core mesogenic structures have been reported, for instance, banana-shaped, V-shaped molecules, boomerang-shaped, hockey stick-shaped, and Yshaped molecules. In this study, the liquid crystals and the reactive mesogens with the hockey-stick shaped mesogens will be described concerning with the structure-property relationship.

Structure-property relationship of 3-(4-substituted benzyl)-1,3-diazaspiro[4.4]nonane-2,4-diones as new potentional anticonvulsant agents. An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Lazić, Anita M.; Božić, Bojan Đ.; Vitnik, Vesna D.; Vitnik, Željko J.; Rogan, Jelena R.; Radovanović, Lidija D.; Valentić, Nataša V.; Ušćumlić, Gordana S.

2017-01-01

The structure-property relationship of newly synthesized 3-(4-substituted benzyl)-1,3-diazaspiro [4.4]nonane-2,4-diones was studied by experimental and calculated methods. The prepared compounds were characterized by UV-Vis, FT-IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. The crystal structure was elucidated by single-crystal X-ray diffraction. The 3-benzyl-1,3-diazaspiro[4.4]nonane-2,4-dione crystallizes in triclinic P-1 space group, with two crystallographically independent molecules in the asymmetric unit. Cyclopentane ring adopts an envelope conformation. A three-dimensional crystal packing is governed by hydrogen N-H⋯O bonds, numerous C-H⋯O/N and C-H … π interactions between neighboring molecules. Density functional theory (DFT) calculations with B3LYP and M06-2X methods using 6-311++G(d,p) basis set were performed to provide structural and spectroscopic information. Comparisons between experimental and calculated UV-Vis spectral properties suggest that the monomeric form of the investigated spirohydantoins is dominant in all used solvents. The effects of substituents on the absorption spectra of spirohydantoins are interpreted by correlation of absorption frequencies with Hammett equation. The lipophilicities of the investigated molecules were estimated by calculation of their log P values. Some of the spirohydantoins synthesized in this work, exhibit the lipophilicities comparable to the standard medicine anticonvulsant drug Phenytoin. The results obtained in this investigation afford guidelines for the preparation of new derivatives of spirohydantoin as potential anticonvulsant agents and for better understanding the structure-activity relationship.

Structure and functionality of nanostructured triacylglycerol crystal networks.

PubMed

Ramel, Pere R; Co, Edmund D; Acevedo, Nuria C; Marangoni, Alejandro G

2016-10-01

In this review, recent advances in the characterization of the nanoscale structure of fat crystal networks are outlined. The effect of different factors on the properties of crystalline nanoplatelets (CNPs) is comprehensively described. These are discussed together with the observed changes in polymorphism and micro- or mesostructural properties so as to have a complete understanding of the influence of different internal and external factors on the material properties of fats. The relationship between the nanostructure and the material properties of fats (i.e., oil binding capacity and rheology) is also described. Characterization of the nanostructure of fats has provided a new dimension to the analysis of fat crystal networks and opportunities for nanoengineering that could result in innovations in the food industry with regards to processing and structuring fatty materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Fragment-based quantitative structure-activity relationship (FB-QSAR) for fragment-based drug design.

PubMed

Du, Qi-Shi; Huang, Ri-Bo; Wei, Yu-Tuo; Pang, Zong-Wen; Du, Li-Qin; Chou, Kuo-Chen

2009-01-30

In cooperation with the fragment-based design a new drug design method, the so-called "fragment-based quantitative structure-activity relationship" (FB-QSAR) is proposed. The essence of the new method is that the molecular framework in a family of drug candidates are divided into several fragments according to their substitutes being investigated. The bioactivities of molecules are correlated with the physicochemical properties of the molecular fragments through two sets of coefficients in the linear free energy equations. One coefficient set is for the physicochemical properties and the other for the weight factors of the molecular fragments. Meanwhile, an iterative double least square (IDLS) technique is developed to solve the two sets of coefficients in a training data set alternately and iteratively. The IDLS technique is a feedback procedure with machine learning ability. The standard Two-dimensional quantitative structure-activity relationship (2D-QSAR) is a special case, in the FB-QSAR, when the whole molecule is treated as one entity. The FB-QSAR approach can remarkably enhance the predictive power and provide more structural insights into rational drug design. As an example, the FB-QSAR is applied to build a predictive model of neuraminidase inhibitors for drug development against H5N1 influenza virus. (c) 2008 Wiley Periodicals, Inc.

Measuring the Readability of Elementary Algebra Using the Cloze Technique.

ERIC Educational Resources Information Center

Kulm, Gerald

The relationship to readability of ten variables characterizing structural properties of mathematical prose was investigated in elementary algebra textbooks. Readability was measured by algebra student's responses to two forms of cloze tests. Linear and currilinear correlations were calculated between each structural variable and the cloze test.…

Ontology for Structural Geology

NASA Astrophysics Data System (ADS)

Zhong, J.; McGuinness, D. L.; Antonellini, M.; Aydin, A.

2005-12-01

We present our comprehensive process-based ontology for Structural Geology. This ontology covers major domain concepts, especially those related to geological structure type, properties of these structures, their deformation mechanisms, and the factors that control which deformation mechanisms may operate under certain conditions. The structure class in our ontology extends the planetary structure class of the SWEET ontology by providing additional information required for use in the structural geology domain. The classification followed the architectures of structures, such as structure element, set, zone, and pattern. Our deformation mechanism class does not have a corresponding class in SWEET. In our ontology, it has two subclasses, Macro- and Micro- mechanisms. The property class and the factor class are both subclasses of the physical property class of SWEET. Relationships among those concepts are also included in our ontology. For example, the class structure element has properties associated with the deformation mechanisms, descriptive properties such as geometry and morphology, and physical properties of rocks such as strength, compressibility, seismic velocity, porosity, and permeability. The subject matter expertise was provided by domain experts. Additionally, we surveyed text books and journal articles with the goal of evaluating the completeness and correctness of the domain terms and we used logical reasoners and validators to eliminate logical problems. We propose that our ontology provides a reusable extension to the SWEET ontology that may be of value to scientists and lay people interested in structural geology issues. We have also implemented prototype services that utilize this ontology for search.

Relationship between mechanical-property and energy-absorption trends for composite tubes

NASA Technical Reports Server (NTRS)

Farley, Gary L.

1992-01-01

U.S. Army helicopters are designed to dissipate prescribed levels of crash impact kinetic energy without compromising the integrity of the fuselage. Because of the complexity of the energy-absorption process it is imperative for designers of energy-absorbing structures to develop an in-depth understanding of how and why composite structures absorb energy. A description of the crushing modes and mechanisms of energy absorption for composite tubes and beams is presented. Three primary crushing modes of composite structures including transverse shearing, lamina bending, and local buckling are described. The experimental data presented show that fiber and matrix mechanical properties and laminate stiffness and strength mechanical properties cannot reliably predict the energy-absorption response of composite tubes.

Exploration of polyamide structure-property relationships by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Barrère, Caroline; Rejaibi, Majed; Curat, Aurélien; Hubert-Roux, Marie; Lavanant, Hélène; Afonso, Carlos; Kebir, Nasreddine; Desilles, Nicolas; Lecamp, Laurence; Burel, Fabrice; Loutelier-Bourhis, Corinne

2014-08-15

Polyamides (PA) are among the most used classes of polymers because of their attractive properties. Depending on the nature and proportion of the co-monomers used for their synthesis, they can exhibit a very large range of melting temperatures (Tm ). This study aims at the correlation of data from mass spectrometry (MS) with differential scanning calorimetry (DSC) and X-ray diffraction analyses to relate molecular structure to physical properties such as melting temperature, enthalpy change and crystallinity rate. Six different PA copolymers with molecular weights around 3500 g mol(-1) were synthesized with varying proportions of different co-monomers (amino-acid AB/di-amine AA/di-acid BB). Their melting temperature, enthalpy change and crystallinity rate were measured by DSC and X-ray diffraction. Their structural characterization was carried out by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Because of the poor solubility of PA, a solvent-free sample preparation strategy was used with 2,5-dihydroxybenzoic acid (2,5-DHB) as the matrix and sodium iodide as the cationizing agent. The different proportions of the repeating unit types led to the formation of PA with melting temperatures ranging from 115°C to 185°C. The structural characterization of these samples by MALDI-TOF-MS revealed a collection of different ion distributions with different sequences of repeating units (AA, BB; AB/AA, BB and AB) in different proportions according to the mixture of monomers used in the synthesis. The relative intensities of these ion distributions were related to sample complexity and structure. They were correlated to DSC and X-ray results, to explain the observed physical properties. The structural information obtained by MALDI-TOF-MS provided a better understanding of the variation of the PA melting temperature and established a structure-properties relationship. This work will allow future PA designs to be monitored. Copyright © 2014 John Wiley & Sons, Ltd.

Density functional theory in materials science.

PubMed

Neugebauer, Jörg; Hickel, Tilmann

2013-09-01

Materials science is a highly interdisciplinary field. It is devoted to the understanding of the relationship between (a) fundamental physical and chemical properties governing processes at the atomistic scale with (b) typically macroscopic properties required of materials in engineering applications. For many materials, this relationship is not only determined by chemical composition, but strongly governed by microstructure. The latter is a consequence of carefully selected process conditions (e.g., mechanical forming and annealing in metallurgy or epitaxial growth in semiconductor technology). A key task of computational materials science is to unravel the often hidden composition-structure-property relationships using computational techniques. The present paper does not aim to give a complete review of all aspects of materials science. Rather, we will present the key concepts underlying the computation of selected material properties and discuss the major classes of materials to which they are applied. Specifically, our focus will be on methods used to describe single or polycrystalline bulk materials of semiconductor, metal or ceramic form.

Nanomechanical strength mechanisms of hierarchical biological materials and tissues.

PubMed

Buehler, Markus J; Ackbarow, Theodor

2008-12-01

Biological protein materials (BPMs), intriguing hierarchical structures formed by assembly of chemical building blocks, are crucial for critical functions of life. The structural details of BPMs are fascinating: They represent a combination of universally found motifs such as alpha-helices or beta-sheets with highly adapted protein structures such as cytoskeletal networks or spider silk nanocomposites. BPMs combine properties like strength and robustness, self-healing ability, adaptability, changeability, evolvability and others into multi-functional materials at a level unmatched in synthetic materials. The ability to achieve these properties depends critically on the particular traits of these materials, first and foremost their hierarchical architecture and seamless integration of material and structure, from nano to macro. Here, we provide a brief review of this field and outline new research directions, along with a review of recent research results in the development of structure-property relationships of biological protein materials exemplified in a study of vimentin intermediate filaments.

Structure–property characterization of the crinkle-leaf peach wood phenotype: a future model system for wood properties research?

Treesearch

Alex C. Wiedenhoeft; Rafael Arévalo; Craig Ledbetter; Joseph E. Jakes

2016-01-01

Nearly 400 million years of evolution and field-testing by the natural world has given humans thousands of wood types, each with unique structure– property relationships to study, exploit, and ideally, to manipulate, but the slow growth of trees makes them a recalcitrant experimental system. Variations in wood features of two genotypes of peach (Prunus persica L.)...

Design and prediction of new anticoagulants as a selective Factor IXa inhibitor via three-dimensional quantitative structure-property relationships of amidinobenzothiophene derivatives.

PubMed

Gao, Jia-Suo; Tong, Xu-Peng; Chang, Yi-Qun; He, Yu-Xuan; Mei, Yu-Dan; Tan, Pei-Hong; Guo, Jia-Liang; Liao, Guo-Chao; Xiao, Gao-Keng; Chen, Wei-Min; Zhou, Shu-Feng; Sun, Ping-Hua

2015-01-01

Factor IXa (FIXa), a blood coagulation factor, is specifically inhibited at the initiation stage of the coagulation cascade, promising an excellent approach for developing selective and safe anticoagulants. Eighty-four amidinobenzothiophene antithrombotic derivatives targeting FIXa were selected to establish three-dimensional quantitative structure-activity relationship (3D-QSAR) and three-dimensional quantitative structure-selectivity relationship (3D-QSSR) models using comparative molecular field analysis and comparative similarity indices analysis methods. Internal and external cross-validation techniques were investigated as well as region focusing and bootstrapping. The satisfactory q (2) values of 0.753 and 0.770, and r (2) values of 0.940 and 0.965 for 3D-QSAR and 3D-QSSR, respectively, indicated that the models are available to predict both the inhibitory activity and selectivity on FIXa against Factor Xa, the activated status of Factor X. This work revealed that the steric, hydrophobic, and H-bond factors should appropriately be taken into account in future rational design, especially the modifications at the 2'-position of the benzene and the 6-position of the benzothiophene in the R group, providing helpful clues to design more active and selective FIXa inhibitors for the treatment of thrombosis. On the basis of the three-dimensional quantitative structure-property relationships, 16 new potent molecules have been designed and are predicted to be more active and selective than Compound 33, which has the best activity as reported in the literature.

Dual Mechanism Nonlinear Response of Selected Metal Organic Chromophores

DTIC Science & Technology

2007-10-01

emission was observed due to the high quantum efficiency of the free ligand despite having a relatively low two photon cross section at this wavelength...nonlinear absorbing chromophores. .............................30 2-1 Beer’s Law relationships of linear absorption...optical processes; (4) structure-property relationships of nonlinear absorption as it relates to two photon absorption and reverse saturable absorption

Noncoded amino acids in protein engineering: Structure-activity relationship studies of hirudin-thrombin interaction.

PubMed

De Filippis, Vincenzo; Acquasaliente, Laura; Pontarollo, Giulia; Peterle, Daniele

2018-01-01

The advent of recombinant DNA technology allowed to site-specifically insert, delete, or mutate almost any amino acid in a given protein, significantly improving our knowledge of protein structure, stability, and function. Nevertheless, a quantitative description of the physical and chemical basis that makes a polypeptide chain to efficiently fold into a stable and functionally active conformation is still elusive. This mainly originates from the fact that nature combined, in a yet unknown manner, different properties (i.e., hydrophobicity, conformational propensity, polarizability, and hydrogen bonding capability) into the 20 standard natural amino acids, thus making difficult, if not impossible, to univocally relate the change in protein stability or function to the alteration of physicochemical properties caused by amino acid exchange(s). In this view, incorporation of noncoded amino acids with tailored side chains, allowing to finely tune the structure at a protein site, would facilitate to dissect the effects of a given mutation in terms of one or a few physicochemical properties, thus much expanding the scope of physical organic chemistry in the study of proteins. In this review, relevant applications from our laboratory will be presented on the use of noncoded amino acids in structure-activity relationships studies of hirudin binding to thrombin. © 2017 International Union of Biochemistry and Molecular Biology, Inc.

Molecularly "engineered" anode adsorbates for probing OLED interfacial structure-charge injection/luminance relationships: large, structure-dependent effects.

PubMed

Huang, Qinglan; Evmenenko, Guennadi; Dutta, Pulak; Marks, Tobin J

2003-12-03

Molecule-scale structure effects at organic light-emitting diodes (OLED) anode-organic transport layer interfaces are probed via a self-assembly approach. A series of ITO anode-linked silyltriarylamine molecules differing in aryl group and linker density are synthesized for this purpose and used to probe the relationship between nanoscale interfacial chemical structure, charge injection and electroluminescence properties. Dramatic variations in hole injection magnitude and OLED performance can be correlated with the molecular structures and electrochemically derived heterogeneous electron-transfer rates of such triarylamine fragments, placed precisely at the anode-hole transport layer interface. Very bright and efficient ( approximately 70 000 cd/m2 and approximately 2.5% forward external quantum efficiency) OLEDs have thereby been fabricated.

Symposium II: Mechanochemistry in Materials Science, MRS Fall Meeting, Nov 30-Dec 4, 2009, Boston, MA

DTIC Science & Technology

2010-09-02

Dynamic Mechanical Analysis (DMA). The fracture behavior of the mechanophore-linked polymer is also examined through the Double Cleavage Drilled ...multinary complex structures. Structural, microstructural, and chemical characterizations were explored by metrological tools to support this...simple hydrocarbons in order to quantitatively define structure-property relationships for reacting materials under shock compression. Embedded gauge

Exploiting mAb structure characteristics for a directed QbD implementation in early process development.

PubMed

Karlberg, Micael; von Stosch, Moritz; Glassey, Jarka

2018-03-07

In today's biopharmaceutical industries, the lead time to develop and produce a new monoclonal antibody takes years before it can be launched commercially. The reasons lie in the complexity of the monoclonal antibodies and the need for high product quality to ensure clinical safety which has a significant impact on the process development time. Frameworks such as quality by design are becoming widely used by the pharmaceutical industries as they introduce a systematic approach for building quality into the product. However, full implementation of quality by design has still not been achieved due to attrition mainly from limited risk assessment of product properties as well as the large number of process factors affecting product quality that needs to be investigated during the process development. This has introduced a need for better methods and tools that can be used for early risk assessment and predictions of critical product properties and process factors to enhance process development and reduce costs. In this review, we investigate how the quantitative structure-activity relationships framework can be applied to an existing process development framework such as quality by design in order to increase product understanding based on the protein structure of monoclonal antibodies. Compared to quality by design, where the effect of process parameters on the drug product are explored, quantitative structure-activity relationships gives a reversed perspective which investigates how the protein structure can affect the performance in different unit operations. This provides valuable information that can be used during the early process development of new drug products where limited process understanding is available. Thus, quantitative structure-activity relationships methodology is explored and explained in detail and we investigate the means of directly linking the structural properties of monoclonal antibodies to process data. The resulting information as a decision tool can help to enhance the risk assessment to better aid process development and thereby overcome some of the limitations and challenges present in QbD implementation today.

Structure-reactivity relationship of naphthenic acids in the photocatalytic degradation process.

PubMed

de Oliveira Livera, Diogo; Leshuk, Tim; Peru, Kerry M; Headley, John V; Gu, Frank

2018-06-01

Bitumen extraction in Canada's oil sands generates oil sands process-affected water (OSPW) as a toxic by-product. Naphthenic acids (NAs) contribute to the water's toxicity, and treatment methods may need to be implemented to enable safe discharge. Heterogeneous photocatalysis is a promising advanced oxidation process (AOP) for OSPW remediation, however, its successful implementation requires understanding of the complicated relationship between structure and reactivity of NAs. This work aimed to study the effect of various structural properties of model compounds on the photocatalytic degradation kinetics via high resolution mass spectrometry (HRMS), including diamondoid structures, heteroatomic species, and degree of unsaturation. The rate of photocatalytic treatment increased significantly with greater structural complexity, namely with carbon number, aromaticity and degree of cyclicity, properties that render particular NAs recalcitrant to biodegradation. It is hypothesized that a superoxide radical-mediated pathway explains these observations and offers additional benefits over traditional hydroxyl radical-based AOPs. Detailed structure-reactivity investigations of NAs in photocatalysis have not previously been undertaken, and the results described herein illustrate the potential benefit of combining photocatalysis and biodegradation as a complete OSPW remediation technology. Copyright © 2018 Elsevier Ltd. All rights reserved.

De novo design of recombinant spider silk proteins for material applications.

PubMed

Zheng, Ke; Ling, Shengjie

2018-05-21

Spider silks are well known for their superior mechanical properties that are stronger and tougher than steel despite being assembled at close to ambient conditions and using water as the solvent. However, it is a significant challenge to utilize spider silks for practical applications due to their limited sources. Fortunately, genetic engineering techniques offer a promising approach to produce useable amounts of spider silk variants. Starting from these recombinant spider silk proteins, a series of experiments and simulations strategies were developed to improve the recombinant spider silk proteins (RSSP) material design and fabrication with the aim of biomimicking the structure-property-function relationships of spider silks. Accordingly, in this review, we first introduce the structure-property-function relationship of spider silks. Then, we discuss the recent progress in the genetic synthesis of RSSPs and summarize their related multiscale self-assembly behaviors. Finally, we outline works utilizing multiscale modeling to assist RSSP material design. This article is protected by copyright. All rights reserved.

Condensation polyimides

NASA Technical Reports Server (NTRS)

Hergenrother, P. M.

1989-01-01

Polyimides belong to a class of polymers known as polyheterocyclics. Unlike most other high temperature polymers, polyimides can be prepared from a variety of inexpensive monomers by several synthetic routes. The glass transition and crystalline melt temperature, thermooxidative stability, toughness, dielectric constant, coefficient of thermal expansion, chemical stability, mechanical performance, etc. of polyimides can be controlled within certain boundaries. This versatility has permitted the development of various forms of polyimides. These include adhesives, composite matrices, coatings, films, moldings, fibers, foams and membranes. Polyimides are synthesized through both condensation (step-polymerization) and addition (chain growth polymerization) routes. The precursor materials used in addition polyimides or imide oligomers are prepared by condensation method. High molecular weight polyimide made via polycondensation or step-growth polymerization is studied. The various synthetic routes to condensation polyimides, structure/property relationships of condensation polyimides and composite properties of condensation polyimides are all studied. The focus is on the synthesis and chemical structure/property relationships of polyimides with particular emphasis on materials for composite application.

The development and psychometric properties of an informant-report form of the personality inventory for DSM-5 (PID-5).

PubMed

Markon, Kristian E; Quilty, Lena C; Bagby, R Michael; Krueger, Robert F

2013-06-01

The current article reports on the development, psychometric properties, and external validity of an informant-report form of the Personality Inventory for DSM-5 (the PID-5-IRF). Using data from two nationally representative samples, as well as an elevated-risk community sample, we report on the PID-5-IRF item characteristics, scale properties, superordinate factor structure, and correlations with other measures. The PID-5-IRF replicates the factor structure of the self-report form and has relationships with other measures (including the PID-5 self-report form and a widely used Big Five measure) that are consistent with previous research and theory. We believe that the PID-5-IRF is a useful measure for a number of scenarios, such as when additional sources of information are desired, where informant measures are expected to provide incremental validity over self-report, where relationships or social perception is a focal interest, or when response bias is a salient concern. Areas for future research are also discussed.

Exploring the Relationship between Structural and Air-Water Interfacial Properties of Wheat (Triticum aestivum L.) Gluten Hydrolysates in a Food System Relevant pH Range.

PubMed

Wouters, Arno G B; Fierens, Ellen; Rombouts, Ine; Brijs, Kristof; Joye, Iris J; Delcour, Jan A

2017-02-15

The relationship between structural and foaming properties of two tryptic and two peptic wheat gluten hydrolysates was studied at different pH conditions. The impact of pH on foam stability (FS) of the samples heavily depended on the peptidase used and the degree of hydrolysis reached. Surface dilatational moduli were in most, but not all, instances related to FS, implying that, although the formation of a viscoelastic protein hydrolysate film is certainly important, this is not the only phenomenon that determines FS. In contrast to what might be expected, surface charge was not a major factor contributing to FS, except when close to the point-of-zero-charge. Surface hydrophobicity and intrinsic fluorescence measurements suggested that changes in protein conformation take place when the pH is varied, which can in turn influence foaming. Finally, hydrolyzed gluten proteins formed relatively large particles, suggesting that protein hydrolysate aggregation probably influences its foaming properties.

Structure Defect Property Relationships in Binary Intermetallics

NASA Astrophysics Data System (ADS)

Medasani, Bharat; Ding, Hong; Chen, Wei; Persson, Kristin; Canning, Andrew; Haranczyk, Maciej; Asta, Mark

2015-03-01

Ordered intermetallics are light weight materials with technologically useful high temperature properties such as creep resistance. Knowledge of constitutional and thermal defects is required to understand these properties. Vacancies and antisites are the dominant defects in the intermetallics and their concentrations and formation enthalpies could be computed by using first principles density functional theory and thermodynamic formalisms such as dilute solution method. Previously many properties of the intermetallics such as melting temperatures and formation enthalpies were statistically analyzed for large number of intermetallics using structure maps and data mining approaches. We undertook a similar exercise to establish the dependence of the defect properties in binary intermetallics on the underlying structural and chemical composition. For more than 200 binary intermetallics comprising of AB, AB2 and AB3 structures, we computed the concentrations and formation enthalpies of vacancies and antisites in a small range of stoichiometries deviating from ideal stoichiometry. The calculated defect properties were datamined to gain predictive capabilities of defect properties as well as to classify the intermetallics for their suitability in high-T applications. Supported by the US DOE under Contract No. DEAC02-05CH11231 under the Materials Project Center grant (Award No. EDCBEE).

Molecular surface area based predictive models for the adsorption and diffusion of disperse dyes in polylactic acid matrix.

PubMed

Xu, Suxin; Chen, Jiangang; Wang, Bijia; Yang, Yiqi

2015-11-15

Two predictive models were presented for the adsorption affinities and diffusion coefficients of disperse dyes in polylactic acid matrix. Quantitative structure-sorption behavior relationship would not only provide insights into sorption process, but also enable rational engineering for desired properties. The thermodynamic and kinetic parameters for three disperse dyes were measured. The predictive model for adsorption affinity was based on two linear relationships derived by interpreting the experimental measurements with molecular structural parameters and compensation effect: ΔH° vs. dye size and ΔS° vs. ΔH°. Similarly, the predictive model for diffusion coefficient was based on two derived linear relationships: activation energy of diffusion vs. dye size and logarithm of pre-exponential factor vs. activation energy of diffusion. The only required parameters for both models are temperature and solvent accessible surface area of the dye molecule. These two predictive models were validated by testing the adsorption and diffusion properties of new disperse dyes. The models offer fairly good predictive ability. The linkage between structural parameter of disperse dyes and sorption behaviors might be generalized and extended to other similar polymer-penetrant systems. Copyright © 2015 Elsevier Inc. All rights reserved.

Structural determinants of hydration, mechanics and fluid flow in freeze-dried collagen scaffolds.

PubMed

Offeddu, G S; Ashworth, J C; Cameron, R E; Oyen, M L

2016-09-01

Freeze-dried scaffolds provide regeneration templates for a wide range of tissues, due to their flexibility in physical and biological properties. Control of structure is crucial for tuning such properties, and therefore scaffold functionality. However, the common approach of modeling these scaffolds as open-cell foams does not fully account for their structural complexity. Here, the validity of the open-cell model is examined across a range of physical characteristics, rigorously linking morphology to hydration and mechanical properties. Collagen scaffolds with systematic changes in relative density were characterized using Scanning Electron Microscopy, X-ray Micro-Computed Tomography and spherical indentation analyzed in a time-dependent poroelastic framework. Morphologically, all scaffolds were mid-way between the open- and closed-cell models, approaching the closed-cell model as relative density increased. Although pore size remained constant, transport pathway diameter decreased. Larger collagen fractions also produced greater volume swelling on hydration, although the change in pore diameter was constant, and relatively small at ∼6%. Mechanically, the dry and hydrated scaffold moduli varied quadratically with relative density, as expected of open-cell materials. However, the increasing pore wall closure was found to determine the time-dependent nature of the hydrated scaffold response, with a decrease in permeability producing increasingly elastic rather than viscoelastic behavior. These results demonstrate that characterizing the deviation from the open-cell model is vital to gain a full understanding of scaffold biophysical properties, and provide a template for structural studies of other freeze-dried biomaterials. Freeze-dried collagen sponges are three-dimensional microporous scaffolds that have been used for a number of exploratory tissue engineering applications. The characterization of the structure-properties relationships of these scaffolds is necessary to understand their biophysical behavior in vivo. In this work, the relationship between morphology and physical properties in the dry and hydrated states was investigated across a range of solid concentrations in the scaffolds. The quantitative results provided can aid the design of scaffolds with a target trade-off between mechanical properties and structural features important for their biological activity. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Application of information theory to a three-body coarse-grained representation of proteins in the PDB: insights into the structural and evolutionary roles of residues in protein structure.

PubMed

Thompson, Jared J; Tabatabaei Ghomi, Hamed; Lill, Markus A

2014-12-01

Knowledge-based methods for analyzing protein structures, such as statistical potentials, primarily consider the distances between pairs of bodies (atoms or groups of atoms). Considerations of several bodies simultaneously are generally used to characterize bonded structural elements or those in close contact with each other, but historically do not consider atoms that are not in direct contact with each other. In this report, we introduce an information-theoretic method for detecting and quantifying distance-dependent through-space multibody relationships between the sidechains of three residues. The technique introduced is capable of producing convergent and consistent results when applied to a sufficiently large database of randomly chosen, experimentally solved protein structures. The results of our study can be shown to reproduce established physico-chemical properties of residues as well as more recently discovered properties and interactions. These results offer insight into the numerous roles that residues play in protein structure, as well as relationships between residue function, protein structure, and evolution. The techniques and insights presented in this work should be useful in the future development of novel knowledge-based tools for the evaluation of protein structure. © 2014 Wiley Periodicals, Inc.

Analytical relationships for prediction of the mechanical properties of additively manufactured porous biomaterials.

PubMed

Zadpoor, Amir Abbas; Hedayati, Reza

2016-12-01

Recent developments in additive manufacturing techniques have motivated an increasing number of researchers to study regular porous biomaterials that are based on repeating unit cells. The physical and mechanical properties of such porous biomaterials have therefore received increasing attention during recent years. One of the areas that have revived is analytical study of the mechanical behavior of regular porous biomaterials with the aim of deriving analytical relationships that could predict the relative density and mechanical properties of porous biomaterials, given the design and dimensions of their repeating unit cells. In this article, we review the analytical relationships that have been presented in the literature for predicting the relative density, elastic modulus, Poisson's ratio, yield stress, and buckling limit of regular porous structures based on various types of unit cells. The reviewed analytical relationships are used to compare the mechanical properties of porous biomaterials based on different types of unit cells. The major areas where the analytical relationships have improved during the recent years are discussed and suggestions are made for future research directions. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 3164-3174, 2016. © 2016 The Authors Journal of Biomedical Materials Research Part A Published by Wiley Periodicals, Inc.

The Processing and Mechanical Properties of High Temperature/High Performance Composites. Book 5. Interface Effects

DTIC Science & Technology

1994-04-01

Interfacial Mechanical Properties in Fiber Reinforced Ceramic Composites," 1. Am. Ceram. Soc., 70 (1987) 542-48. [25] P.D. Jero, R.J. Kerans and T.A...Mater., 40 [611251-57 (1992). [16] D.B. Marshall and W. Oliver, "Measurement of Interfacial Mechanical Properties in Fiber-Reinforced Ceramic...Charlottesville. VA 22903, U.S.A. (Received 14 July 1993;fl/al version acepted IS AustrW 1993) Abstract-The interfacial structure / property relationships of a

Exploring the formation and electronic structure properties of the g-C3N4 nanoribbon with density functional theory

NASA Astrophysics Data System (ADS)

Wu, Hong-Zhang; Zhong, Qing-Hua; Bandaru, Sateesh; Liu, Jin; Lau, Woon Ming; Li, Li-Li; Wang, Zhenling

2018-04-01

The optical properties and condensation degree (structure) of polymeric g-C3N4 depend strongly on the process temperature. For polymeric g-C3N4, its structure and condensation degree depend on the structure of molecular strand(s). Here, the formation and electronic structure properties of the g-C3N4 nanoribbon are investigated by studying the polymerization and crystallinity of molecular strand(s) employing first-principle density functional theory. The calculations show that the width of the molecular strand has a significant effect on the electronic structure of polymerized and crystallized g-C3N4 nanoribbons, a conclusion which would be indirect evidence that the electronic structure depends on the structure of g-C3N4. The edge shape also has a distinct effect on the electronic structure of the crystallized g-C3N4 nanoribbon. Furthermore, the conductive band minimum and valence band maximum of the polymeric g-C3N4 nanoribbon show a strong localization, which is in good agreement with the quasi-monomer characters. In addition, molecular strands prefer to grow along the planar direction on graphene. These results provide new insight on the properties of the g-C3N4 nanoribbon and the relationship between the structure and properties of g-C3N4.

Exploring the formation and electronic structure properties of the g-C3N4 nanoribbon with density functional theory.

PubMed

Wu, Hong-Zhang; Zhong, Qing-Hua; Bandaru, Sateesh; Liu, Jin; Lau, Woon Ming; Li, Li-Li; Wang, Zhenling

2018-04-18

The optical properties and condensation degree (structure) of polymeric g-C 3 N 4 depend strongly on the process temperature. For polymeric g-C 3 N 4 , its structure and condensation degree depend on the structure of molecular strand(s). Here, the formation and electronic structure properties of the g-C 3 N 4 nanoribbon are investigated by studying the polymerization and crystallinity of molecular strand(s) employing first-principle density functional theory. The calculations show that the width of the molecular strand has a significant effect on the electronic structure of polymerized and crystallized g-C 3 N 4 nanoribbons, a conclusion which would be indirect evidence that the electronic structure depends on the structure of g-C 3 N 4 . The edge shape also has a distinct effect on the electronic structure of the crystallized g-C 3 N 4 nanoribbon. Furthermore, the conductive band minimum and valence band maximum of the polymeric g-C 3 N 4 nanoribbon show a strong localization, which is in good agreement with the quasi-monomer characters. In addition, molecular strands prefer to grow along the planar direction on graphene. These results provide new insight on the properties of the g-C 3 N 4 nanoribbon and the relationship between the structure and properties of g-C 3 N 4 .

Microstructural and Mechanical Property Characterization of Shear Formed Aerospace Aluminum Alloys

NASA Technical Reports Server (NTRS)

Troeger, Lillianne P.; Domack, Marcia S.; Wagner, John A.

2000-01-01

Advanced manufacturing processes such as near-net-shape forming can reduce production costs and increase the reliability of launch vehicle and airframe structural components through the reduction of material scrap and part count and the minimization of joints. The current research is an investigation of the processing-microstructure-property relationships for shear formed cylinders of the Al-Cu-Li-Mg-Ag alloy 2195 for space applications and the Al-Cu-Mg-Ag alloy C415 for airframe applications. Cylinders which had undergone various amounts of shear-forming strain were studied to correlate the grain structure, texture, and mechanical properties developed during and after shear forming.

Unraveling Unprecedented Charge Carrier Mobility through Structure Property Relationship of Four Isomers of Didodecyl[1]benzothieno[3,2-b][1]benzothiophene.

PubMed

Tsutsui, Yusuke; Schweicher, Guillaume; Chattopadhyay, Basab; Sakurai, Tsuneaki; Arlin, Jean-Baptiste; Ruzié, Christian; Aliev, Almaz; Ciesielski, Artur; Colella, Silvia; Kennedy, Alan R; Lemaur, Vincent; Olivier, Yoann; Hadji, Rachid; Sanguinet, Lionel; Castet, Frédéric; Osella, Silvio; Dudenko, Dmytro; Beljonne, David; Cornil, Jérôme; Samorì, Paolo; Seki, Shu; Geerts, Yves H

2016-09-01

The structural and electronic properties of four isomers of didodecyl[1]-benzothieno[3,2-b][1]benzothiophene (C12-BTBT) have been investigated. Results show the strong impact of the molecular packing on charge carrier transport and electronic polarization properties. Field-induced time-resolved microwave conductivity measurements unravel an unprecedented high average interfacial mobility of 170 cm(2) V(-1) s(-1) for the 2,7-isomer, holding great promise for the field of organic electronics. © 2016 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Morphology and microstructure of composite materials

NASA Technical Reports Server (NTRS)

Tiwari, S. N.; Srinivansan, K.

1991-01-01

Lightweight continuous carbon fiber based polymeric composites are currently enjoying increasing acceptance as structural materials capable of replacing metals and alloys in load bearing applications. As with most new materials, these composites are undergoing trials with several competing processing techniques aimed at cost effectively producing void free consolidations with good mechanical properties. As metallic materials have been in use for several centuries, a considerable database exists on their morphology - microstructure; and the interrelationships between structure and properties have been well documented. Numerous studies on composites have established the crucial relationship between microstructure - morphology and properties. The various microstructural and morphological features of composite materials, particularly those accompanying different processing routes, are documented.

Structure-property relations and modeling of small crack fatigue behavior of various magnesium alloys

NASA Astrophysics Data System (ADS)

Bernard, Jairus Daniel

Lightweight structural components are important to the automotive and aerospace industries so that better fuel economy can be realized. Magnesium alloys in particular are being examined to fulfill this need due to their attractive stiffness- and strength-to-weight ratios when compared to other materials. However, when introducing a material into new roles, one needs to properly characterize its mechanical properties. Fatigue behavior is especially important considering aerospace and automotive component applications. Therefore, quantifying the structure-property relationships and accurately predicting the fatigue behavior for these materials are vital. This study has two purposes. The first is to quantify the structure-property relationships for the fatigue behavior in an AM30 magnesium alloy. The second is to use the microstructural-based MultiStage Fatigue (MSF) model in order to accurately predict the fatigue behavior of three magnesium alloys: AM30, Elektron 21, and AZ61. While some studies have previously quantified the MSF material constants for several magnesium alloys, detailed research into the fatigue regimes, notably the microstructurally small crack (MSC) region, is lacking. Hence, the contribution of this work is the first of its kind to experimentally quantify the fatigue crack incubation and MSC regimes that are used for the MultiStage Fatigue model. Using a multi-faceted experimental approach, these regimes were explored with a replica method that used a dual-stage silicone based compound along with previously published in situ fatigue tests. These observations were used in calibrating the MultiStage Fatigue model.

Is There Consistency between the Binding Affinity and Inhibitory Potential of Natural Polyphenols as α-amylase Inhibitors?

PubMed

Xu, Wei; Shao, Rong; Xiao, Jianbo

2016-07-26

The inhibitory potential of natural polyphenols for α-amylases has attracted great interests among researchers. The structure-affinity properties of natural polyphenols binding to α-amylase and the structure-activity relationship of dietary polyphenols inhibiting α-amylase were deeply investigated. There is a lack of consistency between the structure-affinity relationship and the structure-activity relationship of natural polyphenols as α-amylase inhibitors. Is it consistent between the binding affinity and inhibitory potential of natural polyphenols as with α-amylase inhibitors? It was found that the consistency between the binding affinity and inhibitory potential of natural polyphenols as with α-amylase inhibitors is not equivocal. For example, there is no consistency between the binding affinity and the inhibitory potential of quercetin and its glycosides as α-amylase inhibitors. However, catechins with higher α-amylase inhibitory potential exhibited higher affinity with α-amylase.

Odd–even structural sensitivity on dynamics in network-forming ionic liquids

DOE PAGES

Yang, Ke; Cai, Zhikun; Tyagi, Madhusudan; ...

