Nonlinear optical (NLO) responses from organic dyes can be maximized when the dyes are aligned in appropriate manners in bulk materials. The use of restricted nanospaces provided by interlayer spacing of inorganic layered materials is a promising strategy for imposing suitable molecular alignments for NLO materials on dyes. The hybrid materials thus obtained exhibit salient NLO responses owing to the improved molecular orientation. In some cases, extension of the π‐electron system as a consequence of improved molecular planarity, obtained by the intercalation of a dye into the 2‐dimensional interlayer space of an inorganic layered material, is also observed as a factor that enhances NLO responses of chromophores at the molecular level. This review focuses on recent progress in the strategies for controlling the molecular orientation of NLO‐phores by employing clay minerals, which are one of the typical inorganic layered materials. In addition, development of a means for fabricating composites that satisfy the properties of an optical material, such as a sufficient size and thickness, a flat surface, and low light‐scattering characteristics is required to utilize the superior NLO properties observed for clay/dye hybrid materials for practical applications. A novel means for obtaining such a hybrid material is also outlined. 相似文献
Synthetic giant multiporphyrin arrays with well-defined architectures are reviewed in terms of artificial light-harvesting materials. Meso,meso-linked porphyrin arrays and multiporphyrin dendrimers have successfully mimicked the light-harvesting function of bacterial photosynthetic systems. We have also developed novel multiporphyrin-modified metal nanoclusters where porphyrins employed as a light-harvesting unit are well organized onto metal nanoclusters by self-assembly processes. Multiporphyrin-modified metal nanoclusters have been applied to photocatalyses and photovoltaic cells. In particular, they have been assembled with fullerenes step-by-step to make large, uniform clusters on nanostructured semiconductor electrodes, which exhibit a high power-conversion efficiency close to 1%. These systems provide valuable information on the design of porphyrin molecular assemblies that can be tailored to construct molecular photonic devices as well as artificial photosynthetic systems. 相似文献
The discovery of surface enhanced Raman scattering (SERS) in the mid-1970s impacted on the surface science community because of its remarkably high and unique surface sensitivity. Surface roughness in scale of 10~100 nm have been found necessary to produce the giant SERS signal. In this paper we will show that SERS is indeed one of the important phenomena not only in surface science but also in nanoscale science[1]. 相似文献
Summary: A “series” hybrid model based on material balances and artificial neural networks to predict the evolution of weight average molecular weight, , in semicontinuous emulsion polymerization with long chain branching kinetics is presented. The core of the model is composed by two artificial neural networks (ANNs) that calculate polymerization rate, Rp, and instantaneous weight‐average molecular weight, from reactor process variables. The subsequent integration of the material balances allowed to obtain the time evolution of conversion and , along the polymerization process. The accuracy of the proposed model under a wide range of conditions was assessed. The low computer‐time load makes the hybrid model suitable for optimization strategies.
Artificial muscles triggered by light are of great importance, especially for the development of non‐contact and remotely controlled materials. Common materials for synthesis of photoinduced artificial muscles typically rely on polymer‐based photomechanical materials. Herein, we are able to prepare artificial muscles using a mixed‐matrix membrane strategy to incorporate photomechanical molecular crystals with connective polymers (e.g. PVDF). The formed hybrid materials inherit not only the advantages of the photomechanical crystals, including faster light response, higher Young's modulus and ordered structure, but also the elastomer properties from polymers. This new type of artificial muscles demonstrates various muscle movements, including lifting objects, grasping objects, crawling and swimming, triggered by light irradiation. These results open a new direction to prepare light‐driven artificial muscles based on molecular crystals. 相似文献
Pyrene as well as other aromatic hydrocarbons could be successfully incorporated into pyrrolidinyl peptide nucleic acid bearing a d-prolyl-2-aminocyclopentane carboxylic acid backbone (acpcPNA) as a base surrogate via a triazole linker employing Cu-catalyzed alkyne–azide cycloaddition (click chemistry). The labeling can be performed via a pre-clicked pyrene monomer or by post-synthetic modification of azide-containing acpcPNA on solid support. Thermal denaturation experiments suggested that the pyrene–triazole unit can behave as a universal base in the acpcPNA system. The mode of base-pairing has been proposed based on molecular dynamics simulations. Importantly, the fluorescence spectra of the pyrene-labeled single stranded acpcPNA and its hybrid with DNA are quite different. The ratio of emissions at 380 and 460 nm changed significantly (up to a factor of 7) upon hybrid formation with complementary DNA. 相似文献
