Chiral Perovskite Nanocrystal Growth inside Helical Hollow Silica Nanoribbons.

Helical perovskite nanocrystals (H-PNCs) were prepared using nanometric silica helical ribbons as platforms for the in situ growth of the crystals using the supersaturated recrystallization method. The H-PNCs grow inside nanometric helical porous silica, and their handedness is determined by the handedness of porous silica templates. They show both strong induced circular dichroism (CD) and strong induced circularly polarized luminescence (CPL) signals, with high dissymmetry g-factors. Right-handed and left-handed PNCs show respectively positive and negative CD and CPL signals, with a dissymmetry g-factor (abs and lum) of ∼±2 × 10-2. Simulations based on the boundary element method demonstrate that the circular dichroism originates from the chiral shape of H-PNCs.

Optically Active Perovskite CsPbBr3 Nanocrystals Helically Arranged on Inorganic Silica Nanohelices.

Perovskite nanocrystals (PNCs) exhibit excellent absorption and luminescent properties. Inorganic silica right (or left) handed nanohelices are used as chiral templates to induce optically active properties to CsPbBr3 PNCs grafted on their surfaces. In suspension, PNCs grafted on the nanohelices do not show any detectable chiroptical properties. In contrast, in a dried film state, they show large circular dichroism (CD) and circularly polarized luminescence (CPL) signals with dissymmetric factor up to 6 × 10-3. Grazing incidence X-ray scattering, tomography, and cryo-electron microscopy (EM) have shown closely and helically packed PNCs on the dried helices and much more loosely organized PNCs on helices in suspension. Simulations based on the coupled dipole method (CDM) demonstrate that the CD comes from the dipolar interaction between PNC assembled into a chiral structure and the CD decreases with the interparticle distance.

Non-invasive force measurement reveals the number of active kinesins on a synaptic vesicle precursor in axonal transport regulated by ARL-8.

Kinesin superfamily protein UNC-104, a member of the kinesin-3 family, transports synaptic vesicle precursors (SVPs). In this study, the number of active UNC-104 molecules hauling a single SVP in axons in the worm Caenorhabditis elegans was counted by applying a newly developed non-invasive force measurement technique. The distribution of the force acting on a SVP transported by UNC-104 was spread out over several clusters, implying the presence of several force-producing units (FPUs). We then compared the number of FPUs in the wild-type worms with that in arl-8 gene-deletion mutant worms. ARL-8 is a SVP-bound arf-like small guanosine triphosphatase, and is known to promote unlocking of the autoinhibition of the motor, which is critical for avoiding unnecessary consumption of adenosine triphosphate when the motor does not bind to a SVP. There were fewer FPUs in the arl-8 mutant worms. This finding indicates that a lack of ARL-8 decreased the number of active UNC-104 motors, which then led to a decrease in the number of motors responsible for SVP transport.

Single-cell E. coli response to an instantaneously applied chemotactic signal.

In response to an attractant or repellant, an Escherichia coli cell controls the rotational direction of its flagellar motor by a chemotaxis system. When an E. coli cell senses an attractant, a reduction in the intracellular concentration of a chemotaxis protein, phosphorylated CheY (CheY-P), induces counterclockwise (CCW) rotation of the flagellar motor, and this cellular response is thought to occur in several hundred milliseconds. Here, to measure the signaling process occurring inside a single E. coli cell, including the recognition of an attractant by a receptor cluster, the inactivation of histidine kinase CheA, and the diffusion of CheY and CheY-P molecules, we applied a serine stimulus by instantaneous photorelease from a caged compound and examined the cellular response at a temporal resolution of several hundred microseconds. We quantified the clockwise (CW) and CCW durations immediately after the photorelease of serine as the response time and the duration of the response, respectively. The results showed that the response time depended on the distance between the receptor and motor, indicating that the decreased CheY-P concentration induced by serine propagates through the cytoplasm from the receptor-kinase cluster toward the motor with a timing that is explained by the diffusion of CheY and CheY-P molecules. The response time included 240 ms for enzymatic reactions in addition to the time required for diffusion of the signaling molecule. The measured response time and duration of the response also revealed that the E. coli cell senses a similar serine concentration regardless of whether the serine concentration is increasing or decreasing. These detailed quantitative findings increase our understanding of the signal transduction process that occurs inside cells during bacterial chemotaxis.

