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An electrochemical synthesis is developed through quantitative electrochemical reaction of N‐alkylcarbazole leading to a novel class of structurally interconnected high‐C60 content (60 wt%) polymer films with negligible doping and intrinsic physicochemical properties of pure C60. This strategy allows preparation of previously unavailable low‐doped fullerene‐containing non‐conjugated polymers and broadens the potential applications of electrochemical synthesis for controlled polymer film structures.

In this article, we propose a novel methodology for the formation of monodisperse regularly sized disks of several nanometer thickness and with diameters of less than 100 nm using Langmuir monolayers as fabrication media. An amphiphilic triimide, tri-n-dodecylmellitic triimide (1), was spread as a monolayer at the air-water interface with a water-soluble macrocyclic oligoamine, 1,4,7,10-tetraazacyclododecane (cyclen), in the subphase. The imide moieties of 1 act as hydrogen bond acceptors and can interact weakly with the secondary amine moieties of cyclen as hydrogen bond donors. The monolayer behavior of 1 was investigated through π-A isotherm measurements and Brewster angle microscopy (BAM). The presence of cyclen in the subphase significantly shifted isotherms and induced the formation of starfish-like microstructures. Transferred monolayers on solid supports were analyzed by reflection absorption FT-IR (FT-IR-RAS) spectroscopy and atomic force microscopy (AFM). The Langmuir monolayer transferred onto freshly cleaved mica by a surface touching (i.e., Langmuir-Schaefer) method contained disk-shaped objects with a defined height of ca. 3 nm and tunable diameter in the tens of nanometers range. Several structural parameters such as the disk height, molecular aggregation numbers in disk units, and 2D disk density per unit surface area are further discussed on the basis of AFM observations together with aggregate structure estimation and thermodynamic calculations. It should be emphasized that these well-defined structures are produced through simple routine procedures such as solution spreading, mechanical compression, and touching a substrate at the surface. The controlled formation of defined nanostructures through easy macroscopic processes should lead to unique approaches for economical, energy-efficient nanofabrication.

This study examines how religiousness influences social network site (SNS) membership and frequency of use for emerging adults between 18 and 23 years old utilizing Wave 3 survey data from the National Study of Youth and Religion (NSYR). Independent of religion promoting a prosocial orientation, organizational involvement, and civic engagement, Catholics and Evangelical Protestants are more likely than the “not religious” to be SNS members, and more Bible reading is associated with lower levels of SNS membership and use. We argue there are both sacred and secular influences on SNS involvement, and social behaviors, such as being in school and participating in more non-religious organizations, generally positively influence becoming a SNS member, yet certain more private behaviors, such as Bible reading, donating money, and helping the needy, lessen SNS participation. We also suggest four areas for future research to help untangle the influence of religiousness on SNS use and vice versa.

A dinuclear manganese(III) complex (1) of an N-(carboxymethyl)-N-[3,5-bis(α,α-dimethylbenzyl-2-hydroxybenzyl)]glycine (HDA) ligand (L) binds a manganese(II) species through displacement of its solvating ligands by appropriately dispositioned carbonyl groups of a dinuclear complex {[Mn(2)(L)(2)(OH)(OCH(3))][Mn(H(2)O)(3)(CH(3)OH)(3)], 2, triclinic P1, a = 13.172(3) Å, b = 15.897(3) Å, c = 19.059(4) Å, V = 3461.9(13) Å(3)} leading to a trinuclear complex {3, monoclinic P21/n, a = 11.7606(8) Å, b = 21.3505(8) Å, c = 26.7827(17) Å, V = 6722.7(7) Å(3)} with cyclization of two of the carboxy groups through the doubly-carboxy group coordinated Mn(2+) ion. The reaction is discussed in terms of its significance as an illustration of how Mn(2+) ions might be sequestered in biological systems. A similar solvato-ligand displacement reaction was used to synthesise coordination polymers of an HDA iron(III) complex involving polymerization through a bridging carboxylato group. Several isostructural polymers (5-7; for 5: orthorhombic Pbca, a = 9.411(5) Å, b = 16.390(8) Å, c = 37.968(19) Å, V = 5856(5) Å(3)) with different coordinated alcohols could be prepared indicating the potential synthetic uses of this method.

Olmstead's crystalline C60-fullerene–Ag(I) organometallic heteronanostructure [C60{AgNO3}5] undergoes an apparently irreversible structural rearrangement upon exposure to low molecular weight aliphatic alcohols leading to a uniquely structured formation of well-oriented fullerene nano/microcrystals (‘bucky cubes’). The mechanism of rearrangement represents a supramolecular analogue of topotactic processes more commonly associated with some purely inorganic materials, such as maghemite, where chemical changes can occur with addition or loss of materials. Hence C60{AgNO3}5, whose rearrangement occurs at the nano/molecular level (i.e. not atomic scale), undergoes a transformation from a crystalline organometallic complex to well ordered cube-shaped arrays of needle-like fullerene microcrystals which reflect the original cubic crystal morphology and internal structure. Processing of bucky cubes by reduction with hydrazine results in a Ag nanoparticle–C60 crystal nanocomposite with potential for SERS analyses.