Three different kinds of mixed self-assembled monolayers have been prepared to mimic photosynthetic energy and electron transfer on a gold surface. Pyrene and boron-dipyrrin were chosen as a light-harvesting model. The mixed self-assembled monolayers of pyrene (or boron-dipyrrin) and porphyrin (energy acceptor model) reveal photoinduced singlet-singlet energy transfer from the pyrene (or boron-dipyrrin) to the porphyrin on the gold surface. The boron-dipyrrin has also been combined with a reaction center model, ferrocene-porphyrin-fullerene triad, to construct integrated artificial photosynthetic assemblies on a gold electrode using mixed monolayers of the respective self-assembled unit. The mixed self-assembled monolayers on the gold electrode have established a cascade of photoinduced energy transfer and multistep electron transfer, leading to the production of photocurrent output with the highest quantum yield (50 +/- 8%, based on the adsorbed photons) ever reported for photocurrent generation at monolayer-modified metal electrodes and across artificial membranes using donor-acceptor linked molecules. The incident photon-to-current efficiency (IPCE) of the photoelectrochemical cell at 510 and 430 nm was determined as 0.6% and 1.6%, respectively. Thus, the present system provides the first example of an artificial photosynthetic system, which not only mimics light-harvesting and charge separation processes in photosynthesis but also acts as an efficient light-to-current converter in molecular devices. 相似文献
To construct a simple model of a cellular system equipped with motor proteins, cell-sized giant liposomes encapsulating various amounts of actoHMM, the complexes of actin filaments (F-actin) and heavy meromyosin (HMM, an actin-related molecular motor), with a depletion reagent to mimic the crowding effect of inside of living cell, were prepared. We adapted the methodology of the spontaneous transfer of water-in-oil (W/O) droplets through a phospholipid monolayer into the bulk aqueous phase and successfully prepared stable giant liposomes encapsulating the solution with a physiological salt concentration containing the desired concentrations of actoHMM, which had been almost impossible to obtain using currently adapted methodologies such as natural swelling and electro-formation on an electrode. We then examined the effect of ATP on the cytoskeleton components confined in those cell-sized liposomes, because ATP is known to drive the sliding motion for actoHMM. We added α-hemolysin, a bacterial membrane pore-forming toxin, to the bathing solution and obtained liposomes with the protein pores embedded on the bilayer membrane to allow the transfer of ATP inside the liposomes. We show that, by the ATP supply, the actoHMM bundles inside the liposomes exhibit specific changes in spatial distribution, caused by the active sliding between F-actin and HMM. Interestingly, all F-actins localized around the inner periphery of liposomes smaller than a critical size, whereas in the bulk solution and also in larger liposomes, the actin bundles formed aster-like structures under the same conditions. 相似文献
Despite the remarkable progress in ultrastrong mechanical laminate materials, the simultaneous achievement of toughness, stretchability and self-healing properties in biomimetic layered nanocomposites remains a great challenge due to the intrinsic limitations of their hard essences and lack of effective stress transfer at the organic-inorganic fragile boundary. Here, an ultratough nanocomposite laminate is prepared by constructing chain-sliding cross-linking at the interface between sulfonated graphene nanosheets and polyurethane layers based on the ring molecules sliding on the linear polymer chains to release stresses. Unlike traditional supramolecular bonding toughening with limited sliding spacing, our strategy enables interfacial molecular chains reversible slippage when the inorganic nanosheets bear stretching force, providing sufficient interlayer spatial distance for relative sliding to dissipate more energy. The resulting laminates exhibit strong strength (22.33 MPa), supertoughness (219.08 MJ m−3), ultrahigh stretchability (>1900 %) and self-healing ability (99.7 %), which far surpass most of reported synthetic and natural laminate materials. Moreover, the fabricated proof-of-concept electronic skin shows excellent flexibility, sensitivity and healability for human physiological signals monitoring. This strategy breaks through the challenge that traditional layered nanocomposites are intrinsically stiff and opens up the functional application of layered nanocomposites in flexible devices. 相似文献
A new layered silicate, HUS-1, was synthesized by hydrothermal synthesis using decomposed FAU- and *BEA-type zeolites as nanosized silica parts. Structural analyses by X-ray powder diffractometry and solid-state magic-angle-spinning (MAS) NMR spectroscopy revealed that HUS-1 has a layered structure containing a silicate layer per unit cell along a stacking direction. Its framework topology is similar to that of SOD-type zeolites and consists of a halved sodalite cage, which includes four- and six-membered Si rings. Structure refinement by the Rietveld method showed that tetramethylammonium (TMA) ions used as a structure-directing agent (SDA) were incorporated into the interlayer. The four methyl groups of the TMA molecule were located orderly in a hemispherical cage in the silicate layer, which suggests restraint of molecular motion. The interlayer distance is estimated at about 0.15 nm, which is unusually short in comparison with that in other layered silicates (e.g., β-HLS or RUB-15) with similar framework topologies. The presence of hydrogen bonding between adjacent terminal O atoms was clearly revealed by the (1)H MAS NMR spectroscopy and by electron-density distribution obtained by the maximum entropy method. 相似文献