2016-04-13

Understanding structural sensitivity on properties of materials is an important step toward the rational design of materials. As a compelling case of sensitive structure-property relationship, an odd-even effect refers to the alternating trend of physical or chemical properties on odd/even number of repeating structural units. In crystalline or semi-crystalline materials, such odd-even variations of macroscopic properties emerge as manifestations of differences in the periodic packing patterns of molecules. Therefore, due to the lack of long-range order, such odd-even phenomenon is not expected in liquids. Herein, we report the discovery of a remarkable odd-even effect of the dynamical properties in themore » liquid phase, which challenges the traditional periodic packing explanations. In a class of network-forming ionic liquid (NIL), using incoherent quasi-elastic neutron scattering measurements, we measured the dynamical properties including the diffusion coefficient and the rotational relaxation time. These dynamical properties showed pronounced alternating trends with increased number of methylene (–CH 2– ) groups in the backbone. Meanwhile, the structure factor S(Q) showed no long-range periodic packing of molecules, while the pair distribution function g(r) revealed subtle differences in the local molecular morphology. As a result, the observed dynamical odd-even phenomenon in liquids showed that profound dynamical changes originate from subtle local structural differences.« less

Selective CB2 receptor agonists. Part 2: Structure-activity relationship studies and optimization of proline-based compounds.

PubMed

Riether, Doris; Zindell, Renee; Wu, Lifen; Betageri, Raj; Jenkins, James E; Khor, Someina; Berry, Angela K; Hickey, Eugene R; Ermann, Monika; Albrecht, Claudia; Ceci, Angelo; Gemkow, Mark J; Nagaraja, Nelamangala V; Romig, Helmut; Sauer, Achim; Thomson, David S

2015-02-01

Through a ligand-based pharmacophore model (S)-proline based compounds were identified as potent cannabinoid receptor 2 (CB2) agonists with high selectivity over the cannabinoid receptor 1 (CB1). Structure-activity relationship investigations for this compound class lead to oxo-proline compounds 21 and 22 which combine an impressive CB1 selectivity profile with good pharmacokinetic properties. In a streptozotocin induced diabetic neuropathy model, 22 demonstrated a dose-dependent reversal of mechanical hyperalgesia. Copyright © 2014 Elsevier Ltd. All rights reserved.

Epitaxial growth and properties of doped transition metal and complex oxide films.

PubMed

Chambers, Scott A

2010-01-12

The detailed science and technology of crystalline oxide film growth using vacuum methods is reviewed and discussed with an eye toward gaining fundamental insights into the relationships between growth process and parameters, film and interface structure and composition, and electronic, magnetic and photochemical properties. The topic is approached first from a comparative point of view based on the most widely used growth methods, and then on the basis of specific material systems that have generated very high levels of interest. Emphasis is placed on the wide diversity of structural, electronic, optical and magnetic properties exhibited by oxides, and the fascinating results that this diversity of properties can produce when combined with the degrees of freedom afforded by heteroepitaxy.

Acoustic Typology of Vowel Inventories and Dispersion Theory: Insights from a Large Cross-Linguistic Corpus

ERIC Educational Resources Information Center

Becker-Kristal, Roy

2010-01-01

This dissertation examines the relationship between the structural, phonemic properties of vowel inventories and their acoustic phonetic realization, with particular focus on the adequacy of Dispersion Theory, which maintains that inventories are structured so as to maximize perceptual contrast between their component vowels. In order to assess…

Structural, morphological, and optical study of titania-based nanopowders suitable for photocatalytic applications

NASA Astrophysics Data System (ADS)

Šćepanović, M.; Grujić-Brojčin, M.; Abramović, B.; Golubović, A.

2017-01-01

Systematic investigation of the relationship between structural, morphological, optical and photocatalytic properties of the titania-based nanopowders is presented. A series of pure and doped titania catalysts with various (anatase and brookite) phase compositions have been prepared by sol-gel or hydrothermal route. The crystal structure and composition of the synthesized samples have been extensively characterised by XRD and Raman scattering measurements. The nanopowder morphology has been studied using microscopic methods (SEM, AFM, and STM), whereas the porous structure has been revealed by the analysis of nitrogen sorption data. The optical and electronic properties have been studied by spectroscopic ellipsometry. All investigated properties have been correlated to photocatalytic activity, tested in degradation of the pharmaceutically active substances (such as metoprolol and alprazolam) induced by UVA or visible radiation. Based on this correlation, the physical properties which contribute most to the increase in photocatalytic activity of synthesized nanopowders have been determined, in order to optimize the synthesis conditions which could lead to the maximal efficiency in degradation of particular pollutant.

Rheological properties in relation to molecular structure of quinoa starch.

PubMed

Li, Guantian; Zhu, Fan

2018-07-15

Quinoa starch granules are small (~0.5 - 3μm) with potentials for some food and other applications. To better exploit it as a new starch resource, this study investigates the steady shear and dynamic oscillatory properties of 9 quinoa starches varying in composition and structure. Steady shear analysis shows that the flow curves could be well described by 4 selected mathematic models. Temperature sweep analysis reveals that the quinoa starch encounters a 4-stage process including 2 phase transitions. Structure-function relationship analysis showed that composition as well as unit and internal chain length distribution of amylopectin have significant impact on the rheological properties (e.g., G' at 90°C) of quinoa starch. The roles of some individual unit chains and super-long unit chains of amylopectin in determining the rheological properties of quinoa starch were revealed. This study may stimulate further interest in understanding the structural basis of starch rheology. Copyright © 2018 Elsevier B.V. All rights reserved.

Fluorination of Metal Phthalocyanines: Single-Crystal Growth, Efficient N-Channel Organic Field-Effect Transistors, and Structure-Property Relationships

PubMed Central

Jiang, Hui; Ye, Jun; Hu, Peng; Wei, Fengxia; Du, Kezhao; Wang, Ning; Ba, Te; Feng, Shuanglong; Kloc, Christian

2014-01-01

The fluorination of p-type metal phthalocyanines produces n-type semiconductors, allowing the design of organic electronic circuits that contain inexpensive heterojunctions made from chemically and thermally stable p- and n-type organic semiconductors. For the evaluation of close to intrinsic transport properties, high-quality centimeter-sized single crystals of F16CuPc, F16CoPc and F16ZnPc have been grown. New crystal structures of F16CuPc, F16CoPc and F16ZnPc have been determined. Organic single-crystal field-effect transistors have been fabricated to study the effects of the central metal atom on their charge transport properties. The F16ZnPc has the highest electron mobility (~1.1 cm2 V−1 s−1). Theoretical calculations indicate that the crystal structure and electronic structure of the central metal atom determine the transport properties of fluorinated metal phthalocyanines. PMID:25524460

Specialisation of extracellular matrix for function in tendons and ligaments

PubMed Central

Birch, Helen L.; Thorpe, Chavaunne T.; Rumian, Adam P.

2013-01-01

Summary Tendons and ligaments are similar structures in terms of their composition, organisation and mechanical properties. The distinction between them stems from their anatomical location; tendons form a link between muscle and bone while ligaments link bones to bones. A range of overlapping functions can be assigned to tendon and ligaments and each structure has specific mechanical properties which appear to be suited for particular in vivo function. The extracellular matrix in tendon and ligament varies in accordance with function, providing appropriate mechanical properties. The most useful framework in which to consider extracellular matrix differences therefore is that of function rather than anatomical location. In this review we discuss what is known about the relationship between functional requirements, structural properties from molecular to gross level, cellular gene expression and matrix turnover. The relevance of this information is considered by reviewing clinical aspects of tendon and ligament repair and reconstructive procedures. PMID:23885341

Predictive modeling: Solubility of C60 and C70 fullerenes in diverse solvents.

PubMed

Gupta, Shikha; Basant, Nikita

2018-06-01

Solubility of fullerenes imposes a major limitation to further advanced research and technological development using these novel materials. There have been continued efforts to discover better solvents and their properties that influence the solubility of fullerenes. Here, we have developed QSPR (quantitative structure-property relationship) models based on structural features of diverse solvents and large experimental data for predicting the solubility of C 60 and C 70 fullerenes. The developed models identified most relevant features of the solvents that encode the polarizability, polarity and lipophilicity properties which largely influence the solubilizing potential of the solvent for the fullerenes. We also established Inter-moieties solubility correlations (IMSC) based quantitative property-property relationship (QPPR) models for predicting solubility of C 60 and C 70 fullerenes. The QSPR and QPPR models were internally and externally validated deriving the most stringent statistical criteria and predicted C 60 and C 70 solubility values in different solvents were in close agreement with the experimental values. In test sets, the QSPR models yielded high correlations (R 2  > 0.964) and low root mean squared error of prediction errors (RMSEP< 0.25). Results of comparison with other studies indicated that the proposed models could effectively improve the accuracy and ability for predicting solubility of C 60 and C 70 fullerenes in solvents with diverse structures and would be useful in development of more effective solvents. Copyright © 2018 Elsevier Ltd. All rights reserved.

Understanding Chemistry: Current and Possible

ERIC Educational Resources Information Center

Sanderson, R. T.

1976-01-01

Describes an instructional approach for teaching the cause-and-effect relationship between the qualities of atoms and the properties of their chemical compositions. Discusses atomic structure, ionization energies, homonuclear and heteronuclear bonding, and bond dissociation. (MLH)

Preferential nucleation during polymorphic transformations

DOE PAGES

Sharma, H.; Sietsma, J.; Offerman, S. E.

2016-08-03

Polymorphism is the ability of a solid material to exist in more than one phase or crystal structure. Polymorphism may occur in metals, alloys, ceramics, minerals, polymers, and pharmaceutical substances. Unresolved are the conditions for preferential nucleation during polymorphic transformations in which structural relationships or special crystallographic orientation relationships (OR’s) form between the nucleus and surrounding matrix grains. We measured in-situ and simultaneously the nucleation rates of grains that have zero, one, two, three and four special OR’s with the surrounding parent grains. These experiments show a trend in which the activation energy for nucleation becomes smaller – and thereforemore » nucleation more probable - with increasing number of special OR’s. As a result, these insights contribute to steering the processing of polymorphic materials with tailored properties, since preferential nucleation affects which crystal structure forms, the average grain size and texture of the material, and thereby - to a large extent - the final properties of the material.« less

MnO2 ultrathin films deposited by means of magnetron sputtering: Relationships between process conditions, structural properties and performance in transparent supercapacitors

NASA Astrophysics Data System (ADS)

Borysiewicz, Michał A.; Wzorek, Marek; Myśliwiec, Marcin; Kaczmarski, Jakub; Ekielski, Marek

2016-12-01

This study focuses on the relationships between the process parameters during magnetron sputter deposition of MnO2 and the resulting film properties. Three MnO2 phases were identified - γ, β and λ and the dependence of MnO2 phase presence on the oxygen content in the sputtering atmosphere was found. Selected MnO2 phases were subsequently applied as ultrathin coatings on top of nanostructured ZnO electrodes for transparent supercapacitors with LiCl-based gel electrolyte. The films containing λ-MnO2 exhibited both the highest optical transparency of 62% at 550 nm as well as the highest specific capacitance in the supercapacitor structure, equal to 73.1 μF/cm2. Initially lower, the capacitance was elevated by charge-discharge conditioning.

Dislocation structures and electrical conduction properties of low angle tilt grain boundaries in LiNbO{sub 3}

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

Furushima, Yuho; Nakamura, Atsutomo, E-mail: nakamura@numse.nagoya-u.ac.jp; Toyoura, Kazuaki

Dislocations in crystalline materials constitute unique, atomic-scale, one-dimensional structure and have a potential to induce peculiar physical properties that are not found in the bulk. In this study, we fabricated LiNbO{sub 3} bicrystals with low angle tilt grain boundaries and investigated the relationship between the atomic structure of the boundary dislocations and their electrical conduction properties. Observations by using transmission electron microscopy revealed that dislocation structures at the (0001) low angle tilt grain boundaries depend on the tilt angle of the boundaries. Specifically, the characteristic dislocation structures with a large Burgers vector were formed in the boundary with the tiltmore » angle of 2°. It is noteworthy that only the grain boundary of 2° exhibits distinct electrical conductivity after reduction treatment, although LiNbO{sub 3} is originally insulating. This unique electrical conductivity is suggested to be due to the characteristic dislocation structures with a large Burgers vector.« less

Assessment of structural, thermal, and mechanical properties of portlandite through molecular dynamics simulations

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

Hajilar, Shahin, E-mail: shajilar@iastate.edu; Shafei, Behrouz, E-mail: shafei@iastate.edu

The structural, thermal, and mechanical properties of portlandite, the primary solid phase of ordinary hydrated cement paste, are investigated using the molecular dynamics method. To understand the effects of temperature on the structural properties of portlandite, the coefficients of thermal expansion of portlandite are determined in the current study and validated with what reported from the experimental tests. The atomic structure of portlandite equilibrated at various temperatures is then subjected to uniaxial tensile strains in the three orthogonal directions and the stress-strain curves are developed. Based on the obtained results, the effect of the direction of straining on the mechanicalmore » properties of portlandite is investigated in detail. Structural damage analysis is performed to reveal the failure mechanisms in different directions. The energies of the fractured surfaces are calculated in different directions and compared to those of the ideal surfaces available in the literature. The key mechanical properties, including tensile strength, Young's modulus, and fracture strain, are extracted from the stress-strain curves. The sensitivity of the obtained mechanical properties to temperature and strain rate is then explored in a systematic way. This leads to valuable information on how the structural and mechanical properties of portlandite are affected under various exposure conditions and loading rates. - Graphical abstract: Fracture mechanism of portlandite under uniaxial strain in the z-direction. - Highlights: • The structural, thermal, and mechanical properties of portlandite are investigated. • The coefficients of thermal expansion are determined. • The stress-strain relationships are studied in three orthogonal directions. • The effects of temperature and strain rate on mechanical properties are examined. • The plastic energy required for fracture in the crystalline structure is reported.« less

Photoelectron spectra and biological activity of cinnamic acid derivatives revisited

NASA Astrophysics Data System (ADS)

Novak, Igor; Klasinc, Leo; McGlynn, Sean P.

2018-01-01

The electronic structures of several derivatives of cinnamic acid have been studied by UV photoelectron spectroscopy (UPS) and Green's function quantum chemical calculations. The spectra reveal the presence of dimers in the gas phase for p-coumaric and ferulic acids. The electronic structure analysis has been related to the biological properties of these compounds through the analysis of some structure-activity relationships (SAR).

International Workshop on Gamma Aluminide Alloy Technology. Section Three

DTIC Science & Technology

1997-04-18

Structure / Property Relationships General Mechanical Behavior Tensile Fracture Toughness Creep Fatigue; FCG, Inverse Ductility/FT Relationship...Workshop on Gamma Titanium Aluminide Alloy Technology. 1 May 1996-3 May 1996 The Topics covered include: Fundamental research issues for...understanding the emerging class of Gamma Titanium Aluminide Alloy Technologies 14. SUBJECT TERMS 15. NUMBER OF PAGES 16. PRICE CODE N/A 17. SECURITY

Structure-activity relationships on the study of β-galactosidase folding/unfolding due to interactions with immobilization additives: Triton X-100 and ethanol.

PubMed

Soto, Dayana; Escobar, Sindy; Guzmán, Fanny; Cárdenas, Constanza; Bernal, Claudia; Mesa, Monica

2017-03-01

Improving the enzyme stability is a challenge for allowing their practical application. The surfactants are stabilizing agents, however, there are still questions about their influence on enzyme properties. The structure-activity/stability relationship for β-galactosidase from Bacillus circulans is studied here by Circular Dichroism and activity measurements, as a function of temperature and pH. The tendency of preserving the β-sheet and α-helix structures at temperatures below 65°C and different pH is the result of the balance between the large- and short-range effects, respecting to the active site. This information is fundamental for explaining the structural changes of this enzyme in the presence of Triton X-100 surfactant and ethanol. The enzyme thermal stabilization in the presence of this surfactant responds to the rearrangement of the secondary structure for having optimal activity/stability. The effect of ethanol is more related with changes in the dielectric properties of the aqueous solution than with protein structural transformations. These results contribute to understand the effects of surfactant-enzyme interactions on the enzyme behavior, from the structural point of view and to rationalize the surfactant-based stabilizing strategies for β-galactosidades. Copyright © 2016 Elsevier B.V. All rights reserved.

Imidazole derivatives as angiotensin II AT1 receptor blockers: Benchmarks, drug-like calculations and quantitative structure-activity relationships modeling

NASA Astrophysics Data System (ADS)

Alloui, Mebarka; Belaidi, Salah; Othmani, Hasna; Jaidane, Nejm-Eddine; Hochlaf, Majdi

2018-03-01

We performed benchmark studies on the molecular geometry, electron properties and vibrational analysis of imidazole using semi-empirical, density functional theory and post Hartree-Fock methods. These studies validated the use of AM1 for the treatment of larger systems. Then, we treated the structural, physical and chemical relationships for a series of imidazole derivatives acting as angiotensin II AT1 receptor blockers using AM1. QSAR studies were done for these imidazole derivatives using a combination of various physicochemical descriptors. A multiple linear regression procedure was used to design the relationships between molecular descriptor and the activity of imidazole derivatives. Results validate the derived QSAR model.

Optical, Structural, and Thermal Properties of Cerium-Doped Zinc Borophosphate Glasses.

PubMed

Choi, Su-Yeon; Ryu, Bong-Ki

2015-11-01

In this study, we verify the relationship between the optical properties and structure of cerium-doped zinc borophosphate glasses that have concurrence of non-bridging oxygen (NBO) and bridging oxygen (BO), Ce3+ and Ce4+, and BO3 structure and BO4 structure. We prepared cerium-doped zinc borophosphate glass with various compositions, given by xCeO2-(100-x)[50ZnO-10B2O3 -40P2O5] (x = 1 mol% to 6 mol%), and analyzed their optical band energy, glass transition temperature, crystallization temperature, density, and molar volume. Some of the techniques used for analysis were Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). In the investigated glasses, the optical band gap energy decreased from 3.28 eV to 1.73 eV. From these results, we can deduce the changes when transitions occur from BO to NBO, from Ce3+ to Ce4+, and from the BO3 structure to the BO4 structure with increasing CeO2 content using FT-IR and XPS analysis. We also verified the changes in structural and physical properties from quantitative properties such as glass transition temperature, crystallization temperature, density, and molar volume.

Friction-induced nano-structural evolution of graphene as a lubrication additive

NASA Astrophysics Data System (ADS)

Zhao, Jun; Mao, Junyuan; Li, Yingru; He, Yongyong; Luo, Jianbin

2018-03-01

Graphene has attracted enormous attention in the field of lubrication based on its excellent physical and chemical properties. Although many studies have obtained thermally or chemically- exfoliated graphene and investigated their wide and important application, few studies have reported their physical nano-structural evolution under friction. In this study, we investigated the lubrication properties of graphene additives with different layer numbers and interlayer spacing by exfoliating. The additives with a higher degrees of exfoliation changed to ordering under friction, and had better lubrication properties, while that with a lower degrees exhibited obvious structural defects and high friction. Therefore, the original degrees of exfoliation plays a key role in the structural evolution of graphene and superior lubrication can be achieved through the physical nano-structure changing to ordering, even graphitization. Furthermore, the ordered tribofilm on the frictional interfaces was parallel to the sliding direction, meaning the highly exfoliated graphene indeed reaching slippage between its layers, which wasn't experimentally discovered in previous studies. This work provides a new understanding of the relationship between friction-induced nano-structural evolution and lubrication properties of graphene as a lubrication additive, and has great potential for the structural design of graphene as a lubrication additive.

Tungsten-incorporation induced red-shift in the bandgap of gallium oxide thin films

NASA Astrophysics Data System (ADS)

Rubio, E. J.; Ramana, C. V.

2013-05-01

Tungsten (W) incorporated Ga2O3 films were produced by co-sputter deposition. W-concentration was varied by the applied sputtering-power. The structure and optical properties of W-incorporated Ga2O3 films were evaluated using X-ray diffraction, scanning electron microscopy, and spectrophotometric measurements. No secondary phase formation was observed in W-incorporated Ga2O3 films. W-induced effects were significant on the structure and optical properties of Ga2O3 films. The bandgap of Ga2O3 films without W-incorporation was ˜5 eV. Red-shift in the bandgap was noted with increasing W-concentration indicating the electronic structure changes in W-Ga2O3 films. A functional relationship between W-concentration and optical property is discussed.

Structure-function relationships of human meniscus.

PubMed

Danso, Elvis K; Oinas, Joonas M T; Saarakkala, Simo; Mikkonen, Santtu; Töyräs, Juha; Korhonen, Rami K

2017-03-01

Biomechanical properties of human meniscus have been shown to be site-specific. However, it is not known which meniscus constituents at different depths and locations contribute to biomechanical properties obtained from indentation testing. Therefore, we investigated the composition and structure of human meniscus in a site- and depth-dependent manner and their relationships with tissue site-specific biomechanical properties. Elastic and poroelastic properties were analyzed from experimental stress-relaxation and sinusoidal indentation measurements with fibril reinforced poroelastic finite element modeling. Proteoglycan (PG) and collagen contents, as well as the collagen orientation angle, were determined as a function of tissue depth using microscopic and spectroscopic methods, and they were compared with biomechanical properties. For all the measurement sites (anterior, middle and posterior) of lateral and medial menisci (n=26), PG content and collagen orientation angle increased as a function of tissue depth while the collagen content had an initial sharp increase followed by a decrease across tissue depth. The highest values (p<0.05) of elastic parameters (equilibrium and instantaneous moduli) and strain-dependent biomechanical parameters (strain-dependent fibril network modulus and permeability) were observed in the anterior horn of the medial meniscus. This location had also higher (p<0.05) PG content in the deep meniscus, higher (p<0.05) collagen content in the entire tissue depth, and lower (p<0.05) collagen orientation angle at the superficial tissue, as compared to many other locations. On the other hand, in certain comparisons (such as anterior vs. middle sites of the medial meniscus) significantly higher (p<0.05) collagen content and lower orientation angle, without any difference in the PG content, were consistent with increased meniscus modulus and/or nonlinear permeability. This study suggests that nonlinear biomechanical properties of meniscus, caused by the collagen network and fluid, may be strongly influenced by tissue osmotic swelling from the deep meniscus caused by the increased PG content, leading to increased collagen fibril tension. These nonlinear biomechanical properties are suggested to be further amplified by higher collagen content at all tissue depths and superficial collagen fibril orientation. However, these structure-function relationships are suggested to be highly site-specific. Copyright © 2016 Elsevier Ltd. All rights reserved.

Oxygen Vacancy-Tuned Physical Properties in Perovskite Thin Films with Multiple B-site Valance States

DOE PAGES

Enriquez, Erik; Chen, Aiping; Harrell, Zach; ...

2017-04-18

Controlling oxygen content in perovskite oxides with ABO 3 structure is one of most critical steps for tuning their functionality. Notably, there have been tremendous efforts to understand the effect of changes in oxygen content on the properties of perovskite thin films that are not composed of cations with multiple valance states. Here, we study the effect of oxygen vacancies on structural and electrical properties in epitaxial thin films of SrFeO 3-δ (SFO), where SFO is a compound with multiple valance states at the B site. Various annealing treatments are used to produce different oxygen contents in the films, whichmore » has resulted in significant structural changes in the fully strained SFO films. The out-of-plane lattice parameter and tetragonality increase with decreasing oxygen concentration, indicating the crystal structure is closely related to the oxygen content. Importantly, variation of the oxygen content in the films significantly affects the dielectric properties, leakage conduction mechanisms, and the resistive hysteresis of the materials. These results establish the relationship between oxygen content and structural and functional properties for a range of multivalent transition metal oxides.« less

Oxygen Vacancy-Tuned Physical Properties in Perovskite Thin Films with Multiple B-site Valance States

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

Enriquez, Erik; Chen, Aiping; Harrell, Zach

Controlling oxygen content in perovskite oxides with ABO 3 structure is one of most critical steps for tuning their functionality. Notably, there have been tremendous efforts to understand the effect of changes in oxygen content on the properties of perovskite thin films that are not composed of cations with multiple valance states. Here, we study the effect of oxygen vacancies on structural and electrical properties in epitaxial thin films of SrFeO 3-δ (SFO), where SFO is a compound with multiple valance states at the B site. Various annealing treatments are used to produce different oxygen contents in the films, whichmore » has resulted in significant structural changes in the fully strained SFO films. The out-of-plane lattice parameter and tetragonality increase with decreasing oxygen concentration, indicating the crystal structure is closely related to the oxygen content. Importantly, variation of the oxygen content in the films significantly affects the dielectric properties, leakage conduction mechanisms, and the resistive hysteresis of the materials. These results establish the relationship between oxygen content and structural and functional properties for a range of multivalent transition metal oxides.« less

Mapping spatial variation in rock properties in relationship to scale-dependent structure using spectral curvature

NASA Astrophysics Data System (ADS)

Stewart, S. A.; Wynn, T. J.

2000-08-01

Maps of the three-dimensional geometry of geologic surfaces show that structural curvature commonly varies with scale of observation: This fact can be viewed as superposition of structures at different wavelengths. Rock properties such as fracture density and orientation reflect the contribution of superimposed structures. For this reason, characterization of geologic surfaces is fundamentally different from purely geometrical characterization, for which local description of surface properties is sufficient. We show that measured curvature decays according to a power law with increasing size of measurement window, so short-wavelength curvatures do not obscure long-wavelength curvatures in the same data set. This property can be taken advantage of in a simple technique for automatically mapping multiwavelength curvatures. At each point on a surface, curvature is measured at a range of wavelengths. This curvature spectrum can be analyzed in map view or collapsed into a single value at each point in space. The results indicate that complex geologic surfaces can be characterized without any prior knowledge of structural wavelengths and orientation. The method should prove useful in applications requiring knowledge of spatial variation in rock properties from remotely sensed data, such as exploration for hydrocarbon reservoirs or nuclear waste repositories.

Aziridinyl-substituted benzo-1,4-quinones: A preliminary investigation on the theoretical and experimental studies of their structure and spectroscopic properties

NASA Astrophysics Data System (ADS)

Šarlauskas, Jonas; Tamulienė, Jelena; Čėnas, Narimantas

2017-05-01

The detailed structure, chemical and spectroscopic properties of the derivatives of the selected 2,5-bis(1-aziridinyl)-benzo-1,4-quinone conformers were studied by applying quantum chemical and experimental methods. The relationship between the structure and chemical activity of the selected 3 bifunctional bioreductive quinonic anticancer agents - aziridinyl benzoquinones (AzBQ compounds) was obtained. The results obtained showed that the position of aziridine rings influenced by the chemical activity of the investigated compound were more significant than the substitutions of the benzene ring of the AzBQ compounds. The solvents influencing this activity were obtained, too.

Table of periodic properties of fullerenes based on structural parameters.

PubMed

Torrens, Francisco

2004-01-01

The periodic table (PT) of the elements suggests that hydrogen could be the origin of everything else. The construction principle is an evolutionary process that is formally similar to those of Darwin and Oparin. The Kekulé structure count and permanence of the adjacency matrix of fullerenes are related to structural parameters involving the presence of contiguous pentagons p, q and r. Let p be the number of edges common to two pentagons, q the number of vertices common to three pentagons, and r the number of pairs of nonadjacent pentagon edges shared between two other pentagons. Principal component analysis (PCA) of the structural parameters and cluster analysis (CA) of the fullerenes permit classifying them and agree. A PT of the fullerenes is built based on the structural parameters, PCA and CA. The periodic law does not have the rank of the laws of physics. (1) The properties of the fullerenes are not repeated; only, and perhaps, their chemical character. (2) The order relationships are repeated, although with exceptions. The proposed statement is the following: The relationships that any fullerene p has with its neighbor p + 1 are approximately repeated for each period.

A new model to simulate the elastic properties of mineralized collagen fibril.

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

Yuan, F.; Stock, S.R.; Haeffner, D.R.

Bone, because of its hierarchical composite structure, exhibits an excellent combination of stiffness and toughness, which is due substantially to the structural order and deformation at the smaller length scales. Here, we focus on the mineralized collagen fibril, consisting of hydroxyapatite plates with nanometric dimensions aligned within a protein matrix, and emphasize the relationship between the structure and elastic properties of a mineralized collagen fibril. We create two- and three-dimensional representative volume elements to represent the structure of the fibril and evaluate the importance of the parameters defining its structure and properties of the constituent mineral and collagen phase. Elasticmore » stiffnesses are calculated by the finite element method and compared with experimental data obtained by synchrotron X-ray diffraction. The computational results match the experimental data well, and provide insight into the role of the phases and morphology on the elastic deformation characteristics. Also, the effects of water, imperfections in the mineral phase and mineral content outside the mineralized collagen fibril upon its elastic properties are discussed.« less

A new model to simulate the elastic properties of mineralized collagen fibril

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

Yuan, F.; Stock, S.R.; Haeffner, D.R.

Bone, because of its hierarchical composite structure, exhibits an excellent combination of stiffness and toughness, which is due substantially to the structural order and deformation at the smaller length scales. Here, we focus on the mineralized collagen fibril, consisting of hydroxyapatite plates with nanometric dimensions aligned within a protein matrix, and emphasize the relationship between the structure and elastic properties of a mineralized collagen fibril. We create two- and three-dimensional representative volume elements to represent the structure of the fibril and evaluate the importance of the parameters defining its structure and properties of the constituent mineral and collagen phase. Elasticmore » stiffnesses are calculated by the finite element method and compared with experimental data obtained by synchrotron X-ray diffraction. The computational results match the experimental data well, and provide insight into the role of the phases and morphology on the elastic deformation characteristics. Also, the effects of water, imperfections in the mineral phase and mineral content outside the mineralized collagen fibril upon its elastic properties are discussed.« less

Fundamentals of biomechanics in tissue engineering of bone.

PubMed

Athanasiou, K A; Zhu, C; Lanctot, D R; Agrawal, C M; Wang, X

2000-08-01

The objective of this review is to provide basic information pertaining to biomechanical aspects of bone as they relate to tissue engineering. The review is written for the general tissue engineering reader, who may not have a biomechanical engineering background. To this end, biomechanical characteristics and properties of normal and repair cortical and cancellous bone are presented. Also, this chapter intends to describe basic structure-function relationships of these two types of bone. Special emphasis is placed on salient classical and modern testing methods, with both material and structural properties described.

Inelastic behavior of structural components

NASA Technical Reports Server (NTRS)

Hussain, N.; Khozeimeh, K.; Toridis, T. G.

1980-01-01

A more accurate procedure was developed for the determination of the inelastic behavior of structural components. The actual stress-strain curve for the mathematical of the structure was utilized to generate the force-deformation relationships for the structural elements, rather than using simplified models such as elastic-plastic, bilinear and trilinear approximations. relationships were generated for beam elements with various types of cross sections. In the generational of these curves, stress or load reversals, kinematic hardening and hysteretic behavior were taken into account. Intersections between loading and unloading branches were determined through an iterative process. Using the inelastic properties obtained, the plastic static response of some simple structural systems composed of beam elements was computed. Results were compared with known solutions, indicating a considerable improvement over response predictions obtained by means of simplified approximations used in previous investigations.

Plasticization effect of triacetin on structure and properties of starch ester film.

PubMed

Zhu, Jie; Li, Xiaoxi; Huang, Chen; Chen, Ling; Li, Lin

2013-05-15

The aim of this work was to evaluate the plasticizing effect of triacetin on the structure and properties of starch ester film and further establish the structure-property relationships. The presence of triacetin resulted in multiple structure changes of the film. The mobility of macromolecular chain was increased to form scattered crystallite during the film formation process. The amorphous region was enlarged to contain more triacetin squeezed from crystalline region. The plasticization of triacetin and restriction of crystallite oppositely influenced the mobility of macromolecular chains in different regions. The thermal stability of triacetin changed along with its fluctuant interaction with macromolecules. Comparatively, the enhanced ether bond and the restriction from crystalline regions on the mobility of the amorphous chain consequently improved the thermal stability of the film matrix. The interaction between triacetin and starch ester was essential to film forming but unexpectedly lowered the triacetin stability. Copyright © 2013 Elsevier Ltd. All rights reserved.

Polymer matrix nanocomposites for automotive structural components

NASA Astrophysics Data System (ADS)

Naskar, Amit K.; Keum, Jong K.; Boeman, Raymond G.

2016-12-01

Over the past several decades, the automotive industry has expended significant effort to develop lightweight parts from new easy-to-process polymeric nanocomposites. These materials have been particularly attractive because they can increase fuel efficiency and reduce greenhouse gas emissions. However, attempts to reinforce soft matrices by nanoscale reinforcing agents at commercially deployable scales have been only sporadically successful to date. This situation is due primarily to the lack of fundamental understanding of how multiscale interfacial interactions and the resultant structures affect the properties of polymer nanocomposites. In this Perspective, we critically evaluate the state of the art in the field and propose a possible path that may help to overcome these barriers. Only once we achieve a deeper understanding of the structure-properties relationship of polymer matrix nanocomposites will we be able to develop novel structural nanocomposites with enhanced mechanical properties for automotive applications.

Polymer matrix nanocomposites for automotive structural components.

PubMed

Naskar, Amit K; Keum, Jong K; Boeman, Raymond G

2016-12-06

Over the past several decades, the automotive industry has expended significant effort to develop lightweight parts from new easy-to-process polymeric nanocomposites. These materials have been particularly attractive because they can increase fuel efficiency and reduce greenhouse gas emissions. However, attempts to reinforce soft matrices by nanoscale reinforcing agents at commercially deployable scales have been only sporadically successful to date. This situation is due primarily to the lack of fundamental understanding of how multiscale interfacial interactions and the resultant structures affect the properties of polymer nanocomposites. In this Perspective, we critically evaluate the state of the art in the field and propose a possible path that may help to overcome these barriers. Only once we achieve a deeper understanding of the structure-properties relationship of polymer matrix nanocomposites will we be able to develop novel structural nanocomposites with enhanced mechanical properties for automotive applications.

Structures composing protein domains.

PubMed

Kubrycht, Jaroslav; Sigler, Karel; Souček, Pavel; Hudeček, Jiří

2013-08-01

This review summarizes available data concerning intradomain structures (IS) such as functionally important amino acid residues, short linear motifs, conserved or disordered regions, peptide repeats, broadly occurring secondary structures or folds, etc. IS form structural features (units or elements) necessary for interactions with proteins or non-peptidic ligands, enzyme reactions and some structural properties of proteins. These features have often been related to a single structural level (e.g. primary structure) mostly requiring certain structural context of other levels (e.g. secondary structures or supersecondary folds) as follows also from some examples reported or demonstrated here. In addition, we deal with some functionally important dynamic properties of IS (e.g. flexibility and different forms of accessibility), and more special dynamic changes of IS during enzyme reactions and allosteric regulation. Selected notes concern also some experimental methods, still more necessary tools of bioinformatic processing and clinically interesting relationships. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

Review: Pressure-Induced Densification of Oxide Glasses at the Glass Transition

NASA Astrophysics Data System (ADS)

Kapoor, Saurabh; Wondraczek, Lothar; Smedskjaer, Morten M.

2017-02-01

Densification of oxide glasses at the glass transition offers a novel route to develop bulk glasses with tailored properties for emerging applications. Such densification can be achieved in the technologically relevant pressure regime of up to 1GPa. However, the present understanding of the composition-structure-property relationships governing these glasses is limited, with key questions, e.g., related to densification mechanism, remaining largely unanswered. Recent advances in structural characterization tools and high-pressure apparatuses have prompted new research efforts. Here, we review this recent progress and the insights gained in the understanding of the influence of isostatic compression at elevated temperature (so-called hot compression) on the composition-structure-property relationships of oxide glasses. We focus on compression at temperatures at or around the glass transition temperature (Tg), with relevant comparisons made to glasses prepared by pressure quenching and cold compression. We show that permanent densification at 1 GPa sets-in at temperatures above 0.7Tg and the degree of densification increases with increasing compression temperature and time, until attaining an approximately constant value for temperatures above Tg. For glasses compressed at the same temperature/pressure conditions, we demonstrate direct relations between the degree of volume densification and the pressure-induced change in micro-mechanical properties such as hardness, elastic moduli, and extent of the indentation size effect across a variety of glass families. Furthermore, we summarize the results on relaxation behavior of hot compressed glasses. All the pressure-induced changes in the structure and properties exhibit strong composition dependence. The experimental results highlight new opportunities for future investigation and identify research challenges that need to be overcome to advance the field.

Structure-property relationship of quinuclidinium surfactants--Towards multifunctional biologically active molecules.

PubMed

Skočibušić, Mirjana; Odžak, Renata; Štefanić, Zoran; Križić, Ivana; Krišto, Lucija; Jović, Ozren; Hrenar, Tomica; Primožič, Ines; Jurašin, Darija

2016-04-01

Motivated by diverse biological and pharmacological activity of quinuclidine and oxime compounds we have synthesized and characterized novel class of surfactants, 3-hydroxyimino quinuclidinium bromides with different alkyl chains lengths (CnQNOH; n=12, 14 and 16). The incorporation of non conventional hydroxyimino quinuclidinium headgroup and variation in alkyl chain length affects hydrophilic-hydrophobic balance of surfactant molecule and thereby physicochemical properties important for its application. Therefore, newly synthesized surfactants were characterized by the combination of different experimental techniques: X-ray analysis, potentiometry, electrical conductivity, surface tension and dynamic light scattering measurements, as well as antimicrobial susceptibility tests. Comprehensive investigation of CnQNOH surfactants enabled insight into structure-property relationship i.e., way in which the arrangement of surfactant molecules in the crystal phase correlates with their solution behavior and biologically activity. The synthesized CnQNOH surfactants exhibited high adsorption efficiency and relatively low critical micelle concentrations. In addition, all investigated compounds showed very potent and promising activity against Gram-positive and clinically relevant Gram-negative bacterial strains compared to conventional antimicrobial agents: tetracycline and gentamicin. The overall results indicate that bicyclic headgroup with oxime moiety, which affects both hydrophilicity and hydrophobicity of CnQNOH molecule in addition to enabling hydrogen bonding, has dominant effect on crystal packing and physicochemical properties. The unique structural features of cationic surfactants with hydroxyimino quinuclidine headgroup along with diverse biological activity have made them promising structures in novel drug discovery. Obtained fundamental understanding how combination of different functionalities in a single surfactant molecule affects its physicochemical properties represents a good starting point for further biological research. Copyright © 2015 Elsevier B.V. All rights reserved.