Carbon nanofibers (CNFs) with high surface area (820 m2/g) have been successfully prepared by a nanocasting approach using silica nanofibers obtained from chromonic liquid crystals as a template. CNFs with randomly oriented graphitic layers show outstanding electrochemical supercapacitance performance, exhibiting a specific capacitance of 327 F/g at a scan rate of 5 mV/s with a long life-cycling capability. Approximately 95% capacitance retention is observed after 1000 charge–discharge cycles. Furthermore, about 80% of capacitance is retained at higher scan rates (up to 500 mV/s) and current densities (from 1 to 10 A/g). The high capacitance of CNFs comes from their porous structure, high pore volume, and electrolyte-accessible high surface area. CNFs with ordered graphitic layers were also obtained upon heat treatment at high temperatures (>1500 °C). Although it is expected that these graphitic CNFs have increased electrical conductivity, in the present case, they exhibited lower capacitance values due t...

Reversible dynamic control of structure is a significant challenge in molecular nanotechnology. Previously, we have reported a mechanically induced continuous (analog) conformational variation in an amphiphilic binaphthyl, where closing of molecular pliers was achieved by compression of a molecular monolayer composed of these molecules at the air-water interface. In this work we report that a phase transition induced by an applied mechanical stress enables discontinuous digital (1/0) opening of simple binaphthyl molecular pliers. A lipid matrix at the air-water interface promotes the formation of quasi-stable nanocrystals, in which binaphthyl molecules have an open transoid configuration. The crystallization/dissolution of quasi-stable binaphthyl crystals with accompanying conformational change is reversible and repeatable.

Here, we report the structural and morphological modulation of fullerene C

An electron-deficient copper(III) corrole was utilized for the construction of donor-acceptor conjugates with zinc(II) porphyrin (ZnP) as a singlet excited state electron donor, and the occurrence of photoinduced charge separation was demonstrated by using transient pump-probe spectroscopic techniques. In these conjugates, the number of copper corrole units was varied from 1 to 2 or 4 units while maintaining a single ZnP entity to observe the effect of corrole multiplicity in facilitating the charge-separation process. The conjugates and control compounds were electrochemically and spectroelectrochemically characterized. Computational studies revealed ground state geometries of the compounds and the electron-deficient nature of the copper(III) corrole. An energy level diagram was established to predict the photochemical events by using optical, emission, electrochemical, and computational data. The occurrence of charge separation from singlet excited zinc porphyrin and charge recombination to yield directly the ground state species were evident from the diagram. Femtosecond transient absorption spectroscopy studies provided spectral evidence of charge separation in the form of the zinc porphyrin radical cation and copper(II) corrole species as products. Rates of charge separation in the conjugates were found to be of the order of 10(10) s(-1) and increased with increasing multiplicity of copper(III) corrole entities. The present study demonstrates the importance of copper(III) corrole as an electron acceptor in building model photosynthetic systems.

A new class of fullerene (C(60)) crystals with bimodal pore architectures consisting of macropores and mesopores was synthesized by using a liquid-liquid interfacial precipitation (LLIP) method involving an interface between isopropyl alcohol (IPA) and a saturated solution of C(60) in a mixture of benzene and carbon tetrachloride (CCl(4)). By varying the mixing fraction of CCl(4) in benzene, the porosity and electrochemically active surface area can be flexibly controlled.

The synthesis and structures of the N-[(2-hydroxy-3-methyl-5-dodecylphenyl)methyl]-N-(carboxymethyl)glycine disodium salt (HL) ligand and its neutral mononuclear complex [Fe(III) (L)(EtOH)(2)] (1) are reported. Structural and electronic properties of 1 were investigated by using scanning tunneling microscopy (STM) and current imaging tunneling spectroscopy (CITS) techniques. These studies reveal that molecules of 1 form well-ordered self-assemblies when deposited on a highly oriented pyrolytic graphite (HOPG) surface. At low concentrations, single or double chains (i.e., nanowires) of the complex were observed, whereas at high concentration the complex forms crystals and densely packed one-dimensional structures. In STM topographies, the dimensions of assemblies of 1 found on the surface are consistent with dimensions obtained from X-ray crystallography, which indicates the strong similarities between the crystal form and surface assembled states. Double chains are attributed to hydrogen-bonding interactions and the molecules align preferentially along graphite defects. In the CITS image of complex 1 a strong tunneling current contrast at the positions of the metal ions was observed. These data were interpreted and reveal that the bonds coordinating the metal ions are weaker than those of the surrounding ligands; therefore the energy levels next to the Fermi energy of the molecule should be dominated by metal-ion orbitals.

Formation of reverse micelles at room temperature generally requires inclusion of water or other polar molecules in a mixture of long chain ionic surfactant and an organic solvent. In this paper, we report the formulation of nonionic reverse micelles at room temperature in an aromatic solvent, ethylbenzene using short-chain glycerol-based surfactants, and investigated the microstructure transformations induced by surfactant chain length, concentration, and temperature using SAXS and rheometry. We have also determined water solubility in reverse micelle and investigated water induced microstructure transitions. We found that a short chain nonionic surfactant, diglycerol monocaprate (C10G2), spontaneously self-assembles into an ellipsoidal prolate type micelle. Increasing surfactant chain induces a prolate-to-globular type transition forming globular micelles in diglycerol monomyristate (C14G2), which is expected to be caused by an increase in the lipophilicity of the surfactant. Increases in surfactant concentration favored one-dimensional micellar growth; the micellar size increases ca. 4.5–7.25 nm upon increase in the surfactant concentration from 3 to 20% while the cross-sectional radius maintained almost constant ca. 1.10 nm in the diglycerol monolaurate (C12G2) system. In contrast to the nonionic micelles in aqueous systems, reverse micelles get smaller with increasing temperature, which is similar to a rod-to-sphere type transition. Addition of trace water promotes a significant micellar growth; both the maximum dimension and radius of micelles increases and the size of the water-incorporated micelles was approximately three times greater than the micelles in the absence of water. Microstructure transitions revealed by SAXS are supported by rheological measurements; the relative zero-shear viscosity decreased with increase in the chain length of surfactant. On the other hand, relative viscosity increased nearly one order of magnitude upon increase in surfactant concentration from 3 to 20%.