Micrometer-size vesicle formation triggered by UV light.

Vesicle formation is a fundamental kinetic process related to the vesicle budding and endocytosis in a cell. In the vesicle formation by artificial means, transformation of lamellar lipid aggregates into spherical architectures is a key process and known to be prompted by e.g. heat, infrared irradiation, and alternating electric field induction. Here we report UV-light-driven formation of vesicles from particles consisting of crumpled phospholipid multilayer membranes involving a photoactive amphiphilic compound composed of 1,4-bis(4-phenylethynyl)benzene (BPEB) units. The particles can readily be prepared from a mixture of these components, which is casted on the glass surface followed by addition of water under ultrasonic radiation. Interestingly, upon irradiation with UV light, micrometer-size vesicles were generated from the particles. Neither infrared light irradiation nor heating prompted the vesicle formation. Taking advantage of the benefits of light, we successfully demonstrated micrometer-scale spatiotemporal control of single vesicle formation. It is also revealed that the BPEB units in the amphiphile are essential for this phenomenon.

Fractionation of beech wood cell walls into digestible cellulose-rich residues and photoluminescent lignin-rich precipitates via semi-flow hot-compressed water treatment with 2-naphthol.

Utilization of cell wall components of woody biomass has attracted attention as alternatives for fossil fuels towards a sustainable society. A semi-flow hydrothermal treatment was used to fractionate the beech (Fagus crenata) wood into cellulose-rich residues and lignin-rich precipitates. The enzymatic saccharification of the cellulose component in the residue was enhanced significantly because the preferential delignification from the secondary wall increased enzyme accessibility. Meanwhile, the precipitated lignin was soluble in organic solvent and exhibited clear photoluminescence (PL) according to the chromophore distances. Furthermore, the carbocation scavenger, 2-naphthol, was impregnated into the beech wood to inhibit the lignin re-condensation reaction. As a result, the digestibility of the cellulose component in the residue increased because unproductive enzymatic binding of lignin and lignin re-condensation were both suppressed. In addition, the PL intensity of the precipitates was significantly enhanced, indicating that 2-naphthol bound to the lignin molecules influenced the PL properties. Overall, fractionation using a semi-flow hydrothermal treatment efficiently uses both polysaccharides and lignin, especially the impregnation of 2-naphthol provided advantages for both saccharides and lignin. Monosaccharides can be converted into valuable products via a sugar platform, and the lignin precipitates exhibit useful PL properties that give them significant potential as a feedstock for numerous valuable materials, such as fluorescence reagents and spectral conversion agents. The results presented herein provide insights that are crucial for the comprehensive utilization of cell wall components for sustainable biorefinery systems.

Effects of the morphology of nanostructured ZnO and interface modification on the device configuration and charge transport of ZnO/polymer hybrid solar cells.

In an organic-based solar cell, the short exciton diffusion length of organic materials requires effective donor-acceptor heterojunction at the nanoscale. In this work, hybrid inorganic/polymer solar cells based on ZnO nanostructures and poly(3-hexylthiophene) (P3HT) are constructed to study the effects of ZnO morphologies and wettability of the surface on the P3HT infiltration ability and charge transport mechanisms. The P3HT infiltrates the ZnO nanorod (NR) more remarkably than ZnO nanoparticle (NP) substrates. Although surface modification with indoline D205 dye molecules improves the wettability (viz. enlarges the contact angle) of NP surface, the P3HT infiltration distance decreases in comparison with the pristine NP case. This leads to relatively low short-circuit current density (Jsc) of the NP devices in comparison with that of the NR devices, even though the surface area of NP layers is larger than that of NR ones. Moreover, surface modification with squaraine dye onto the NR surface shows more significant improvement in Jsc than the NP case. This is due to the well-aligned morphology of the NRs, which facilitates dye modification, P3HT infiltration, and charge transport processes. These indicate that the NRs are more qualified as electron accepting substrates and transport pathway in hybrid solar cells than NPs.