Mechanical properties of carbon nanotubes

NASA Astrophysics Data System (ADS)

Salvetat, J.-P.; Bonard, J.-M.; Thomson, N. H.; Kulik, A. J.; Forró, L.; Benoit, W.; Zuppiroli, L.

A variety of outstanding experimental results on the elucidation of the elastic properties of carbon nanotubes are fast appearing. These are based mainly on the techniques of high-resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM) to determine the Young's moduli of single-wall nanotube bundles and multi-walled nanotubes, prepared by a number of methods. These results are confirming the theoretical predictions that carbon nanotubes have high strength plus extraordinary flexibility and resilience. As well as summarising the most notable achievements of theory and experiment in the last few years, this paper explains the properties of nanotubes in the wider context of materials science and highlights the contribution of our research group in this rapidly expanding field. A deeper understanding of the relationship between the structural order of the nanotubes and their mechanical properties will be necessary for the development of carbon-nanotube-based composites. Our research to date illustrates a qualitative relationship between the Young's modulus of a nanotube and the amount of disorder in the atomic structure of the walls. Other exciting results indicate that composites will benefit from the exceptional mechanical properties of carbon nanotubes, but that the major outstanding problem of load transfer efficiency must be overcome before suitable engineering materials can be produced.

Developing descriptors to predict mechanical properties of nanotubes.

PubMed

Borders, Tammie L; Fonseca, Alexandre F; Zhang, Hengji; Cho, Kyeongjae; Rusinko, Andrew

2013-04-22

Descriptors and quantitative structure property relationships (QSPR) were investigated for mechanical property prediction of carbon nanotubes (CNTs). 78 molecular dynamics (MD) simulations were carried out, and 20 descriptors were calculated to build quantitative structure property relationships (QSPRs) for Young's modulus and Poisson's ratio in two separate analyses: vacancy only and vacancy plus methyl functionalization. In the first analysis, C(N2)/C(T) (number of non-sp2 hybridized carbons per the total carbons) and chiral angle were identified as critical descriptors for both Young's modulus and Poisson's ratio. Further analysis and literature findings indicate the effect of chiral angle is negligible at larger CNT radii for both properties. Raman spectroscopy can be used to measure C(N2)/C(T), providing a direct link between experimental and computational results. Poisson's ratio approaches two different limiting values as CNT radii increases: 0.23-0.25 for chiral and armchair CNTs and 0.10 for zigzag CNTs (surface defects <3%). In the second analysis, the critical descriptors were C(N2)/C(T), chiral angle, and M(N)/C(T) (number of methyl groups per total carbons). These results imply new types of defects can be represented as a new descriptor in QSPR models. Finally, results are qualified and quantified against experimental data.

Structure-property correlation study through sum-over-state approach

NASA Astrophysics Data System (ADS)

Nandi, P. K.; Hatua, K.; Bansh, A. K.; Panja, N.; Ghanty, T. K.

2015-01-01

The use of Thomas Kuhn (TK) sum rule in the expanded sum-over-state (SOS) expression of hyperpolarizabilities leads to various relationships between different order of polarizabilities and ground state dipole moment etc.

Abstract Profiles of Structural Stability Point to Universal Tendencies, Family-Specific Factors, and Ancient Connections between Languages

PubMed Central

Dediu, Dan; Levinson, Stephen C.

2012-01-01

Language is the best example of a cultural evolutionary system, able to retain a phylogenetic signal over many thousands of years. The temporal stability (conservatism) of basic vocabulary is relatively well understood, but the stability of the structural properties of language (phonology, morphology, syntax) is still unclear. Here we report an extensive Bayesian phylogenetic investigation of the structural stability of numerous features across many language families and we introduce a novel method for analyzing the relationships between the “stability profiles” of language families. We found that there is a strong universal component across language families, suggesting the existence of universal linguistic, cognitive and genetic constraints. Against this background, however, each language family has a distinct stability profile, and these profiles cluster by geographic area and likely deep genealogical relationships. These stability profiles seem to show, for example, the ancient historical relationships between the Siberian and American language families, presumed to be separated by at least 12,000 years, and possible connections between the Eurasian families. We also found preliminary support for the punctuated evolution of structural features of language across families, types of features and geographic areas. Thus, such higher-level properties of language seen as an evolutionary system might allow the investigation of ancient connections between languages and shed light on the peopling of the world. PMID:23028843

Abstract profiles of structural stability point to universal tendencies, family-specific factors, and ancient connections between languages.

PubMed

Dediu, Dan; Levinson, Stephen C

2012-01-01

Language is the best example of a cultural evolutionary system, able to retain a phylogenetic signal over many thousands of years. The temporal stability (conservatism) of basic vocabulary is relatively well understood, but the stability of the structural properties of language (phonology, morphology, syntax) is still unclear. Here we report an extensive Bayesian phylogenetic investigation of the structural stability of numerous features across many language families and we introduce a novel method for analyzing the relationships between the "stability profiles" of language families. We found that there is a strong universal component across language families, suggesting the existence of universal linguistic, cognitive and genetic constraints. Against this background, however, each language family has a distinct stability profile, and these profiles cluster by geographic area and likely deep genealogical relationships. These stability profiles seem to show, for example, the ancient historical relationships between the Siberian and American language families, presumed to be separated by at least 12,000 years, and possible connections between the Eurasian families. We also found preliminary support for the punctuated evolution of structural features of language across families, types of features and geographic areas. Thus, such higher-level properties of language seen as an evolutionary system might allow the investigation of ancient connections between languages and shed light on the peopling of the world.

Revisiting Robustness and Evolvability: Evolution in Weighted Genotype Spaces

PubMed Central

Partha, Raghavendran; Raman, Karthik

2014-01-01

Robustness and evolvability are highly intertwined properties of biological systems. The relationship between these properties determines how biological systems are able to withstand mutations and show variation in response to them. Computational studies have explored the relationship between these two properties using neutral networks of RNA sequences (genotype) and their secondary structures (phenotype) as a model system. However, these studies have assumed every mutation to a sequence to be equally likely; the differences in the likelihood of the occurrence of various mutations, and the consequence of probabilistic nature of the mutations in such a system have previously been ignored. Associating probabilities to mutations essentially results in the weighting of genotype space. We here perform a comparative analysis of weighted and unweighted neutral networks of RNA sequences, and subsequently explore the relationship between robustness and evolvability. We show that assuming an equal likelihood for all mutations (as in an unweighted network), underestimates robustness and overestimates evolvability of a system. In spite of discarding this assumption, we observe that a negative correlation between sequence (genotype) robustness and sequence evolvability persists, and also that structure (phenotype) robustness promotes structure evolvability, as observed in earlier studies using unweighted networks. We also study the effects of base composition bias on robustness and evolvability. Particularly, we explore the association between robustness and evolvability in a sequence space that is AU-rich – sequences with an AU content of 80% or higher, compared to a normal (unbiased) sequence space. We find that evolvability of both sequences and structures in an AU-rich space is lesser compared to the normal space, and robustness higher. We also observe that AU-rich populations evolving on neutral networks of phenotypes, can access less phenotypic variation compared to normal populations evolving on neutral networks. PMID:25390641

The relationships between electricity consumption and GDP in Asian countries, using hierarchical structure methods

NASA Astrophysics Data System (ADS)

Kantar, Ersin; Keskin, Mustafa

2013-11-01

This study uses hierarchical structure methods (minimal spanning tree (MST) and hierarchical tree (HT)) to examine the relationship between energy consumption and economic growth in a sample of 30 Asian countries covering the period 1971-2008. These countries are categorized into four panels based on the World Bank income classification, namely high, upper middle, lower middle, and low income. In particular, we use the data of electricity consumption and real gross domestic product (GDP) per capita to detect the topological properties of the countries. We show a relationship between electricity consumption and economic growth by using the MST and HT. We also use the bootstrap technique to investigate a value of the statistical reliability to the links of the MST. Finally, we use a clustering linkage procedure in order to observe the cluster structure. The results of the structural topologies of these trees are as follows: (i) we identified different clusters of countries according to their geographical location and economic growth, (ii) we found a strong relationship between energy consumption and economic growth for all income groups considered in this study and (iii) the results are in good agreement with the causal relationship between electricity consumption and economic growth.

Pore scale modelling of electrical and hydraulic properties of a semi-consolidated sandstone under unsaturated conditions

NASA Astrophysics Data System (ADS)

Cassiani, G.; dalla, E.; Brovelli, A.; Pitea, D.; Binley, A. M.

2003-04-01

The development of reliable constitutive laws to translate geophysical properties into hydrological ones is the fundamental step for successful applications of hydrogeophysical techniques. Many such laws have been proposed and applied, particularly with regard to two types of relationships: (a) between moisture content and dielectric properties, and (b) between electrical resistivity, rock structure and water saturation. The classical Archie's law belongs to this latter category. Archie's relationship has been widely used, starting from borehole logs applications, to translate geoelectrical measurements into estimates of saturation. However, in spite of its popularity, it remains an empirical relationship, the parameters of which must be calibrated case by case, e.g. on laboratory data. Pore-scale models have been recently recognized and used as powerful tools to investigate the constitutive relations of multiphase soils from a pore-scale point of view, because they bridge the microscopic and macroscopic scales. In this project, we develop and validate a three-dimensional pore-scale method to compute electrical properties of unsaturated and saturated porous media. First we simulate a random packing of spheres [1] that obeys the grain-size distribution and porosity of an experimental porous medium system; then we simulate primary drainage with a morphological approach [2]; finally, for each state of saturation during the drainage process, we solve the electrical conduction equation within the grain structure with a new numerical model and compute the apparent electrical resistivity of the porous medium. We apply the new method to a semi-consolidated Permo-Triassic Sandstone from the UK (Sherwood Sandstone) for which both pressure-saturation (Van Genuchten) and Archie's law parameters have been measured on laboratory samples. A comparison between simulated and measured relationships has been performed.

Tailoring the Electrochemical Properties of Carbon Nanotube Modified Indium Tin Oxide via in Situ Grafting of Aryl Diazonium.

PubMed

Hicks, Jacqueline M; Wong, Zhi Yi; Scurr, David J; Silman, Nigel; Jackson, Simon K; Mendes, Paula M; Aylott, Jonathan W; Rawson, Frankie J

2017-05-23

Our ability to tailor the electronic properties of surfaces by nanomodification is paramount for various applications, including development of sensing, fuel cell, and solar technologies. Moreover, in order to improve the rational design of conducting surfaces, an improved understanding of structure/function relationships of nanomodifications and effect they have on the underlying electronic properties is required. Herein, we report on the tuning and optimization of the electrochemical properties of indium tin oxide (ITO) functionalized with single-walled carbon nanotubes (SWCNTs). This was achieved by controlling in situ grafting of aryl amine diazonium films on the nanoscale which were used to covalently tether SWCNTs. The structure/function relationship of these nanomodifications on the electronic properties of ITO was elucidated via time-of-flight secondary ion mass spectrometry and electrochemical and physical characterization techniques which has led to new mechanistic insights into the in situ grafting of diazonium. We discovered that the connecting bond is a nitro group which is covalently linked to a carbon on the aryl amine. The increased understanding of the surface chemistry gained through these studies enabled us to fabricate surfaces with optimized electron transfer kinetics. The knowledge gained from these studies allows for the rational design and tuning of the electronic properties of ITO-based conducting surfaces important for development of various electronic applications.

Structure Property Relationships of Biobased Epoxy Resins

NASA Astrophysics Data System (ADS)

Maiorana, Anthony Surraht

The thesis is about the synthesis, characterization, development, and application of epoxy resins derived from sustainable feedstocks such as lingo-cellulose, plant oils, and other non-food feedstocks. The thesis can be divided into two main topics 1) the synthesis and structure property relationship investigation of new biobased epoxy resin families and 2) mixing epoxy resins with reactive diluents, nanoparticles, toughening agents, and understanding co-curing reactions, filler/matrix interactions, and cured epoxy resin thermomechanical, viscoelastic, and dielectric properties. The thesis seeks to bridge the gap between new epoxy resin development, application for composites and advanced materials, processing and manufacturing, and end of life of thermoset polymers. The structures of uncured epoxy resins are characterized through traditional small molecule techniques such as nuclear magnetic resonance, high resolution mass spectrometry, and infrared spectroscopy. The structure of epoxy resin monomers are further understood through the process of curing the resins and cured resins' properties through rheology, chemorheology, dynamic mechanical analysis, tensile testing, fracture toughness, differential scanning calorimetry, scanning electron microscopy, thermogravimetric analysis, and notched izod impact testing. It was found that diphenolate esters are viable alternatives to bisphenol A and that the structure of the ester side chain can have signifi-cant effects on monomer viscosity. The structure of the cured diphenolate based epoxy resins also influence glass transition temperature and dielectric properties. Incorporation of reactive diluents and flexible resins can lower viscosity, extend gel time, and enable processing of high filler content composites and increase fracture toughness. Incorpora-tion of high elastic modulus nanoparticles such as graphene can provide increases in physical properties such as elastic modulus and fracture toughness. The synthesis of epoxy resins with aliphatic esters in the main chain of the polymer allow for chemical recycling under alkaline conditions and changing the hydrophobicity and access of main chain esters influences the rate of polymer degradation. The thesis further provides strategies and concepts that will allow for future researchers to rapidly understand how to manipulate epoxy resins for specific end uses and supplements current understanding of epoxy curing agents, accelerators, and interactions with fillers.

On the Development and Use of Large Chemical Similarity Networks, Informatics Best Practices and Novel Chemical Descriptors Towards Materials Quantitative Structure Property Relationships

NASA Astrophysics Data System (ADS)

Krein, Michael

After decades of development and use in a variety of application areas, Quantitative Structure Property Relationships (QSPRs) and related descriptor-based statistical learning methods have achieved a level of infamy due to their misuse. The field is rife with past examples of overtrained models, overoptimistic performance assessment, and outright cheating in the form of explicitly removing data to fit models. These actions do not serve the community well, nor are they beneficial to future predictions based on established models. In practice, in order to select combinations of descriptors and machine learning methods that might work best, one must consider the nature and size of the training and test datasets, be aware of existing hypotheses about the data, and resist the temptation to bias structure representation and modeling to explicitly fit the hypotheses. The definition and application of these best practices is important for obtaining actionable modeling outcomes, and for setting user expectations of modeling accuracy when predicting the endpoint values of unknowns. A wide variety of statistical learning approaches, descriptor types, and model validation strategies are explored herein, with the goals of helping end users understand the factors involved in creating and using QSPR models effectively, and to better understand relationships within the data, especially by looking at the problem space from multiple perspectives. Molecular relationships are commonly envisioned in a continuous high-dimensional space of numerical descriptors, referred to as chemistry space. Descriptor and similarity metric choice influence the partitioning of this space into regions corresponding to local structural similarity. These regions, known as domains of applicability, are most likely to be successfully modeled by a QSPR. In Chapter 2, the network topology and scaling relationships of several chemistry spaces are thoroughly investigated. Chemistry spaces studied include the ZINC data set, a qHTS PubChem bioassay, as well as the protein binding sites from the PDB. The characteristics of these networks are compared and contrasted with those of the bioassay Structure Activity Landscape Index (SALI) subnetwork, which maps discontinuities or cliffs in the structure activity landscape. Mapping this newly generated information over underlying chemistry space networks generated using different descriptors demonstrates local modeling capacity and can guide the choice of better local representations of chemistry space. Chapter 2 introduces and demonstrates this novel concept, which also enables future work in visualization and interpretation of chemical spaces. Initially, it was discovered that there were no community-available tools to leverage best-practice ideas to comprehensively build, compare, and interpret QSPRs. The Yet Another Modeling System (YAMS) tool performs a series of balanced, rational decisions in dataset preprocessing and parameter/feature selection over a choice of modeling methods. To date, YAMS is the only community-available informatics tool that performs such decisions consistently between methods while also providing multiple model performance comparisons and detailed descriptor importance information. The focus of the tool is thus to convey rich information about model quality and predictions that help to "close the loop" between modeling and experimental efforts, for example, in tailoring nanocomposite properties. Polymer nanocomposites (PNC) are complex material systems encompassing many potential structures, chemistries, and self assembled morphologies that could significantly impact commercial and military applications. There is a strong desire to characterize and understand the tradespace of nanocomposites, to identify the important factors relating nanostructure to materials properties and determine an effective way to control materials properties at the manufacturing scale. Due to the complexity of the systems, existing design approaches rely heavily on trial-and-error learning. By leveraging existing experimental data, Materials Quantitative Structure-Property Relationships (MQSPRs) relate molecular structures to the polar and dispersive components of corresponding surface tensions. In turn, existing theories relate polymer and nanofiller polar and dispersive surface tension components to the dispersion state and interfacial polymer relaxation times. These quantities may, in the future, be used as input to continuum mechanics approaches shown able to predict the thermomechanical response of nanocomposites. For a polymer dataset and a particle dataset, multiple structural representations and descriptor sets are benchmarked, including a set of high performance surface-property descriptors developed as part of this work. The systematic variation of structural representations as part of the informatics approach reveals important insight in modeling polymers, and should become common practice when defining new problem spaces.

The relationships between deformation mechanisms and mechanical properties of additively manufactured porous biomaterials.

PubMed

Kadkhodapour, J; Montazerian, H; Darabi, A Ch; Zargarian, A; Schmauder, S

2017-06-01

Modulating deformation mechanism through manipulating morphological parameters of scaffold internal pore architecture provides potential to tailor the overall mechanical properties under physiological loadings. Whereas cells sense local strains, cell differentiation is also impressed by the elastic deformations. In this paper, structure-property relations were developed for Ti6-Al-4V scaffolds designed based on triply periodic minimal surfaces. 10mm cubic scaffolds composed of 5×5×5 unit cells formed of F-RD (bending dominated) and I-WP (stretching dominated) architectures were additively manufactured at different volume fractions and subjected to compressive tests. The first stages of deformation for stretching dominated structure, was accompanied by bilateral layer-by-layer failure of unit cells owing to the buckling of micro-struts, while for bending dominated structure, namely F-RD, global shearing bands appeared since the shearing failure of struts in the internal architecture. Promoted mechanical properties were found for stretching dominated structure since the global orientation of struts were parallel to loading direction while inclination of struts diminished specific properties for bending dominated structure. Moreover, elastic-plastic deformation was computationally studied by applying Johnson-Cook damage model to the voxel-based models in FE analysis. Scaling analysis was performed for mechanical properties with respect to the relative density thereby failure mechanism was correlated to the constants of power law describing mechanical properties. Copyright © 2016 Elsevier Ltd. All rights reserved.

How the Dynamics of a Supramolecular Polymer Determines Its Dynamic Adaptivity and Stimuli-Responsiveness: Structure-Dynamics-Property Relationships From Coarse-Grained Simulations.

PubMed

Torchi, Andrea; Bochicchio, Davide; Pavan, Giovanni M

2018-04-12

The rational design of supramolecular polymers that can adapt or respond in time to specific stimuli in a controlled way is interesting for many applications, but this requires understanding the molecular factors that make the material faster or slower in responding to the stimulus. To this end, it is necessary to study the dynamic adaptive properties at submolecular resolution, which is difficult at an experimental level. Here we show coarse-grained molecular dynamics simulations (<5 Å resolution) demonstrating how the dynamic adaptivity and stimuli responsiveness of a supramolecular polymer is controlled by the intrinsic dynamics of the assembly, which is in turn determined by the structure of the monomers. As a representative case, we focus on a water-soluble 1,3,5-benzenetricarboxamide (BTA) supramolecular polymer incorporating (charged) receptor monomers, experimentally seen to undergo dynamic clustering following the superselective binding to a multivalent recruiter. Our simulations show that the dynamic reorganization of the supramolecular structure proceeds via monomer diffusion on the dynamic fiber surface (exchange within the fiber). Rationally changing the structure of the monomers to make the fiber surface more or less dynamic allows tuning the rate of response to the stimulus and of supramolecular reconfiguration. Simple in silico experiments draw a structure-dynamics-property relationship revealing the key factors underpinning the dynamic adaptivity and stimuli-responsiveness of these supramolecular polymers. We come out with clear evidence that to master the bioinspired properties of these fibers, it is necessary to control their intrinsic dynamics, while the high-resolution of our molecular models permits us to show how.

Experimental study and numerical simulation on the structural and mechanical properties of Typha leaves through multimodal microscopy approaches.

PubMed

Liu, Jingjing; Zhang, Zhihui; Yu, Zhenglei; Liang, Yunhong; Li, Xiujuan; Ren, Luquan

2018-01-01

The Typha leaf, with special multi-level structure, low density and excellent mechanical properties, is an ideal bionic prototype utilized for lightweight design. In order to further study the relationship between the structure and mechanical properties, the three-dimensional macroscopic morphology of Typha leaves was characterized by micro computed tomography (Micro-CT) and its internal microstructure was observed by scanning electron microscopy (SEM). The combination of experimental and computational research was carried out in this paper, to reveal and verify the effect of multi-level structure on the mechanical properties. A universal testing machine and a self-developed mechanical testing apparatus with high precision and low load were used to measure the mechanical properties of the axial compression and lateral bending of the leaves, respectively. Three models with different internal structures were established based on the above-mentioned three-dimensional morphologies. The result demonstrated that the structure of partitions and diaphragms within the Typha leaf could form a reinforcement ribs structure which could provide multiple load paths and make the process of compression and bending difficult. The further nonlinear finite element analysis through LS-DYNA proved that internal structure could improve the ability of the models to resist compression and deformation. The investigation can be the reference for lightweight thin-walled structure design and inspire the application of the bionic structural materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

Relationships between Structural and Acoustic Properties of Maternal Talk and Children's Early Word Recognition

ERIC Educational Resources Information Center

Suttora, Chiara; Salerni, Nicoletta; Zanchi, Paola; Zampini, Laura; Spinelli, Maria; Fasolo, Mirco

2017-01-01

This study aimed to investigate specific associations between structural and acoustic characteristics of infant-directed (ID) speech and word recognition. Thirty Italian-acquiring children and their mothers were tested when the children were 1;3. Children's word recognition was measured with the looking-while-listening task. Maternal ID speech was…

Structure, Electronic Properties, and Electrochemical Behavior of a Boron-Doped Diamond/Quartz Optically Transparent Electrode.

PubMed

Wächter, Naihara; Munson, Catherine; Jarošová, Romana; Berkun, Isil; Hogan, Timothy; Rocha-Filho, Romeu C; Swain, Greg M

2016-10-26

The morphology, microstructure, chemistry, electronic properties, and electrochemical behavior of a boron-doped nanocrystalline diamond (BDD) thin film grown on quartz were evaluated. Diamond optically transparent electrodes (OTEs) are useful for transmission spectroelectrochemical measurements, offering excellent stability during anodic and cathodic polarization and exposure to a variety of chemical environments. We report on the characterization of a BDD OTE by atomic force microscopy, optical spectroscopy, Raman spectroscopic mapping, alternating-current Hall effect measurements, X-ray photoelectron spectroscopy, and electrochemical methods. The results reported herein provide the first comprehensive study of the relationship between the physical and chemical structure and electronic properties of a diamond OTE and the electrode's electrochemical activity.

Correlation between structure, retention, property, and activity of biologically relevant 1,7-bis(aminoalkyl)diazachrysene derivatives.

PubMed

Šegan, Sandra; Trifković, Jelena; Verbić, Tatjana; Opsenica, Dejan; Zlatović, Mario; Burnett, James; Šolaja, Bogdan; Milojković-Opsenica, Dušanka

2013-01-01

The physicochemical properties, retention parameters (R(M)(0)), partition coefficients (logP(OW)), and pK(a) values for a series of thirteen 1,7-bis(aminoalkyl) diazachrysene (1,7-DAAC) derivatives were determined in order to reveal the characteristics responsible for their biological behavior. The investigated compounds inhibit three unrelated pathogens (the Botulinum neurotoxin serotype A light chain (BoNT/A LC), Plasmodium falciparum malaria, and Ebola filovirus) via three different mechanisms of action. To determine the most influential factors governing the retention and activities of the investigated diazachrysenes, R(M)(0), logP(OW), and biological activity values were correlated with 2D and 3D molecular descriptors, using a partial least squares regression. The resulting quantitative structure-retention (property) relationships indicate the importance of descriptors related to the hydrophobicity of the molecules (e.g., predicted partition coefficients and hydrophobic surface area). Quantitative structure-activity relationship models for describing biological activity against the BoNT/A LC and malarial strains also include overall compound polarity, electron density distribution, and proton donor/acceptor potential. Furthermore, models for Ebola filovirus inhibition are presented qualitatively to provide insights into parameters that may contribute to the compounds' antiviral activities. Overall, the models form the basis for selecting structural features that significantly affect the compound's absorption, distribution, metabolism, excretion, and toxicity profiles. Copyright © 2012 Elsevier B.V. All rights reserved.

Structure guided design of a series of selective pyrrolopyrimidinone MARK inhibitors

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

Katz, Jason D.; Haidle, Andrew; Childers, Kaleen K.

2017-01-01

The initial structure activity relationships around an isoindoline uHTS hit will be described. Information gleaned from ligand co-crystal structures allowed for rapid refinements in both MARK potency and kinase selectivity. These efforts allowed for the identification of a compound with properties suitable for use as an in vitro tool compound for validation studies on MARK as a viable target for Alzheimer’s disease.

Molecular-Level Control of Ciclopirox Olamine Release from Poly(ethylene oxide)-Based Mucoadhesive Buccal Films: Exploration of Structure-Property Relationships with Solid-State NMR.

PubMed

Urbanova, Martina; Gajdosova, Marketa; Steinhart, Miloš; Vetchy, David; Brus, Jiri

2016-05-02

Mucoadhesive buccal films (MBFs) provide an innovative way to facilitate the efficient site-specific delivery of active compounds while simultaneously separating the lesions from the environment of the oral cavity. The structural diversity of these complex multicomponent and mostly multiphase systems as well as an experimental strategy for their structural characterization at molecular scale with atomic resolution were demonstrated using MBFs of ciclopirox olamine (CPX) in a poly(ethylene oxide) (PEO) matrix as a case study. A detailed description of each component of the CPX/PEO films was followed by an analysis of the relationships between each component and the physicochemical properties of the MBFs. Two distinct MBFs were identified by solid-state NMR spectroscopy: (i) at low API (active pharmaceutical ingredient) loading, a nanoheterogeneous solid solution of CPX molecularly dispersed in an amorphous PEO matrix was created; and (ii) at high API loading, a pseudoco-crystalline system containing CPX-2-aminoethanol nanocrystals incorporated into the interlamellar space of a crystalline PEO matrix was revealed. These structural differences were found to be closely related to the mechanical and physicochemical properties of the prepared MBFs. At low API loading, the polymer chains of PEO provided sufficient quantities of binding sites to stabilize the CPX that was molecularly dispersed in the highly amorphous semiflexible polymer matrix. Consequently, the resulting MBFs were soft, with low tensile strength, plasticity, and swelling index, supporting rapid drug release. At high CPX content, however, the active compounds and the polymer chains simultaneously cocrystallized, leaving the CPX to form nanocrystals grown directly inside the spherulites of PEO. Interfacial polymer-drug interactions were thus responsible not only for the considerably enhanced plasticity of the system but also for the exclusive crystallization of CPX in the thermodynamically most stable polymorphic form, Form I, which exhibited reduced dissolution kinetics. The bioavailability of CPX olamine formulated as PEO-based MBFs can thus be effectively controlled by inducing the complete dispersion and/or microsegregation and nanocrystallization of CPX olamine in the polymer matrix. Solid-state NMR spectroscopy is an efficient tool for exploring structure-property relationships in these complex pharmaceutical solids.

Thermoviscoplastic nonlinear constitutive relationships for structural analysis of high temperature metal matrix composites

NASA Technical Reports Server (NTRS)

Chamis, C. C.; Hopkins, D. A.

1985-01-01

A set of thermoviscoplastic nonlinear constitutive relationships (1VP-NCR) is presented. The set was developed for application to high temperature metal matrix composites (HT-MMC) and is applicable to thermal and mechanical properties. Formulation of the TVP-NCR is based at the micromechanics level. The TVP-NCR are of simple form and readily integrated into nonlinear composite structural analysis. It is shown that the set of TVP-NCR is computationally effective. The set directly predicts complex materials behavior at all levels of the composite simulation, from the constituent materials, through the several levels of composite mechanics, and up to the global response of complex HT-MMC structural components.

Universal fragment descriptors for predicting properties of inorganic crystals

NASA Astrophysics Data System (ADS)

Isayev, Olexandr; Oses, Corey; Toher, Cormac; Gossett, Eric; Curtarolo, Stefano; Tropsha, Alexander

2017-06-01

Although historically materials discovery has been driven by a laborious trial-and-error process, knowledge-driven materials design can now be enabled by the rational combination of Machine Learning methods and materials databases. Here, data from the AFLOW repository for ab initio calculations is combined with Quantitative Materials Structure-Property Relationship models to predict important properties: metal/insulator classification, band gap energy, bulk/shear moduli, Debye temperature and heat capacities. The prediction's accuracy compares well with the quality of the training data for virtually any stoichiometric inorganic crystalline material, reciprocating the available thermomechanical experimental data. The universality of the approach is attributed to the construction of the descriptors: Property-Labelled Materials Fragments. The representations require only minimal structural input allowing straightforward implementations of simple heuristic design rules.

Universal fragment descriptors for predicting properties of inorganic crystals.

PubMed

Isayev, Olexandr; Oses, Corey; Toher, Cormac; Gossett, Eric; Curtarolo, Stefano; Tropsha, Alexander

2017-06-05

Although historically materials discovery has been driven by a laborious trial-and-error process, knowledge-driven materials design can now be enabled by the rational combination of Machine Learning methods and materials databases. Here, data from the AFLOW repository for ab initio calculations is combined with Quantitative Materials Structure-Property Relationship models to predict important properties: metal/insulator classification, band gap energy, bulk/shear moduli, Debye temperature and heat capacities. The prediction's accuracy compares well with the quality of the training data for virtually any stoichiometric inorganic crystalline material, reciprocating the available thermomechanical experimental data. The universality of the approach is attributed to the construction of the descriptors: Property-Labelled Materials Fragments. The representations require only minimal structural input allowing straightforward implementations of simple heuristic design rules.

Structure-property relationships of a biological mesocrystal in the adult sea urchin spine

PubMed Central

Seto, Jong; Ma, Yurong; Davis, Sean A.; Meldrum, Fiona; Gourrier, Aurelien; Kim, Yi-Yeoun; Schilde, Uwe; Sztucki, Michael; Burghammer, Manfred; Maltsev, Sergey; Jäger, Christian; Cölfen, Helmut

2012-01-01

Structuring over many length scales is a design strategy widely used in Nature to create materials with unique functional properties. We here present a comprehensive analysis of an adult sea urchin spine, and in revealing a complex, hierarchical structure, show how Nature fabricates a material which diffracts as a single crystal of calcite and yet fractures as a glassy material. Each spine comprises a highly oriented array of Mg-calcite nanocrystals in which amorphous regions and macromolecules are embedded. It is postulated that this mesocrystalline structure forms via the crystallization of a dense array of amorphous calcium carbonate (ACC) precursor particles. A residual surface layer of ACC and/or macromolecules remains around the nanoparticle units which creates the mesocrystal structure and contributes to the conchoidal fracture behavior. Nature’s demonstration of how crystallization of an amorphous precursor phase can create a crystalline material with remarkable properties therefore provides inspiration for a novel approach to the design and synthesis of synthetic composite materials. PMID:22343283

Polaronic transport in Ag-based quaternary chalcogenides

NASA Astrophysics Data System (ADS)

Wei, Kaya; Khabibullin, Artem R.; Stedman, Troy; Woods, Lilia M.; Nolas, George S.

2017-09-01

Low temperature resistivity measurements on dense polycrystalline quaternary chalcogenides Ag2+xZn1-xSnSe4, with x = 0, 0.1, and 0.3, indicate polaronic type transport which we analyze employing a two-component Holstein model based on itinerant and localized polaron contributions. Electronic structure property calculations via density functional theory simulations on Ag2ZnSnSe4 for both energetically similar kesterite and stannite structure types were also performed in order to compare our results to those of the compositionally similar but well known Cu2ZnSnSe4. This theoretical comparison is crucial in understanding the bonding that results in polaronic type transport for Ag2ZnSnSe4, as well as the structural and electronic properties of both crystal structure types. In addition to possessing this unique electronic transport, the thermal conductivity of Ag2ZnSnSe4 is low and decreases with increasing silver content. This work reveals unique structure-property relationships in materials that continue to be of interest for thermoelectric and photovoltaic applications.

Structure-property relationships of a biological mesocrystal in the adult sea urchin spine.

PubMed

Seto, Jong; Ma, Yurong; Davis, Sean A; Meldrum, Fiona; Gourrier, Aurelien; Kim, Yi-Yeoun; Schilde, Uwe; Sztucki, Michael; Burghammer, Manfred; Maltsev, Sergey; Jäger, Christian; Cölfen, Helmut

2012-03-06

Structuring over many length scales is a design strategy widely used in Nature to create materials with unique functional properties. We here present a comprehensive analysis of an adult sea urchin spine, and in revealing a complex, hierarchical structure, show how Nature fabricates a material which diffracts as a single crystal of calcite and yet fractures as a glassy material. Each spine comprises a highly oriented array of Mg-calcite nanocrystals in which amorphous regions and macromolecules are embedded. It is postulated that this mesocrystalline structure forms via the crystallization of a dense array of amorphous calcium carbonate (ACC) precursor particles. A residual surface layer of ACC and/or macromolecules remains around the nanoparticle units which creates the mesocrystal structure and contributes to the conchoidal fracture behavior. Nature's demonstration of how crystallization of an amorphous precursor phase can create a crystalline material with remarkable properties therefore provides inspiration for a novel approach to the design and synthesis of synthetic composite materials.

Comparative analysis of machine learning methods in ligand-based virtual screening of large compound libraries.

PubMed

Ma, Xiao H; Jia, Jia; Zhu, Feng; Xue, Ying; Li, Ze R; Chen, Yu Z

2009-05-01

Machine learning methods have been explored as ligand-based virtual screening tools for facilitating drug lead discovery. These methods predict compounds of specific pharmacodynamic, pharmacokinetic or toxicological properties based on their structure-derived structural and physicochemical properties. Increasing attention has been directed at these methods because of their capability in predicting compounds of diverse structures and complex structure-activity relationships without requiring the knowledge of target 3D structure. This article reviews current progresses in using machine learning methods for virtual screening of pharmacodynamically active compounds from large compound libraries, and analyzes and compares the reported performances of machine learning tools with those of structure-based and other ligand-based (such as pharmacophore and clustering) virtual screening methods. The feasibility to improve the performance of machine learning methods in screening large libraries is discussed.

Differential effects of genetically distinct mechanisms of elevating amylose on barley starch characteristics.

PubMed

Regina, Ahmed; Blazek, Jaroslav; Gilbert, Elliot; Flanagan, Bernadine M; Gidley, Michael J; Cavanagh, Colin; Ral, Jean-Philippe; Larroque, Oscar; Bird, Anthony R; Li, Zhongyi; Morell, Matthew K

2012-07-01

The relationships between starch structure and functionality are important in underpinning the industrial and nutritional utilisation of starches. In this work, the relationships between the biosynthesis, structure, molecular organisation and functionality have been examined using a series of defined genotypes in barley with low (<20%), standard (20-30%), elevated (30-50%) and high (>50%) amylose starches. A range of techniques have been employed to determine starch physical features, higher order structure and functionality. The two genetic mechanisms for generating high amylose contents (down-regulation of branching enzymes and starch synthases, respectively) yielded starches with very different amylopectin structures but similar gelatinisation and viscosity properties driven by reduced granular order and increased amylose content. Principal components analysis (PCA) was used to elucidate the relationships between genotypes and starch molecular structure and functionality. Parameters associated with granule order (PC1) accounted for a large percentage of the variance (57%) and were closely related to amylose content. Parameters associated with amylopectin fine structure accounted for 18% of the variance but were less closely aligned to functionality parameters. Copyright © 2012 Elsevier Ltd. All rights reserved.

Unraveling the Solution-State Supramolecular Structures of Donor-Acceptor Polymers and their Influence on Solid-State Morphology and Charge-Transport Properties.

PubMed

Zheng, Yu-Qing; Yao, Ze-Fan; Lei, Ting; Dou, Jin-Hu; Yang, Chi-Yuan; Zou, Lin; Meng, Xiangyi; Ma, Wei; Wang, Jie-Yu; Pei, Jian

2017-11-01

Polymer self-assembly in solution prior to film fabrication makes solution-state structures critical for their solid-state packing and optoelectronic properties. However, unraveling the solution-state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution-state structure and the charge-transport properties in field-effect transistors. Here, for the first time, it is revealed that the thin-film morphology of a conjugated polymer inherits the features of its solution-state supramolecular structures. A "solution-state supramolecular structure control" strategy is proposed to increase the electron mobility of a benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)-based polymer. It is shown that the solution-state structures of the BDOPV-based conjugated polymer can be tuned such that it forms a 1D rod-like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution-state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V -1 s -1 . This work demonstrates that "solution-state supramolecular structure" control is critical for understanding and optimization of the thin-film morphology and charge-transport properties of conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic scale structure and chemistry of interfaces by Z-contrast imaging and electron energy loss spectroscopy in the STEM

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

McGibbon, M.M.; Browning, N.D.; Chisholm, M.F.