Yuvaraj Manoharan,1,* Qingmin Ji,2,* Tomohiko Yamazaki,2,3 Shanmugavel Chinnathambi,1 Song Chen,2,4 Ganesan Singaravelu,1 Jonathan P Hill,2 Katsuhiko Ariga,2,5 Nobutaka Hanagata3,6 1Department of Medical Physics, Anna University, Chennai, India; 2Research Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba, Ibarak, 3Graduate School of Life Science, Hokkaido University, Kita-ku, Sapporo, 4JSPS Research Fellow, Chiyoda-ku, Tokyo, 5JST and CREST, National Institute for Materials Science, Tsukuba, Ibaraki, Japan; 6Nanotechnology Innovation Station, National Institute for Materials Science, Tsukuba, Ibaraki, Japan*These authors contributed equally to this workBackground: Class B CpG oligodeoxynucleotides primarily interact with Toll-like receptor 9 (TLR9) in B cells and enhance the immune system through induction of various interleukins including interleukin-6 in these immune cells. Although free class B CpG oligodeoxynucleotides do not induce interferon (IFN)-α production, CpG oligodeoxynucleotide molecules have been reported to induce IFN-α when loaded onto nanoparticles. Here, we investigated the in vitro induction of IFN-α by a nanocarrier delivery system for class B CpG oligodeoxynucleotide molecules.Methods: For improving the capacity to load CpG oligodeoxynucleotide molecules, flake-shell SiO2 nanoparticles with a specific surface area approximately 83-fold higher than that of smooth-surfaced SiO2 nanoparticles were prepared by coating SiO2 nanoparticles with polyethyleneimine (PEI) of three different number-average molecular weights (Mns 600, 1800, and 10,000 Da).Results: The capacity of the flake-shell SiO2 nanoparticles to load CpG oligodeoxynucleotides was observed to be 5.8-fold to 6.7-fold higher than that of smooth-surfaced SiO2 nanoparticles and was found to increase with an increase in the Mn of the PEI because the Mn contributed to the positive surface charge density of the nanoparticles. Further, the flake-shell SiO2 nanoparticles showed much higher levels of IFN-α induction than the smooth-surfaced SiO2 nanoparticles. The highest IFN-α induction potential was observed for CpG oligodeoxynucleotide molecules loaded onto flake-shell SiO2 nanoparticles coated with PEI of Mn 600 Da, although the CpG oligodeoxynucleotide density was lower than that on flake-shell SiO2 nanoparticles coated with PEI of Mns 1800 and 10,000 Da. Even with the same density of CpG oligodeoxynucleotides on flake-shell SiO2 nanoparticles, PEI with an Mn of 600 Da caused a markedly higher level of IFN-α induction than that with Mns of 1800 Da and 10,000 Da. The higher TLR9-mediated IFN-α induction by CpG oligodeoxynucleotides on flake-shell SiO2 nanoparticles coated with a PEI of Mn 600 Da is attributed to residence of the CpG oligodeoxynucleotide molecules in endolysosomes.Keywords: CpG oligodeoxynucleotides, polyethyleneimine, Toll-like receptor 9, silica nanoparticles, delivery, interferon-&alpha

Using small-angle X-ray scattering (SAXS) we have investigated the shape and size of diglycerol monomyristate (designated as C14G2) nonionic surfactant reverse micelles in aromatic solvent ethylbenzene as a function of surfactant concentration, temperature, and water. When C14G2 is added into ethylbenzene globular type reverse micelles with maximum core diameter ca. 4.5 nm are formed under ambient conditions. The micellar structure (shape and size) did not change with the surfactant concentration. However, an increase in temperature decreased the micellar size due to an increase in the critical packing parameter (cpp). Surfactant becomes more lipophilic upon heating and the micellar curvature tends to become more negative at higher temperature. Addition of a small amount of water caused a significant micellar growth. For instance, incorporation of 0.3% water in the 5% C14G2/ethylbenzene system resulted in the formation of 2.1 time bigger micelles with a small water pool in the micellar core. Besides the micellar shape is modified into an ellipsoidal prolate, whose scenario can be understood in terms of hydration of the surfactant's headgroup. Hydration decreases the cpp and favors micellar growth. An increase of temperature of a water incorporated system decreased the micellar size due to dehydration, which is equivalent to rod-to-sphere type transition.

Aggregation of gold nanoparticles (AuNPs) can be utilized in chemical and biomolecular sensing as a sensitive and easy-to-visualize process. However, interpretation of experimental results requires a clear understanding of physicochemical processes that take place upon multiple interactions between an analyte and AuNPs. In this article, interactions between citrate-stabilized AuNPs and organic compounds bearing various functional groups in an aqueous medium were experimentally and theoretically studied using spectrophotometry of the localized surface plasmon resonance (LSPR), transmission electron microscopy (TEM), conductometry, zeta potential measurements, and finite-difference time-domain (FDTD) modeling. As a result, it has been found that organic compounds containing both thiol and amine groups strongly promote the aggregation of AuNPs due to their cooperative functionalities. FDTD modeling has enabled consideration of the light extinction (i.e., LSPR response) properties of nanoparticle aggregates i...