Solubilization of sulfuric acid lignin by ball mill treatment with excess amounts of organic compounds.

In order to improve the solubility of sulfuric acid lignin (SL) in N,N-dimethylformamide (DMF), dry ball milling with excess amounts of additives such as l-tartaric acid was performed. Although the ball-milled SL without any additives was not soluble in DMF, when the SL was ball milled with an excessive amount of l-tartaric acid (the concentration of SL to be 0.1%), the dispersion and solubility of SL in DMF detected by the dynamic light scattering was greatly improved. Furthermore, the DMF solution showed clear photoluminescence, indicating that the distance between luminophores was modulated due to dispersion on the nanoscale. The structural analysis of the isolated lignin showed a decrease in molecular weight and the introduction of carboxylic acid groups. In other words, the introduction of hydrophilic functional groups into the lignin and simultaneously decrease in the molecular weight due to the cleavage of lignin linkages is considered to result in good dispersion in DMF on both the micro and macro scales. Similar effects were observed with the other chemicals containing several hydrophilic groups such as citric acid, d-glucose, and polyacrylic acid. Furthermore, this method is applicable to various lignins other than SL, and it is expected to utilize unused lignin resources.

Efficient and Stable Carbon-Based Perovskite Solar Cells Enabled by Mixed CuPc:CuSCN Hole Transporting Layer for Indoor Applications.

Perovskite solar cells (PSCs) are an innovative technology with great potential to offer cost-effective and high-performance devices for converting light into electricity that can be used for both outdoor and indoor applications. In this study, a novel hole-transporting layer (HTL) was created by mixing copper phthalocyanine (CuPc) molecules into a copper(I) thiocyanate (CuSCN) film and was applied to carbon-based PSCs with cesium/formamidinium (Cs0.17FA0.83Pb(I0.83Br0.17)3) as a photoabsorber. At the optimum concentration, a high power conversion efficiency (PCE) of 15.01% was achieved under AM1.5G test conditions, and 32.1% PCE was acquired under low-light 1000 lux conditions. It was discovered that the mixed CuPc:CuSCN HTL helps reduce trap density and improve the perovskite/HTL interface as well as the HTL/carbon interface. Moreover, the PSCs based on the mixed CuPc:CuSCN HTL provided better stability over 1 year due to the hydrophobicity of CuPc material. In addition, thermal stability was tested at 85 °C and the devices achieved an average efficiency drop of approximately 50% of the initial PCE value after 1000 h. UV light stability was also examined, and the results revealed that the average efficiency drop of 40% of the initial value for 70 min of exposure was observed. The work presented here represents an important step toward the practical implementation of the PSC as it paves the way for the development of cost-effective, stable, yet high-performance PSCs for both outdoor and indoor applications.

Tunable Light Emission from Lignin: Various Photoluminescence Properties Controlled by the Lignocellulosic Species, Extraction Method, Solvent, and Polymer.

This report describes the tunable light emission from lignin, which was achieved by carefully selecting the lignocellulosic species, extraction method, solvent, and polymer. Lignins comprising various taxonomic species with distinct primary structures exhibited diverse photoluminescence (PL) intensities and spectral patterns. Investigations probing how the solvent affects the PL properties revealed that the PL quenching phenomenon originated from the decreasing distance between aromatic moieties (luminophores). Therefore, polymers can play key roles as media to modulate the distance between luminophores, and the PL intensity can be enhanced by employing a relatively stiff polymer. In terms of the emission color, the PL spectral pattern can be tuned by changing the lignin primary structures or by deprotonating the phenolic hydroxyl groups. By modulating these influencing factors, various light emissions were obtained from lignins in solutions and transparent solid materials.

Bayesian-based decipherment of in-depth information in bacterial chemical sensing beyond pleasant/unpleasant responses.