The macroscopic properties of many materials are controlled by the structure and chemistry at the grain boundaries. A basic understanding of the structure-property relationship requires a technique which probes both composition and chemical bonding on an atomic scale. The high-resolution Z-contrast imaging technique in the scanning transmission electron microscope (STEM) forms an incoherent image in which changes in atomic structure and composition can be interpreted intuitively. This direct image allows the electron probe to be positioned over individual atomic columns for parallel detection electron energy loss spectroscopy (PEELS) at a spatial resolution approaching 0.22nm. The bonding information which can bemore » obtained from the fine structure within the PEELS edges can then be used in conjunction with the Z-contrast images to determine the structure at the grain boundary. In this paper we present 3 examples of correlations between the structural, chemical and electronic properties at materials interfaces in metal-semiconductor systems, superconducting and ferroelectric materials.« less

The effect of radiation on the thermal properties of chitosan/mimosa tenuiflora and chitosan/mimosa tenuiflora/multiwalled carbon nanotubes (MWCNT) composites for bone tissue engineering

NASA Astrophysics Data System (ADS)

Martel-Estrada, S. A.; Santos-Rodríguez, E.; Olivas-Armendáriz, I.; Cruz-Zaragoza, E.; Martínez-Pérez, C. A.

2014-07-01

The purpose of this study is to examine the effect of gamma radiation and UV radiation on the microstructure, chemical structure and thermal stability of Chitosan/Mimosa Tenuiflora and Chitosan/Mimosa Tenuiflora/MWCNT composites scaffolds produced by thermally induced phase separation. The composites were irradiated and observed to undergo radiation-induced degradation through chain scission. Morphology, thermal properties and effects on chemical and semi-crystalline structures were obtained by scanning electronic microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), FT-IR analysis and X-ray Diffraction. A relationship between radiation type and the thermal stability of the composites, were also established. This relationship allows a more accurate and precise control of the life span of Chitosan/Mimosa Tenuiflora and Chitosan/Mimosa Tenuiflora/MWCNT composites through the use of radiation in materials for use in tissue engineering.

Morphological and physical behavior of styrenic, phosphonium-containing ionomers

NASA Astrophysics Data System (ADS)

Beyer, Rick; Stokes, Kristoffer

2010-03-01

Despite many years of effort, a clear understanding of the factors controlling morphology in Nafion and other ionomers has not been achieved. The increasing need for fuel cell technology continues to drive efforts to develop materials having better performance characteristics even though fundamental structure-property relationships remain unclarified. Alkaline fuel cells (AFCs) present several benefits over proton exchange membrane (PEM) fuel cells, including cost of manufacture (less expensive catalysts) and a significantly shorter path to commercialization. Here we present the most recent findings from our efforts to examine structure-morphology-property relationships for a series of model cationic ionomers. A series of statistical copolymers of styrene and p-vinylbenzyl-trimethyl-phosphonium chloride have been prepared via RAFT polymerization, allowing us to investigate the effect of ion content on physical behavior. Chemical, physical, and morphological characterization has been undertaken using NMR, TGA, DSC, SAXS, and TEM.

Experimental Analysis and Mathematical Modeling on Mg-Li Alloy Sheets with Three Crystal Structures during Cold Rolling and Heat Treatment.

PubMed

Tang, Yan; Le, Qichi; Wang, Tong; Chen, Xingrui

2017-10-12

The microstructural evolution, mechanical properties, and mathematical relationship of an α, α + β, and β phase Mg-Li alloy during the cold rolling and annealing process were investigated. The results showed that the increased Li element gradually transformed the Mg matrix structure from hcp to bcc. Simultaneously, the alloy plasticity was improved remarkably during cold rolling. In the annealing process, a sort of abnormal grain growth was found in Mg-11Li-3Al-2Zn-0.2Y, but was not detected in Mg-5Li-3Al-2Zn-0.2Y and Mg-8Li-3Al-2Zn-0.2Y. Moreover, the mechanical properties of alloy were evidently improved through a kind of solid solution in the β matrix. To accurately quantify this strengthening effect, the method of mathematical modeling was used to determine the relationship between strength and multiple factors.

Investigations on the Mechanical Properties of Conducting Polymer Coating-Substrate Structures and Their Influencing Factors

PubMed Central

Wang, Xi-Shu; Tang, Hua-Ping; Li, Xu-Dong; Hua, Xin

2009-01-01

This review covers recent advances and work on the microstructure features, mechanical properties and cracking processes of conducting polymer film/coating- substrate structures under different testing conditions. An attempt is made to characterize and quantify the relationships between mechanical properties and microstructure features. In addition, the film cracking mechanism on the micro scale and some influencing factors that play a significant role in the service of the film-substrate structure are presented. These investigations cover the conducting polymer film/coating nucleation process, microstructure-fracture characterization, translation of brittle-ductile fractures, and cracking processes near the largest inherent macromolecule defects under thermal-mechanical loadings, and were carried out using in situ scanning electron microscopy (SEM) observations, as a novel method for evaluation of interface strength and critical failure stress. PMID:20054470

Alternative Fluoropolymers to Avoid the Challenges Associated with Perfluorooctanoic Acid

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

Guo,J.; Resnick, P.; Efimenko, K.

2008-01-01

The degradation of stain-resistant coating materials leads to the release of biopersistent perfluorooctanoic acid (PFOA) to the environment. In order to find the environmentally friendly substitutes, we have designed and synthesized a series of nonbiopersistant fluorinated polymers containing perfluorobutyl groups in the side chains. The surface properties of the new coating materials were characterized by static and dynamic contact angle measurements. The new coating materials demonstrate promising hydrophobic and oleophobic properties with low surfaces tensions. The wetting properties and surface structure of the polymers were tuned by varying the 'spacer' structures between the polymer backbones and the perfluorinated groups ofmore » the side chains. The relationship between orientations of the fluorinated side chains and performances of polymer surfaces were further investigated by near-edge X-ray fine absorption structure (NEXAFS) experiments and differential scanning calorimetry (DSC).« less

[Zn(C 7H 3O 5N)] n · nH 2O: A third-order NLO Zn coordination polymer with spiroconjugated structure

NASA Astrophysics Data System (ADS)

Zhou, Guo-Wei; Lan, You-Zhao; Zheng, Fa-Kun; Zhang, Xin; Lin, Meng-Hai; Guo, Guo-Cong; Huang, Jin-Shun

2006-08-01

[Zn(C 7H 3O 5N)] n · nH 2O ( 1) possesses an anticlockwise windmill-like framework structure and formats spiroconjugation over the infinite molecular layer that is predicted to have large static third-order polarizability and the convergence value of γxxxx reaches 6.86 × 10 -33 esu in the case of zero input photon energy. The third-order NLO properties of 1 were investigated via Z-scan techniques at wavelength of 532 nm. It showed strong third-order NLO absorptive properties, and its n2 value was calculated to be 4.15 × 10 -11 esu. The relationship between the spiroconjugated structure and the NLO property has been discussed, which supposed to be more valuable for the NLO research.

Screened Hybrid and DFT + U Studies of the Structural, Electronic, and Optical Properties of U3O8

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

Wen, Xiaodong; Martin, Richard L.; Scuseria, Gustavo E.

2012-11-26

A systematic comparison of the structures and electronic and optical properties of U3O8 in the c2mm, P¯62m, and P21/m structures (the α, β, and γ phases, respectively) is performed using density functional theory + U (PBE + U) and the Heyd–Scuseria–Ernzerhof screened hybrid functional (HSE). The relationship between the semiconducting C2mm phase of U3O8 and the high temperature, metallic P¯62m phase is explored in more detail. Our calculated results show that the HSE functional gives a better description of the electronic and optical properties when compared with available experimental data for the α and β phases, but neither approach doesmore » particularly well for the high pressure γ phase.« less

Interplay between structure and transport properties of molten salt mixtures of ZnCl2-NaCl-KCl: A molecular dynamics study.

PubMed

Manga, Venkateswara Rao; Swinteck, Nichlas; Bringuier, Stefan; Lucas, Pierre; Deymier, Pierre; Muralidharan, Krishna

2016-03-07

Molten mixtures of network-forming covalently bonded ZnCl2 and network-modifying ionically bonded NaCl and KCl salts are investigated as high-temperature heat transfer fluids for concentrating solar power plants. Specifically, using molecular dynamics simulations, the interplay between the extent of the network structure, composition, and the transport properties (viscosity, thermal conductivity, and diffusion) of ZnCl2-NaCl-KCl molten salts is characterized. The Stokes-Einstein/Eyring relationship is found to break down in these network-forming liquids at high concentrations of ZnCl2 (>63 mol. %), while the Eyring relationship is seen with increasing KCl concentration. Further, the network modification due to the addition of K ions leads to formation of non-bridging terminal Cl ions, which in turn lead to a positive temperature dependence of thermal conductivity in these melts. This new understanding of transport in these ternary liquids enables the identification of appropriate concentrations of the network formers and network modifiers to design heat transfer fluids with desired transport properties for concentrating solar power plants.

Chemical properties and biotoxicity of several chromium picolinate derivatives.

PubMed

Liu, Bin; Liu, Yanfei; Chai, Jie; Hu, Xiangquan; Wu, Duoming; Yang, Binsheng

2016-11-01

As a man-made additive, chromium picolinate Cr(pic) 3 has become a popular dietary supplement worldwide. In this paper Cr(pic) 3 and its new derivatives Cr(6-CH 3 -pic) 3 (1), [Cr(6-NH 2 -pic) 2 (H 2 O) 2 ]NO 3 (2) and Cr(3-NH 2 -pic) 3 (3) were synthesized, and complexes 1 and 2 were characterized by X-ray crystal structure (where pic=2-carboxypyridine). The relationship between the chemical properties and biotoxicity of these complexes was fully discussed: (1) The dynamics stability of chromium picolinate complexes mainly depends on the CrN bonds length. (2) There is a positive correlation between the dynamics stability, electrochemical potentials and generation of reactive oxygen species through Fenton-like reaction. (3) However, no biological toxicity was observed through MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) and sub-chronic oral toxicity study for these chromium picolinate compounds. Together, our findings establish a framework for understanding the structure-property-toxicity relationships of the chromium picolinate complexes. Copyright © 2016 Elsevier Inc. All rights reserved.

Impact of hygrothermal aging on structure/function relationship of perfluorosulfonic-acid membrane

DOE PAGES

Shi, Shouwen; Dursch, Thomas J.; Blake, Colin; ...

2015-10-20

Perfluorosulfonic-acid (PFSA) membranes are widely used as the solid electrolyte in electrochemical devices where their main functionalities are ion (proton) conduction and gas separation in a thermomechanically stable matrix. Due to prolonged operational requirements in these devices, PFSA membranes’ properties change with time due to hygrothermal aging. This paper studies the evolution of PFSA structure/property relationship changes during hygrothermal aging, including chemical changes leading to changes in ion-exchange capacity (IEC), nanostructure, water-uptake behavior, conductivity, and mechanical properties. Our findings demonstrate that with hygrothermal aging, the storage modulus increases, while IEC and water content decrease, consistent with the changes in nanostructure,more » that is, water- and crystalline-domain spacings inferred from small- and wide-angle X-ray scattering (SAXS/WAXS) experiments. In addition, the impact of aging is found to depend on the membrane's thermal prehistory and post-treatments, although universal correlations exist between nanostructural changes and water uptake. Lastly, the findings have impact on understanding lifetime, durability, and use of these and related polymers in various technologies.« less

First principles view on chemical compound space: Gaining rigorous atomistic control of molecular properties

DOE PAGES

von Lilienfeld, O. Anatole

2013-02-26

A well-defined notion of chemical compound space (CCS) is essential for gaining rigorous control of properties through variation of elemental composition and atomic configurations. Here, we give an introduction to an atomistic first principles perspective on CCS. First, CCS is discussed in terms of variational nuclear charges in the context of conceptual density functional and molecular grand-canonical ensemble theory. Thereafter, we revisit the notion of compound pairs, related to each other via “alchemical” interpolations involving fractional nuclear charges in the electronic Hamiltonian. We address Taylor expansions in CCS, property nonlinearity, improved predictions using reference compound pairs, and the ounce-of-gold prizemore » challenge to linearize CCS. Finally, we turn to machine learning of analytical structure property relationships in CCS. Here, these relationships correspond to inferred, rather than derived through variational principle, solutions of the electronic Schrödinger equation.« less

Structure-activity relationships amongst 4-position quinoline methanol antimalarials that inhibit the growth of drug sensitive and resistant strains of Plasmodium falciparum.

PubMed

Milner, Erin; McCalmont, William; Bhonsle, Jayendra; Caridha, Diana; Carroll, Dustin; Gardner, Sean; Gerena, Lucia; Gettayacamin, Montip; Lanteri, Charlotte; Luong, Thulan; Melendez, Victor; Moon, Jay; Roncal, Norma; Sousa, Jason; Tungtaeng, Anchalee; Wipf, Peter; Dow, Geoffrey

2010-02-15

Utilizing mefloquine as a scaffold, a next generation quinoline methanol (NGQM) library was constructed to identify early lead compounds that possess biological properties consistent with the target product profile for malaria chemoprophylaxis while reducing permeability across the blood-brain barrier. The library of 200 analogs resulted in compounds that inhibit the growth of drug sensitive and resistant strains of Plasmodium falciparum. Herein we report selected chemotypes and the emerging structure-activity relationship for this library of quinoline methanols. Published by Elsevier Ltd.

Tandem Repeat Proteins Inspired By Squid Ring Teeth

NASA Astrophysics Data System (ADS)

Pena-Francesch, Abdon

Proteins are large biomolecules consisting of long chains of amino acids that hierarchically assemble into complex structures, and provide a variety of building blocks for biological materials. The repetition of structural building blocks is a natural evolutionary strategy for increasing the complexity and stability of protein structures. However, the relationship between amino acid sequence, structure, and material properties of protein systems remains unclear due to the lack of control over the protein sequence and the intricacies of the assembly process. In order to investigate the repetition of protein building blocks, a recently discovered protein from squids is examined as an ideal protein system. Squid ring teeth are predatory appendages located inside the suction cups that provide a strong grasp of prey, and are solely composed of a group of proteins with tandem repetition of building blocks. The objective of this thesis is the understanding of sequence, structure and property relationship in repetitive protein materials inspired in squid ring teeth for the first time. Specifically, this work focuses on squid-inspired structural proteins with tandem repeat units in their sequence (i.e., repetition of alternating building blocks) that are physically cross-linked via beta-sheet structures. The research work presented here tests the hypothesis that, in these systems, increasing the number of building blocks in the polypeptide chain decreases the protein network defects and improves the material properties. Hence, the sequence, nanostructure, and properties (thermal, mechanical, and conducting) of tandem repeat squid-inspired protein materials are examined. Spectroscopic structural analysis, advanced materials characterization, and entropic elasticity theory are combined to elucidate the structure and material properties of these repetitive proteins. This approach is applied not only to native squid proteins but also to squid-inspired synthetic polypeptides that allow for a fine control of the sequence and network morphology. The results provided in this work establish a clear dependence between the repetitive building blocks, the network morphology, and the properties of squid-inspired repetitive protein materials. Increasing the number of tandem repeat units in SRT-inspired proteins led to more effective protein networks with superior properties. Through increasing tandem repetition and optimization of network morphology, highly efficient protein materials capable of withstanding deformations up to 400% of their original length, with MPa-GPa modulus, high energy absorption (50 MJ m-3), peak proton conductivity of 3.7 mS cm-1 (at pH 7, highest reported to date for biological materials), and peak thermal conductivity of 1.4 W m-1 K -1 (which exceeds that of most polymer materials) were developed. These findings introduce new design rules in the engineering of proteins based on tandem repetition and morphology control, and provide a novel framework for tailoring and optimizing the properties of protein-based materials.

Applications of acoustics in the measurement of coal slab thickness

NASA Technical Reports Server (NTRS)

Hadden, W. J., Jr.; Mills, J. M.; Pierce, A. D.

1980-01-01

The determination of the possibility of employing acoustic waves at ultrasonic frequencies for measurements of thicknesses of slabs of coal backed by shale is investigated. Fundamental information concerning the acoustical properties of coal, and the relationship between these properties and the structural and compositional parameters used to characterize coal samples was also sought. The testing device, which utilizes two matched transducers, is described.

Notes on quantitative structure-properties relationships (QSPR) (1): A discussion on a QSPR dimensionality paradox (QSPR DP) and its quantum resolution.

PubMed

Carbó-Dorca, Ramon; Gallegos, Ana; Sánchez, Angel J

2009-05-01

Classical quantitative structure-properties relationship (QSPR) statistical techniques unavoidably present an inherent paradoxical computational context. They rely on the definition of a Gram matrix in descriptor spaces, which is used afterwards to reduce the original dimension via several possible kinds of algebraic manipulations. From there, effective models for the computation of unknown properties of known molecular structures are obtained. However, the reduced descriptor dimension causes linear dependence within the set of discrete vector molecular representations, leading to positive semi-definite Gram matrices in molecular spaces. To resolve this QSPR dimensionality paradox (QSPR DP) here is proposed to adopt as starting point the quantum QSPR (QQSPR) computational framework perspective, where density functions act as infinite dimensional descriptors. The fundamental QQSPR equation, deduced from employing quantum expectation value numerical evaluation, can be approximately solved in order to obtain models exempt of the QSPR DP. The substitution of the quantum similarity matrix by an empirical Gram matrix in molecular spaces, build up with the original non manipulated discrete molecular descriptor vectors, permits to obtain classical QSPR models with the same characteristics as in QQSPR, that is: possessing a certain degree of causality and explicitly independent of the descriptor dimension. 2008 Wiley Periodicals, Inc.

Study on bond behaviour exposed to fire using beam specimen

NASA Astrophysics Data System (ADS)

Suhaib Ahmad, Mohammad; Bhargava, Pradeep; Sharma, Umesh Kumar

2018-04-01

The composite action of concrete and steel in a reinforced concrete structure depends upon the bond between them. Bond behaviour is studied in terms of bond-slip relationship. The bond between them depends upon mechanical properties of concrete and steel. In an event of fire these mechanical properties degrades and hence the bond behaviour changes. Some researches were performed to study the effect of temperature on the bond-slip relationship which are based on pull out specimens. Generally these relationships are obtained using pull out specimen which over estimates the bond properties. In this study beam specimens were used which is recommended by Rilem. These specimens were exposed to elevated temperatures up to 650 °C and there bond-slip behaviour were studied. The study shows that bond strength decreases while peak slip increases with increases in temperature. Also an equation proposed was proposed which can predict the bond strength between concrete and steel exposed up to the temperature of 650 °C.

Phonon vibrational frequencies of all single-wall carbon nanotubes at the lambda point: reduced matrix calculations.

PubMed

Wang, Yufang; Wu, Yanzhao; Feng, Min; Wang, Hui; Jin, Qinghua; Ding, Datong; Cao, Xuewei

2008-12-01

With a simple method-the reduced matrix method, we simplified the calculation of the phonon vibrational frequencies according to SWNTs structure and their phonon symmetric property and got the dispersion properties of all SWNTs at Gamma point in Brillouin zone, whose diameters lie between 0.6 and 2.5 nm. The calculating time is shrunk about 2-4 orders. A series of the dependent relationships between the diameters of SWNTs and the frequencies of Raman and IR active modes are given. Several fine structures including "glazed tile" structures in omega approximately d figures are found, which might predict a certain macro-quantum phenomenon of the phonons in SWNTs.

Improved glucose-neopentyl glycol (GNG) amphiphiles for membrane protein solubilization and stabilization.

PubMed

Cho, Kyung Ho; Bae, Hyoung Eun; Das, Manabendra; Gellman, Samuel H; Chae, Pil Seok

2014-02-01

Membrane proteins are inherently amphipathic and undergo dynamic conformational changes for proper function within native membranes. Maintaining the functional structures of these biomacromolecules in aqueous media is necessary for structural studies but difficult to achieve with currently available tools, thus necessitating the development of novel agents with favorable properties. This study introduces several new glucose-neopentyl glycol (GNG) amphiphiles and reveals some agents that display favorable behaviors for the solubilization and stabilization of a large, multi-subunit membrane protein assembly. Furthermore, a detergent structure-property relationship that could serve as a useful guideline for the design of novel amphiphiles is discussed. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thiophene-Based Organic Semiconductors.

PubMed

Turkoglu, Gulsen; Cinar, M Emin; Ozturk, Turan

2017-10-24

Thiophene-based π-conjugated organic small molecules and polymers are the research subject of significant current interest owing to their potential use as organic semiconductors in material chemistry. Despite simple and similar molecular structures, the hitherto reported properties of thiophene-based organic semiconductors are rather diverse. Design of high performance organic semiconducting materials requires a thorough understanding of inter- and intra-molecular interactions, solid-state packing, and the influence of both factors on the charge carrier transport. In this chapter, thiophene-based organic semiconductors, which are classified in terms of their chemical structures and their structure-property relationships, are addressed for the potential applications as organic photovoltaics (OPVs), organic field-effect transistors (OFETs) and organic light emitting diodes (OLEDs).

Computational characterization of ordered nanostructured surfaces

NASA Astrophysics Data System (ADS)

Mohieddin Abukhdeir, Nasser

2016-08-01

A vital and challenging task for materials researchers is to determine relationships between material characteristics and desired properties. While the measurement and assessment of material properties can be complex, quantitatively characterizing their structure is frequently a more challenging task. This issue is magnified for materials researchers in the areas of nanoscience and nanotechnology, where material structure is further complicated by phenomena such as self-assembly, collective behavior, and measurement uncertainty. Recent progress has been made in this area for both self-assembled and nanostructured surfaces due to increasing accessibility of imaging techniques at the nanoscale. In this context, recent advances in nanomaterial surface structure characterization are reviewed including the development of new theory and image processing methods.

Adiposity is associated with structural properties of the adolescent brain.

PubMed

Schwartz, Deborah H; Dickie, Erin; Pangelinan, Melissa M; Leonard, Gabriel; Perron, Michel; Pike, G Bruce; Richer, Louis; Veillette, Suzanne; Pausova, Zdenka; Paus, Tomáš

2014-12-01

Obesity, a major risk factor for cardiometabolic disease, is associated with variations in a number of structural properties in the adult brain, as assessed with magnetic resonance imaging (MRI). In this study, we investigated the cross-sectional relationship between visceral fat (VF), total body fat (TBF) and three MRI parameters in the brains of typically developing adolescents: (i) T1-weighted (T1W) signal intensity; (ii) T1W signal contrast between white matter (WM) and gray matter (GM); and (iii) magnetization transfer ratio (MTR). In a community-based sample of 970 adolescents (12-18 years old, 466 males), VF was quantified using MRI, and total body fat was measured using a multifrequency bioimpedance. T1W images of the brain were used to determine signal intensity in lobar GM and WM, as well as WM:GM signal contrast. A magnetization transfer (MT) sequence of MT(ON) and MT(OFF) was used to obtain MTR in GM and WM. We found that both larger volumes of VF and more TBF were independently associated with higher signal intensity in WM and higher WM:GM signal contrast, as well as higher MTR in both GM and WM. These relationships were independent of a number of potential confounders, including age, sex, puberty stage, household income and height. Our results suggest that both visceral fat and fat deposited elsewhere in the body are associated independently with structural properties of the adolescent brain. We speculate that these relationships suggest the presence of adiposity-related variations in phospholipid composition of brain lipids. Copyright © 2014. Published by Elsevier Inc.

Emergence of scale-free close-knit friendship structure in online social networks.

PubMed

Cui, Ai-Xiang; Zhang, Zi-Ke; Tang, Ming; Hui, Pak Ming; Fu, Yan

2012-01-01

Although the structural properties of online social networks have attracted much attention, the properties of the close-knit friendship structures remain an important question. Here, we mainly focus on how these mesoscale structures are affected by the local and global structural properties. Analyzing the data of four large-scale online social networks reveals several common structural properties. It is found that not only the local structures given by the indegree, outdegree, and reciprocal degree distributions follow a similar scaling behavior, the mesoscale structures represented by the distributions of close-knit friendship structures also exhibit a similar scaling law. The degree correlation is very weak over a wide range of the degrees. We propose a simple directed network model that captures the observed properties. The model incorporates two mechanisms: reciprocation and preferential attachment. Through rate equation analysis of our model, the local-scale and mesoscale structural properties are derived. In the local-scale, the same scaling behavior of indegree and outdegree distributions stems from indegree and outdegree of nodes both growing as the same function of the introduction time, and the reciprocal degree distribution also shows the same power-law due to the linear relationship between the reciprocal degree and in/outdegree of nodes. In the mesoscale, the distributions of four closed triples representing close-knit friendship structures are found to exhibit identical power-laws, a behavior attributed to the negligible degree correlations. Intriguingly, all the power-law exponents of the distributions in the local-scale and mesoscale depend only on one global parameter, the mean in/outdegree, while both the mean in/outdegree and the reciprocity together determine the ratio of the reciprocal degree of a node to its in/outdegree. Structural properties of numerical simulated networks are analyzed and compared with each of the four real networks. This work helps understand the interplay between structures on different scales in online social networks.

Emergence of Scale-Free Close-Knit Friendship Structure in Online Social Networks

PubMed Central

Cui, Ai-Xiang; Zhang, Zi-Ke; Tang, Ming; Hui, Pak Ming; Fu, Yan

2012-01-01

Although the structural properties of online social networks have attracted much attention, the properties of the close-knit friendship structures remain an important question. Here, we mainly focus on how these mesoscale structures are affected by the local and global structural properties. Analyzing the data of four large-scale online social networks reveals several common structural properties. It is found that not only the local structures given by the indegree, outdegree, and reciprocal degree distributions follow a similar scaling behavior, the mesoscale structures represented by the distributions of close-knit friendship structures also exhibit a similar scaling law. The degree correlation is very weak over a wide range of the degrees. We propose a simple directed network model that captures the observed properties. The model incorporates two mechanisms: reciprocation and preferential attachment. Through rate equation analysis of our model, the local-scale and mesoscale structural properties are derived. In the local-scale, the same scaling behavior of indegree and outdegree distributions stems from indegree and outdegree of nodes both growing as the same function of the introduction time, and the reciprocal degree distribution also shows the same power-law due to the linear relationship between the reciprocal degree and in/outdegree of nodes. In the mesoscale, the distributions of four closed triples representing close-knit friendship structures are found to exhibit identical power-laws, a behavior attributed to the negligible degree correlations. Intriguingly, all the power-law exponents of the distributions in the local-scale and mesoscale depend only on one global parameter, the mean in/outdegree, while both the mean in/outdegree and the reciprocity together determine the ratio of the reciprocal degree of a node to its in/outdegree. Structural properties of numerical simulated networks are analyzed and compared with each of the four real networks. This work helps understand the interplay between structures on different scales in online social networks. PMID:23272067

Structural complexities in the active layers of organic electronics.

PubMed

Lee, Stephanie S; Loo, Yueh-Lin

2010-01-01

The field of organic electronics has progressed rapidly in recent years. However, understanding the direct structure-function relationships between the morphology in electrically active layers and the performance of devices composed of these materials has proven difficult. The morphology of active layers in organic electronics is inherently complex, with heterogeneities existing across multiple length scales, from subnanometer to micron and millimeter range. A major challenge still facing the organic electronics community is understanding how the morphology across all of the length scales in active layers collectively determines the device performance of organic electronics. In this review we highlight experiments that have contributed to the elucidation of structure-function relationships in organic electronics and also point to areas in which knowledge of such relationships is still lacking. Such knowledge will lead to the ability to select active materials on the basis of their inherent properties for the fabrication of devices with prespecified characteristics.

Segmented molecular design of self-healing proteinaceous materials

NASA Astrophysics Data System (ADS)

Sariola, Veikko; Pena-Francesch, Abdon; Jung, Huihun; Çetinkaya, Murat; Pacheco, Carlos; Sitti, Metin; Demirel, Melik C.

2015-09-01

Hierarchical assembly of self-healing adhesive proteins creates strong and robust structural and interfacial materials, but understanding of the molecular design and structure-property relationships of structural proteins remains unclear. Elucidating this relationship would allow rational design of next generation genetically engineered self-healing structural proteins. Here we report a general self-healing and -assembly strategy based on a multiphase recombinant protein based material. Segmented structure of the protein shows soft glycine- and tyrosine-rich segments with self-healing capability and hard beta-sheet segments. The soft segments are strongly plasticized by water, lowering the self-healing temperature close to body temperature. The hard segments self-assemble into nanoconfined domains to reinforce the material. The healing strength scales sublinearly with contact time, which associates with diffusion and wetting of autohesion. The finding suggests that recombinant structural proteins from heterologous expression have potential as strong and repairable engineering materials.

Segmented molecular design of self-healing proteinaceous materials.

PubMed

Sariola, Veikko; Pena-Francesch, Abdon; Jung, Huihun; Çetinkaya, Murat; Pacheco, Carlos; Sitti, Metin; Demirel, Melik C

2015-09-01

Hierarchical assembly of self-healing adhesive proteins creates strong and robust structural and interfacial materials, but understanding of the molecular design and structure-property relationships of structural proteins remains unclear. Elucidating this relationship would allow rational design of next generation genetically engineered self-healing structural proteins. Here we report a general self-healing and -assembly strategy based on a multiphase recombinant protein based material. Segmented structure of the protein shows soft glycine- and tyrosine-rich segments with self-healing capability and hard beta-sheet segments. The soft segments are strongly plasticized by water, lowering the self-healing temperature close to body temperature. The hard segments self-assemble into nanoconfined domains to reinforce the material. The healing strength scales sublinearly with contact time, which associates with diffusion and wetting of autohesion. The finding suggests that recombinant structural proteins from heterologous expression have potential as strong and repairable engineering materials.

Design and Structure-Function Characterization of 3D Printed Synthetic Porous Biomaterials for Tissue Engineering.

PubMed

Kelly, Cambre N; Miller, Andrew T; Hollister, Scott J; Guldberg, Robert E; Gall, Ken

2018-04-01

3D printing is now adopted for use in a variety of industries and functions. In biomedical engineering, 3D printing has prevailed over more traditional manufacturing methods in tissue engineering due to its high degree of control over both macro- and microarchitecture of porous tissue scaffolds. However, with the improved flexibility in design come new challenges in characterizing the structure-function relationships between various architectures and both mechanical and biological properties in an assortment of clinical applications. Presently, the field of tissue engineering lacks a comprehensive body of literature that is capable of drawing meaningful relationships between the designed structure and resulting function of 3D printed porous biomaterial scaffolds. This work first discusses the role of design on 3D printed porous scaffold function and then reviews characterization of these structure-function relationships for 3D printed synthetic metallic, polymeric, and ceramic biomaterials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Augmented multivariate image analysis applied to quantitative structure-activity relationship modeling of the phytotoxicities of benzoxazinone herbicides and related compounds on problematic weeds.

PubMed

Freitas, Mirlaine R; Matias, Stella V B G; Macedo, Renato L G; Freitas, Matheus P; Venturin, Nelson

2013-09-11

Two of major weeds affecting cereal crops worldwide are Avena fatua L. (wild oat) and Lolium rigidum Gaud. (rigid ryegrass). Thus, development of new herbicides against these weeds is required; in line with this, benzoxazinones, their degradation products, and analogues have been shown to be important allelochemicals and natural herbicides. Despite earlier structure-activity studies demonstrating that hydrophobicity (log P) of aminophenoxazines correlates to phytotoxicity, our findings for a series of benzoxazinone derivatives do not show any relationship between phytotoxicity and log P nor with other two usual molecular descriptors. On the other hand, a quantitative structure-activity relationship (QSAR) analysis based on molecular graphs representing structural shape, atomic sizes, and colors to encode other atomic properties performed very accurately for the prediction of phytotoxicities of these compounds against wild oat and rigid ryegrass. Therefore, these QSAR models can be used to estimate the phytotoxicity of new congeners of benzoxazinone herbicides toward A. fatua L. and L. rigidum Gaud.

Electrooptical properties and structural features of amorphous ITO

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

Amosova, L. P., E-mail: l-amosova@mail.ru

2015-03-15

Thin indium-tin oxide (ITO) films are deposited onto cold substrates by magnetron-assisted sputtering. The dependences of the structural, electrical, and optical properties of the films on the oxygen content in the atmosphere of sputtering and the growth rate are studied. It is shown that, if the substrate temperature is no higher than the ITO crystallization temperature and the conditions of growth deviate from the optimal relationship between the oxygen pressure and the growth rate, the resistance of the layers can be six or seven orders of magnitude higher than the resistance of conducting amorphous layers and reach hundreds of megaohms.more » At the same time, the optical properties of insulating layers in the visible spectral region are completely identical to the properties of the conducing amorphous modification. A conceptual model of defects responsible for the insulating properties of amorphous ITO is proposed.« less

Effect of HNT on the Microstructure, Thermal and Mechanical Properties of Al/FACS-HNT Composites Produced by GPI

NASA Astrophysics Data System (ADS)

Siewiorek, A.; Malczyk, P.; Sobczak, N.; Sobczak, J. J.; Czulak, A.; Kozera, R.; Gude, M.; Boczkowska, A.; Homa, M.

2016-08-01

To develop an optimised manufacturing method of fly ash-reinforced metal matrix composites, the preliminary tests were performed on the cenospheres selected from fly ash (FACS) with halloysite nanotubes (HNTs) addition. The preform made out of FACS with and without the addition of HNT (with 5 and 10 wt.%) has been infiltrated by the pure aluminium (Al) via adapted gas pressure infiltration process. This paper reveals the influence of HNT addition on the microstructure (analysis was done by computed tomography and scanning electron microscopy combined with energy-dispersive x-ray spectroscopy), thermal properties (thermal expansion coefficient, thermal conductivity and specific heat) and the mechanical properties (hardness and compression test) of manufactured composites. The analysis of structure-property relationships for Al/FACS-HNT composites produced shows that the addition of 5 wt.% of HNT to FACS preform contributes to receiving of the best mechanical and structural properties of investigated composites.

Molecular modeling of polymers 16. Gaseous diffusion in polymers: a quantitative structure-property relationship (QSPR) analysis.

PubMed

Patel, H C; Tokarski, J S; Hopfinger, A J

1997-10-01

The purpose of this study was to identify the key physicochemical molecular properties of polymeric materials responsible for gaseous diffusion in the polymers. Quantitative structure-property relationships, QSPRs were constructed using a genetic algorithm on a training set of 16 polymers for which CO2, N2, O2 diffusion constants were measured. Nine physicochemical properties of each of the polymers were used in the trial basis set for QSPR model construction. The linear cross-correlation matrices were constructed and investigated for colinearity among the members of the training sets. Common water diffusion measures for a limited training set of six polymers was used to construct a "semi-QSPR" model. The bulk modulus of the polymer was overwhelmingly found to be the dominant physicochemical polymer property that governs CO2, N2 and O2 diffusion. Some secondary physicochemical properties controlling diffusion, including conformational entropy, were also identified as correlation descriptors. Very significant QSPR diffusion models were constructed for all three gases. Cohesive energy was identified as the main correlation physicochemical property with aqueous diffusion measures. The dominant role of polymer bulk modulus on gaseous diffusion makes it difficult to develop criteria for selective transport of gases through polymers. Moreover, high bulk moduli are predicted to be necessary for effective gas barrier materials. This property requirement may limit the processing and packaging features of the material. Aqueous diffusion in polymers may occur by a different mechanism than gaseous diffusion since bulk modulus does not correlate with aqueous diffusion, but rather cohesive energy of the polymer.

Highly optical transparency and thermally stable polyimides containing pyridine and phenyl pendant.

PubMed

Yao, Jianan; Wang, Chunbo; Tian, Chengshuo; Zhao, Xiaogang; Zhou, Hongwei; Wang, Daming; Chen, Chunhai

2017-01-01

In order to obtain highly optical transparency polyimides, two novel aromatic diamine monomers containing pyridine and kinky structures, 1,1-bis[4-(5-amino-2-pyridinoxy)phenyl]diphenylmethane (BAPDBP) and 1,1-bis[4-(5-amino-2-pyridinoxy)phenyl]-1-phenylethane (BAPDAP), were designed and synthesized. Polyimides based on BAPDBP, BAPDAP, 2,2-bis[4-(5-amino-2-pyridinoxy)phenyl]propane (BAPDP) with various commercial dianhydrides were prepared for comparison and structure-property relationships study. The structures of the polyimides were characterized by Fourier transform infrared (FT-IR) spectrometer, wide-angle X-ray diffractograms (XRD) and elemental analysis. Film properties including solubility, optical transparency, water uptake, thermal and mechanical properties were also evaluated. The introduction of pyridine and kinky structure into the backbones that polyimides presented good optical properties with 91-97% transparent at 500 nm and a low cut-off wavelength at 353-398 nm. Moreover, phenyl pendant groups of the polyimides showed high glass transition temperatures ( T g ) in the range of 257-281 °C. These results suggest that the incorporating pyridine, kinky and bulky substituents to polymer backbone can improve the optical transparency effectively without sacrificing the thermal properties.

Nanoscale structural and functional mapping of nacre by scanning probe microscopy techniques

NASA Astrophysics Data System (ADS)

Zhou, Xilong; Miao, Hongchen; Li, Faxin

2013-11-01

Nacre has received great attention due to its nanoscale hierarchical structure and extraordinary mechanical properties. Meanwhile, the nanoscale piezoelectric properties of nacre have also been investigated but the structure-function relationship has never been addressed. In this work, firstly we realized quantitative nanomechanical mapping of nacre of a green abalone using atomic force acoustic microscopy (AFAM). The modulus of the mineral tablets is determined to be ~80 GPa and that of the organic biopolymer no more than 23 GPa, and the organic-inorganic interface width is determined to be about 34 +/- 9 nm. Then, we conducted both AFAM and piezoresponse force microscopy (PFM) mapping in the same scanning area to explore the correlations between the nanomechanical and piezoelectric properties. The PFM testing shows that the organic biopolymer exhibits a significantly stronger piezoresponse than the mineral tablets, and they permeate each other, which is very difficult to reproduce in artificial materials. Finally, the phase hysteresis loops and amplitude butterfly loops were also observed using switching spectroscopy PFM, implying that nacre may also be a bio-ferroelectric material. The obtained nanoscale structural and functional properties of nacre could be very helpful in understanding its deformation mechanism and designing biomimetic materials of extraordinary properties.