The global environment has been variously compromised leading to problems such as global warming and radioactive contamination. In this feature article, we will focus especially on materials for environmental remediation based on the concept of materials nanoarchitectonics. The topics are classified into three categories: removal and degradation of toxic substances including waste due to fossil fuel usage and organic pollutants (continuously arising problems), current emerging topics concerning oil spills and nuclear waste (current urgent problems), and advanced methods based on supramolecular chemistry and nanotechnology (including breakthroughs for future development).

In the molecular machine concept, single molecules and/or small molecular assemblies operate as independent machines in the ultimate miniaturization of functional systems. For the development of molecular machines, changing the medium of operation from solution to solid surface satisfies several demands for machine functions including allowing direct observation, enabling connection with devices and facilitation of sequential actions. However, the field of molecular machines on solid surfaces is still immature when compared with the sophisticated molecular mechanical systems observed in Nature. Required further developments of molecular machines include improved dynamic operations so that investigations of molecular machine functionality at dynamic interfacial media have become important. In this paper, the development of research on molecular machines in solution and at solid interfaces is described together with an introduction of recent challenges in the operation of molecular machines at soft matter interfaces.

Inorganic structures and their assemblies play important roles in artificial materials for biological applications. In this short review, we briefly summarize recent research on bioapplicable materials supported by inorganic structures possibly reflecting the concept of nanoarchitectonics, according to classification of unit nanostructures (nanoparticles, nanospheres, nanosheets, layer-structures, and nanotubes), internally nanostructured materials (mesoporous materials), organized assemblies (mainly layer-by-layer (LbL) assemblies), and hierarchical structures. Bioapplications such as sensing, drug delivery, and cell imaging are described. Refereed/Peer-reviewed

Manipulation of self-assembly processes to construct predesigned supramolecular architectures in a controllable manner is of utmost importance in the field of nanotechnology for the development of application-oriented devices. We here summarize recent progress in the current strategies for the manipulation of thin film assemblies on solid surfaces and at interfaces, as well as in freestanding thin film structures. We also highlight our recent progress including a description of the concept of hand-operating nanotechnology for controlling thin film assemblies at dynamic interfaces. This review is organized into three sections: (i) functionalization and manipulation of solid surfaces to assist molecular self-assembly; (ii) manipulation of freestanding ultrathin films by self-assembly; and (iii) molecular assembly at dynamic interfaces.

Previous research on charitable giving has identified a significant relationship between political conservatism and greater financial giving to charitable causes. Yet that research has not adequately explored the important role of religion in that relationship, nor differences in financial giving targets (i.e., religious congregations, noncongregational religious organizations, and nonreligious organizations). Support for competing theories concerning political ideology, religious practice, and charitable financial giving is assessed using data from the Panel Study on American Ethnicity and Religion (PS-ARE). For both religious and nonreligious giving, the effect of political ideology is completely mediated by participation in religious and civic practices. These findings support recent arguments on “practice theory” in cultural sociology and suggest that it is less the effect of ideology than of active participation in religious, political, and community organizations that explains Americans’ financial giving to religious and nonreligious organizations.

Ultrasmall ZnS or PbS nanorods encapsulated in fluid-like soft organic surfactants show excellent miscibility in the nematic liquid crystal (LC ZLI-4792) host resulting in a novel soft matter type blend with enhanced electro-optic properties. The ultranarrow ZnS rods are of wurtzite phase and possess a chemical bipolarity and a net dipole moment. The centrosymmetric ultranarrow PbS rods possess a finite size and shape dependent inherent dipole moment despite their cubic rock-salt structure. When an electric field is applied, the blend aligns along the direction of the field producing a local unidirectional orientation of the rods and LC directors, and defining a unique axis for the system. The local ordering significantly affects the global ordering of the blend allowing a more rapid response of the electro-optic properties. The degree and switching speed of the blends depend upon the magnitude of dipole moments present in the dopant nanorods. We show how a non-mesogenic element designed with preferential crystallographic phase can be introduced within a LC for improvement of the switching properties of the LC blend. These types of unique blends are a model for fundamental conceptual advances in general understanding of interaction behaviour leading consequently to a significant technological advancement for superior device fabrication.

Research on philanthropy has not sufficiently examined whether charitable giving to religious causes impinges on giving to secular causes. Examining three waves of national panel data, we find that the relationship between religious and secular giving is generally not of a zero-sum nature; families that increase their religious giving also increase their secular giving. We argue that this finding is best accounted for by a practice theory of social action which emphasizes how religious congregations foster skills and practices related to charitable giving. We also argue that denominational variation in the influence of religious giving is best accounted for by the financial structuring of the denomination. We conclude with the implications for studies of religious causal influence more generally.

This study examines the impact of educational enrollment and attainment on several measures of religious belief using nationally representative panel data. Although college does not appear to substantially alter the religious beliefs of most emerging adults, findings do reveal a modest increase in skepticism toward super-empirical religious beliefs among college students and graduates compared to those who have never attended any form of postsecondary education. This effect is dependent on college type, with students attending elite universities exhibiting the greatest increase in skepticism. Apart from changes in super-empirical belief, graduating from college modestly increases preferences for institutionalized religion while simultaneously reducing adherence to exclusivist religious belief. Faculty commitment to secularism, the degree of student academic engagement, and developing social identities may play a role in religious belief change, particularly at elite universities.