Hybrid films of a layered silicate and an amphiphilic alkylammonium (hexadecyltrimethylammonium) cation have been prepared by Langmuir–Blodgett (LB) method and transferred onto a polyamide surface by dip coating. This is the first time that stable LB hybrid monolayer and multilayer films have been formed on rough polymeric surfaces. The films were characterized by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and water contact angle measurements. XRD and FTIR showed that the hybrid multilayer was well-organized and the thickness of one layer was calculated to be 1.6 nm. Furthermore, the layered silicate was determined to be on the substrate side and the amphiphilic molecule layer was exposed to the air side. This provides a novel methodology for the surface modification of polymers. 相似文献
A hydrotalcite clay/dendrimer nanocomposite prepared by the ionic exchange process was adsorbed from suspension of the nanocomposite on a Langmuir monolayer of arachidic acid at the air/water interface, followed by compressing and transferring onto an arachidic acid monolayer Langmuir-Blodgett (LB) film on mica. For comparison, the hydrotalcite-adsorbed hybrid film was also prepared. The morphology of hydrotalcite and the nanocomposite studied by transmission electron microscopy indicated the layered structures with respectively 1.2 +/- 0.3 and 3.2 +/- 0.5 nm repeating distances. The hybrid Langmuir films displayed the occupied surface area of 0.24 nm2 for both hydrotalcite and the nanocomposite. The formation of hybrid Langmuir films was confirmed by Brewster angle microscopy. Atomic force microscopic images of hybrid LB films revealed the formation of plateau domains with the height difference of 6 nm for hydrotalcite and 12 nm for the nanocomposite and the presence of dendrimers adsorbed on the clay surface of the nanocomposite. 相似文献
Tin halide perovskites are potential alternatives of lead halide perovskites. However, the easy oxidation of Sn2+ to Sn4+ brings in a challenge. Recently, layered two-dimensional hybrid tin halide perovskites have been shown to partially resist the oxidation process because of the presence of hydrophobic organic molecules. Consequently, such layered hybrid perovskites are being explored for optoelectronic applications. The optical properties of layered tin halide perovskites depend on the interlayer separation and the dielectric mismatch between the organic and inorganic layers. Intercalation (insertion) of a molecular species between the layers modifies the interlayer interactions affecting the optical properties of layered hybrid perovskites. We investigated the effect of hexafluorobenzene (HFB) intercalation in phenethylammonium tin iodide [(PEA)2SnI4] using temperature-dependent (6 K to 300 K) photoluminescence (PL). HFB intercalation increases the bandgap. A strong PL quenching is observed in pristine (PEA)2SnI4 below 150 K, probably because of the presence of non-emissive states. HFB intercalation suppresses the influence of such non-emissive states resulting in an increase in PL intensity at the cryogenic temperatures. Our results highlight that a simple molecular intercalation (non-covalent interaction) into layered hybrid perovskites can significantly tailor the electronic and optical properties. 相似文献
Novel conjugated polymers based on squaric acid having 2,5-Bis[(E)-N-alkylpyrrol-2-ylvinyl]-3-alkylthiophene(PVTVP) unit in the main chain were successfully synthesized in good yields through polycondensation reaction.Their molecular structures were characterized by FT-IR and ~1H NMR.They have good solubility in common organic solvents,good thermal stability by thermal gravimetric analysis and high molecular weights.Their optical properties were investigated by UV-vis absorption spectra in CH_2Cl_2 solution,the results indicated all these compounds showed broad and strong spectral responses from 200nm to 900nm, suggesting their potential for application as organic plastic solar cells. 相似文献
Nacre (mother-of-pearl), made of inorganic and organic constituents (95 vol% aragonite calcium carbonate (CaCO(3)) platelets and 5 vol% elastic biopolymers), possesses a unique combination of remarkable strength and toughness, which is compatible for conventional high performance materials. The excellent mechanical properties are related to its hierarchical structure and precisely designed organic-inorganic interface. The rational design of aragonite platelet strength, aspect ratio of aragonite platelets, and interface strength ensures that the strength of nacre is maximized under platelet pull-out failure mode. At the same time, the synergy of strain hardening mechanisms acting over multiple scales results in platelets sliding on one another, and thus maximizes the energy dissipation of viscoplastic biopolymers. The excellent integrated mechanical properties with hierarchical structure have inspired chemists and materials scientists to develop biomimetic strategies for artificial nacre materials. This critical review presents a broad overview of the state-of-the-art work on the preparation of layered organic-inorganic nanocomposites inspired by nacre, in particular, the advantages and disadvantages of various biomimetic strategies. Discussion is focused on the effect of the layered structure, interface, and component loading on strength and toughness of nacre-mimic layered nanocomposites (148 references). 相似文献