Different behavioral effect dose–response profiles in mice exposed to two-carbon chlorinated hydrocarbons: Influence of structural and physical properties

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

Umezu, Toyoshi, E-mail: umechan2@nies.go.jp; Shibata, Yasuyuki, E-mail: yshibata@nies.go.jp

2014-09-01

The present study aimed to clarify whether dose–response profiles of acute behavioral effects of 1,2-dichloroethane (DCE), 1,1,1-trichloroethane (TCE), trichloroethylene (TRIC), and tetrachloroethylene (PERC) differ. A test battery involving 6 behavioral endpoints was applied to evaluate the effects of DCE, TCE, TRIC, and PERC in male ICR strain mice under the same experimental conditions. The behavioral effect dose–response profiles of these compounds differed. Regression analysis was used to evaluate the relationship between the dose–response profiles and structural and physical properties of the compounds. Dose–response profile differences correlated significantly with differences in specific structural and physical properties. These results suggest that differencesmore » in specific structural and physical properties of DCE, TCE, TRIC, and PERC are responsible for differences in behavioral effects that lead to a variety of dose–response profiles. - Highlights: • We examine effects of 4 chlorinated hydrocarbons on 6 behavioral endpoints in mice. • The behavioral effect dose–response profiles for the 4 compounds are different. • We utilize regression analysis to clarify probable causes of the different profiles. • The compound's physicochemical properties probably produce the different profiles.« less

Independence May Feel Strange

ERIC Educational Resources Information Center

Meyer, Joerg M.

2017-01-01

Stochastic independence is not an easy notion. Because it is part of the probability structure, it can have some surprising non-properties, which is beneficial for teachers and students to see illustrated. Neither is the relationship to causal independence an easy one.

Association of Structural Global Brain Network Properties with Intelligence in Normal Aging

PubMed Central

Fischer, Florian U.; Wolf, Dominik; Scheurich, Armin; Fellgiebel, Andreas

2014-01-01

Higher general intelligence attenuates age-associated cognitive decline and the risk of dementia. Thus, intelligence has been associated with cognitive reserve or resilience in normal aging. Neurophysiologically, intelligence is considered as a complex capacity that is dependent on a global cognitive network rather than isolated brain areas. An association of structural as well as functional brain network characteristics with intelligence has already been reported in young adults. We investigated the relationship between global structural brain network properties, general intelligence and age in a group of 43 cognitively healthy elderly, age 60–85 years. Individuals were assessed cross-sectionally using Wechsler Adult Intelligence Scale-Revised (WAIS-R) and diffusion-tensor imaging. Structural brain networks were reconstructed individually using deterministic tractography, global network properties (global efficiency, mean shortest path length, and clustering coefficient) were determined by graph theory and correlated to intelligence scores within both age groups. Network properties were significantly correlated to age, whereas no significant correlation to WAIS-R was observed. However, in a subgroup of 15 individuals aged 75 and above, the network properties were significantly correlated to WAIS-R. Our findings suggest that general intelligence and global properties of structural brain networks may not be generally associated in cognitively healthy elderly. However, we provide first evidence of an association between global structural brain network properties and general intelligence in advanced elderly. Intelligence might be affected by age-associated network deterioration only if a certain threshold of structural degeneration is exceeded. Thus, age-associated brain structural changes seem to be partially compensated by the network and the range of this compensation might be a surrogate of cognitive reserve or brain resilience. PMID:24465994

Lattice thermal conductivity of monolayer AsP from first-principles molecular dynamics.

PubMed

Sun, Yajing; Shuai, Zhigang; Wang, Dong

2018-05-23

Few-layered arsenic-phosphorus alloys, AsxP(1-x), with a puckered structure have been recently synthesized and demonstrated with fully tunable band gaps and optical properties. It is predicted that the carrier mobility of monolayer AsP compounds is even higher than that of black phosphorene (b-P). The anisotropic and orthogonal electrical and thermal transport properties of the puckered group VA elements make them intriguing materials for thermoelectric applications. Herein, we investigated the thermal transport properties of AsP based on first-principles molecular dynamics and the Boltzmann transport equation. We reveal that monolayer AsP with three different chemical structures possesses thermal conductivities lower than b-P, but with increased anisotropy. Further, these structures behave profoundly different on heat conduction. This can be attributed to the distinct low-frequency optical modes associated with their bonding nature. Our results highlight the impact of atomic arrangement on the thermal conductivity of AsP, and the structure-property relationship established may guide the fabrication of thermoelectric materials via the engineered alloying method.

Relationships between physical properties and sequence in silkworm silks

PubMed Central

Malay, Ali D.; Sato, Ryota; Yazawa, Kenjiro; Watanabe, Hiroe; Ifuku, Nao; Masunaga, Hiroyasu; Hikima, Takaaki; Guan, Juan; Mandal, Biman B.; Damrongsakkul, Siriporn; Numata, Keiji

2016-01-01

Silk has attracted widespread attention due to its superlative material properties and promising applications. However, the determinants behind the variations in material properties among different types of silk are not well understood. We analysed the physical properties of silk samples from a variety of silkmoth cocoons, including domesticated Bombyx mori varieties and several species from Saturniidae. Tensile deformation tests, thermal analyses, and investigations on crystalline structure and orientation of the fibres were performed. The results showed that saturniid silks produce more highly-defined structural transitions compared to B. mori, as seen in the yielding and strain hardening events during tensile deformation and in the changes observed during thermal analyses. These observations were analysed in terms of the constituent fibroin sequences, which in B. mori are predicted to produce heterogeneous structures, whereas the strictly modular repeats of the saturniid sequences are hypothesized to produce structures that respond in a concerted manner. Within saturniid fibroins, thermal stability was found to correlate with the abundance of poly-alanine residues, whereas differences in fibre extensibility can be related to varying ratios of GGX motifs versus bulky hydrophobic residues in the amorphous phase. PMID:27279149

Relationships between physical properties and sequence in silkworm silks

NASA Astrophysics Data System (ADS)

Malay, Ali D.; Sato, Ryota; Yazawa, Kenjiro; Watanabe, Hiroe; Ifuku, Nao; Masunaga, Hiroyasu; Hikima, Takaaki; Guan, Juan; Mandal, Biman B.; Damrongsakkul, Siriporn; Numata, Keiji

2016-06-01

Silk has attracted widespread attention due to its superlative material properties and promising applications. However, the determinants behind the variations in material properties among different types of silk are not well understood. We analysed the physical properties of silk samples from a variety of silkmoth cocoons, including domesticated Bombyx mori varieties and several species from Saturniidae. Tensile deformation tests, thermal analyses, and investigations on crystalline structure and orientation of the fibres were performed. The results showed that saturniid silks produce more highly-defined structural transitions compared to B. mori, as seen in the yielding and strain hardening events during tensile deformation and in the changes observed during thermal analyses. These observations were analysed in terms of the constituent fibroin sequences, which in B. mori are predicted to produce heterogeneous structures, whereas the strictly modular repeats of the saturniid sequences are hypothesized to produce structures that respond in a concerted manner. Within saturniid fibroins, thermal stability was found to correlate with the abundance of poly-alanine residues, whereas differences in fibre extensibility can be related to varying ratios of GGX motifs versus bulky hydrophobic residues in the amorphous phase.

Photoelectron spectra and biological activity of cinnamic acid derivatives revisited.

PubMed

Novak, Igor; Klasinc, Leo; McGlynn, Sean P

2018-01-15

The electronic structures of several derivatives of cinnamic acid have been studied by UV photoelectron spectroscopy (UPS) and Green's function quantum chemical calculations. The spectra reveal the presence of dimers in the gas phase for p-coumaric and ferulic acids. The electronic structure analysis has been related to the biological properties of these compounds through the analysis of some structure-activity relationships (SAR). Copyright © 2017 Elsevier B.V. All rights reserved.

Design of Semiconducting Tetrahedral Mn 1-xZn xO Alloys and Their Application to Solar Water Splitting

DOE PAGES

Peng, Haowei; Ndione, Paul F.; Ginley, David S.; ...

2015-03-18

Transition metal oxides play important roles as contact and electrode materials, but their use as active layers in solar energy conversion requires achieving semiconducting properties akin to those of conventional semiconductors like Si or GaAs. In particular, efficient bipolar carrier transport is a challenge in these materials. Based on the prediction that a tetrahedral polymorph of MnO should have such desirable semiconducting properties, and the possibility to overcome thermodynamic solubility limits by nonequilibrium thin-film growth, we exploit both structure-property and composition-structure relationships to design and realize novel wurtzite-structure Mn 1₋xZn xO alloys. At Zn compositions above x≈0.3, thin films ofmore » these alloys assume the tetrahedral wurtzite structure instead of the octahedral rocksalt structure of MnO, thereby enabling semiconductor properties that are unique among transition metal oxides, i.e., a band gap within the visible spectrum, a band-transport mechanism for both electron and hole carriers, electron doping, and a band lineup suitable for solar hydrogen generation. In conclusion, a proof of principle is provided by initial photo-electrocatalytic device measurements, corroborating, in particular, the predicted favorable hole-transport properties of these alloys.« less

Computational and Statistical Analyses of Amino Acid Usage and Physico-Chemical Properties of the Twelve Late Embryogenesis Abundant Protein Classes

PubMed Central

Jaspard, Emmanuel; Macherel, David; Hunault, Gilles

2012-01-01

Late Embryogenesis Abundant Proteins (LEAPs) are ubiquitous proteins expected to play major roles in desiccation tolerance. Little is known about their structure - function relationships because of the scarcity of 3-D structures for LEAPs. The previous building of LEAPdb, a database dedicated to LEAPs from plants and other organisms, led to the classification of 710 LEAPs into 12 non-overlapping classes with distinct properties. Using this resource, numerous physico-chemical properties of LEAPs and amino acid usage by LEAPs have been computed and statistically analyzed, revealing distinctive features for each class. This unprecedented analysis allowed a rigorous characterization of the 12 LEAP classes, which differed also in multiple structural and physico-chemical features. Although most LEAPs can be predicted as intrinsically disordered proteins, the analysis indicates that LEAP class 7 (PF03168) and probably LEAP class 11 (PF04927) are natively folded proteins. This study thus provides a detailed description of the structural properties of this protein family opening the path toward further LEAP structure - function analysis. Finally, since each LEAP class can be clearly characterized by a unique set of physico-chemical properties, this will allow development of software to predict proteins as LEAPs. PMID:22615859

Double dissociation of structure-function relationships in memory and fluid intelligence observed with magnetic resonance elastography.

PubMed

Johnson, Curtis L; Schwarb, Hillary; Horecka, Kevin M; McGarry, Matthew D J; Hillman, Charles H; Kramer, Arthur F; Cohen, Neal J; Barbey, Aron K

2018-05-01

Brain tissue mechanical properties, measured in vivo with magnetic resonance elastography (MRE), have proven to be sensitive metrics of neural tissue integrity. Recently, our group has reported on the positive relationship between viscoelasticity of the hippocampus and performance on a relational memory task in healthy young adults, which highlighted the potential of sensitive MRE measures for studying brain health and its relation to cognitive function; however, structure-function relationships outside of the hippocampus have not yet been explored. In this study, we examined the relationships between viscoelasticity of both the hippocampus and the orbitofrontal cortex and performance on behavioral assessments of relational memory and fluid intelligence. In a sample of healthy, young adults (N = 53), there was a significant, positive relationship between orbitofrontal cortex viscoelasticity and fluid intelligence performance (r = 0.42; p = .002). This finding is consistent with the previously reported relationship between hippocampal viscoelasticity and relational memory performance (r = 0.41; p = .002). Further, a significant double dissociation between the orbitofrontal-fluid intelligence relationship and the hippocampal-relational memory relationship was observed. These data support the specificity of regional brain MRE measures in support of separable cognitive functions. This report of a structure-function relationship observed with MRE beyond the hippocampus suggests a future role for MRE as a sensitive neuroimaging technique for brain mapping. Copyright © 2018 Elsevier Inc. All rights reserved.

Characterizing microstructural features of biomedical samples by statistical analysis of Mueller matrix images

NASA Astrophysics Data System (ADS)

He, Honghui; Dong, Yang; Zhou, Jialing; Ma, Hui

2017-03-01

As one of the salient features of light, polarization contains abundant structural and optical information of media. Recently, as a comprehensive description of polarization property, the Mueller matrix polarimetry has been applied to various biomedical studies such as cancerous tissues detections. In previous works, it has been found that the structural information encoded in the 2D Mueller matrix images can be presented by other transformed parameters with more explicit relationship to certain microstructural features. In this paper, we present a statistical analyzing method to transform the 2D Mueller matrix images into frequency distribution histograms (FDHs) and their central moments to reveal the dominant structural features of samples quantitatively. The experimental results of porcine heart, intestine, stomach, and liver tissues demonstrate that the transformation parameters and central moments based on the statistical analysis of Mueller matrix elements have simple relationships to the dominant microstructural properties of biomedical samples, including the density and orientation of fibrous structures, the depolarization power, diattenuation and absorption abilities. It is shown in this paper that the statistical analysis of 2D images of Mueller matrix elements may provide quantitative or semi-quantitative criteria for biomedical diagnosis.

Derivatives of Ergot-alkaloids: Molecular structure, physical properties, and structure-activity relationships

NASA Astrophysics Data System (ADS)

Ivanova, Bojidarka B.; Spiteller, Michael

2012-09-01

A comprehensive screening of fifteen functionalized Ergot-alkaloids, containing bulk aliphatic cyclic substituents at D-ring of the ergoline molecular skeleton was performed, studying their structure-active relationships and model interactions with α2A-adreno-, serotonin (5HT2A) and dopamine D3 (D3A) receptors. The accounted high affinity to the receptors binding loops and unusual bonding situations, joined with the molecular flexibility of the substituents and the presence of proton accepting/donating functional groups in the studied alkaloids, may contribute to further understanding the mechanisms of biological activity in vivo and in predicting their therapeutic potential in central nervous system (CNS), including those related the Schizophrenia. Since the presented correlation between the molecular structure and properties, was based on the comprehensively theoretical computational and experimental physical study on the successfully isolated derivatives, through using routine synthetic pathways in a relatively high yields, marked these derivatives as 'treasure' for further experimental and theoretical studied in areas such as: (a) pharmacological and clinical testing; (b) molecular-drugs design of novel psychoactive substances; (c) development of the analytical protocols for determination of Ergot-alkaloids through a functionalization of the ergoline-skeleton, and more.

Molecular modeling of the microstructure evolution during carbon fiber processing

NASA Astrophysics Data System (ADS)

Desai, Saaketh; Li, Chunyu; Shen, Tongtong; Strachan, Alejandro

2017-12-01

The rational design of carbon fibers with desired properties requires quantitative relationships between the processing conditions, microstructure, and resulting properties. We developed a molecular model that combines kinetic Monte Carlo and molecular dynamics techniques to predict the microstructure evolution during the processes of carbonization and graphitization of polyacrylonitrile (PAN)-based carbon fibers. The model accurately predicts the cross-sectional microstructure of the fibers with the molecular structure of the stabilized PAN fibers and physics-based chemical reaction rates as the only inputs. The resulting structures exhibit key features observed in electron microcopy studies such as curved graphitic sheets and hairpin structures. In addition, computed X-ray diffraction patterns are in good agreement with experiments. We predict the transverse moduli of the resulting fibers between 1 GPa and 5 GPa, in good agreement with experimental results for high modulus fibers and slightly lower than those of high-strength fibers. The transverse modulus is governed by sliding between graphitic sheets, and the relatively low value for the predicted microstructures can be attributed to their perfect longitudinal texture. Finally, the simulations provide insight into the relationships between chemical kinetics and the final microstructure; we observe that high reaction rates result in porous structures with lower moduli.

Transport Studies and Modeling in PEM Fuel Cells

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

Mittelsteadt, Cortney K.; Xu, Hui; Brawn, Shelly

2014-07-30

This project’s aim was to develop fuel cell components (i.e. membranes, gas-diffusion media (GDM), bipolar plates and flow fields) that possess specific properties (i.e. water transport and conductivity). A computational fluid dynamics model was developed to elucidate the effect of certain parameters on these specific properties. Ultimately, the model will be used to determine sensitivity of fuel cell performance to component properties to determine limiting components and to guide research. We have successfully reached our objectives and achieved most of the milestones of this project. We have designed and synthesized a variety of hydrocarbon block polymer membranes with lower equivalentmore » weight, structure, chemistry, phase separation and process conditions. These membranes provide a broad selection with optimized water transport properties. We have also designed and constructed a variety of devices that are capable of accurately measuring the water transport properties (water uptake, water diffusivity and electro-osmatic drag) of these membranes. These transport properties are correlated to the membranes’ structures derived from X-ray and microscopy techniques to determine the structure-property relationship. We successfully integrated hydrocarbon membrane MEAs with a current distribution board (CBD) to study the impact of hydrocarbon membrane on water transport in fuel cells. We have designed and fabricated various GDM with varying substrate, diffusivity and micro-porous layers (MPL) and characterized their pore structure, tortuosity and hydrophobicity. We have derived a universal chart (MacMullin number as function of wet proofing and porosity) that can be used to characterize various GDM. The abovementioned GDMs have been evaluated in operating fuel cells; their performance is correlated to various pore structure, tortuosity and hydrophobicity of the GDM. Unfortunately, determining a universal relationship between the MacMullin number and these properties was not achieved. We have simulated fuel cell performance, current distribution and water distribution at various values of the water uptake, membrane diffusivity, and electro-osmotic drag coefficient (EODC) and compared modeling results with segmented-cell data for both serpentine and parallel flow-fields. We have developed iterations of fuel cell flow fields to achieve specific water transport and thermal management targets. This work demonstrated the importance of membrane diffusivity on fuel cell performance, the necessity of a high membrane diffusion coefficient, and the desirability of a low EODC at low levels of relative humidity.« less

Glycyrrhetinic Acid and Its Derivatives: Anti-Cancer and Cancer Chemopreventive Properties, Mechanisms of Action and Structure- Cytotoxic Activity Relationship.

PubMed

Roohbakhsh, Ali; Iranshahy, Milad; Iranshahi, Mehrdad

2016-01-01

The anti-cancer properties of liquorice have been attributed, at least in part, to glycyrrhizin (GL). However, GL is not directly absorbed through the gastrointestinal tract. It is hydrolyzed to 18-β-glycyrrhetinic acid (GA), the pharmacologically active metabolite, by human intestinal microflora. GA exhibits remarkable cytotoxic and anti-tumor properties. The pro-apoptotic targets and mechanisms of action of GA have been extensively studied over the past decade. In addition, GA is an inexpensive and available triterpene with functional groups (COOH and OH) in its structure, which make it an attractive lead compound for medicinal chemists to prepare a large number of analogues. To date, more than 400 cytotoxic derivatives have been prepared on the basis of GA scaffold, including 128 cytotoxic derivatives with IC50 values less than 30 µM. Researchers have also succeeded in synthesizing very potent cytotoxic derivatives with IC50s ≤ 1 µM. Studies have shown that the introduction of a double bound at the C1-C2 position combined with an electronegative functional group, such as CN, CF3 or iodine at C2 position, and the oxidation of the hydroxyl group of C3 to the carbonyl group, significantly increased cytotoxicity. This review describes the cytotoxic and anti-tumor properties of GA and its derivatives, targets and mechanisms of action and provides insight into the structure-activity relationship of GA derivatives.

Characterization of synthetic foam structures used to manufacture artificial vertebral trabecular bone.

PubMed

Fürst, David; Senck, Sascha; Hollensteiner, Marianne; Esterer, Benjamin; Augat, Peter; Eckstein, Felix; Schrempf, Andreas

2017-07-01

Artificial materials reflecting the mechanical properties of human bone are essential for valid and reliable implant testing and design. They also are of great benefit for realistic simulation of surgical procedures. The objective of this study was therefore to characterize two groups of self-developed synthetic foam structures by static compressive testing and by microcomputed tomography. Two mineral fillers and varying amounts of a blowing agent were used to create different expansion behavior of the synthetic open-cell foams. The resulting compressive and morphometric properties thus differed within and also slightly between both groups. Apart from the structural anisotropy, the compressive and morphometric properties of the synthetic foam materials were shown to mirror the respective characteristics of human vertebral trabecular bone in good approximation. In conclusion, the artificial materials created can be used to manufacture valid synthetic bones for surgical training. Further, they provide novel possibilities for studying the relationship between trabecular bone microstructure and biomechanical properties. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural and spectroscopic investigation of new luminescent hybrid materials based on calix[4]arene-tetracarboxylate and Ln3+ ions (Ln = Gd, Tb or Eu)

NASA Astrophysics Data System (ADS)

Viana, R. S.; Oliveira, C. A. F.; Chojnacki, J.; Barros, B. S.; Alves-Jr, S.; Kulesza, J.

2017-07-01

Lanthanide-calixarene hybrid materials are of particular interest due to the combination of the interesting properties of the ligand cavity-like structure and the luminescent features of lanthanides. The aim of this study was to synthesize and investigate the photophysical properties of Eu3+, Tb3+ and Gd3+ hybrids based on calix[4]arene-tetracarboxylate. The preparation of two structurally different Tb3+ compounds (calix-TA-SC-Tb and calix-TA-Tb) was dictated by the ligand to metal molar ratio and the synthesis time. Analysis of calix-TA-SC-Tb monocrystals revealed the formation of a mononuclear complex of C2 symmetry containing Tb3+ coordinated by four calixarene ionized groups and formate anion encapsulated within the upper cavity. Syntheses of other hybrids failed in producing high-quality crystals and the structures could not be solved. The solid-state luminescent properties of hybrids were evaluated, and the structure/property relationship was investigated. Based on the emission and excitation spectra, the energy diagrams for calix-TA-Eu, calix-TA-Tb and calix-TA-Gd were proposed.

Partitioning and lipophilicity in quantitative structure-activity relationships.

PubMed Central

Dearden, J C

1985-01-01

The history of the relationship of biological activity to partition coefficient and related properties is briefly reviewed. The dominance of partition coefficient in quantitation of structure-activity relationships is emphasized, although the importance of other factors is also demonstrated. Various mathematical models of in vivo transport and binding are discussed; most of these involve partitioning as the primary mechanism of transport. The models describe observed quantitative structure-activity relationships (QSARs) well on the whole, confirming that partitioning is of key importance in in vivo behavior of a xenobiotic. The partition coefficient is shown to correlate with numerous other parameters representing bulk, such as molecular weight, volume and surface area, parachor and calculated indices such as molecular connectivity; this is especially so for apolar molecules, because for polar molecules lipophilicity factors into both bulk and polar or hydrogen bonding components. The relationship of partition coefficient to chromatographic parameters is discussed, and it is shown that such parameters, which are often readily obtainable experimentally, can successfully supplant partition coefficient in QSARs. The relationship of aqueous solubility with partition coefficient is examined in detail. Correlations are observed, even with solid compounds, and these can be used to predict solubility. The additive/constitutive nature of partition coefficient is discussed extensively, as are the available schemes for the calculation of partition coefficient. Finally the use of partition coefficient to provide structural information is considered. It is shown that partition coefficient can be a valuable structural tool, especially if the enthalpy and entropy of partitioning are available. PMID:3905374

Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts

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

Bedford, Nicholas M.; Ramezani-Dakhel, Hadi; Slocik, Joseph M.

Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved via peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, whichmore » was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C-C coupling and olefin hydrogenation were then eluddated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences« less

Probing the Unique Role of Gallium in Amorphous Oxide Semiconductors through Structure-Property Relationships

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

Moffitt, Stephanie L.; Zhu, Qimin; Ma, Qing

This study explores the unique role of Ga in amorphous (a-) In[BOND]Ga[BOND]O oxide semiconductors through combined theory and experiment. It reveals substitutional effects that have not previously been attributed to Ga, and that are investigated by examining how Ga influences structure–property relationships in a series of pulsed laser deposited a-In[BOND]Ga[BOND]O thin films. Element-specific structural studies (X-ray absorption and anomalous scattering) show good agreement with the results of ab initio molecular dynamics simulations. This structural knowledge is used to understand the results of air-annealing and Hall effect electrical measurements. The crystallization temperature of a-IO is shown to increase by as muchmore » as 325 °C on substituting Ga for In. This increased thermal stability is understood on the basis of the large changes in local structure that Ga undergoes, as compared to In, during crystallization. Hall measurements reveal an initial sharp drop in both carrier concentration and mobility with increasing Ga incorporation, which moderates at >20 at% Ga content. This decline in both the carrier concentration and mobility with increasing Ga is attributed to dilution of the charge-carrying In[BOND]O matrix and to increased structural disorder. The latter effect saturates at high at% Ga.« less

Elucidation of peptide-directed palladium surface structure for biologically tunable nanocatalysts.

PubMed

Bedford, Nicholas M; Ramezani-Dakhel, Hadi; Slocik, Joseph M; Briggs, Beverly D; Ren, Yang; Frenkel, Anatoly I; Petkov, Valeri; Heinz, Hendrik; Naik, Rajesh R; Knecht, Marc R

2015-05-26

Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved via peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, which was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C-C coupling and olefin hydrogenation were then elucidated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences.

Study of structural, elastic, electronic and optical properties of seven SrZrO{sub 3} phases: First-principles calculations

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

Liu, Qi-Jun, E-mail: dianerliu@yahoo.com.cn; Liu, Zheng-Tang; Feng, Li-Ping

2012-12-15

On the plane-wave ultrasoft pseudopotential technique based on the first-principles density functional theory (DFT), we calculated the structural, elastic, electronic and optical properties of the seven different phases of SrZrO{sub 3}. The obtained ground-state properties are in good agreement with previous experiments and calculations, which indicate that the most stable phase is orthorhombic Pnma structure. Seven phases of SrZrO{sub 3} are mechanically stable with cubic, tetragonal and orthorhombic structures. The mechanical and thermodynamic properties have been obtained by using the Voigt-Reuss-Hill approach and Debye-Grueneisen model. The electronic structures and optical properties are obtained and compared with the available experimental andmore » theoretical data. - Graphical abstract: Energy versus volume of seven phases SrZrO{sub 3} shows the Pnma phase has the minimum ground-state energy. Highlights: Black-Right-Pointing-Pointer We calculated the physical and chemical properties of seven SrZrO{sub 3} polymorphs. Black-Right-Pointing-Pointer The order of stability is Pnma>Imma>Cmcm>I4/mcm>P4/mbm>P4mm>Pm3-bar m. Black-Right-Pointing-Pointer The most stable phase is orthorhombic Pnma structure. Black-Right-Pointing-Pointer Seven phases of SrZrO{sub 3} are mechanically stable. Black-Right-Pointing-Pointer The relationship between n and {rho}{sub m} is n=1+0.18{rho}{sub m}.« less

Spatial characterization of soil properties and influence in soil formation in oak-grassland of Sierra Morena, S Spain

NASA Astrophysics Data System (ADS)

Román-Sánchez, Andrea; Cáceres, Francisco; Pédèches, Remi; Giráldez Cervera, Juan Vicente; Vanwalleghem, Tom

2016-04-01

The Mediterranean oak-grassland ecosystem is very important for the rural economy and for the biodiversity of south-western European countries like Spain and Portugal. Nevertheless these ecosystems are not well characterized especially their soils. In this report soil carbon has been evaluated and related to other properties. The principal factors controlling the structure, productivity and evolution of forest ecosystems are bedrock, climate, relief, vegetation and time. Soil carbon has an important influence in the soil and ecosystem structures. The purpose of this study is to determine the relationship between relief, soil properties, spatial distribution of soil carbon and their influence in soil formation and geomorphology. This work is part of another study which aims to elucidate the processes involved in the soil formation and to examine their behaviour on long-term with a modelling. In our study area, located in oak-grassland of Sierra Morena, in Cordoba, S Spain, have been studied 67 points at 6 depths in 262 hectares in order to determine carbon content varying between 0-6%, soil properties such as soil depth between 0-4 m, horizon depth and the rocks amount in surface. The relationship between the soil carbon, soil properties and the relief characteristic like slope, aspect, curvature can shed light the processes that affect the mechanisms of bedrock weathering and their interrelationship with geomorphological processes.

Fundamental optical properties of linear and cyclic alkanes: VUV absorbance and index of refraction.

PubMed

Costner, Elizabeth A; Long, Brian K; Navar, Carlos; Jockusch, Steffen; Lei, Xuegong; Zimmerman, Paul; Campion, Alan; Turro, Nicholas J; Willson, C Grant

2009-08-20

VUV absorbance and index of refraction data for a series of linear and cyclic alkanes have been collected in order to understand the relationship between the electronic excitation wavelength (or absorbance edge), index of refraction, and molecular structure. The absorbance edge and index for a homologous series of both linear and cyclic alkanes increase with increasing carbon number. The optical properties of complex cycloalkanes do not vary predictably with increasing carbon number but instead depend on variations in the hydrocarbon structure in addition to hydrocarbon size. An understanding of the fundamental optical properties of this class of compounds is directly applicable to the identification of a high index and low-absorbance fluid for 193 nm immersion lithography.

The impact behaviour of silk cocoons.

PubMed

Chen, Fujia; Hesselberg, Thomas; Porter, David; Vollrath, Fritz

2013-07-15

Silk cocoons, constructed by silkmoths (Lepidoptera), are protective structural composites. Some cocoons appear to have evolved towards structural and material optimisation in order to sustain impact strikes from predators and hinder parasite ingress. This study investigates the protective properties of silk cocoons with different morphologies by evaluating their impact resistance and damage tolerance. Finite element analysis was used to analyse empirical observations of the quasi-static impact response of the silk cocoons, and to evaluate the separate benefits of the structures and materials through the deformation and damage mechanism. We use design principles from composite engineering in order to understand the structure-property-function relationship of silkworm cocoons. Understanding the highly evolved survival strategies of the organisms building natural cocoons will hopefully lead to inspiration that in turn could lead to improved composite design.

Structural evolution and properties of small-size thiol-protected gold nanoclusters

NASA Astrophysics Data System (ADS)

Ma, Miaomiao; Liu, Liren; Zhu, Hengjiang; Lu, Junzhe; Tan, Guiping

2018-07-01

Ligand-protected gold clusters are widely used in biosensors and catalysis. Understanding the structural evolution of these kinds of nanoclusters is important for experimental synthesis. Herein, based on the particle swarm optimisation algorithm and density functional theory method, we use [Au1(SH)2]n, [Au2(SH)3]n, [Au3(SH)4]n (n = 1-3) as basic units to research the structural evolution relationships from building blocks to the final whole structures. Results show that there is a 'line-ring-core' structural evolution pattern in the growth process of the nanoclusters. The core structures of the ligand-protected gold clusters consist of Au3, Au4, Au6 and Au7 atoms. The electronics and optics analysis reflects that stability and optical properties gradually enhance with increase in size. These results can be used to understand the initial growth stage and design new ligand-protected nanoclusters.

Inorganic pyrophosphatases: structural diversity serving the function

NASA Astrophysics Data System (ADS)

Samygina, V. R.

2016-05-01

The review is devoted to ubiquitous enzymes, inorganic pyrophosphatases, which are essential in all living organisms. Despite the long history of investigations, these enzymes continue to attract interest. The review focuses on the three-dimensional structures of various representatives of this class of proteins. The structural diversity, the relationship between the structure and some properties of pyrophosphatases and various mechanisms of enzyme action related to the structural diversity of these enzymes are discussed. Interactions of pyrophosphatase with other proteins and possible practical applications are considered. The bibliography includes 56 references.

Brain white matter structure and COMT gene are linked to second-language learning in adults

PubMed Central

Mamiya, Ping C.; Richards, Todd L.; Coe, Bradley P.; Eichler, Evan E.; Kuhl, Patricia K.

2016-01-01

Adult human brains retain the capacity to undergo tissue reorganization during second-language learning. Brain-imaging studies show a relationship between neuroanatomical properties and learning for adults exposed to a second language. However, the role of genetic factors in this relationship has not been investigated. The goal of the current study was twofold: (i) to characterize the relationship between brain white matter fiber-tract properties and second-language immersion using diffusion tensor imaging, and (ii) to determine whether polymorphisms in the catechol-O-methyltransferase (COMT) gene affect the relationship. We recruited incoming Chinese students enrolled in the University of Washington and scanned their brains one time. We measured the diffusion properties of the white matter fiber tracts and correlated them with the number of days each student had been in the immersion program at the time of the brain scan. We found that higher numbers of days in the English immersion program correlated with higher fractional anisotropy and lower radial diffusivity in the right superior longitudinal fasciculus. We show that fractional anisotropy declined once the subjects finished the immersion program. The relationship between brain white matter fiber-tract properties and immersion varied in subjects with different COMT genotypes. Subjects with the Methionine (Met)/Valine (Val) and Val/Val genotypes showed higher fractional anisotropy and lower radial diffusivity during immersion, which reversed immediately after immersion ended, whereas those with the Met/Met genotype did not show these relationships. Statistical modeling revealed that subjects’ grades in the language immersion program were best predicted by fractional anisotropy and COMT genotype. PMID:27298360

Brain white matter structure and COMT gene are linked to second-language learning in adults.

PubMed

Mamiya, Ping C; Richards, Todd L; Coe, Bradley P; Eichler, Evan E; Kuhl, Patricia K

2016-06-28

Adult human brains retain the capacity to undergo tissue reorganization during second-language learning. Brain-imaging studies show a relationship between neuroanatomical properties and learning for adults exposed to a second language. However, the role of genetic factors in this relationship has not been investigated. The goal of the current study was twofold: (i) to characterize the relationship between brain white matter fiber-tract properties and second-language immersion using diffusion tensor imaging, and (ii) to determine whether polymorphisms in the catechol-O-methyltransferase (COMT) gene affect the relationship. We recruited incoming Chinese students enrolled in the University of Washington and scanned their brains one time. We measured the diffusion properties of the white matter fiber tracts and correlated them with the number of days each student had been in the immersion program at the time of the brain scan. We found that higher numbers of days in the English immersion program correlated with higher fractional anisotropy and lower radial diffusivity in the right superior longitudinal fasciculus. We show that fractional anisotropy declined once the subjects finished the immersion program. The relationship between brain white matter fiber-tract properties and immersion varied in subjects with different COMT genotypes. Subjects with the Methionine (Met)/Valine (Val) and Val/Val genotypes showed higher fractional anisotropy and lower radial diffusivity during immersion, which reversed immediately after immersion ended, whereas those with the Met/Met genotype did not show these relationships. Statistical modeling revealed that subjects' grades in the language immersion program were best predicted by fractional anisotropy and COMT genotype.

Prediction of Physicochemical Properties of Energetic Materials for Identification of Treatment Technologies for Waste Streams

DTIC Science & Technology

2010-11-01

estimate the pharmacokinetics of potential drugs (Horning and Klamt 2005). QSPR/ QSARs also have potential applications in the fuel science field...group contribution methods, and (2) quantitative structure-property/activity relationships (QSPR/ QSAR ). The group contribution methods are primarily...development of QSPR/ QSARs is the identification of the ap- propriate set of descriptors that allow the desired attribute of the compound to be adequately

Structure/Property Relationships of Cyanate Ester Resins from Renewable Sources

DTIC Science & Technology

2013-04-11

derived from lignin . These materials possess favorable thermal and water uptake properties with dry glass transition temperatures above 200°C and wet...distribution is unlimited. Creosol as a Monomer Source 7 • Input material cost is an important consideration for cyanate ester resins • Lignin is...from lignin • Oxidative and reductive coupling reactions lead to precursor phenols, which are then treated with cyanogen bromide to generate cyanate

Structure-Property Relationships in Surface-Modified Ceramics. NATO advanced Science Institutes, Series E: Applied Sciences, Volume 170

DTIC Science & Technology

1989-01-01

channelling and scanning electron microscopy (SEM) of highly oriented pyrolytic graphite ( HOPG ), comparative scratch testing results and some ideas on...electrode graphite , HOPG and carbon fibers also show enhanced wear resistance followoing irradiation (6), the extent of which depends upon the initial...literature dealing with damage effects and physical property changes following neutron irradiation of graphite (single and polycrystalline ) in nuclear

Dielectric and structural characterisation of chalcogenide glasses via terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Ravagli, A.; Naftaly, M.; Craig, C.; Weatherby, E.; Hewak, D. W.

2017-07-01

Terahertz time-domain spectroscopy (THz TDS) was used to investigate a series of chalcogenide glasses. In particular, the dielectric properties at terahertz frequencies were determined and correlated with the glass composition. The experimental results showed a strong relationship between the dielectric properties and the polarizability of the glasses studied. A new explanation based on the coordination number of the metallic cations was proposed to understand these observations.

Review on Abyssomicins: Inhibitors of the Chorismate Pathway and Folate Biosynthesis.

PubMed

Sadaka, Carmen; Ellsworth, Edmund; Hansen, Paul Robert; Ewin, Richard; Damborg, Peter; Watts, Jeffrey L

2018-06-06

Antifolates targeting folate biosynthesis within the shikimate-chorismate-folate metabolic pathway are ideal and selective antimicrobials, since higher eukaryotes lack this pathway and rely on an exogenous source of folate. Resistance to the available antifolates, inhibiting the folate pathway, underlines the need for novel antibiotic scaffolds and molecular targets. While para-aminobenzoic acid synthesis within the chorismate pathway constitutes a novel molecular target for antifolates, abyssomicins are its first known natural inhibitors. This review describes the abyssomicin family, a novel spirotetronate polyketide Class I antimicrobial. It summarizes synthetic and biological studies, structural, biosynthetic, and biological properties of the abyssomicin family members. This paper aims to explain their molecular target, mechanism of action, structure⁻activity relationship, and to explore their biological and pharmacological potential. Thirty-two natural abyssomicins and numerous synthetic analogues have been reported. The biological activity of abyssomicins includes their antimicrobial activity against Gram-positive bacteria and mycobacteria, antitumor properties, latent human immunodeficiency virus (HIV) reactivator, anti-HIV and HIV replication inducer properties. Their antimalarial properties have not been explored yet. Future analoging programs using the structure⁻activity relationship data and synthetic approaches may provide a novel abyssomicin structure that is active and devoid of cytotoxicity. Abyssomicin J and atrop- o -benzyl-desmethylabyssomicin C constitute promising candidates for such programs.

Quantitative structure--property relationships for enhancing predictions of synthetic organic chemical removal from drinking water by granular activated carbon.