There are several requirements for the safe and effective delivery of therapeutic agents for human use. Direct injection of drugs may cause side effects due to their permeation to other, undiseased regions of the body so that concealment and targeting with appropriate materials is a critical consideration in the design of practical drug delivery systems. In particular, carriers with structures which can be flexibly controlled are more useful since functional structure units can be assembled in component-by-component and/or layer-by-layer fashion. In this review, we focus on preparation of layer-by-layer shells directed at drug delivery applications. After a description of the fundamentals of layer-by-layer (LbL) assembly, recent progress in the field of self-assembled microshells and nanoshells for drug delivery applications are summarized. In addition, concepts developed to solve current difficulties are also described. Encapsulation of insoluble drugs in nanoshells and their delivery can satisfy some of the demands of practical medical use. Thus, aqueous suspensions of insoluble drugs have been subjected to powerful ultrasonic treatment followed by sequential addition of polycations and polyanions to the particle solution leading to assembly of ultra-thin polyelectrolyte shells on the nano-sized drug particles. In another innovative example, stepwise release of drugs from LbL films of mesoporous capsules to the exterior in the absence of external stimuli was demonstrated. It can be regarded as stimuli-free auto-modulated material release.

The study of religious motivation has been an important area of research in the psychology of religion since Allport and Ross (1967) developed their measure of intrinsic/extrinsic religion. Batson (1976) expanded the model of religious motivation by proposing the quest construct and its measurement with the Interactional Scale. Two additional measures of quest were developed by Altemeyer and Hunsberger (1992) and Dudley and Cruise (1990). Questions have been raised about the reliability and validity of the quest construct and its measures. The present study investigates the dimensionality and convergence of three measures of quest using a sample of 1200 undergraduates from nine Christian liberal arts colleges. Exploratory and confirmatory factor analyses identified five quest dimensions. The correlations of the five quest dimensions with several measures of religious functioning and religious fundamentalism were examined. Differences across four college classes on the quest dimensions were also tested. The three quest measures converged on two dimensions labeled Belief Change Expected and Doubts Value. These dimensions were uncorrected with measures of God awareness and religious well-being and negatively correlated with religious fundamentalism. The three other dimensions identified were unique to one of the measures. The dimension regarding existential questions was not well sampled by our pool of items. The dimensions Reason versus Faith and Religion as Quest were correlated negatively with God awareness and religious well-being as well as religious fundamentalism. The quest dimensions of change and doubt are core facets of Batson's original formulation and our results validate these two dimensions of his model. Measurement of the questions dimension requires further development. The validity and utility of the other two dimensions as aspects of quest will require further investigation. The empirical study of religion as an important social and personal variable has been a viable, if somewhat less than mainstream, pursuit in psychology for several decades. Psychology of religion research increased substantially when Allport and Ross (1967) developed their measure of intrinsic (I) and extrinsic (E) motivation (the Religious Orientation Scale, ROS). The measure was based upon Gordon Ailport's (Ailport, 1950) conceptualization of mature versus immature religious motivation. Allport (1950) proposed his model distinguishing between intrinsic and extrinsic motivation as a way to understand the observed association between prejudice and religious belief. While the intrinsic and extrinsic constructs and the ROS measure have been subjected to extensive review and critique (Donahue, 1985; Gorsuch & McPherson, 1989; Kirkpatrick, 1988), the I/E model of religious motivation has proved to be useful (Kirkpatrick & Hood, 1990) for psychology of religion research. Batson and his colleagues (Batson, 1976; Batson & Ventis, 1982; Batson, Schoenrade, & Ventis, 1993) provided another advance in psychology of religion with their proposal of a third dimension of religious motivation, which they called religion as Quest. They argued that the Religious Orientation Scale (ROS) did not adequately measure all facets of Allport's original model of mature religion. Specifically, they suggested that the ROS excluded salient facets such as openness, flexibility, tentativeness, and doubt (Batson, Schoenrade, & Ventis, 1993). They argued that these facets were particularly important for understanding the relationship between religion and prejudice. The quest motivation describes individuals for whom religion is an on-going, open-minded exploration of existential questions, acceptance of the fact that many important religious questions do not have clear-cut answers, and a tentativeness of belief that remains open to change as one grows and develops. Batson & Ventis (1982) proposed a six-item measure of quest called the Interactional Scale (IS). …

Selective molecular recognition is an important subject in supramolecular science as well as in practical applications such as sensing, drug delivery, and biomedical processes. In this research we have investigated adsorption behavior of nucleosides (adenosine, guanosine, and thymidine) onto various porous supports. When compared with mesoporous silica, porous carbons exhibit superior adsorptive performance. We serendipitously observed a pronounced selectivity between purinebase and pyrimidine-base nucleosides by carbon naonocage. These findings are useful for design of materials for applications in adsorption-based separations and as column stationary phases for separation of costly and important biomolecules. Refereed/Peer-reviewed

Electrochemical-coupling layer-by-layer (ECC-LbL) assembly is introduced as a novel fabrication methodology for preparing layered thin films. This method allows us to covalently immobilize functional units (e.g., porphyrin, fullerene, and fluorene) into thin films having desired thicknesses and designable sequences for both homo- and heteroassemblies while ensuring efficient layer-to-layer electronic interactions. Films were prepared using a conventional electrochemical setup by a simple and inexpensive process from which various layering sequences can be obtained, and the photovoltaic functions of a prototype p/n heterojunction device were demonstrated.