Chemical sensing is vital to the survival of all organisms. Bacterial chemotaxis is conducted by multiple receptors that sense chemicals to regulate a single signalling system controlling the transition between the direction (clockwise vs. counterclockwise) of flagellar rotation. Such an integrated system seems better suited to judge chemicals as either favourable or unfavourable, but not for identification purposes though differences in their affinities to the receptors may cause difference in response strength. Here, an experimental setup was developed to monitor behaviours of multiple cells stimulated simultaneously as well as a statistical framework based on Bayesian inferences. Although responses of individual cells varied substantially, ensemble averaging of the time courses seemed characteristic to attractant species, indicating we can extract information of input chemical species from responses of the bacterium. Furthermore, two similar, but distinct, beverages elicited attractant responses of cells with profiles distinguishable with the Bayesian procedure. These results provide a basis for novel bio-inspired sensors that could be used with other cell types to sense wider ranges of chemicals.

Coordinated reversal of flagellar motors on a single Escherichia coli cell.

An Escherichia coli cell transduces extracellular stimuli sensed by chemoreceptors to the state of an intracellular signal molecule, which regulates the switching of the rotational direction of the flagellar motors from counterclockwise (CCW) to clockwise (CW) and from CW back to CCW. Here, we performed high-speed imaging of flagellar motor rotation and show that the switching of two different motors on a cell is controlled coordinatedly by an intracellular signal protein, phosphorylated CheY (CheY-P). The switching is highly coordinated with a subsecond delay between motors in clear correlation with the distance of each motor from the chemoreceptor patch localized at a cell pole, which would be explained by the diffusive motion of CheY-P molecules in the cell. The coordinated switching becomes disordered by the expression of a constitutively active CheY mutant that mimics the CW-rotation stimulating function. The coordinated switching requires CheZ, which is the phosphatase for CheY-P. Our results suggest that a transient increase and decrease in the concentration of CheY-P caused by a spontaneous burst of its production by the chemoreceptor patch followed by its dephosphorylation by CheZ, which is probably a wavelike propagation in a subsecond timescale, triggers and regulates the coordinated switching of flagellar motors.

Hyper-mobility of water around actin filaments revealed using pulse-field gradient spin-echo 1H NMR and fluorescence spectroscopy.

This paper reports that water molecules around F-actin, a polymerized form of actin, are more mobile than those around G-actin or in bulk water. A measurement using pulse-field gradient spin-echo (1)H NMR showed that the self-diffusion coefficient of water in aqueous F-actin solution increased with actin concentration by ∼5%, whereas that in G-actin solution was close to that of pure water. This indicates that an F-actin/water interaction is responsible for the high self-diffusion of water. The local viscosity around actin was also investigated by fluorescence measurements of Cy3, a fluorescent dye, conjugated to Cys 374 of actin. The steady-state fluorescence anisotropy of Cy3 attached to F-actin was 0.270, which was lower than that for G-actin, 0.334. Taking into account the fluorescence lifetimes of the Cy3 bound to actin, their rotational correlation times were estimated to be 3.8 and 9.1ns for F- and G-actin, respectively. This indicates that Cy3 bound to F-actin rotates more freely than that bound to G-actin, and therefore the local water viscosity is lower around F-actin than around G-actin.

Noncovalent one-to-one donor-acceptor assembled systems based on porphyrin molecular gels for unusually high electron-transfer efficiency.

A new approach for fabricating donor-acceptor assembled systems is demonstrated, based on J-type ordered aggregation of a low-molecular zinc porphyrin derivative and subsequent integration of a pyridylated fullerene derivative with coordination and orientation onto the porphyrin aggregates. This system achieves unusually high efficiencies in fluorescence quenching during one-to-one mixing of the donor and acceptor. Moreover, the Stern-Volmer constant (K(SV)) and association constant (K) of this system are 2520 and 56 times higher, respectively, than those of the corresponding nonassembled system. The quenching efficiency is thermotropically switchable, since ordered-to-disordered transitions are essential characteristics of noncovalent low molecular assemblies.

Synthesis of SnS nanoparticles by SILAR method for quantum dot-sensitized solar cells.

SnS-sensitized TiO2 electrodes were applied in quantum dot-sensitized solar cells (QDSSCs) which are environmentally more favorable than conventional Cd or Pb-chalcogenide-sensitized electrodes. SnS nanoparticles were well-distributed over the surface of TiO2 nanoparticles by the successive ionic layer adsorption and reaction (SILAR) method. Deposited SnS nanoparticles had diameter about 3 nm. Under AM1.5 irradiation with 100 mW/cm2 light intensity (at 1 sun), the energy conversion efficiency of obtained cells reached a value of 0.21% (0.25 cm2) at SILAR coating cycles of 5. In addition, the photovoltaic performance was improved by additional ZnS coating on the surface of SnS-sensitized TiO2 electrodes.