PubMed

Magnuson, Matthew L; Speth, Thomas F

2005-10-01

Granular activated carbon is a frequently explored technology for removing synthetic organic contaminants from drinking water sources. The success of this technology relies on a number of factors based not only on the adsorptive properties of the contaminant but also on properties of the water itself, notably the presence of substances in the water which compete for adsorption sites. Because it is impractical to perform field-scale evaluations for all possible contaminants, the pore surface diffusion model (PSDM) has been developed and used to predict activated carbon column performance using single-solute isotherm data as inputs. Many assumptions are built into this model to account for kinetics of adsorption and competition for adsorption sites. This work further evaluates and expands this model, through the use of quantitative structure-property relationships (QSPRs) to predict the effect of natural organic matter fouling on activated carbon adsorption of specific contaminants. The QSPRs developed are based on a combination of calculated topographical indices and quantum chemical parameters. The QSPRs were evaluated in terms of their statistical predictive ability,the physical significance of the descriptors, and by comparison with field data. The QSPR-enhanced PSDM was judged to give results better than what could previously be obtained.

Searching for “Environmentally-Benign” Antifouling Biocides

PubMed Central

Cui, Yan Ting; Teo, Serena L. M.; Leong, Wai; Chai, Christina L. L.

2014-01-01

As the result of the ecological impacts from the use of tributyltins (TBT) in shipping, environmental legislation for the registration of chemicals for use in the environment has grown to a monumental challenge requiring product dossiers to include information on the environmental fate and behavior of any chemicals. Specifically, persistence, bioaccumulation and toxicity, collectively known as PBT, are properties of concern in the assessment of chemicals. However, existing measurements of PBT properties are a cumbersome and expensive process, and thus not applied in the early stages of the product discovery and development. Inexpensive methods for preliminary PBT screening would minimize risks arising with the subsequent registration of products. In this article, we evaluated the PBT properties of compounds reported to possess anti-fouling properties using QSAR (quantitative structure-activity relationship) prediction programs such as BIOWIN™ (a biodegradation probability program), KOWWIN™ (log octanol-water partition coefficient calculation program) and ECOSAR™ (Ecological Structure Activity Relationship Programme). The analyses identified some small (Mr < 400) synthetic and natural products as potential candidates for environmentally benign biocides. We aim to demonstrate that while these methods of estimation have limitations, when applied with discretion, they are powerful tools useful in the early stages of research for compound selection for further development as anti-foulants. PMID:24865489

[Adsorption of Cu on Core-shell Structured Magnetic Particles: Relationship Between Adsorption Performance and Surface Properties].

PubMed

Li, Qiu-mei; Chen, Jing; Li, Hai-ning; Zhang, Xiao-lei; Zhang, Gao-sheng

2015-12-01

In order to reveal the relationship between the adsorption performance of adsorbents and their compositions, structure, and surface properties, the core-shell structured Fe₃O₄/MnO2 and Fe-Mn/Mn₂2 magnetic particles were systematically characterized using multiple techniques and their Cu adsorption behaviors as well as mechanism were also investigated in details. It was found that both Fe₃O4 and Fe-Mn had spinel structure and no obvious crystalline phase change was observed after coating with MnO₂. The introduction of Mn might improve the affinity between the core and the shell, and therefore enhanced the amount and distribution uniformity of the MnO₂ coated. Consequently, Fe-Mn/MnO₂ exhibited a higher BET specific surface area and a lower isoelectric point. The results of sorption experiments showed that Fe-Mn had a higher maximal Cu adsorption capacity of 33.7 mg · g⁻¹ at pH 5.5, compared with 17.5 mg · g⁻¹ of Fe₃O4. After coating, the maximal adsorption capacity of Fe-Mn/MnO₂ was increased to 58.2 mg · g⁻¹, which was 2.6 times as high as that of Fe₃O₄/MnO₂ and outperformed the majority of magnetic adsorbents reported in literature. In addition, a specific adsorption of Cu occurred at the surface of Fe₃O₄/MnO₂ or Fe-Mn/MnO₂ through the formation of inner-sphere complexes. In conclusion, the adsorption performance of the magnetic particles was positively related to their compositions, structure, and surface properties.

A hybrid organic-inorganic perovskite dataset

NASA Astrophysics Data System (ADS)

Kim, Chiho; Huan, Tran Doan; Krishnan, Sridevi; Ramprasad, Rampi

2017-05-01

Hybrid organic-inorganic perovskites (HOIPs) have been attracting a great deal of attention due to their versatility of electronic properties and fabrication methods. We prepare a dataset of 1,346 HOIPs, which features 16 organic cations, 3 group-IV cations and 4 halide anions. Using a combination of an atomic structure search method and density functional theory calculations, the optimized structures, the bandgap, the dielectric constant, and the relative energies of the HOIPs are uniformly prepared and validated by comparing with relevant experimental and/or theoretical data. We make the dataset available at Dryad Digital Repository, NoMaD Repository, and Khazana Repository (http://khazana.uconn.edu/), hoping that it could be useful for future data-mining efforts that can explore possible structure-property relationships and phenomenological models. Progressive extension of the dataset is expected as new organic cations become appropriate within the HOIP framework, and as additional properties are calculated for the new compounds found.

Polymer matrix nanocomposites for automotive structural components

DOE PAGES

Naskar, Amit K.; Keum, Jong K.; Boeman, Raymond G.

2016-12-06

Over the past several decades, the automotive industry has expended significant effort to develop lightweight parts from new easy-to-process polymeric nanocomposites. These materials have been particularly attractive because they can increase fuel efficiency and reduce greenhouse gas emissions. However, attempts to reinforce soft matrices by nanoscale reinforcing agents at commercially deployable scales have been only sporadically successful to date. This situation is due primarily to the lack of fundamental understanding of how multiscale interfacial interactions and the resultant structures affect the properties of polymer nanocomposites. In this paper, we critically evaluate the state of the art in the field andmore » propose a possible path that may help to overcome these barriers. Finally, only once we achieve a deeper understanding of the structure–properties relationship of polymer matrix nanocomposites will we be able to develop novel structural nanocomposites with enhanced mechanical properties for automotive applications.« less

Understanding to Hierarchical Microstructures of Crab (Chinese hairy) Shell as a Natural Architecture

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

Chuanqiang, Zhou; Xiangxiang, Gong; School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou

This work was done to better understand the microstructures, composition and mechanical properties of Chinese hairy crab shell. For fully revealing its hierarchical microstructure, the crab shell was observed with electron microscope under different magnifications from different facets. XRD, EDS, FTIR and TGA techniques have been used to characterize the untreated and chemically-treated crab shells, which provided enough information to determine the species and relative content of components in this biomaterial. Combined the microstructures with constituents analysis, the structural principles of crab shell was detailedly realized from different structural levels beyond former reports. To explore the relationship between structure andmore » function, the mechanical properties of shell have been measured through performing tensile tests. The contributions of organics and minerals in shell to the mechanical properties were also discussed by measuring the tensile strength of de-calcification samples treated with HCl solution.« less

Tunable Thermosetting Epoxies Based on Fractionated and Well-Characterized Lignins.

PubMed

Gioia, Claudio; Lo Re, Giada; Lawoko, Martin; Berglund, Lars

2018-03-21

Here we report the synthesis of thermosetting resins from low molar mass Kraft lignin fractions of high functionality, refined by solvent extraction. Such fractions were fully characterized by 31 P NMR, 2D-HSQC NMR, SEC, and DSC in order to obtain a detailed description of the structures. Reactive oxirane moieties were introduced on the lignin backbone under mild reaction conditions and quantified by simple 1 H NMR analysis. The modified fractions were chemically cross-linked with a flexible polyether diamine ( M n ≈ 2000), in order to obtain epoxy thermosets. Epoxies from different lignin fractions, studied by DSC, DMA, tensile tests, and SEM, demonstrated substantial differences in terms of thermo-mechanical properties. For the first time, strong relationships between lignin structures and epoxy properties could be demonstrated. The suggested approach provides unprecedented possibilities to tune network structure and properties of thermosets based on real lignin fractions, rather than model compounds.

Identifying Atomic Scale Structure in Undoped/Doped Semicrystalline P3HT Using Inelastic Neutron Scattering

DOE PAGES

Harrelson, Thomas F.; Cheng, Yongqiang Q.; Li, Jun; ...

2017-03-07

The greatest advantage of organic materials is the ability to synthetically tune desired properties. However, structural heterogeneity often obfuscates the relationship between chemical structure and functional properties. Inelastic neutron scattering (INS) is sensitive to both local structure and chemical environment and provides atomic level details that cannot be obtained through other spectroscopic or diffraction methods. INS data are composed of a density of vibrational states with no selection rules, which means that every structural configuration is equally weighted in the spectrum. This allows the INS spectrum to be quantitatively decomposed into different structural motifs. Here in this paper we presentmore » INS measurements of the semiconducting polymer P3HT doped with F4TCNQ supported by density functional theory calculations to identify two dominant families of undoped crystalline structures and one dominant doped structural motif, in spite of considerable heterogeneity. The differences between the undoped and doped structures indicate that P3HT side chains flatten upon doping.« less

Microstructure of Tablet-Pharmaceutical Significance, Assessment, and Engineering.

PubMed

Sun, Changquan Calvin

2017-05-01

To summarize the microstructure - property relationship of pharmaceutical tablets and approaches to improve tablet properties through tablet microstructure engineering. The main topics reviewed here include: 1) influence of material properties and manufacturing process parameters on the evolution of tablet microstructure; 2) impact of tablet structure on tablet properties; 3) assessment of tablet microstructure; 4) development and engineering of tablet microstructure. Microstructure plays a decisive role on important pharmaceutical properties of a tablet, such as disintegration, drug release, and mechanical strength. Useful information on mechanical properties of a powder can be obtained from analyzing tablet porosity-pressure data. When helium pycnometry fails to accurately measure true density of a water-containing powder, non-linear regression of tablet density-pressure data is a useful alternative method. A component that is more uniformly distributed in a tablet generally exerts more influence on the overall tablet properties. During formulation development, it is highly recommended to examine the relationship between any property of interest and tablet porosity when possible. Tablet microstructure can be engineered by judicious selection of formulation composition, including the use of the optimum solid form of the drug and appropriate type and amount of excipients, and controlling manufacturing process.

Towards enamel biomimetics: Structure, mechanical properties and biomineralization of dental enamel

NASA Astrophysics Data System (ADS)

Fong, Hanson Kwok

Dental enamel is the most mineralized tissue in the human body. This bioceramic, composed largely of hydroxyapatite (HAp), is also one of the most durable tissues despite a lifetime of masticatory loading and bacterial attack. The biosynthesis of enamel, which occurs in physiological conditions is a complex orchestration of protein assembly and mineral formation. The resulting product is the hardest tissue in the vertebrate body with the longest and most organized arrangement of hydroxyapatite crystals known to biomineralizing systems. Detail understanding of the structure of enamel in relationship to its mechanical function and the biomineralization process will provide a framework for enamel regeneration as well as potential lessons in the design of engineering materials. The objective of this study, therefore, is twofold: (1) establish the structure-function relationship of enamel as well as the dentine-enamel junction (DEJ) and (2) determine the effect of proteins on the enamel biomineralization process. A hierarchy in the enamel structure was established by means of various microscopy techniques (e.g. SEM, TEM, AFM). Mechanical properties (hardness and elastic modulus) associated with the microstructural features were also determined by nanoindentation. Furthermore, the DEJ was found to have a width in the range of micrometers to 10s of micrometers with continuous change in structure and mechanical properties. Indentation tests and contact fatigue tests using a spherical indenter have revealed that the structural features in the enamel and the DEJ played important roles in containing crack propagation emanating from the enamel tissue. To further understand the effect of this protein on the biominerailzation process, we have studied genetically engineered animals that express altered amelogenin which lack the known self-assembly properties. This in vivo study has revealed that, without the proper self-assembly of the amelogenin protein as demonstrated by the altered amelogenin, the crystal organization of the apatite phase was severely disrupted at the nucleation stage resulting in lower mineral density at the mature stage. Consequently measurably inferior mechanical properties were found in the mature enamel grown with altered amelogenin when compared to the age matched wild-type.

Molecular tandem repeat strategy for elucidating mechanical properties of high-strength proteins

PubMed Central

Jung, Huihun; Pena-Francesch, Abdon; Saadat, Alham; Sebastian, Aswathy; Kim, Dong Hwan; Hamilton, Reginald F.; Albert, Istvan; Allen, Benjamin D.; Demirel, Melik C.

2016-01-01

Many globular and structural proteins have repetitions in their sequences or structures. However, a clear relationship between these repeats and their contribution to the mechanical properties remains elusive. We propose a new approach for the design and production of synthetic polypeptides that comprise one or more tandem copies of a single unit with distinct amorphous and ordered regions. Our designed sequences are based on a structural protein produced in squid suction cups that has a segmented copolymer structure with amorphous and crystalline domains. We produced segmented polypeptides with varying repeat number, while keeping the lengths and compositions of the amorphous and crystalline regions fixed. We showed that mechanical properties of these synthetic proteins could be tuned by modulating their molecular weights. Specifically, the toughness and extensibility of synthetic polypeptides increase as a function of the number of tandem repeats. This result suggests that the repetitions in native squid proteins could have a genetic advantage for increased toughness and flexibility. PMID:27222581

Understanding nanocellulose chirality and structure–properties relationship at the single fibril level

PubMed Central

Usov, Ivan; Nyström, Gustav; Adamcik, Jozef; Handschin, Stephan; Schütz, Christina; Fall, Andreas; Bergström, Lennart; Mezzenga, Raffaele

2015-01-01

Nanocellulose fibrils are ubiquitous in nature and nanotechnologies but their mesoscopic structural assembly is not yet fully understood. Here we study the structural features of rod-like cellulose nanoparticles on a single particle level, by applying statistical polymer physics concepts on electron and atomic force microscopy images, and we assess their physical properties via quantitative nanomechanical mapping. We show evidence of right-handed chirality, observed on both bundles and on single fibrils. Statistical analysis of contours from microscopy images shows a non-Gaussian kink angle distribution. This is inconsistent with a structure consisting of alternating amorphous and crystalline domains along the contour and supports process-induced kink formation. The intrinsic mechanical properties of nanocellulose are extracted from nanoindentation and persistence length method for transversal and longitudinal directions, respectively. The structural analysis is pushed to the level of single cellulose polymer chains, and their smallest associated unit with a proposed 2 × 2 chain-packing arrangement. PMID:26108282

Carbide-derived carbons - From porous networks to nanotubes and graphene

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

Presser, V.; Heon, M.; Gogotsi, Y.

2011-02-09

Carbide-derived carbons (CDCs) are a large family of carbon materials derived from carbide precursors that are transformed into pure carbon via physical (e.g., thermal decomposition) or chemical (e.g., halogenation) processes. Structurally, CDC ranges from amorphous carbon to graphite, carbon nanotubes or graphene. For halogenated carbides, a high level of control over the resulting amorphous porous carbon structure is possible by changing the synthesis conditions and carbide precursor. The large number of resulting carbon structures and their tunability enables a wide range of applications, from tribological coatings for ceramics, or selective sorbents, to gas and electrical energy storage. In particular, themore » application of CDC in supercapacitors has recently attracted much attention. This review paper summarizes key aspects of CDC synthesis, properties, and applications. It is shown that the CDC structure and properties are sensitive to changes of the synthesis parameters. Understanding of processing–structure–properties relationships facilitates tuning of the carbon material to the requirements of a certain application.« less

Mechanical Properties in Metal-Organic Frameworks: Emerging Opportunities and Challenges for Device Functionality and Technological Applications.

PubMed

Burtch, Nicholas C; Heinen, Jurn; Bennett, Thomas D; Dubbeldam, David; Allendorf, Mark D

2017-11-17

Some of the most remarkable recent developments in metal-organic framework (MOF) performance properties can only be rationalized by the mechanical properties endowed by their hybrid inorganic-organic nanoporous structures. While these characteristics create intriguing application prospects, the same attributes also present challenges that will need to be overcome to enable the integration of MOFs with technologies where these promising traits can be exploited. In this review, emerging opportunities and challenges are identified for MOF-enabled device functionality and technological applications that arise from their fascinating mechanical properties. This is discussed not only in the context of their more well-studied gas storage and separation applications, but also for instances where MOFs serve as components of functional nanodevices. Recent advances in understanding MOF mechanical structure-property relationships due to attributes such as defects and interpenetration are highlighted, and open questions related to state-of-the-art computational approaches for quantifying their mechanical properties are critically discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unveiling relationships between crime and property in England and Wales via density scale-adjusted metrics and network tools.

PubMed

Ribeiro, Haroldo V; Hanley, Quentin S; Lewis, Dan

2018-01-01

Scale-adjusted metrics (SAMs) are a significant achievement of the urban scaling hypothesis. SAMs remove the inherent biases of per capita measures computed in the absence of isometric allometries. However, this approach is limited to urban areas, while a large portion of the world's population still lives outside cities and rural areas dominate land use worldwide. Here, we extend the concept of SAMs to population density scale-adjusted metrics (DSAMs) to reveal relationships among different types of crime and property metrics. Our approach allows all human environments to be considered, avoids problems in the definition of urban areas, and accounts for the heterogeneity of population distributions within urban regions. By combining DSAMs, cross-correlation, and complex network analysis, we find that crime and property types have intricate and hierarchically organized relationships leading to some striking conclusions. Drugs and burglary had uncorrelated DSAMs and, to the extent property transaction values are indicators of affluence, twelve out of fourteen crime metrics showed no evidence of specifically targeting affluence. Burglary and robbery were the most connected in our network analysis and the modular structures suggest an alternative to "zero-tolerance" policies by unveiling the crime and/or property types most likely to affect each other.

Unveiling relationships between crime and property in England and Wales via density scale-adjusted metrics and network tools

PubMed Central

Hanley, Quentin S.; Lewis, Dan

2018-01-01

Scale-adjusted metrics (SAMs) are a significant achievement of the urban scaling hypothesis. SAMs remove the inherent biases of per capita measures computed in the absence of isometric allometries. However, this approach is limited to urban areas, while a large portion of the world’s population still lives outside cities and rural areas dominate land use worldwide. Here, we extend the concept of SAMs to population density scale-adjusted metrics (DSAMs) to reveal relationships among different types of crime and property metrics. Our approach allows all human environments to be considered, avoids problems in the definition of urban areas, and accounts for the heterogeneity of population distributions within urban regions. By combining DSAMs, cross-correlation, and complex network analysis, we find that crime and property types have intricate and hierarchically organized relationships leading to some striking conclusions. Drugs and burglary had uncorrelated DSAMs and, to the extent property transaction values are indicators of affluence, twelve out of fourteen crime metrics showed no evidence of specifically targeting affluence. Burglary and robbery were the most connected in our network analysis and the modular structures suggest an alternative to “zero-tolerance” policies by unveiling the crime and/or property types most likely to affect each other. PMID:29470499

Age and sex alone are insufficient to predict human rib structural response to dynamic A-P loading.

PubMed

Schafman, Michelle A; Kang, Yun-Seok; Moorhouse, Kevin; White, Susan E; Bolte, John H; Agnew, Amanda M

2016-10-03

Thoracic injuries from motor vehicle crashes (MVCs) are common in children and the elderly and are associated with a high rate of mortality for both groups. Rib fractures, in particular, are linked to high mortality rates which increase with the number of fractures sustained. Anthropomorphic test devices (ATDs) and computational models have been developed to improve vehicle safety, however these tools are constructed based on limited physical datasets. To-date, no study has explored variation of rib structural properties across the entire age spectrum with data obtained using the same experimental methodology to allow for comparison. One-hundred eighty-four ribs from 93 post mortem human subjects (PMHS) (70 male, 23 female; ages 4-99) were subjected to dynamic bending tests simulating a frontal impact to the thorax. Structural mechanical properties were calculated and a multi-level statistical model quantified the sample variance as explained by age and sex. Displacement (δ X ), peak force (F peak ), linear structural stiffness (K), energy absorption to fracture (U tot ), and plastic properties including post-yield energy absorption (U Pl ), plastic displacement (δ Pl ), and the ratio of elastic to secant stiffness (K-ratio) all showed negative relationships with age, while only F peak , K, and U tot were dependent on sex. Despite these relationships being statistically significant, only 7-39% of variance is explained by age and only 3-17% of variance is explained by sex. This demonstrates that variability in bone properties is more complex than simply chronological age- and sex-dependence and should be explored in the context of biological mechanisms instead. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rapid experimental measurements of physicochemical properties to inform models and testing.

PubMed

Nicolas, Chantel I; Mansouri, Kamel; Phillips, Katherine A; Grulke, Christopher M; Richard, Ann M; Williams, Antony J; Rabinowitz, James; Isaacs, Kristin K; Yau, Alice; Wambaugh, John F

2018-05-02

The structures and physicochemical properties of chemicals are important for determining their potential toxicological effects, toxicokinetics, and route(s) of exposure. These data are needed to prioritize the risk for thousands of environmental chemicals, but experimental values are often lacking. In an attempt to efficiently fill data gaps in physicochemical property information, we generated new data for 200 structurally diverse compounds, which were rigorously selected from the USEPA ToxCast chemical library, and whose structures are available within the Distributed Structure-Searchable Toxicity Database (DSSTox). This pilot study evaluated rapid experimental methods to determine five physicochemical properties, including the log of the octanol:water partition coefficient (known as log(K ow ) or logP), vapor pressure, water solubility, Henry's law constant, and the acid dissociation constant (pKa). For most compounds, experiments were successful for at least one property; log(K ow ) yielded the largest return (176 values). It was determined that 77 ToxPrint structural features were enriched in chemicals with at least one measurement failure, indicating which features may have played a role in rapid method failures. To gauge consistency with traditional measurement methods, the new measurements were compared with previous measurements (where available). Since quantitative structure-activity/property relationship (QSAR/QSPR) models are used to fill gaps in physicochemical property information, 5 suites of QSPRs were evaluated for their predictive ability and chemical coverage or applicability domain of new experimental measurements. The ability to have accurate measurements of these properties will facilitate better exposure predictions in two ways: 1) direct input of these experimental measurements into exposure models; and 2) construction of QSPRs with a wider applicability domain, as their predicted physicochemical values can be used to parameterize exposure models in the absence of experimental data. Published by Elsevier B.V.

Segmented molecular design of self-healing proteinaceous materials

PubMed Central

Sariola, Veikko; Pena-Francesch, Abdon; Jung, Huihun; Çetinkaya, Murat; Pacheco, Carlos; Sitti, Metin; Demirel, Melik C.

2015-01-01

Hierarchical assembly of self-healing adhesive proteins creates strong and robust structural and interfacial materials, but understanding of the molecular design and structure–property relationships of structural proteins remains unclear. Elucidating this relationship would allow rational design of next generation genetically engineered self-healing structural proteins. Here we report a general self-healing and -assembly strategy based on a multiphase recombinant protein based material. Segmented structure of the protein shows soft glycine- and tyrosine-rich segments with self-healing capability and hard beta-sheet segments. The soft segments are strongly plasticized by water, lowering the self-healing temperature close to body temperature. The hard segments self-assemble into nanoconfined domains to reinforce the material. The healing strength scales sublinearly with contact time, which associates with diffusion and wetting of autohesion. The finding suggests that recombinant structural proteins from heterologous expression have potential as strong and repairable engineering materials. PMID:26323335

Music algorithm for imaging of a sound-hard arc in limited-view inverse scattering problem

NASA Astrophysics Data System (ADS)

Park, Won-Kwang

2017-07-01

MUltiple SIgnal Classification (MUSIC) algorithm for a non-iterative imaging of sound-hard arc in limited-view inverse scattering problem is considered. In order to discover mathematical structure of MUSIC, we derive a relationship between MUSIC and an infinite series of Bessel functions of integer order. This structure enables us to examine some properties of MUSIC in limited-view problem. Numerical simulations are performed to support the identified structure of MUSIC.

Relationships between structural fat properties with sensory, physical and textural attributes of yeast-leavened laminated salty baked product.

PubMed

de la Horra, Ana E; Barrera, Gabriela N; Steffolani, Eugenia M; Ribotta, Pablo D; León, Alberto E

2017-08-01

The aim of this study was to establish relationships between structural fat properties and sensory, physical and textural attributes of yeast-leavened laminated salty products. Refined bovine fat (MG1) and shortening (MG2), with a solid fat content (SFC) higher than 20% at temperature range of 15-35 °C were more viscous and less sensitive to temperature changes. The micrographs of dough|fat|dough sections corresponding to samples with MG1 and MG2 revealed a lower penetration of the fat sheet in the dough section due to the more entangled fat structures that did not allow a great flow throughout the dough layer. Consequently, the structure of laminated dough pieces made the systems highly resistant to deformation. The laminated dough pieces elaborated with these fats showed the highest increments in their height and maintained symmetry. Products with fat with least SFC and higher destructuration rate produced smoother laminated structures due to the presence of pores. While products with MG1 and MG2 showed tortuous images and complex structures, associated to layers and extended pores. MG1 and MG2 products were preferred (flavor and appearance) over those with MG3. The highest ranking samples in the acceptability analysis were symmetric, presented very flaky crusts and had a high level of lamination.

Metabolic and Demographic Feedbacks Shape the Emergent Spatial Structure and Function of Microbial Communities

PubMed Central

Estrela, Sylvie; Brown, Sam P.

2013-01-01

Microbes are predominantly found in surface-attached and spatially structured polymicrobial communities. Within these communities, microbial cells excrete a wide range of metabolites, setting the stage for interspecific metabolic interactions. The links, however, between metabolic and ecological interactions (functional relationships), and species spatial organization (structural relationships) are still poorly understood. Here, we use an individual-based modelling framework to simulate the growth of a two-species surface-attached community where food (resource) is traded for detoxification (service) and investigate how metabolic constraints of individual species shape the emergent structural and functional relationships of the community. We show that strong metabolic interdependence drives the emergence of mutualism, robust interspecific mixing, and increased community productivity. Specifically, we observed a striking and highly stable emergent lineage branching pattern, generating a persistent lineage mixing that was absent when the metabolic exchange was removed. These emergent community properties are driven by demographic feedbacks, such that aid from neighbouring cells directly enhances focal cell growth, which in turn feeds back to neighbour fecundity. In contrast, weak metabolic interdependence drives conflict (exploitation or competition), and in turn greater interspecific segregation. Together, these results support the idea that species structural and functional relationships represent the net balance of metabolic interdependencies. PMID:24385891

Structure to function: Spider silk and human collagen

NASA Astrophysics Data System (ADS)

Rabotyagova, Olena S.

Nature has the ability to assemble a variety of simple molecules into complex functional structures with diverse properties. Collagens, silks and muscles fibers are some examples of fibrous proteins with self-assembling properties. One of the great challenges facing Science is to mimic these designs in Nature to find a way to construct molecules that are capable of organizing into functional supra-structures by self-assembly. In order to do so, a construction kit consisting of molecular building blocks along with a complete understanding on how to form functional materials is required. In this current research, the focus is on spider silk and collagen as fibrous protein-based biopolymers that can shed light on how to generate nanostructures through the complex process of self-assembly. Spider silk in fiber form offers a unique combination of high elasticity, toughness, and mechanical strength, along with biological compatibility and biodegrability. Spider silk is an example of a natural block copolymer, in which hydrophobic and hydrophilic blocks are linked together generating polymers that organize into functional materials with extraordinary properties. Since silks resemble synthetic block copolymer systems, we adopted the principles of block copolymer design from the synthetic polymer literature to build block copolymers based on spider silk sequences. Moreover, we consider spider silk to be an important model with which to study the relationships between structure and properties in our system. Thus, the first part of this work was dedicated to a novel family of spider silk block copolymers, where we generated a new family of functional spider silk-like block copolymers through recombinant DNA technology. To provide fundamental insight into relationships between peptide primary sequence, block composition, and block length and observed morphological and structural features, we used these bioengineered spider silk block copolymers to study secondary structure, morphological features and assembly. Aside from fundamental perspectives, we anticipate that these results will provide a blueprint for the design of precise materials for a range of potential applications such as controlled release devices, functional coatings, components of tissue regeneration materials and environmentally friendly polymers in future studies. In the second part of this work, human collagen type I was studied as another representative of the family of fibrous proteins. Collagen type I is the most abundant extracellular matrix protein in the human body, providing the basis for tissue structure and directing cellular functions. Collagen has a complex structural hierarchy, organized at different length scales, including the characteristic triple helical feature. In the present study we assessed the relationship between collagen structure (native vs. denatured) and sensitivity to UV radiation with a focus on changes in the primary structure, conformation, microstructure and material properties. Free radical reactions are involved in collagen degradation and a mechanism for UV-induced collagen degradation related to structure was proposed. The results from this study demonstrated the role of collagen supramolecular organization (triple helix) in the context of the effects of electromagnetic radiation on extracellular matrices. Owing to the fact that both silks and collagens are proteins that have found widespread interest for biomaterial related needs, we anticipate that the current studies will serve as a foundation for future biomaterial designs with controlled properties. Furthermore, fundamental insight into self-assembly and environmentally-2mediated degradation, will build a foundation for fundamental understanding of the remodeling and functions of these types of fibrous proteins in vivo and in vitro. This type of insight is essential for many areas of scientific inquiry, from drug delivery, to scaffolds for tissue engineering, and to the stability of materials in space.

The Dimensions of Facebook Addiction as Measured by Facebook Addiction Italian Questionnaire and Their Relationships with Individual Differences.

PubMed

Caci, Barbara; Cardaci, Maurizio; Scrima, Fabrizio; Tabacchi, Marco Elio

2017-04-01

The studies reported analyze the factorial structure of Facebook Addiction Italian Questionnaire (FAIQ), a variant of 20-item Young's Internet Addiction Test (IAT). In Study 1, we tested FAIQ psychometric properties using exploratory factor analysis (EFA). In Study 2, we performed a confirmatory factor analysis (CFA) to verify the FAIQ factorial structure identified through EFA. Results from CFA confirm the presence of a four-factor model accounting for 58 percent of total variance, plus a general higher order factor that best fits the data. Further relationships between FAIQ factor scores, personality, and Facebook usage have been explored.

The intrinsic dependence structure of peak, volume, duration, and average intensity of hyetographs and hydrographs

NASA Astrophysics Data System (ADS)

Serinaldi, Francesco; Kilsby, Chris G.

2013-06-01

The information contained in hyetographs and hydrographs is often synthesized by using key properties such as the peak or maximum value Xp, volume V, duration D, and average intensity I. These variables play a fundamental role in hydrologic engineering as they are used, for instance, to define design hyetographs and hydrographs as well as to model and simulate the rainfall and streamflow processes. Given their inherent variability and the empirical evidence of the presence of a significant degree of association, such quantities have been studied as correlated random variables suitable to be modeled by multivariate joint distribution functions. The advent of copulas in geosciences simplified the inference procedures allowing for splitting the analysis of the marginal distributions and the study of the so-called dependence structure or copula. However, the attention paid to the modeling task has overlooked a more thorough study of the true nature and origin of the relationships that link Xp,V,D, and I. In this study, we apply a set of ad hoc bootstrap algorithms to investigate these aspects by analyzing the hyetographs and hydrographs extracted from 282 daily rainfall series from central eastern Europe, three 5 min rainfall series from central Italy, 80 daily streamflow series from the continental United States, and two sets of 200 simulated universal multifractal time series. Our results show that all the pairwise dependence structures between Xp,V,D, and I exhibit some key properties that can be reproduced by simple bootstrap algorithms that rely on a standard univariate resampling without resort to multivariate techniques. Therefore, the strong similarities between the observed dependence structures and the agreement between the observed and bootstrap samples suggest the existence of a numerical generating mechanism based on the superposition of the effects of sampling data at finite time steps and the process of summing realizations of independent random variables over random durations. We also show that the pairwise dependence structures are weakly dependent on the internal patterns of the hyetographs and hydrographs, meaning that the temporal evolution of the rainfall and runoff events marginally influences the mutual relationships of Xp,V,D, and I. Finally, our findings point out that subtle and often overlooked deterministic relationships between the properties of the event hyetographs and hydrographs exist. Confusing these relationships with genuine stochastic relationships can lead to an incorrect application of multivariate distributions and copulas and to misleading results.

Structure and Function of Iron-Loaded Synthetic Melanin

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

Li, Yiwen; Xie, Yijun; Wang, Zhao

We describe a synthetic method for increasing and controlling the iron loading of synthetic melanin nanoparticles and use the resulting materials to perform a systematic quantitative investigation on their structure- property relationship. A comprehensive analysis by magnetometry, electron paramagnetic resonance, and nuclear magnetic relaxation dispersion reveals the complexities of their magnetic behavior and how these intraparticle magnetic interactions manifest in useful material properties such as their performance as MRI contrast agents. This analysis allows predictions of the optimal iron loading through a quantitative modeling of antiferromagnetic coupling that arises from proximal iron ions. This study provides a detailed understanding ofmore » this complex class of synthetic biomaterials and gives insight into interactions and structures prevalent in naturally occurring melanins.« less

Orally active achiral N-hydroxyformamide inhibitors of ADAM-TS4 (aggrecanase-1) and ADAM-TS5 (aggrecanase-2) for the treatment of osteoarthritis.

PubMed

De Savi, Chris; Pape, Andrew; Sawyer, Yvonne; Milne, David; Davies, Chris; Cumming, John G; Ting, Attilla; Lamont, Scott; Smith, Peter D; Tart, Jonathon; Page, Ken; Moore, Peter

2011-06-01

A new achiral class of N-hydroxyformamide inhibitor of both ADAM-TS4 and ADAM-TS5, 2 has been discovered through modification of the complex P1 group present in historical inhibitors 1. This structural change improved the DMPK properties and greatly simplified the synthesis whilst maintaining excellent cross-MMP selectivity profiles. Investigation of structure-activity and structure-property relationships in the P1 group resulted in both ADAM-TS4 selective and mixed ADAM-TS4/5 inhibitors. This led to the identification of a pre-clinical candidate with excellent bioavailability across three species and predicting once daily dosing kinetics. Copyright © 2011 Elsevier Ltd. All rights reserved.

In Situ Identification of Nanoparticle Structural Information Using Optical Microscopy.

PubMed

Culver, Kayla S B; Liu, Tingting; Hryn, Alexander J; Fang, Ning; Odom, Teri W

2018-05-11

Diffraction-limited optical microscopy lacks the resolution to characterize directly nanoscale features of single nanoparticles. This paper describes how surprisingly rich structural features of small gold nanostars can be identified using differential interference contrast (DIC) microscopy. First, we established a library of structure-property relationships between nanoparticle shape and DIC optical image and then validated the correlation with electrodynamic simulations and electron microscopy. We found that DIC image patterns of single nanostars could be differentiated between 2D and 3D geometries. Also, DIC images could elucidate the symmetry properties and orientation of nanoparticles. Finally, we demonstrated how this wide-field optical technique can be used for in situ characterization of single nanoparticles rotating at a glass-water interface.

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

Du, Jincheng; Rimsza, Jessica

Computational simulations at the atomistic level play an increasing important role in understanding the structures, behaviors, and the structure-property relationships of glass and amorphous materials. In this paper, we reviewed atomistic simulation methods ranging from first principles calculations and ab initio molecular dynamics (AIMD), to classical molecular dynamics (MD) and meso-scale kinetic Monte Carlo (KMC) simulations and their applications to glass-water interactions and glass dissolutions. Particularly, the use of these simulation methods in understanding the reaction mechanisms of water with oxide glasses, water-glass interfaces, hydrated porous silica gels formation, the structure and properties of multicomponent glasses, and microstructure evolution aremore » reviewed. Here, the advantages and disadvantageous of these methods are discussed and the current challenges and future direction of atomistic simulations in glass dissolution are presented.« less

Visual Exploration of Semantic Relationships in Neural Word Embeddings

DOE PAGES

Liu, Shusen; Bremer, Peer-Timo; Thiagarajan, Jayaraman J.; ...

2017-08-29

Constructing distributed representations for words through neural language models and using the resulting vector spaces for analysis has become a crucial component of natural language processing (NLP). But, despite their widespread application, little is known about the structure and properties of these spaces. To gain insights into the relationship between words, the NLP community has begun to adapt high-dimensional visualization techniques. Particularly, researchers commonly use t-distributed stochastic neighbor embeddings (t-SNE) and principal component analysis (PCA) to create two-dimensional embeddings for assessing the overall structure and exploring linear relationships (e.g., word analogies), respectively. Unfortunately, these techniques often produce mediocre or evenmore » misleading results and cannot address domain-specific visualization challenges that are crucial for understanding semantic relationships in word embeddings. We introduce new embedding techniques for visualizing semantic and syntactic analogies, and the corresponding tests to determine whether the resulting views capture salient structures. Additionally, we introduce two novel views for a comprehensive study of analogy relationships. Finally, we augment t-SNE embeddings to convey uncertainty information in order to allow a reliable interpretation. Combined, the different views address a number of domain-specific tasks difficult to solve with existing tools.« less

Visual Exploration of Semantic Relationships in Neural Word Embeddings

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

Liu, Shusen; Bremer, Peer-Timo; Thiagarajan, Jayaraman J.

Constructing distributed representations for words through neural language models and using the resulting vector spaces for analysis has become a crucial component of natural language processing (NLP). But, despite their widespread application, little is known about the structure and properties of these spaces. To gain insights into the relationship between words, the NLP community has begun to adapt high-dimensional visualization techniques. Particularly, researchers commonly use t-distributed stochastic neighbor embeddings (t-SNE) and principal component analysis (PCA) to create two-dimensional embeddings for assessing the overall structure and exploring linear relationships (e.g., word analogies), respectively. Unfortunately, these techniques often produce mediocre or evenmore » misleading results and cannot address domain-specific visualization challenges that are crucial for understanding semantic relationships in word embeddings. We introduce new embedding techniques for visualizing semantic and syntactic analogies, and the corresponding tests to determine whether the resulting views capture salient structures. Additionally, we introduce two novel views for a comprehensive study of analogy relationships. Finally, we augment t-SNE embeddings to convey uncertainty information in order to allow a reliable interpretation. Combined, the different views address a number of domain-specific tasks difficult to solve with existing tools.« less

Re-Examining the Dimensions of Obligatory Exercise

ERIC Educational Resources Information Center

Duncan, Lindsay R.; Hall, Craig R.; Fraser, Shawn N.; Rodgers, Wendy M.; Wilson, Philip M.; Loitz, Christina C.