High-performance drug delivery systems are always made through assembly and hybridization of multiple components, each of which possesses its own role within the unified delivery function. The layer-by-layer (LbL) adsorption technique offers huge freedom in material selection and flexibility of structural design, which are fully matched with the fabrication needs of drug delivery materials requiring complicated designs.In this review, film-type LbL assemblies and their drug delivery application are focused on, with selected examples from recent years. In addition to a description of the general progress of this technique in bio-related areas, examples of the delivery of low-molecular-mass drugs, DNA, peptides and proteins are summarized, as well as recent advances in film structures composed of organic/inorganic hybrids.The authors expect that the highly versatile nature of the LbL assembly can overcome any remaining practical difficulties in delivering therapeutics, because the layer structure, component selection, and the surface nature including biocompatibility, degradability and size/dimension are all adjustable. Furthermore, the simple and inexpensive nature of this technique can also satisfy strict demands from an economic point of view.

Nanotechnology from a bottom-up approach relies heavily on supramolecular chemistry that can potentially provide nano- and microstructures with molecular level precision of internal configurations through low-energy spontaneous processes. Moreover, supramolecular assemblies at the two-dimensional interface have great potential to be integrated into artificial devices. Studies on supramolecular chemistry at interfaces are, therefore, highly relevant for the development of nanotechnology. Another distinct aspect of supermolecules exists in their advanced dynamic properties that are anticipated to provide various stimuli-responsive systems. Here, we summarise the recent literature describing the dynamic behaviours of supermolecules at interfaces and supramolecular chemistry at dynamic interfaces categorised into three classes: (i) dynamic behaviour at solid surfaces, (ii) supermolecules at dynamic interfaces in liquid media and (iii) supermolecules at the air–water interface.

The cholesterol-armed cyclen Na(+) complex formed stable Langmuir monolayers at the air-water interface. The π-A isotherm displayed a reasonable limiting molecular area of ∼1.57 nm(2) and the areas expanded when amino acids were dissolved in water, indicating the efficient accommodation in the monolayers. Brewster angle microscopy (BAM) images exhibited almost no defects of the compressed Langmuir monolayers regardless of the presence of amino acids. Based on the idea that the increase in the limiting molecular areas corresponds to the amount of the adsorbed amino acid, the binding constants of three enantiomeric amino acids, namely valine (Val), leucine (Leu), and phenylalanine (Phe), were calculated at different surface pressures. Remarkably, a surface pressure dependent enantioselectivity of amino acid recognition was observed. Upon compression of the monolayers, the binding constants of amino acids increased accompanying an inversion of chiral selectivity from the D- to L-form in the case of Val and, conversely, from L- to D-form in the case of Phe.

We present a structural and electronic inspection of reduced pyrazinacenes within the DFT framework. Our analysis provides a clear indication that compounds in which reduced pyrazine rings are well separated from each other are rather stable. Conversely, if the reduced pyrazine rings approach each other or cluster together, the compounds become increasingly unstable. The tautomers analyzed are likely to possess properties suitable for application as proton transport materials due to protic isomerism processes. On the basis of our findings, we propose that protic transport should occur through a concerted proton transfer without involving intramolecular aggregation of the dihydropyrazine groups. Furthermore, the electronic structure analysis shows that this class of compounds can be classified as small bandgap semiconducting materials, possessing even metallic character depending on the tautomeric structure, and with potential nanotechnological applications in molecular electronics and fuel cells.

Nanomaterials have been prepared over a wide range of length scales from nanoscopic objects to bulk structural materials. Recent investigations have been focused on the regulation and control of nanoscopic structures for the modulation of the properties of even macroscopic objects. As an emerging concept, nanoarchitectonics has been proposed as a technology system to be used for arranging nanoscale structural units--i.e., the nanostructure unit as a group of atoms or molecules--in a predesignated configuration. In this review, we summarize recent research on nanomaterials including design, synthesis, fabrication and functionalization based on the nanoarchitectonics concept. Examples are roughly classified according to their dimensionalities: (i) OD nanomaterials (quantum dots, nanocrystals, nanoparticles and nanospheres); (ii) 1D nanomaterials (nanorods, nanowires, nanobelts, nanowhiskers and nanotubes), (iii) 2D nanomaterials (nanosheets, graphene, self-assemble monolayers, Langmuir-Blodgett films, layer-by-layer assemblies and interfacial structures), and (iv) 3D nanomaterials (bulk materials with nanoscale structural control, nanohybrids, nanocomposites and mesoporous materials).

The potential usefulness and importance of nanomaterials are now well recognized. However, currently available synthetic nanomaterials are generally used in their bulk form and control of nanosystems at the nanoscale on demand has not been realized. To solve this problem, the use of macroscopic mechanical stimuli to drive nano/molecular systems is considered to be a key technique. If direct manipulation of nano/molecular systems could be achieved by applying macroscopic mechanical stimuli, we might exert control over nanotechnological systems according to our needs. In this perspective, recent methodologies for controlling nano/molecular systems through application of macroscopic mechanical forces are introduced. Application of mechanical processes is known to affect some molecular association and chemical reactions, causing variation of optical properties, sometimes resulting in self-healing functions or capture and release of molecules under macroscopic mechanical motions. We might be able to realize the great potential of nanoscale and molecular systems by accessing nanoscience and nanotechnology from the macroscopic world.