Wet chemical synthesis and self-assembly of SnS2 nanoparticles on TiO2 for quantum dot-sensitized solar cells.

SnS2 nanoparticles were synthesized through a simple wet chemical process at room temperature. The SnS2 nanoparticles were approximately spherical in shape and had diameter about 3-4 nm. SnS2-sensitized TiO2 electrodes were fabricated by the immersion of chemically modified TiO2 to well-dispersed SnS2 solution for 72 h (i.e., self-assembly method.) SnS2-sensitized TiO2 electrodes were applied in quantum dot-sensitized solar cells (QDSSCs). Under AM1.5 irradiation with 100 mW/cm2 light intensity (at 1 sun), the short-circuit current density (J(sc)), the open-circuit voltage (V(oc)), the fill factor (FF), and the energy conversion efficiency (eta) were 0.47 mA/cm2, 0.29 V, 0.58 and 0.081%, respectively.

Chiral optical scattering from helical and twisted silica nanoribbons.

Helical and twisted silica nanoribbons, deposited in an in-plane direction and with a random orientation, on a quartz substrate showed chiral optical scattering, and the helical nanoribbons had a g-factor of the order of 10-2 below 250 nm. Their signs depend on the handedness of the nanohelices. The effect of the morphology and the orientation of the helices on the chiral optical scattering were investigated with simulations via the boundary element method.

Chirality Induction to CdSe Nanocrystals Self-Organized on Silica Nanohelices: Tuning Chiroptical Properties.

CdSe nanocrystals (NCs) were grafted on chiral silica nanoribbons, and the mechanism of resulting chirality induction was investigated. Because of their chiral organization, these NCs show optically active properties that depend strongly on their grafting densities and sizes of the NCs. The effect of the morphology of the chiral silica templates between helical (cylindrical curvature) vs twisted (saddle like curvature) ribbons was investigated. The g-factor of NCs-silica helical ribbons is larger than that of the NCs-silica twisted ribbons. Finally, rod-like NCs (QR) with different lengths were grafted on the twisted silica ribbons. Interestingly, their grafting direction with respect to the helix surface changed from side-grafting for short QR to tip-grafting for long rods and the corresponding CD spectra switched signs.

The effect of water on colloidal quantum dot solar cells.

Almost all surfaces sensitive to the ambient environment are covered by water, whereas the impacts of water on surface-dominated colloidal quantum dot (CQD) semiconductor electronics have rarely been explored. Here, strongly hydrogen-bonded water on hydroxylated lead sulfide (PbS) CQD is identified. The water could pilot the thermally induced evolution of surface chemical environment, which significantly influences the nanostructures, carrier dynamics, and trap behaviors in CQD solar cells. The aggravation of surface hydroxylation and water adsorption triggers epitaxial CQD fusion during device fabrication under humid ambient, giving rise to the inter-band traps and deficiency in solar cells. To address this problem, meniscus-guided-coating technique is introduced to achieve dense-packed CQD solids and extrude ambient water, improving device performance and thermal stability. Our works not only elucidate the water involved PbS CQD surface chemistry, but may also achieve a comprehensive understanding of the impact of ambient water on CQD based electronics.

Versatile chiroptics of peptide-induced assemblies of metalloporphyrins.

Zinc porphyrin functionalized with double long-chain alkylated L-glutamide (GTPP-Zn) was synthesized for the first time, and its self-assembling behaviour was investigated in nonpolar organic solvents. The uniqueness of this functionalized porphyrin is characterized by its drastic colour change from dark green to purple via the formation of chirally stacked structures through selective axial coordination on zinc with pyridine derivatives. In this paper, we report the versatility of the GTPP-Zn assembly process as a stimuli-responsive chiroptical switching system and describe the remarkable ligand-specific induction of secondary chirality accompanied by aggregation morphological change.