2012-01-01

The authors examined the factor structure and psychometric properties of the Obligatory Exercise Questionnaire using exploratory factor analyses (Study 1), and confirmatory factor analyses (Study 2). The relationships between obligatory exercise and other psychological variables including: motivation, subjective well-being, physical self-concept,…

Relationship between the erosion properties of soils and other parameters

USDA-ARS?s Scientific Manuscript database

Soil parameters are essential for erosion process prediction and ultimately improved model development, especially as they relate to dam and levee failure. Soil parameters including soil texture and structure, soil classification, soil compaction, moisture content, and degree of saturation can play...

Overview of T.E.S.T. (Toxicity Estimation Software Tool)

EPA Science Inventory

This talk provides an overview of T.E.S.T. (Toxicity Estimation Software Tool). T.E.S.T. predicts toxicity values and physical properties using a variety of different QSAR (quantitative structure activity relationship) approaches including hierarchical clustering, group contribut...

Design, Synthesis and Optoelectronic Properties of Unsymmetrical Oxadiazole Based Indene Substituted Derivatives as Deep Blue Fluoroscent Materials.

PubMed

Belavagi, Ningaraddi S; Deshapande, Narahari; Pujar, G H; Wari, M N; Inamdar, S R; Khazi, Imtiyaz Ahmed M

2015-09-01

A series of novel unsymmetrically substituted indene-oxadiazole derivatives (3a-f) have been designed and synthesized by employing palladium catalysed Suzuki cross coupling reaction in high yields. The structural integrity of all the novel compounds was established by (1)H, (13)C NMR and LC/MS analysis. These compounds are amorphous in nature and are remarkably stable to long term storage under ambient conditions. The optoelectronic properties have been studied in detail using UV-Vis absorption and Fluorescence spectroscopy. All compounds emit intense blue to green-blue fluoroscence with high quantum yields. Time resolved measurments have shown life times in the range of 1.28 to 4.51 ns. The density functional theory (DFT) calculations were carried out for all the molecules to understand their structure-property relationships. Effect of concentration studies has been carried out in different concentrations for both absorption and emission properties and from this we have identified the optimized fluoroscence concentrations for all these compounds. The indene substituted anthracene-oxadiazole derivative (3f) showed significant red shift (λmax (emi) = 490 nm) and emits intense green-blue fluoroscence with largest stokes shift of 145 nm. This compound also exhibited highest fluoroscence life time (τ) of 4.51 ns, which is very close to the standard dye coumarin-540A (4.63 ns) and better than fluorescein-548 (4.10 ns). The results demonstrated that the novel unsymmetrical indene-substituted oxadiazole derivatives could play important role in organic optoelectronic applications, such as organic light-emitting diodes (OLEDs) or as models for investigating the fluorescent structure-property relationship of the indene-functionalized oxadiazole derivatives.

Correlation Between Structural, Spectroscopic, and Reactivity Properties Within a Series of Structurally Analogous Metastable Manganese(III)-Alkylperoxo Complexes

PubMed Central

Coggins, Michael K.; Martin-Diaconescu, Vlad; DeBeer, Serena; Kovacs, Julie A.

2013-01-01

Manganese–peroxos are proposed as key intermediates in a number of important biochemical and synthetic transformations. Our understanding of the structural, spectroscopic, and reactivity properties of these metastable species is limited, however, and correlations between these properties have yet to be established experimentally. Herein we report the crystallographic structures of a series of structurally related metastable Mn(III)–OOR compounds, and examine their spectroscopic and reactivity properties. The four reported Mn(III)–OOR compounds extend the number of known end-on Mn(III)–(η1-peroxos) to six. The ligand backbone is shown to alter the metal–ligand distances and modulate the electronic properties key to bonding and activation of the peroxo. The mechanism of thermal decay of these metastable species is examined via variable-temperature kinetics. Strong correlations between structural (O–O and Mn⋯Npy,quin distances), spectroscopic (E(πv*(O–O) → Mn CT band), νO–O), and kinetic (ΔH‡ and ΔS‡) parameters for these complexes provide compelling evidence for rate-limiting O–O bond cleavage. Products identified in the final reaction mixtures of Mn(III)–OOR decay are consistent with homolytic O–O bond scission. The N-heterocyclic amines and ligand backbone (Et vs Pr) are found to modulate structural and reactivity properties, and O–O bond activation is shown, both experimentally and theoretically, to track with metal ion Lewis acidity. The peroxo O–O bond is shown to gradually become more activated as the N-heterocyclic amines move closer to the metal ion causing a decrease in π-donation from the peroxo πv*(O–O) orbital. The reported work represents one of very few examples of experimentally verified relationships between structure and function. PMID:23432090

Mechanical properties of additively manufactured octagonal honeycombs.

PubMed

Hedayati, R; Sadighi, M; Mohammadi-Aghdam, M; Zadpoor, A A

2016-12-01

Honeycomb structures have found numerous applications as structural and biomedical materials due to their favourable properties such as low weight, high stiffness, and porosity. Application of additive manufacturing and 3D printing techniques allows for manufacturing of honeycombs with arbitrary shape and wall thickness, opening the way for optimizing the mechanical and physical properties for specific applications. In this study, the mechanical properties of honeycomb structures with a new geometry, called octagonal honeycomb, were investigated using analytical, numerical, and experimental approaches. An additive manufacturing technique, namely fused deposition modelling, was used to fabricate the honeycomb from polylactic acid (PLA). The honeycombs structures were then mechanically tested under compression and the mechanical properties of the structures were determined. In addition, the Euler-Bernoulli and Timoshenko beam theories were used for deriving analytical relationships for elastic modulus, yield stress, Poisson's ratio, and buckling stress of this new design of honeycomb structures. Finite element models were also created to analyse the mechanical behaviour of the honeycombs computationally. The analytical solutions obtained using Timoshenko beam theory were close to computational results in terms of elastic modulus, Poisson's ratio and yield stress, especially for relative densities smaller than 25%. The analytical solutions based on the Timoshenko analytical solution and the computational results were in good agreement with experimental observations. Finally, the elastic properties of the proposed honeycomb structure were compared to those of other honeycomb structures such as square, triangular, hexagonal, mixed, diamond, and Kagome. The octagonal honeycomb showed yield stress and elastic modulus values very close to those of regular hexagonal honeycombs and lower than the other considered honeycombs. Copyright © 2016 Elsevier B.V. All rights reserved.

Correlation between structural, spectroscopic, and reactivity properties within a series of structurally analogous metastable manganese(III)-alkylperoxo complexes.

PubMed

Coggins, Michael K; Martin-Diaconescu, Vlad; DeBeer, Serena; Kovacs, Julie A

2013-03-20

Manganese-peroxos are proposed as key intermediates in a number of important biochemical and synthetic transformations. Our understanding of the structural, spectroscopic, and reactivity properties of these metastable species is limited, however, and correlations between these properties have yet to be established experimentally. Herein we report the crystallographic structures of a series of structurally related metastable Mn(III)-OOR compounds, and examine their spectroscopic and reactivity properties. The four reported Mn(III)-OOR compounds extend the number of known end-on Mn(III)-(η(1)-peroxos) to six. The ligand backbone is shown to alter the metal-ligand distances and modulate the electronic properties key to bonding and activation of the peroxo. The mechanism of thermal decay of these metastable species is examined via variable-temperature kinetics. Strong correlations between structural (O-O and Mn···N(py,quin) distances), spectroscopic (E(πv*(O-O) → Mn CT band), ν(O-O)), and kinetic (ΔH(‡) and ΔS(‡)) parameters for these complexes provide compelling evidence for rate-limiting O-O bond cleavage. Products identified in the final reaction mixtures of Mn(III)-OOR decay are consistent with homolytic O-O bond scission. The N-heterocyclic amines and ligand backbone (Et vs Pr) are found to modulate structural and reactivity properties, and O-O bond activation is shown, both experimentally and theoretically, to track with metal ion Lewis acidity. The peroxo O-O bond is shown to gradually become more activated as the N-heterocyclic amines move closer to the metal ion causing a decrease in π-donation from the peroxo πv*(O-O) orbital. The reported work represents one of very few examples of experimentally verified relationships between structure and function.

Relationships between residue Voronoi volume and sequence conservation in proteins.

PubMed

Liu, Jen-Wei; Cheng, Chih-Wen; Lin, Yu-Feng; Chen, Shao-Yu; Hwang, Jenn-Kang; Yen, Shih-Chung

2018-02-01

Functional and biophysical constraints can cause different levels of sequence conservation in proteins. Previously, structural properties, e.g., relative solvent accessibility (RSA) and packing density of the weighted contact number (WCN), have been found to be related to protein sequence conservation (CS). The Voronoi volume has recently been recognized as a new structural property of the local protein structural environment reflecting CS. However, for surface residues, it is sensitive to water molecules surrounding the protein structure. Herein, we present a simple structural determinant termed the relative space of Voronoi volume (RSV); it uses the Voronoi volume and the van der Waals volume of particular residues to quantify the local structural environment. RSV (range, 0-1) is defined as (Voronoi volume-van der Waals volume)/Voronoi volume of the target residue. The concept of RSV describes the extent of available space for every protein residue. RSV and Voronoi profiles with and without water molecules (RSVw, RSV, VOw, and VO) were compared for 554 non-homologous proteins. RSV (without water) showed better Pearson's correlations with CS than did RSVw, VO, or VOw values. The mean correlation coefficient between RSV and CS was 0.51, which is comparable to the correlation between RSA and CS (0.49) and that between WCN and CS (0.56). RSV is a robust structural descriptor with and without water molecules and can quantitatively reflect evolutionary information in a single protein structure. Therefore, it may represent a practical structural determinant to study protein sequence, structure, and function relationships. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular Design and Evaluation of Biodegradable Polymers Using a Statistical Approach

PubMed Central

Lewitus, Dan; Rios, Fabian; Rojas, Ramiro; Kohn, Joachim

2013-01-01

The challenging paradigm of bioresorbable polymers, whether in drug delivery or tissue engineering, states that a fine-tuning of the interplay between polymer properties (e.g., thermal, degradation), and the degree of cell/tissue replacement and remodeling is required. In this paper we describe how changes in the molecular architecture of a series of terpolymers allow for the design of polymers with varying glass transition temperatures and degradation rates. The effect of each component in the terpolymers is quantified via design of experiment (DoE) analysis. A linear relationship between terpolymer components and resulting Tg (ranging from 34 to 86 °C) was demonstrated. These findings were further supported with mass-per-flexible-bond (MPFB) analysis. The effect of terpolymer composition on the in vitro degradation of these polymers revealed molecular weight loss ranging from 20 to 60% within the first 24 hours. DoE modeling further illustrated the linear (but reciprocal) relationship between structure elements and degradation for these polymers. Thus, we describe a simple technique to provide insight into the structure property relationship of degradable polymers, specifically applied using a new family of tyrosine-derived polycarbonates, allowing for optimal design of materials for specific applications. PMID:23888354

Measuring the Developing Therapeutic Relationship Between Pregnant Women and Community Health Workers Over the Course of the Pregnancy in a Study Intervention

PubMed Central

Lichtveld, Maureen Y.; Shankar, Arti; Mundorf, Chris; Hassan, Anna; Drury, Stacy

2016-01-01

The Scale to Assess the Therapeutic Relationship in Community Mental Health Care (STAR) is a frequently-administered tool for measuring therapeutic relationships between clinicians and patients. This manuscript tested the STAR’s psychometric properties within a community health worker (CHW)-led intervention study involving pregnant and postpartum women. Women (n = 141) enrolled in the study completed the 12-item participant STAR survey (STAR-P) at two time points over the course of pregnancy and at two time points after delivery. The factor structure of the STAR-P proved to be unstable with this population. However, a revised 9-item STAR-P revealed a two-factor model of positive and negative interactions, and demonstrated strong internal consistency at postpartum time points. The revised STAR-P shows strong psychometric properties, and is suitable for use to evaluate the relationship developed between CHWs and pregnant and postpartum women in an intervention program. PMID:27116361

Measuring the Developing Therapeutic Relationship Between Pregnant Women and Community Health Workers Over the Course of the Pregnancy in a Study Intervention.

PubMed

Lichtveld, Maureen Y; Shankar, Arti; Mundorf, Chris; Hassan, Anna; Drury, Stacy

2016-12-01

The Scale to Assess the Therapeutic Relationship in Community Mental Health Care (STAR) is a frequently-administered tool for measuring therapeutic relationships between clinicians and patients. This manuscript tested the STAR's psychometric properties within a community health worker (CHW)-led intervention study involving pregnant and postpartum women. Women (n = 141) enrolled in the study completed the 12-item participant STAR survey (STAR-P) at two time points over the course of pregnancy and at two time points after delivery. The factor structure of the STAR-P proved to be unstable with this population. However, a revised 9-item STAR-P revealed a two-factor model of positive and negative interactions, and demonstrated strong internal consistency at postpartum time points. The revised STAR-P shows strong psychometric properties, and is suitable for use to evaluate the relationship developed between CHWs and pregnant and postpartum women in an intervention program.

Characteristics of interplanetary type II radio emission and the relationship to shock and plasma properties

NASA Technical Reports Server (NTRS)

Lengyel-Frey, D.; Stone, R. G.

1989-01-01

A large sample of type II events is the basis of the present study of the properties of interplanetary type II bursts' radio-emission properties. Type II spectra seem to be composed of fundamental and harmonic components of plasma emission, where the intensity of the fundamental component increases relative to the harmonic as the burst evolves with heliocentric distance; burst average flux density increases as a power of the associated shock's average velocity. Solar wind density structures may have a significant influence on type II bandwidths.

Modeling the mechanical properties of ultra-thin polymer films [Structural modeling of films of atomic scale thickness

DOE PAGES

Espinosa-Loza, Francisco; Stadermann, Michael; Aracne-Ruddle, Chantel; ...

2017-11-16

A modeling method to extract the mechanical properties of ultra-thin films (10–100 nm thick) from experimental data generated by indentation of freestanding circular films using a spherical indenter is presented. The relationship between the mechanical properties of the film and experimental parameters including load, and deflection are discussed in the context of a constitutive material model, test variables, and analytical approaches. As a result, elastic and plastic regimes are identified by comparison of finite element simulation and experimental data.

Modeling the mechanical properties of ultra-thin polymer films [Structural modeling of films of atomic scale thickness

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

Espinosa-Loza, Francisco; Stadermann, Michael; Aracne-Ruddle, Chantel

A modeling method to extract the mechanical properties of ultra-thin films (10–100 nm thick) from experimental data generated by indentation of freestanding circular films using a spherical indenter is presented. The relationship between the mechanical properties of the film and experimental parameters including load, and deflection are discussed in the context of a constitutive material model, test variables, and analytical approaches. As a result, elastic and plastic regimes are identified by comparison of finite element simulation and experimental data.

Network Structure and the Risk for HIV Transmission Among Rural Drug Users

PubMed Central

Young, A. M.; Jonas, A. B.; Mullins, U. L.; Halgin, D. S.

2012-01-01

Research suggests that structural properties of drug users’ social networks can have substantial effects on HIV risk. The purpose of this study was to investigate if the structural properties of Appalachian drug users’ risk networks could lend insight into the potential for HIV transmission in this population. Data from 503 drug users recruited through respondent-driven sampling were used to construct a sociometric risk network. Network ties represented relationships in which partners had engaged in unprotected sex and/or shared injection equipment. Compared to 1,000 randomly generated networks, the observed network was found to have a larger main component and exhibit more cohesiveness and centralization than would be expected at random. Thus, the risk network structure in this sample has many structural characteristics shown to be facilitative of HIV transmission. This underscores the importance of primary prevention in this population and prompts further investigation into the epidemiology of HIV in the region. PMID:23184464

Effect of BaTiO3 Nanopowder Concentration on Rheological Behaviour of Ceramic Inkjet Inks

NASA Astrophysics Data System (ADS)

Kyrpal, R.; Dulina, I.; Ragulya, A.

2015-04-01

The relationship between rheological properties of ceramic inkjet inks based on BaTiO3 nanopowder and solid phase concentration has been investigated. In the ink volume takes place the formation periodic colloidal structures (PCS). The determining factor of structure formation is powder-dispersant ratio. Structural constitution of in the system with the low pigment concentration represented as PCS2, that contains solid particles in deflocculated that stabilized by the presence of adsorption-solvate layers. Dilatant structure formation for such inks explained by constrained conditions of the interaction. Samples with high BaTiO3 concentration have been classified as PKS1. Dilatant properties of the PKS1 resulted in particles rearrangement under the influence of the flow. In the region of some values powder-dispersant ratio take place conversation PKS2 to PKS1 and ink structure transformation from monodisperse to aggregate state.

Characterization of pi-Conjugated Polymers for Transistor and Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Paulsen, Bryan D.

pi-Conjugated polymers represent a unique class of optoelectronic materials. Being polymers, they are solution processable and inherently "soft" materials. This makes them attractive candidates for the production of roll-to-roll printed electronic devices on flexible substrates. The optical and electronic properties of pi-conjugated polymers are synthetically tunable allowing material sets to be tailored to specific applications. Two of the most heavily researched applications are the thin film transistor, the building block of electronic circuits, and the bulk heterojunction solar cell, which holds great potential as a renewable energy source. Key to developing commercially feasible pi-conjugated polymer devices is a thorough understanding of the electronic structure and charge transport behavior of these materials in relationship with polymer structure. Here this structure property relationship has been investigated through electrical and electrochemical means in concert with a variety of other characterization techniques and device test beds. The tunability of polymer optical band gap and frontier molecular orbital energy level was investigated in systems of vinyl incorporating statistical copolymers. Energy levels and band gaps are crucial parameters in developing efficient photovoltaic devices, with control of these parameters being highly desirable. Additionally, charge transport and density of electronic states were investigated in pi-conjugated polymers at extremely high electrochemically induced charge density. Finally, the effects of molecular weight on pi-conjugated polymer optical properties, energy levels, charge transport, morphology, and photovoltaic device performance was examined.

Designing protein-based biomaterials for medical applications.

PubMed

Gagner, Jennifer E; Kim, Wookhyun; Chaikof, Elliot L

2014-04-01

Biomaterials produced by nature have been honed through billions of years, evolving exquisitely precise structure-function relationships that scientists strive to emulate. Advances in genetic engineering have facilitated extensive investigations to determine how changes in even a single peptide within a protein sequence can produce biomaterials with unique thermal, mechanical and biological properties. Elastin, a naturally occurring protein polymer, serves as a model protein to determine the relationship between specific structural elements and desirable material characteristics. The modular, repetitive nature of the protein facilitates the formation of well-defined secondary structures with the ability to self-assemble into complex three-dimensional architectures on a variety of length scales. Furthermore, many opportunities exist to incorporate other protein-based motifs and inorganic materials into recombinant protein-based materials, extending the range and usefulness of these materials in potential biomedical applications. Elastin-like polypeptides (ELPs) can be assembled into 3-D architectures with precise control over payload encapsulation, mechanical and thermal properties, as well as unique functionalization opportunities through both genetic and enzymatic means. An overview of current protein-based materials, their properties and uses in biomedicine will be provided, with a focus on the advantages of ELPs. Applications of these biomaterials as imaging and therapeutic delivery agents will be discussed. Finally, broader implications and future directions of these materials as diagnostic and therapeutic systems will be explored. Copyright © 2013 Elsevier Ltd. All rights reserved.

Designing Protein-Based Biomaterials for Medical Applications

PubMed Central

Gagner, Jennifer E.; Kim, Wookhyun; Chaikof, Elliot L.

2013-01-01

Biomaterials produced by nature have been honed through billions of years, evolving exquisitely precise structure-function relationships that scientists strive to emulate. Advances in genetic engineering have facilitated extensive investigations to determine how changes in even a single peptide within a protein sequence can produce biomaterials with unique thermal, mechanical and biological properties. Elastin, a naturally occurring protein polymer, serves as a model protein to determine the relationship between specific structural elements and desirable material characteristics. The modular, repetitive nature of the protein facilitates the formation of well-defined secondary structures with the ability to self-assemble into complex three-dimensional architectures on a variety of length scales. Furthermore, many opportunities exist to incorporate other protein-based motifs and inorganic materials into recombinant protein-based materials, extending the range and usefulness of these materials in potential biomedical applications. Elastin-like polypeptides can be assembled into 3D architectures with precise control over payload encapsulation, mechanical and thermal properties, as well as unique functionalization opportunities through both genetic and enzymatic means. An overview of current protein-based materials, their properties and uses in biomedicine will be provided, with a focus on the advantages of elastin-like polypeptides. Applications of these biomaterials as imaging and therapeutic delivery agents will be discussed. Finally, broader implications and future directions of these materials as diagnostic and therapeutic systems will be explored. PMID:24121196

Graph Kernels for Molecular Similarity.

PubMed

Rupp, Matthias; Schneider, Gisbert

2010-04-12

Molecular similarity measures are important for many cheminformatics applications like ligand-based virtual screening and quantitative structure-property relationships. Graph kernels are formal similarity measures defined directly on graphs, such as the (annotated) molecular structure graph. Graph kernels are positive semi-definite functions, i.e., they correspond to inner products. This property makes them suitable for use with kernel-based machine learning algorithms such as support vector machines and Gaussian processes. We review the major types of kernels between graphs (based on random walks, subgraphs, and optimal assignments, respectively), and discuss their advantages, limitations, and successful applications in cheminformatics. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A force field for dynamic Cu-BTC metal-organic framework.

PubMed

Zhao, Lei; Yang, Qingyuan; Ma, Qintian; Zhong, Chongli; Mi, Jianguo; Liu, Dahuan

2011-02-01

A new force field that can describe the flexibility of Cu-BTC metal-organic framework (MOF) was developed in this work. Part of the parameters were obtained using density functional theory calculations, and the others were taken from other force fields. The new force field could reproduce well the experimental crystal structure, negative thermal expansion, vibrational properties as well as adsorption behavior in Cu-BTC. In addition, the bulk modulus of Cu-BTC was predicted using the new force field. We believe the new force field is useful in understanding the structure-property relationships for MOFs, and the approach can be extended to other MOFs.

Process parameter-growth environment-film property relationships for reactive sputter deposited metal (V, Nb, Zr, Y, Au) oxide, nitride, and oxynitride films. Final report, 1 January 1989-30 June 1993

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

Aita, C.R.

1993-09-30

The research developed process parameter-growth environment-film property relations (phase maps) for model sputter-deposited transition metal oxides, nitrides, and oxynitrides grown by reactive sputter deposition at low temperature. Optical emission spectrometry was used for plasma diagnostics. The results summarized here include the role of sputtered metal-oxygen molecular flux in oxide film growth; structural differences in highest valence oxides including conditions for amorphous growth; and using fundamental optical absorption edge features to probe short range structural disorder. Eight appendices containing sixteen journal articles are included.

Transport properties and Stokes-Einstein relation in Al-rich liquid alloys

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

Jakse, N.; Pasturel, A.

We use ab initio molecular dynamics simulations to study the transport properties and the validity of the Stokes-Einstein relation in Al-rich liquid alloys with Ni, Cu, and Zn as alloying elements. First, we show that the composition and temperature dependence of their transport properties present different behaviors, which can be related to their local structural ordering. Then, we evidence that the competition between the local icosahedral ordering and the local chemical ordering may cause the breakdown of the Stokes–Einstein relation even in the liquid phase. We demonstrate that this breakdown can be captured by entropy-scaling relationships developed by Rosenfeld andmore » using the two-body excess entropy. Our findings provide a unique framework to study the relation between structure, thermodynamics, and dynamics in metallic melts and pave the way towards the explanation of various complex transport properties in metallic melts.« less

Materials by Design—A Perspective From Atoms to Structures

PubMed Central

Buehler, Markus J.

2013-01-01

Biological materials are effectively synthesized, controlled, and used for a variety of purposes—in spite of limitations in energy, quality, and quantity of their building blocks. Whereas the chemical composition of materials in the living world plays a some role in achieving functional properties, the way components are connected at different length scales defines what material properties can be achieved, how they can be altered to meet functional requirements, and how they fail in disease states and other extreme conditions. Recent work has demonstrated this by using large-scale computer simulations to predict materials properties from fundamental molecular principles, combined with experimental work and new mathematical techniques to categorize complex structure-property relationships into a systematic framework. Enabled by such categorization, we discuss opportunities based on the exploitation of concepts from distinct hierarchical systems that share common principles in how function is created, linking music to materials science. PMID:24163499

Effect of Sm on dielectric, ferroelectric and piezoelectric properties of BPTNZ system

NASA Astrophysics Data System (ADS)

Kumar, Parveen; Juneja, J. K.; Prakash, Chandra; Raina, K. K.; Singh, Sangeeta

2013-10-01

Study on structural, dielectric and ferroelectric properties of Sm substituted BPTNZ system with compositional formula Ba0.80-xSmxPb0.20Zr0.10Ti0.90O3+0.5% Nb2O5 by weight, (x=0 to 0.01 in the steps of 0.0025) was done. Conventional solid state method was adopted for the synthesis of the samples. The single phase was confirmed by X-ray diffraction (XRD) analysis. Scanning electron microscopy was done for microstructural analysis. The dielectric properties were measured as a function of temperature and frequency. Ferroelectric P-E loops were recorded for all the samples at room temperature. Piezoelectric parameters such as ‘d33’ and electromechanical coupling coefficient ‘kp’ were also measured at room temperature for all the samples. The relationship between properties and structure of the prepared ceramics was established and results are discussed here.

Transport properties and Stokes-Einstein relation in Al-rich liquid alloys

NASA Astrophysics Data System (ADS)

Jakse, N.; Pasturel, A.

2016-06-01

We use ab initio molecular dynamics simulations to study the transport properties and the validity of the Stokes-Einstein relation in Al-rich liquid alloys with Ni, Cu, and Zn as alloying elements. First, we show that the composition and temperature dependence of their transport properties present different behaviors, which can be related to their local structural ordering. Then, we evidence that the competition between the local icosahedral ordering and the local chemical ordering may cause the breakdown of the Stokes-Einstein relation even in the liquid phase. We demonstrate that this breakdown can be captured by entropy-scaling relationships developed by Rosenfeld and using the two-body excess entropy. Our findings provide a unique framework to study the relation between structure, thermodynamics, and dynamics in metallic melts and pave the way towards the explanation of various complex transport properties in metallic melts.

Correlation of the protein structure and gelling properties in dried egg white products.

PubMed

Handa, A; Hayashi, K; Shidara, H; Kuroda, N

2001-08-01

The relationship between protein structure and aggregation, as well as heat-induced gelling properties, of seven dried egg white (DEW) products was investigated. Strong correlations were found between average molecular weight and hydrophobicity plus surface SH groups of DEW-soluble protein aggregate (SPA). This suggests that hydrophobic interactions and disulfide bond formation between protein molecules were involved in the aggregation. The average molecular weight of DEW products with alkaline pHs was relatively higher than those with neutral pHs and the same degree of protein unfolding, probably because of more disulfide bond formation between protein molecules. In addition, strong correlations were found between hydrophobicity, surface SH groups plus average molecular weight of DEW-SPA, and physical properties of the gels from DEW products. These data indicated that controlling the aggregation of DEW proteins in the dry state is crucial to controlling the gelling properties of DEW.

Bioinspired Design: Magnetic Freeze Casting

NASA Astrophysics Data System (ADS)

Porter, Michael Martin

Nature is the ultimate experimental scientist, having billions of years of evolution to design, test, and adapt a variety of multifunctional systems for a plethora of diverse applications. Next-generation materials that draw inspiration from the structure-property-function relationships of natural biological materials have led to many high-performance structural materials with hybrid, hierarchical architectures that fit form to function. In this dissertation, a novel materials processing method, magnetic freeze casting, is introduced to develop porous scaffolds and hybrid composites with micro-architectures that emulate bone, abalone nacre, and other hard biological materials. This method uses ice as a template to form ceramic-based materials with continuously, interconnected microstructures and magnetic fields to control the alignment of these structures in multiple directions. The resulting materials have anisotropic properties with enhanced mechanical performance that have potential applications as bone implants or lightweight structural composites, among others.

Relationship of microstructure properties to oxygen impurities in nanocrystalline silicon photovoltaic materials

NASA Astrophysics Data System (ADS)

Xu, H.; Wen, C.; Liu, H.; Li, Z. P.; Shen, W. Z.

2013-03-01

We have fully investigated the correlation of microstructure properties and oxygen impurities in hydrogenated nanocrystalline silicon photovoltaic films. The achievement has been realized through a series of different hydrogen dilution ratio treatment by plasma enhanced chemical vapor deposition system. Raman scattering, x-ray diffraction, and ultraviolet-visible transmission techniques have been employed to characterize the physical structural characterization and to elucidate the structure evolution. The bonding configuration of the oxygen impurities was investigated by x-ray photoelectron spectroscopy and the Si-O stretching mode of infrared-transmission, indicating that the films were well oxidized in SiO2 form. Based on the consistence between the proposed structure factor and the oxygen content, we have demonstrated that there are two dominant disordered structure regions closely related to the post-oxidation contamination: plate-like configuration and clustered microvoids.

Tree-Structured Infinite Sparse Factor Model

PubMed Central

Zhang, XianXing; Dunson, David B.; Carin, Lawrence

2013-01-01

A tree-structured multiplicative gamma process (TMGP) is developed, for inferring the depth of a tree-based factor-analysis model. This new model is coupled with the nested Chinese restaurant process, to nonparametrically infer the depth and width (structure) of the tree. In addition to developing the model, theoretical properties of the TMGP are addressed, and a novel MCMC sampler is developed. The structure of the inferred tree is used to learn relationships between high-dimensional data, and the model is also applied to compressive sensing and interpolation of incomplete images. PMID:25279389

Molecular dynamics simulations: advances and applications

PubMed Central

Hospital, Adam; Goñi, Josep Ramon; Orozco, Modesto; Gelpí, Josep L

2015-01-01

Molecular dynamics simulations have evolved into a mature technique that can be used effectively to understand macromolecular structure-to-function relationships. Present simulation times are close to biologically relevant ones. Information gathered about the dynamic properties of macromolecules is rich enough to shift the usual paradigm of structural bioinformatics from studying single structures to analyze conformational ensembles. Here, we describe the foundations of molecular dynamics and the improvements made in the direction of getting such ensemble. Specific application of the technique to three main issues (allosteric regulation, docking, and structure refinement) is discussed. PMID:26604800

Mechanical Properties of Optimized Diamond Lattice Structure for Bone Scaffolds Fabricated via Selective Laser Melting.

PubMed

Liu, Fei; Zhang, David Z; Zhang, Peng; Zhao, Miao; Jafar, Salman

2018-03-03

Developments in selective laser melting (SLM) have enabled the fabrication of periodic cellular lattice structures characterized by suitable properties matching the bone tissue well and by fluid permeability from interconnected structures. These multifunctional performances are significantly affected by cell topology and constitutive properties of applied materials. In this respect, a diamond unit cell was designed in particular volume fractions corresponding to the host bone tissue and optimized with a smooth surface at nodes leading to fewer stress concentrations. There were 33 porous titanium samples with different volume fractions, from 1.28 to 18.6%, manufactured using SLM. All of them were performed under compressive load to determine the deformation and failure mechanisms, accompanied by an in-situ approach using digital image correlation (DIC) to reveal stress-strain evolution. The results showed that lattice structures manufactured by SLM exhibited comparable properties to those of trabecular bone, avoiding the effects of stress-shielding and increasing longevity of implants. The curvature of optimized surface can play a role in regulating the relationship between density and mechanical properties. Owing to the release of stress concentration from optimized surface, the failure mechanism of porous titanium has been changed from the pattern of bottom-up collapse by layer (or cell row) to that of the diagonal (45°) shear band, resulting in the significant enhancement of the structural strength.

Mechanical Properties of Optimized Diamond Lattice Structure for Bone Scaffolds Fabricated via Selective Laser Melting

PubMed Central

Zhang, David Z.; Zhang, Peng; Zhao, Miao; Jafar, Salman

2018-01-01

Developments in selective laser melting (SLM) have enabled the fabrication of periodic cellular lattice structures characterized by suitable properties matching the bone tissue well and by fluid permeability from interconnected structures. These multifunctional performances are significantly affected by cell topology and constitutive properties of applied materials. In this respect, a diamond unit cell was designed in particular volume fractions corresponding to the host bone tissue and optimized with a smooth surface at nodes leading to fewer stress concentrations. There were 33 porous titanium samples with different volume fractions, from 1.28 to 18.6%, manufactured using SLM. All of them were performed under compressive load to determine the deformation and failure mechanisms, accompanied by an in-situ approach using digital image correlation (DIC) to reveal stress–strain evolution. The results showed that lattice structures manufactured by SLM exhibited comparable properties to those of trabecular bone, avoiding the effects of stress-shielding and increasing longevity of implants. The curvature of optimized surface can play a role in regulating the relationship between density and mechanical properties. Owing to the release of stress concentration from optimized surface, the failure mechanism of porous titanium has been changed from the pattern of bottom-up collapse by layer (or cell row) to that of the diagonal (45°) shear band, resulting in the significant enhancement of the structural strength. PMID:29510492

Non-destructive thermo-mechanical behavior assessment of glass-ceramics for dental applications

NASA Astrophysics Data System (ADS)

Kordatos, E. Z.; Abdulkadhim, Z.; Feteira, A. M.

2017-05-01

Every year millions of people seek dental treatment to either repair damaged, unaesthetic and dysfunctional teeth or replace missing natural teeth. Several dental materials have been developed to meet the stringent requirements in terms of mechanical properties, aesthetics and chemical durability in the oral environment. Glass-ceramics exhibit a suitable combination of these properties for dental restorations. This research is focused on the assessment of the thermomechanical behavior of bio-ceramics and particularly lithium aluminosilicate glass-ceramics (LAS glass-ceramics). Specifically, methodologies based on Infrared Thermography (IRT) have been applied in order the structure - property relationship to be evaluated. Non-crystallized, partially crystallized and fully crystallized glass-ceramic samples have been non-destructively assessed in order their thermo-mechanical behavior to be associated with their micro-structural features.

Structural and functional neural correlates of self-reported attachment in healthy adults: evidence for an amygdalar involvement.

PubMed

Rigon, Arianna; Duff, Melissa C; Voss, Michelle W

2016-12-01

The concept of attachment in long-term interpersonal relationships has been linked to relationship outcome and social-emotional health. To date, no relationship between the structural properties of the human amygdala and attachment in romantic relationships (measured through self-reported attachment related anxiety and avoidance) has been described. The aim of the current study was to investigate the relationship between amygdala structure as well as amygdala structural and functional connectivity and attachment anxiety and avoidance. To this end, we collected self-report attachment data on a sample of female young adults. We then examined associations between attachment and mean diffusivity, fractional anisotropy and resting state functional connectivity MRI (rs-FC) of the amygdala and its white matter connections with the prefrontal cortex. We found that lower integrity of the left amygdala was linked with attachment avoidance (e.g., being less comfortable in seeking proximity with others and depending on others) and that greater structural integrity of the uncinate fasciculus was positively associated with avoidance. Lastly, we found that stronger rs-FC between the bilateral amygdala and medial prefrontal regions was linked with greater avoidance. Our findings are compatible with and expand previous results reported by studies that have taken a task-related fMRI approach, furthering our understanding of the neurobiological mechanisms of attachment, and in particular implicating the system formed by amygdala and prefrontal areas in the patterns of behavior that regulate emotional proximity in romantic relationships. These findings have the potential to further our understanding of the affective mechanisms underlying attachment behavior.

Fabrication and electric measurements of nanostructures inside transmission electron microscope.

PubMed

Chen, Qing; Peng, Lian-Mao

2011-06-01

Using manipulation holders specially designed for transmission electron microscope (TEM), nanostructures can be characterized, measured, modified and even fabricated in-situ. In-situ TEM techniques not only enable real-time study of structure-property relationships of materials at atomic scale, but also provide the ability to control and manipulate materials and structures at nanoscale. This review highlights in-situ electric measurements and in-situ fabrication and structure modification using manipulation holder inside TEM. Copyright © 2011 Elsevier B.V. All rights reserved.

Group-theoretical analysis of two-dimensional hexagonal materials

NASA Astrophysics Data System (ADS)

Minami, Susumu; Sugita, Itaru; Tomita, Ryosuke; Oshima, Hiroyuki; Saito, Mineo

2017-10-01

Two-dimensional hexagonal materials such as graphene and silicene have highly symmetric crystal structures and Dirac cones at the K point, which induce novel electronic properties. In this report, we calculate their electronic structures by using density functional theory and analyze their band structures on the basis of the group theory. Dirac cones frequently appear when the symmetry at the K point is high; thus, two-dimensional irreducible representations are included. We discuss the relationship between symmetry and the appearance of the Dirac cone.

Perovskite oxides: Oxygen electrocatalysis and bulk structure

NASA Technical Reports Server (NTRS)

Carbonio, R. E.; Fierro, C.; Tryk, D.; Scherson, D.; Yeager, Ernest

1987-01-01

Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

Establishment of a structure-activity relationship of 1H-imidazo[4,5-c]quinoline-based kinase inhibitor NVP-BEZ235 as a lead for African sleeping sickness.

PubMed

Seixas, João D; Luengo-Arratta, Sandra A; Diaz, Rosario; Saldivia, Manuel; Rojas-Barros, Domingo I; Manzano, Pilar; Gonzalez, Silvia; Berlanga, Manuela; Smith, Terry K; Navarro, Miguel; Pollastri, Michael P

2014-06-12

Compound NVP-BEZ235 (1) is a potent inhibitor of human phospoinositide-3-kinases and mammalian target of rapamycin (mTOR) that also showed high inhibitory potency against Trypanosoma brucei cultures. With an eye toward using 1 as a starting point for anti-trypanosomal drug discovery, we report efforts to reduce host cell toxicity, to improve the physicochemical properties, and to improve the selectivity profile over human kinases. In this work, we have developed structure-activity relationships for analogues of 1 and have prepared analogues of 1 with improved solubility properties and good predicted central nervous system exposure. In this way, we have identified 4e, 9, 16e, and 16g as the most promising leads to date. We also report cell phenotype and phospholipidomic studies that suggest that these compounds exert their anti-trypanosomal effects, at least in part, by inhibition of lipid kinases.