Rumblings of the ‘return’ of religion to American colleges and universities have been growing louder in recent years. Alongside various forms of secularism, public religions are re-emerging in new ...

Studies on a resistive switching memory based on a silver-ion-conductive solid polymer electrolyte (SPE) are reported. Simple Ag/SPE/Pt structures containing polyethylene oxide–silver perchlorate complexes exhibit bipolar resistive switching under bias voltage sweeping. The switching behavior depends strongly on the silver perchlorate concentration. From the results of thermal, transport, and electrochemical measurements, it is concluded that the observed switching originates from formation and dissolution of a silver metal fi lament inside the SPE fi lm caused by electrochemical reactions. This is the fi rst report of an electrochemical “atomic switch” realized using an organic material. The devices also show ON/OFF resistance ratios greater than 10 5 , programming speeds higher than 1 μ s, and retention times longer than 1 week. These results suggest that SPE-based electrochemical devices might be suitable for fl exible switch and memory applications.

Dispersion of ultranarrow PbS nanorods of 1.8 nm diameter, encapsulated by a fluidlike soft trioctylamine layer, in the nematic liquid crystal (LC ZLI-4792) results in a novel soft matter type blend with enhanced electro-optic properties. Despite having a cubic rock-salt structure, the ultranarrow rods possess a finite inherent dipole moment and show excellent miscibility in the LC host. The local ordering significantly affects the global ordering of the blend allowing a more rapid response of the electro-optic properties. These unique blends are obtainable only by doping with one-dimensional nanorods of ultrasmall dimensions and illustrates how a nonmesogenic element can be introduced within a liquid crystal for improvement of the switching properties of the blend. The unique blend could be a model for fundamental conceptual advances in general understanding of interaction behavior, leading consequently to a significant technological advancement for superior device fabrications.

Self-assembled helical supramolecular structures are widely found in nature and have also been observed in several systems based on synthetic amphiphiles. Such structures often exhibit interesting properties that can be utilized in different nanotechnological applications. Based on previous work concerning the form factor of helical filaments with a finite cross section, the present work gives the helical form factor generalized for a tape containingNlayers. The presented form factor is applied to the characterization of an intermediate structure obtained during the formation of self-assembled graphitic nanotubes. The structure was modeled as a centrosymmetric bilayer containing five layers including a structure factor. These results have been compared with that obtained using a model based on polydisperse cylinders, and it is shown that the full description with helical model and structure factor is the superior one.

Topologically asymmetric compounds, important as chiral nanoscale building blocks, were synthesized using stepwise N-alkylation on tetrakis (3,5-di- t -butyl-4-oxocyclohexadien-2,5-yl) porphyrinogen as revealed by X-ray crystallographic studies on a porphyrinogen molecule bearing four different N-substituents.

The conjugated calix[4]pyrrole tetrakis(3,5-di-t-butyl-4-oxocyclohexadien-2,5-yl)porphyrinogen (OxP) is a highly coloured macrocycle with excellent potential as a sensing element in various applications. The first of these is chiral sensing where guest binding at the macrocyclic NH groups allows for estimation of enantiomeric excesses in non-racemic mixtures of chiral analytes. This feature is permitted by the relatively weak binding of the guest resulting in its rapid exchange so that the molecule essentially acts as a probe of average solution chirality. Chirality sensing in OxP is complicated by tautomeric processes when an acid analyte is used. This has allowed us also to develop an acidity sensor for use in non-polar media. More recently, we have designed a series of OxP type molecules that undergo modulation of halochromic (sensitivity to acid) properties and the development of colour scales based on the blocking of OxP binding sites and involving allied protic tautomerization of the OxP chromophore. We will discuss the sensing properties of OxP in relation to chirality, tautomeric processes and the complicating factor of solvatochromism.

Layer-by-layer (LbL) thin film assembly behaviors of the polymethylene-type polyelectrolytes poly(fumaric acid) andpoly(methyleneamine) were comprehensively studiedas afunctionofthedipping solution pH values. Since polymethylene-type polyelectrolytes can possess double the density of side-chain charges of conventional vinyl (or polyethylene-type) polyelectrolytes, they exhibited stronger intramolecular side-chain interactions, which were revealed by potentiometric titrations and their sequential adsorption behaviors. Thicknesses of the LbL thin films obtained decreased with the degree of ionization of both polyelectrolytes. The pH-dependent variation in film thickness was subtle and continuous when compared with the vinyl polyelectrolytes, probably because of the large variation in pKa of the polymethylene-type polyelectrolytes in the multilayer thin films. Refractive indices of the thin films were not positively correlated with their thicknesses, but the pH matrix displayed maximum values for the combination of almost fully charged polycation and polyanion. The main chains of highly charged polyelectrolytes are apparently substantially extended, resulting in the optimal packing of polycations and polyanions, in terms of the electrostatic attractions, to form high-density polymer films. AFM measurements revealed that the high-density thin films are composed of densely assembled almost monodispersed polymer nanoparticles with an average diameter of 17 nm. In contrast, flexible polymers with fewer side-chain charges are loosely assembled, giving thicker films of relatively low density. Thus, the pH matrix of the refractive indices is inversely correlated with that of the roughness parameters determined by AFM measurements. Finally, FT-IR-RAS spectra revealed the presence of charged species in all the LbL thin films, suggesting a significantly decreased pKa for poly(fumaric acid). These results illustrate some of the most fundamental and unexplored aspects of LbL film assemblies based on the simplest of chemical structures.