The role of nuclear sensors and positrons for engineering nano and microtechnologies

NASA Astrophysics Data System (ADS)

Smith, Suzanne V.

2011-01-01

A sustainable nano-manufacturing future relies on optimisation of the design and synthetic approach, detailed understanding of structure/properties relationships and the ability to measure a products impact in the environment. This article outlines how bench-top PALS and nuclear techniques can be used in the routine analysis of a wide range of nanomaterials. Traditionally used in the semiconductor industry, PALS has proven to be useful not only in measuring porosity in polymeric materials but also in the monitoring of milling processes used to produce natural fibre powders. Nuclear sensors (radiotracers), designed to probe charge, size and hydrophilicity of nanomaterials, are used to evaluate the connectivity (availability) of these pores for interaction with media. Together they provide valuable information on structure/properties relationship of nanomaterials and insight into how the design of a material can be optimised. Furthermore, the highly sensitive nuclear sensors can be adapted for monitoring the impact of nanomaterials in vivo and the environment.

Perovskite-type oxides - Oxygen electrocatalysis and bulk structure

NASA Technical Reports Server (NTRS)

Carbonio, R. E.; Fierro, C.; Tryk, D.; Scherson, D.; Yeager, E.

1988-01-01

Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

Quantitative Structure – Property Relationship Modeling of Remote Liposome Loading Of Drugs

PubMed Central

Cern, Ahuva; Golbraikh, Alexander; Sedykh, Aleck; Tropsha, Alexander; Barenholz, Yechezkel; Goldblum, Amiram

2012-01-01

Remote loading of liposomes by trans-membrane gradients is used to achieve therapeutically efficacious intra-liposome concentrations of drugs. We have developed Quantitative Structure Property Relationship (QSPR) models of remote liposome loading for a dataset including 60 drugs studied in 366 loading experiments internally or elsewhere. Both experimental conditions and computed chemical descriptors were employed as independent variables to predict the initial drug/lipid ratio (D/L) required to achieve high loading efficiency. Both binary (to distinguish high vs. low initial D/L) and continuous (to predict real D/L values) models were generated using advanced machine learning approaches and five-fold external validation. The external prediction accuracy for binary models was as high as 91–96%; for continuous models the mean coefficient R2 for regression between predicted versus observed values was 0.76–0.79. We conclude that QSPR models can be used to identify candidate drugs expected to have high remote loading capacity while simultaneously optimizing the design of formulation experiments. PMID:22154932

Theoretical Study of tip apex electronic structure in Scanning Tunneling Microscope

NASA Astrophysics Data System (ADS)

Choi, Heesung; Huang, Min; Randall, John; Cho, Kyeongjae

2011-03-01

Scanning Tunneling Microscope (STM) has been widely used to explore diverse surface properties with an atomic resolution, and STM tip has played a critical role in controlling surface structures. However, detailed information of atomic and electronic structure of STM tip and the fundamental understanding of STM images are still incomplete. Therefore, it is important to develop a comprehensive understanding of the electronic structure of STM tip. We have studied the atomic and electronic structures of STM tip with various transition metals (TMs) by DFT method. The d-electrons of TM tip apex atoms show different orbital states near the Fermi level. We will present comprehensive data of STM tips from our DFT calculation. Verified quantification of the tip electronic structures will lead to fundamental understanding of STM tip structure-property relationship. This work is supported by the DARPA TBN Program and the Texas ETF. DARPA Tip Based Nanofabrication Program and the Emerging Technology Fund of the State of Texas.

Crystal growth of device quality GaAs in space

NASA Technical Reports Server (NTRS)

Gatos, H. C.; Lagowski, J.

1985-01-01

The present program has been aimed at solving the fundamental and technological problems associated with Crystal Growth of Device Quality in Space. The initial stage of the program was devoted strictly to ground-based research. The unsolved problems associated with the growth of bulk GaAs in the presence of gravitational forces were explored. Reliable chemical, structural and electronic characterization methods were developed which would permit the direct relation of the salient materials parameters (particularly those affected by zero gravity conditions) to the electronic characteristics of single crystal GaAs, in turn to device performance. These relationships are essential for the development of optimum approaches and techniques. It was concluded that the findings on elemental semiconductors Ge and Si regarding crystal growth, segregation, chemical composition, defect interactions, and materials properties-electronic properties relationships are not necessarily applicable to GaAs (and to other semiconductor compounds). In many instances totally unexpected relationships were found to prevail.

Physico-chemical properties and cytotoxic effects of sugar-based surfactants: Impact of structural variations.

PubMed

Lu, Biao; Vayssade, Muriel; Miao, Yong; Chagnault, Vincent; Grand, Eric; Wadouachi, Anne; Postel, Denis; Drelich, Audrey; Egles, Christophe; Pezron, Isabelle

2016-09-01

Surfactants derived from the biorefinery process can present interesting surface-active properties, low cytotoxicity, high biocompatibility and biodegradability. They are therefore considered as potential sustainable substitutes to currently used petroleum-based surfactants. To better understand and anticipate their performances, structure-property relationships need to be carefully investigated. For this reason, we applied a multidisciplinary approach to systematically explore the effect of subtle structural variations on both physico-chemical properties and biological effects. Four sugar-based surfactants, each with an eight carbon alkyl chain bound to a glucose or maltose head group by an amide linkage, were synthesized and evaluated together along with two commercially available standard surfactants. Physico-chemical properties including solubility, Krafft point, surface-tension lowering and critical micellar concentration (CMC) in water and biological medium were explored. Cytotoxicity evaluation by measuring proliferation index and metabolic activity against dermal fibroblasts showed that all surfactants studied may induce cell death at low concentrations (below their CMC). Results revealed significant differences in both physico-chemical properties and cytotoxic effects depending on molecule structural features, such as the position of the linkage on the sugar head-group, or the orientation of the amide linkage. Furthermore, the cytotoxic response increased with the reduction of surfactant CMC. This study underscores the relevance of a methodical and multidisciplinary approach that enables the consideration of surfactant solution properties when applied to biological materials. Overall, our results will contribute to a better understanding of the concomitant impact of surfactant structure at physico-chemical and biological levels. Copyright © 2016 Elsevier B.V. All rights reserved.

Unraveling Structure-Property Relationships in Polymer Blends for Intelligent Materials Design

NASA Astrophysics Data System (ADS)

Irwin, Matthew Tyler

Block polymers provide an accessible route to structured, composite materials by combining two or more components with disparate mechanical, chemical, and electrical properties into a single bulk material with nanoscale domains. However, the characteristic lengthscale of these systems is limited, and the choice of components is restricted to those that are able to undergo microstructural ordering at accessible temperatures. This thesis details routes to overcoming these limitations through the addition of a lithium salt, a blend of homopolymers, or both. Chapter 2 describes a study wherein complex sphere phases such as the Frank-Kasper sigma phase can be observed in otherwise disordered asymmetric block polymers through the addition of a lithium salt. Chapter 3 discusses the development and characterization of a ternary polymer blend of an AB diblock copolymer and A and B homopolymers doped with a lithium salt. Detailed characterization showed that doping blends that are otherwise disordered with lithium salt induced microstructural ordering and largely recovers the phase behavior of traditional ternary polymer blends. A systematic study of the ionic conductivity of the blends at a fixed salt concentration demonstrates that, at a given composition, disordered, yet highly structured blends consistently exhibit better conductivity than polycrystalline morphologies with long range order. Chapter 4 extends the methodology of Chapter 3 and details a systematic study of the effects of cross-linker concentration on the performance of polymer electrolyte membranes produced via polymerization-induced microphase separation that exhibit a highly structured, globally disordered microstructure. Finally, Chapter 5 details efforts to develop a water filtration membrane using a polyethylene template derived from a polymeric bicontinuous microemulsion. Throughout all of this work, the goal is to better understand structure-property relationships at the molecular level in order to ultimately inform design criteria for materials where simultaneous control over morphology and mechanical, chemical, or electrical properties is important.

Structure‐function relationships at the human spinal disc‐vertebra interface

PubMed Central

Berg‐Johansen, Britta; Fields, Aaron J.; Liebenberg, Ellen C.; Li, Alfred

2017-01-01

ABSTRACT Damage at the intervertebral disc‐vertebra interface associates with back pain and disc herniation. However, the structural and biomechanical properties of the disc‐vertebra interface remain underexplored. We sought to measure mechanical properties and failure mechanisms, quantify architectural features, and assess structure‐function relationships at this vulnerable location. Vertebra‐disc‐vertebra specimens from human cadaver thoracic spines were scanned with micro‐computed tomography (μCT), surface speckle‐coated, and loaded to failure in uniaxial tension. Digital image correlation (DIC) was used to calculate local surface strains. Failure surfaces were scanned using scanning electron microscopy (SEM), and adjacent sagittal slices were analyzed with histology and SEM. Seventy‐one percent of specimens failed initially at the cartilage endplate‐bone interface of the inner annulus region. Histology and SEM both indicated a lack of structural integration between the cartilage endplate (CEP) and bone. The interface failure strength was increased in samples with higher trabecular bone volume fraction in the vertebral endplates. Furthermore, failure strength decreased with degeneration, and in discs with thicker CEPs. Our findings indicate that poor structural connectivity between the CEP and vertebra may explain the structural weakness at this region, and provide insight into structural features that may contribute to risk for disc‐vertebra interface injury. The disc‐vertebra interface is the site of failure in the majority of herniation injuries. Here we show new structure‐function relationships at this interface that may motivate the development of diagnostics, prevention strategies, and treatments to improve the prognosis for many low back pain patients with disc‐vertebra interface injuries. © 2017 The Authors. Journal of Orthopaedic Research® Published by Wiley Periodicals, Inc. on behalf of Orthopaedic Research Society. J Orthop Res 36:192–201, 2018. PMID:28590060

Investigations of Sayre's Equation.

NASA Astrophysics Data System (ADS)

Shiono, Masaaki

Available from UMI in association with The British Library. Since the discovery of X-ray diffraction, various methods of using it to solve crystal structures have been developed. The major methods used can be divided into two categories: (1) Patterson function based methods; (2) Direct phase-determination methods. In the early days of structure determination from X-ray diffraction, Patterson methods played the leading role. Direct phase-determining methods ('direct methods' for short) were introduced by D. Harker and J. S. Kasper in the form of inequality relationships in 1948. A significant development of direct methods was produced by Sayre (1952). The equation he introduced, generally called Sayre's equation, gives exact relationships between structure factors for equal atoms. Later Cochran (1955) derived the so-called triple phase relationship, the main means by which it has become possible to find the structure factor phases automatically by computer. Although the background theory of direct methods is very mathematical, the user of direct-methods computer programs needs no detailed knowledge of these automatic processes in order to solve structures. Recently introduced direct methods are based on Sayre's equation, so it is important to investigate its properties thoroughly. One such new method involves the Sayre equation tangent formula (SETF) which attempts to minimise the least square residual for the Sayre's equations (Debaerdemaeker, Tate and Woolfson; 1985). In chapters I-III the principles and developments of direct methods will be described and in chapters IV -VI the properties of Sayre's equation and its modification will be discussed. Finally, in chapter VII, there will be described the investigation of the possible use of an equation, similar in type to Sayre's equation, derived from the characteristics of the Patterson function.

Individual structural differences in left inferior parietal area are associated with schoolchildrens' arithmetic scores

PubMed Central

Li, Yongxin; Hu, Yuzheng; Wang, Yunqi; Weng, Jian; Chen, Feiyan

2013-01-01

Arithmetic skill is of critical importance for academic achievement, professional success and everyday life, and childhood is the key period to acquire this skill. Neuroimaging studies have identified that left parietal regions are a key neural substrate for representing arithmetic skill. Although the relationship between functional brain activity in left parietal regions and arithmetic skill has been studied in detail, it remains unclear about the relationship between arithmetic achievement and structural properties in left inferior parietal area in schoolchildren. The current study employed a combination of voxel-based morphometry (VBM) for high-resolution T1-weighted images and fiber tracking on diffusion tensor imaging (DTI) to examine the relationship between structural properties in the inferior parietal area and arithmetic achievement in 10-year-old schoolchildren. VBM of the T1-weighted images revealed that individual differences in arithmetic scores were significantly and positively correlated with the gray matter (GM) volume in the left intraparietal sulcus (IPS). Fiber tracking analysis revealed that the forceps major, left superior longitudinal fasciculus (SLF), bilateral inferior longitudinal fasciculus (ILF) and inferior fronto-occipital fasciculus (IFOF) were the primary pathways connecting the left IPS with other brain areas. Furthermore, the regression analysis of the probabilistic pathways revealed a significant and positive correlation between the fractional anisotropy (FA) values in the left SLF, ILF and bilateral IFOF and arithmetic scores. The brain structure-behavior correlation analyses indicated that the GM volumes in the left IPS and the FA values in the tract pathways connecting left IPS were both related to children's arithmetic achievement. The present findings provide evidence that individual structural differences in the left IPS are associated with arithmetic scores in schoolchildren. PMID:24367320

Synthesis and Characterization of Composite Membranes made of Graphene and Polymers of Intrinsic Microporosity

DTIC Science & Technology

2016-02-16

group of polymers with molecular sieve behaviour due to their rigid, contorted macromolecular backbones. They show great potential in organophilic...ageing is expected by adding graphene as a nanofiller. Little is experimentally known about how the material disperses in the polymer. Here we used Raman...effective understanding of the structure-property relationships of the composite. Obtaining such structural infor- mation, however, is experimentally

Evaluation of the Molecular Structural Parameters of Normal Rice Starch and Their Relationships with Its Thermal and Digestion Properties.

PubMed

Lin, Lingshang; Zhang, Qing; Zhang, Long; Wei, Cunxu

2017-09-12

The molecular structural parameters of six normal rice starches with different amylose contents were investigated through their iodine absorption spectra and gel permeation chromatography of fully branched and debranched starches. The thermal and digestion properties of starches were also determined and their relationships with molecular structural parameters were analyzed. Results showed that the molecular structural parameters of maximum absorption wavelength, blue value (BV), optical density 620 nm/550 nm (OD 620/550), amylose, intermediate component, and amylopectin, including its short branch-chains, long branch-chains, and branching degree, had high correlation in different determining methods. The intermediate component of starch was significantly positively related to amylose and negatively related to amylopectin, and the amylopectin branching degree was significantly positively related to amylopectin content and negatively related to amylose content. The gelatinization temperatures and enthalpy of native starch were significantly positively related to BV, OD 620/550, and amylose content and negatively related to amylopectin short branch-chains. The gelatinization temperatures and enthalpy of retrograded starch were significantly negatively related to amylopectin branching degree. The digestions of gelatinized and retrograded starches were significantly negatively related to the BV, OD 620/550, amylose, and intermediate component and positively related to amylopectin and its short branch-chains and branching degree.

Structure of superhard tungsten tetraboride: A missing link between MB2 and MB12 higher borides

PubMed Central

Lech, Andrew T.; Turner, Christopher L.; Mohammadi, Reza; Tolbert, Sarah H.; Kaner, Richard B.

2015-01-01

Superhard metals are of interest as possible replacements with enhanced properties over the metal carbides commonly used in cutting, drilling, and wear-resistant tooling. Of the superhard metals, the highest boride of tungsten—often referred to as WB4 and sometimes as W1–xB3—is one of the most promising candidates. The structure of this boride, however, has never been fully resolved, despite the fact that it was discovered in 1961—a fact that severely limits our understanding of its structure–property relationships and has generated increasing controversy in the literature. Here, we present a new crystallographic model of this compound based on refinement against time-of-flight neutron diffraction data. Contrary to previous X-ray–only structural refinements, there is strong evidence for the presence of interstitial arrangements of boron atoms and polyhedral bonding. The formation of these polyhedra—slightly distorted boron cuboctahedra—appears to be dependent upon the defective nature of the tungsten-deficient metal sublattice. This previously unidentified structure type has an intermediary relationship between MB2 and MB12 type boride polymorphs. Manipulation of the fractionally occupied metal and boron sites may provide insight for the rational design of new superhard metals. PMID:25733870

Predicting total organic halide formation from drinking water chlorination using quantitative structure-property relationships.

PubMed

Luilo, G B; Cabaniss, S E

2011-10-01

Chlorinating water which contains dissolved organic matter (DOM) produces disinfection byproducts, the majority of unknown structure. Hence, the total organic halide (TOX) measurement is used as a surrogate for toxic disinfection byproducts. This work derives a robust quantitative structure-property relationship (QSPR) for predicting the TOX formation potential of model compounds. Literature data for 49 compounds were used to train the QSPR in moles of chlorine per mole of compound (Cp) (mol-Cl/mol-Cp). The resulting QSPR has four descriptors, calibration [Formula: see text] of 0.72 and standard deviation of estimation of 0.43 mol-Cl/mol-Cp. Internal and external validation indicate that the QSPR has good predictive power and low bias (‰<‰1%). Applying this QSPR to predict TOX formation by DOM surrogates - tannic acid, two model fulvic acids and two agent-based model assemblages - gave a predicted TOX range of 136-184 µg-Cl/mg-C, consistent with experimental data for DOM, which ranged from 78 to 192 µg-Cl/mg-C. However, the limited structural variation in the training data may limit QSPR applicability; studies of more sulfur-containing compounds, heterocyclic compounds and high molecular weight compounds could lead to a more widely applicable QSPR.

The structure of mushroom polysaccharides and their beneficial role in health.

PubMed

Huang, Xiaojun; Nie, Shaoping

2015-10-01

Mushroom is a kind of fungus that has been popular for its special flavour and renowned biological values. The polysaccharide contained in mushroom is regarded as one of the primary bioactive constituents and is beneficial for health. The structural features and bioactivities of mushroom polysaccharides have been studied extensively. It is believed that the diverse biological bioactivities of polysaccharides are closely related to their structure or conformation properties. In this review, the structural characteristics, conformational features and bioactivities of several mushroom polysaccharides are summarized, and their beneficial mechanisms and the relationships between their structure and bioactivities are also discussed.

Structure Diversity, Synthesis, and Biological Activity of Cyathane Diterpenoids in Higher Fungi.

PubMed

Tang, Hao-Yu; Yin, Xia; Zhang, Cheng-Chen; Jia, Qian; Gao, Jin-Ming

2015-01-01

Cyathane diterpenoids, occurring exclusively in higher basidiomycete (mushrooms), represent a structurally diverse class of natural products based on a characteristic 5-6-7 tricyclic carbon scaffold, including 105 members reported to date. These compounds show a diverse range of biological activities, such as antimicrobial, anti-MRSA, agonistic toward the kappa-opioid receptor, antiinflammatory, anti-proliferative and nerve growth factor (NGF)-like properties. The present review focuses on the structure diversity, structure elucidation and biological studies of these compounds, including mechanisms of actions and structure-activity relationships (SARs). In addition, new progress in chemical synthesis of cyathane diterpenoids is discussed.

Physicochemical properties of black pepper (Piper nigrum) starch.

PubMed

Zhu, Fan; Mojel, Reuben; Li, Guantian

2018-02-01

Black pepper (Piper nigrum) is among the most popular spices around the world. Starch is the major component of black pepper. However, little is known about functional properties of this starch. In this study, swelling, solubility, thermal properties, rheology, and enzyme susceptibility of 2 black pepper starches were studied and compared with those of maize starch. Pepper starch had lower water solubility and swelling power than maize starch. It had higher viscosity during pasting event. In dynamic oscillatory analysis, pepper starch had lower storage modulus. Thermal analysis showed that pepper starch had much higher gelatinization temperatures (e.g., conclusion temperature of 94°C) than maize starch. The susceptibility to α-amylolysis of pepper starch was not very different from that of maize starch. Overall, the differences in the physicochemical properties of the 2 pepper starches are non-significant. The relationships between structure (especially amylopectin internal molecular structure) and properties of starch components are highlighted. Copyright © 2017 Elsevier Ltd. All rights reserved.

Structure-function relationships in the evolutionary framework of spermine oxidase.

PubMed

Cervelli, Manuela; Salvi, Daniele; Polticelli, Fabio; Amendola, Roberto; Mariottini, Paolo

2013-06-01

Spermine oxidase is a FAD-dependent enzyme that specifically oxidizes spermine, and plays a central role in the highly regulated catabolism of polyamines in vertebrates. The spermine oxidase substrate is specifically spermine, a tetramine that plays mandatory roles in several cell functions, such as DNA synthesis, cellular proliferation, modulation of ion channels function, cellular signalling, nitric oxide synthesis and inhibition of immune responses. The oxidative products of spermine oxidase activity are spermidine, H2O2 and the aldehyde 3-aminopropanal that spontaneously turns into acrolein. In this study the reconstruction of the phylogenetic relationships among spermine oxidase proteins from different vertebrate taxa allowed to infer their molecular evolutionary history, and assisted in elucidating the conservation of structural and functional properties of this enzyme family. The amino acid residues, which have been hypothesized or demonstrated to play a pivotal role in the enzymatic activity, and substrate specificity are here analysed to obtain a comprehensive and updated view of the structure-function relationships in the evolution of spermine oxidase.

Suitability of a three-dimensional model to measure empathy and its relationship with social and normative adjustment in Spanish adolescents: a cross-sectional study

PubMed Central

Gómez-Ortiz, Olga; Ortega-Ruiz, Rosario; Jolliffe, Darrick; Romera, Eva M.

2017-01-01

Objectives (1) To examine the psychometric properties of the Basic Empathy Scale (BES) with Spanish adolescents, comparing a two and a three-dimensional structure;(2) To analyse the relationship between the three-dimensional empathy and social and normative adjustment in school. Design Transversal and ex post facto retrospective study. Confirmatory factorial analysis, multifactorial invariance analysis and structural equations models were used. Participants 747 students (51.3% girls) from Cordoba, Spain, aged 12–17 years (M=13.8; SD=1.21). Results The original two-dimensional structure was confirmed (cognitive empathy, affective empathy), but a three-dimensional structure showed better psychometric properties, highlighting the good fit found in confirmatory factorial analysis and adequate internal consistent valued, measured with Cronbach’s alpha and McDonald’s omega. Composite reliability and average variance extracted showed better indices for a three-factor model. The research also showed evidence of measurement invariance across gender. All the factors of the final three-dimensional BES model were direct and significantly associated with social and normative adjustment, being most strongly related to cognitive empathy. Conclusions This research supports the advances in neuroscience, developmental psychology and psychopathology through a three-dimensional version of the BES, which represents an improvement in the original two-factorial model. The organisation of empathy in three factors benefits the understanding of social and normative adjustment in adolescents, in which emotional disengagement favours adjusted peer relationships. Psychoeducational interventions aimed at improving the quality of social life in schools should target these components of empathy. PMID:28951400

Relationships between microstructure and mechanical properties of Ti-5Al-5Mo-5V-3Cr-1Zr alloy

NASA Astrophysics Data System (ADS)

Li, Z. Y.; Wu, G. Q.; Huang, Z.

2018-03-01

Through a statistical, quantitative analysis on microstructure of Ti-5Al-5Mo-5V-3Cr-1Zr (Ti55531) alloy, the relationships between microstructure and mechanical properties and heat treatment temperatures were investigated. The results show that in Widmanstätten structure, the size of β grain is greatly increased with increasing annealing temperature. Static toughness is related to grain boundary alpha phase discontinuity, the tensile strength is related to acicular alpha phase interface length and acicular alpha phase proportion. In duplex microstructure, the tensile strength is related to the equiaxed alpha proportion. Elongation, static toughness and crack forming work are related to the equiaxed alpha proportion and negatively related to secondary phase proportion. The microstructure can be described quantitatively and the mechanical properties can be predicted by analysis of microstructure.

Porous Nb-Ti-Ta alloy scaffolds for bone tissue engineering: Fabrication, mechanical properties and in vitro/vivo biocompatibility.

PubMed

Liu, Jue; Ruan, Jianming; Chang, Lin; Yang, Hailin; Ruan, Wei

2017-09-01

Porous Nb-Ti-Ta (at.%) alloys with the pore size of 100-600μm and the porosity of 50%-80% were fabricated by the combination of the sponge impregnation technique and sintering method. The results revealed that the pores were well connected with three-dimensional (3D) network structure, which showed morphological similarity to the anisotropic porous structure of human bones. The results also showed that the alloys could provide the compressive Young's modulus of 0.11±0.01GPa to 2.08±0.09GPa and the strength of 17.45±2.76MPa to 121.67±1.76MPa at different level of porosity, indicating that the mechanical properties of the alloys are similar to those of human bones. Pore structure on the compressive properties was also discussed on the basis of the deformation mode. The relationship between compressive properties and porosity was well consistent with the Gibson-Ashby model. The mechanical properties could be tailored to match different requirements of the human bones. Moreover, the alloys had good biocompatibility due to the porous structure with higher surface, which were suitable for apatite formation and cell adhesion. In conclusion, the porous Nb-Ti-Ta alloy is potentially useful in the hard tissue implants for the appropriate mechanical properties as well as the good biocompatible properties. Copyright © 2017. Published by Elsevier B.V.

Structure-property relationships in hybrid dental nanocomposite resins containing monofunctional and multifunctional polyhedral oligomeric silsesquioxanes.

PubMed

Wang, Weiguo; Sun, Xiang; Huang, Li; Gao, Yu; Ban, Jinghao; Shen, Lijuan; Chen, Jihua

2014-01-01

Organic-inorganic hybrid materials, such as polyhedral oligomeric silsesquioxanes (POSS), have the potential to improve the mechanical properties of the methacrylate-based composites and resins used in dentistry. In this article, nanocomposites of methacryl isobutyl POSS (MI-POSS [bears only one methacrylate functional group]) and methacryl POSS (MA-POSS [bears eight methacrylate functional groups]) were investigated to determine the effect of structures on the properties of dental resin. The structures of the POSS-containing networks were determined by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. Monofunctional POSS showed a strong tendency toward aggregation and crystallization, while multifunctional POSS showed higher miscibility with the dimethacrylate monomer. The mechanical properties and wear resistance decreased with increasing amounts of MI-POSS, indicating that the MI-POSS agglomerates act as the mechanical weak point in the dental resins. The addition of small amounts of MA-POSS improved the mechanical and shrinkage properties. However, samples with a higher MA-POSS concentration showed lower flexural strength and flexural modulus, indicating that there is a limited range in which the reinforcement properties of MA-POSS can operate. This concentration dependence is attributed to phase separation at higher concentrations of POSS, which affects the structural integrity, and thus, the mechanical and shrinkage properties of the dental resin. Our results show that resin with 3% MA-POSS is a potential candidate for resin-based dental materials.

A Short Review of the Generation of Molecular Descriptors and Their Applications in Quantitative Structure Property/Activity Relationships.

PubMed

Sahoo, Sagarika; Adhikari, Chandana; Kuanar, Minati; Mishra, Bijay K

2016-01-01

Synthesis of organic compounds with specific biological activity or physicochemical characteristics needs a thorough analysis of the enumerable data set obtained from literature. Quantitative structure property/activity relationships have made it simple by predicting the structure of the compound with any optimized activity. For that there is a paramount data set of molecular descriptors (MD). This review is a survey on the generation of the molecular descriptors and its probable applications in QSP/AR. Literatures have been collected from a wide class of research journals, citable web reports, seminar proceedings and books. The MDs were classified according to their generation. The applications of the MDs on the QSP/AR have also been reported in this review. The MDs can be classified into experimental and theoretical types, having a sub classification of the later into structural and quantum chemical descriptors. The structural parameters are derived from molecular graphs or topology of the molecules. Even the pixel of the molecular image can be used as molecular descriptor. In QSPR studies the physicochemical properties include boiling point, heat capacity, density, refractive index, molar volume, surface tension, heat of formation, octanol-water partition coefficient, solubility, chromatographic retention indices etc. Among biological activities toxicity, antimalarial activity, sensory irritant, potencies of local anesthetic, tadpole narcosis, antifungal activity, enzyme inhibiting activity are some important parameters in the QSAR studies. The classification of the MDs is mostly generic in nature. The application of the MDs in QSP/AR also has a generic link. Experimental MDs are more suitable in correlation analysis than the theoretical ones but are more expensive for generation. In advent of sophisticated computational tools and experimental design proliferation of MDs is inevitable, but for a highly optimized MD, studies on generation of MD is an unending process.

Regulation of Silk Material Structure by Temperature-Controlled Water Vapor Annealing

PubMed Central

Hu, Xiao; Shmelev, Karen; Sun, Lin; Gil, Eun-Seok; Park, Sang-Hyug; Cebe, Peggy; Kaplan, David L.

2011-01-01

We present a simple and effective method to obtain refined control of the molecular structure of silk biomaterials through physical temperature-controlled water vapor annealing (TCWVA). The silk materials can be prepared with control of crystallinity, from a low content using conditions at 4°C (alpha-helix dominated silk I structure), to highest content of ~60% crystallinity at 100°C (beta-sheet dominated silk II structure). This new physical approach covers the range of structures previously reported to govern crystallization during the fabrication of silk materials, yet offers a simpler, green chemistry, approach with tight control of reproducibility. The transition kinetics, thermal, mechanical, and biodegradation properties of the silk films prepared at different temperatures were investigated and compared by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), uniaxial tensile studies, and enzymatic degradation studies. The results revealed that this new physical processing method accurately controls structure, in turn providing control of mechanical properties, thermal stability, enzyme degradation rate, and human mesenchymal stem cell interactions. The mechanistic basis for the control is through the temperature controlled regulation of water vapor, to control crystallization. Control of silk structure via TCWVA represents a significant improvement in the fabrication of silk-based biomaterials, where control of structure-property relationships is key to regulating material properties. This new approach to control crystallization also provides an entirely new green approach, avoiding common methods which use organic solvents (methanol, ethanol) or organic acids. The method described here for silk proteins would also be universal for many other structural proteins (and likely other biopolymers), where water controls chain interactions related to material properties. PMID:21425769

Semantic modeling of the structural and process entities during plastic deformation of crystals and rocks

NASA Astrophysics Data System (ADS)

Babaie, Hassan; Davarpanah, Armita

2016-04-01

We are semantically modeling the structural and dynamic process components of the plastic deformation of minerals and rocks in the Plastic Deformation Ontology (PDO). Applying the Ontology of Physics in Biology, the PDO classifies the spatial entities that participate in the diverse processes of plastic deformation into the Physical_Plastic_Deformation_Entity and Nonphysical_Plastic_Deformation_Entity classes. The Material_Physical_Plastic_Deformation_Entity class includes things such as microstructures, lattice defects, atoms, liquid, and grain boundaries, and the Immaterial_Physical_Plastic_Deformation_Entity class includes vacancies in crystals and voids along mineral grain boundaries. The objects under the many subclasses of these classes (e.g., crystal, lattice defect, layering) have spatial parts that are related to each other through taxonomic (e.g., Line_Defect isA Lattice_Defect), structural (mereological, e.g., Twin_Plane partOf Twin), spatial-topological (e.g., Vacancy adjacentTo Atom, Fluid locatedAlong Grain_Boundary), and domain specific (e.g., displaces, Fluid crystallizes Dissolved_Ion, Void existsAlong Grain_Boundary) relationships. The dynamic aspect of the plastic deformation is modeled under the dynamical Process_Entity class that subsumes classes such as Recrystallization and Pressure_Solution that define the flow of energy amongst the physical entities. The values of the dynamical state properties of the physical entities (e.g., Chemical_Potential, Temperature, Particle_Velocity) change while they take part in the deformational processes such as Diffusion and Dislocation_Glide. The process entities have temporal parts (phases) that are related to each other through temporal relations such as precedes, isSubprocessOf, and overlaps. The properties of the physical entities, defined under the Physical_Property class, change as they participate in the plastic deformational processes. The properties are categorized into dynamical, constitutive, spatial, temporal, statistical, and thermodynamical. The dynamical properties, categorized under the Dynamical_Rate_Property and Dynamical_State_Property classes, subsume different classes of properties (e.g., Fluid_Flow_Rate, Temperature, Chemical_Potential, Displacement, Electrical_Charge) based on the physical domain (e.g., fluid, heat, chemical, solid, electrical). The properties are related to the objects under the Physical_Entity class through diverse object type (e.g., physicalPropertyOf) and data type (e.g., Fluid_Pressure unit 'MPa') properties. The changes of the dynamical properties of the physical entities, described by the empirical laws (equations) modeled by experimental structural geologists, are modeled through the Physical_Property_Dependency class that subsumes the more specialized constitutive, kinetic, and thermodynamic expressions of the relationships among the dynamic properties. Annotation based on the PDO will make it possible to integrate and reuse experimental plastic deformation data, knowledge, and simulation models, and conduct semantic-based search of the source data originating from different rock testing laboratories.

Structural and dynamical properties of the porins OmpF and OmpC: insights from molecular simulations

NASA Astrophysics Data System (ADS)

Kumar, Amit; Hajjar, Eric; Ruggerone, Paolo; Ceccarelli, Matteo

2010-11-01

In this paper we investigate the structural and dynamical properties of the two major porins (OmpF and OmpC) in Escherichia coli, using molecular dynamics (MD) simulations. In particular we characterized the atomic fluctuations, correlated motions, temperature dependence, solvent-accessible cross-sectional area and water dynamics in the key regions of the two channels. Our in-depth analysis allows us to highlight the importance of both the key conserved and substituted residues between OmpF and OmpC. The latter is characterized by a narrower and longer constriction region with respect to OmpF. OmpC also showed a higher stability upon increasing temperature. We then present the results of transport properties by using accelerated MD simulations to probe the diffusion of norfloxacin (a fluoroquinolone antibiotic) through the two porins OmpF/OmpC. Our study constitutes a step forward towards understanding the structure-function relationship of the two porins' channels. This will benefit the research of antibacterials with improved permeation properties and nanopores that aim to use these porins as sensing systems.

77 FR 68773 - FIFRA Scientific Advisory Panel; Notice of Public Meeting

Federal Register 2010, 2011, 2012, 2013, 2014

2012-11-16

... for physical chemical properties that cannot be easily tested in in vitro systems or stable enough for.... Quantitative structural-activity relationship (QSAR) models and estrogen receptor (ER) expert systems development. High-throughput data generation and analysis (expertise focused on how this methodology can be...

Estimation of Physical Properties and Chemical Reactivity Parameters of Organic Compounds for Environmental Modeling by SPARC

EPA Science Inventory

Mathematical models for predicting the transport and fate of pollutants in the environment require reactivity parameter values that is value of the physical and chemical constants that govern reactivity. Although empirical structure activity relationships have been developed th...

Probing the water distribution in porous model sands with two immiscible fluids: A nuclear magnetic resonance micro-imaging study

NASA Astrophysics Data System (ADS)

Lee, Bum Han; Lee, Sung Keun

2017-10-01

The effect of the structural heterogeneity of porous networks on the water distribution in porous media, initially saturated with immiscible fluid followed by increasing durations of water injection, remains one of the important problems in hydrology. The relationship among convergence rates (i.e., the rate of fluid saturation with varying injection time) and the macroscopic properties and structural parameters of porous media have been anticipated. Here, we used nuclear magnetic resonance (NMR) micro-imaging to obtain images (down to ∼50 μm resolution) of the distribution of water injected for varying durations into porous networks that were initially saturated with silicone oil. We then established the relationships among the convergence rates, structural parameters, and transport properties of porous networks. The volume fraction of the water phase increases as the water injection duration increases. The 3D images of the water distributions for silica gel samples are similar to those of the glass bead samples. The changes in water saturation (and the accompanying removal of silicone oil) and the variations in the volume fraction, specific surface area, and cube-counting fractal dimension of the water phase fit well with the single-exponential recovery function { f (t) = a [ 1 -exp (- λt) ] } . The asymptotic values (a, i.e., saturated value) of the properties of the volume fraction, specific surface area, and cube-counting fractal dimension of the glass bead samples were greater than those for the silica gel samples primarily because of the intrinsic differences in the porous networks and local distribution of the pore size and connectivity. The convergence rates of all of the properties are inversely proportional to the entropy length and permeability. Despite limitations of the current study, such as insufficient resolution and uncertainty for the estimated parameters due to sparsely selected short injection times, the observed trends highlight the first analyses of the cube-counting fractal dimension (and other structural properties) and convergence rates in porous networks consisting of two fluid components. These results indicate that the convergence rates correlate with the geometric factor that characterizes the porous networks and transport property of the porous networks.

Structures and spectroscopic properties of nonperipherally and peripherally substituted metal-free phthalocyanines: a substitution effect study based on density functional theory calculations.

PubMed

Zhong, Aimin; Zhang, Yuexing; Bian, Yongzhong

2010-11-01

The molecular structures, molecular orbitals, atomic charges, electronic absorption spectra, and infrared (IR) and Raman spectra of a series of substituted metal-free phthalocyanine compounds with four (1, 3, 5, 7) or eight (2, 4, 6, 8) methoxyl (1, 2, 5, 6) or methylthio groups (3, 4, 7, 8) on the nonperipheral (1-4) or peripheral positions (5-8) of the phthalocyanine ring are studied by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The calculated structural parameters and simulated electronic absorption and IR spectra are compared with the X-ray crystallography structures and the experimentally observed electronic absorption and IR spectra of the similar molecules, and good agreement between the calculated and experimental results is found. The substitution of the methoxyl or methylthio groups at the nonperipheral positions of the phthalocyanine ring has obvious effects on the molecular structure and spectroscopic properties of the metal-free phthalocyanine. Nonperipheral substitution has a more significant influence than peripheral substitution. The substitution effect increases with an increase in the number of substituents. The methylthio group shows more significant influence than the methoxyl group, despite the stronger electron-donating property of the methoxyl group than the methylthio group. The octa-methylthio-substituted metal-free phthalocyanine compounds have nonplanar structures whose low-lying occupied molecular orbitals and electronic absorption spectra are significantly changed by the substituents. The present systematical study will be helpful for understanding the relationship between structures and properties in phthalocyanine compounds and designing phthalocyanines with typical properties. Copyright © 2010 Elsevier Inc. All rights reserved.

Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study

NASA Astrophysics Data System (ADS)

Helmbrecht, C.; Lützenkirchen-Hecht, D.; Frank, W.

2015-03-01

Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time.Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time. Electronic supplementary information (ESI) available: The deconvoluted reference spectra are given in ESI Fig. 1-9. See DOI: 10.1039/c4nr07051h