Top-down nanofabrication techniques, especially photolithography, have advanced nanotechnology to a point where system-process integration with bottom-up self-assembly is now required. Because most lithographic techniques are constrained to two-dimensional planes, investigation of integrated self-assembly systems should focus on two-dimensional organization. In this review, research on two-dimensional nanoartchitectonics is classified and summarized according to the type of interface used. Pattern formation following deposition of vaporized molecules onto a solid surface can be analyzed with high structural precision using scanning probe microscopy under ultra high vacuum. Transitions of adsorbed phases and adjustment of pattern mismatch by conformational changes of adsorbed molecules are discussed, in addition to the forces constraining pattern formation, i.e., two-dimensional hydrogen bond networks, van der Waals forces, and molecule-surface interactions. Molecular deposition at a liquid-solid interface broadens the range of molecules that can be investigated. The more complex molecules discussed in this work are C(60)-fullerene derivatives and designer DNA strands. Gas-liquid interfaces, e.g. between air and water, allow dynamic formations that can adjust to molecular conformational changes. In this case, any resulting patterns can be modulated by varying conditions macroscopically. Using flexible molecules at the fluid air-water interface also permits dynamic operation of molecular machines by macroscopic mechanical motion, thus enabling, hand-operated nanotechnology.

New soluble polymers derived from oxidation of 1H,2H-dihyroperimidines and related to poly(1,8-diaminonaphthalene) were synthesized and found to form hexagonally structured macroporous films (macroporous poly(aromatic amine)) derived from the formation of breath figures. The polymers formed well-ordered macroporous films with homogeneous hole sizes between 0.2 and 1 μm. The polymers also formed other structures including nanofibers, microparticles and hollow membranous objects.

Inorganic materials of nanometric dimensions and controllable morphologies are now widely available permitting their use as building blocks in supramolecular structures. Incorporation of inorganic blocks into hybrid structures can yield unique materials that have no naturally occurring or organic synthetic analogues. In this short review, we describe the construction and functions of supramolecular materials prepared using inorganic building blocks, with emphasis on material-like components. Examples described in this review are categorized as (i) inorganic structures within organic assemblies (silica-supported Langmuir monolayers, organic-inorganic lipid bilayer vesicles etc.), (ii) organic components in inorganic nanospaces (mesoporous materials including biocomponents such as peptides and proteins), (iii) organic/inorganic nanohybrid blends (nanorod-liquid crystal blends and surfactant-guided gold nanostructures), and (iv) hierarchic structures (layer-by-layer assemblies of mesoporlous carbons and capsules). Refereed/Peer-reviewed

Monoprotic and diprotic NH tautomerism in reduced oligoazaacenes, the pyrazinacenes, was studied by using first principles simulations. Stepwise reductions in the metadynamics-sampled free energy profile were observed during consecutive monoprotic tautomerizations, with energy barriers gradually reducing with increasing proton separation during monoprotic processes. This is accompanied by an increasing contribution from the quinoidal electronic structure, as evidenced by the computed highest occupied molecular orbital (HOMO) structure. An unusual odd-even effect in the free energy profiles is also observed upon changing the length of the pyrazinacene. Calculated HOMO structures reveal an increasing tendency for delocalization of pyrazine lone pairs with an increasing number of ring annelations. The influence of tautomerism on the pyrazine lone pair delocalization was also observed. Tautomers with protons situated centrally on the pyrazinacene backbone are predicted to be more stable due to a combination of (enamine) delocalization and a loss of Clar sextet resonance stabilization in tautomers with protons at terminal pyrazine rings. Experimental evidence suggesting the structure of pyrazinacene tautomers is included and discussed as a support to the calculation.

There is great potential in nanoscale science and technology, and construction of macrosized materials and systems possessing nanoscale structural features is a crucial factor in the everyday application of nanoscience and nanotechnology. Because nanoscale substances are often constructed through self-assembly of unit molecules and nanomaterials, control of the self-assembly process is required. In order to establish general guidelines for the fabrication of materials with nanoscale structural characteristics, i.e., nanoscaled materials, we introduce here examples of recent research in related fields categorised as: (i) self-assembled structures with forms generally determined by intrinsic interactions between molecules and/or unit nanomaterials, (ii) self-assemblies influenced by their surrounding media, especially interfacial environments, (iii) modulation of self-assembly by artificial operation or external stimuli. Examples are not limited to organic molecules, which are often regarded as the archetypal species in self-assembly chemistry, and many examples of inorganic assemblies and hybrid structures are included in this review.

A central claim of the religious economies model is that religious competition affects levels of religious participation and commitment primarily because religious competition pushes the suppliers of religion (religious leaders and organizations) to market their faith more vigorously and effectively. We examine whether U.S. congregations experiencing greater religious competition measured by their smaller religious market share do more to recruit new members, offer more services to current followers, and whether their clergy work longer hours. The efforts of congregations and clergy do vary substantially, but this variation is not related to their denomination's market share. The variations are also not due to religious pluralism, intradenominational competition, or evangelical market share. Members of small market share congregations are more committed, but this higher commitment does not appear to arise because religious suppliers are responding to religious competition. Several alternative explanations for the higher commitment levels of small market share groups are offered with a discussion of the implications for theories of religious competition.