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Existing methods for generating circularly polarized (CP) light from an unpolarized light source without using external electrical energy have drawbacks, such as a trade-off relationship between CP light intensity and purity. Here, we demonstrate an approach for the generation of high-purity, high-intensity CP light based on a luminescence-based CP convertor composed of a linearly polarized luminescence (LPL) film and a quarter-wave plate. The LPL films, fabricated by one-dimensional alignment of semiconductor quantum rods and laminated with a quarter-wave plate, enabled effective conversion of LPL to high-purity CP light and retained the photoluminescent spectral pattern, light intensity, and the large degree of polarization. The sign of CP light was easily switched by changing the orientation of the quarter-wave plate and the LPL polarization plane. Furthermore, we also demonstrate the first example of parallel-type and multi-layered luminescence-based CP light convertors for multiplexing optical information. Our findings will aid the design of next-generation CP light-generating materials., 発光式円偏光コンバータの開発に成功 --円偏光純度と明るさを両立させる新たな円偏光生成技術として期待--. 京都大学プレスリリース. 2023-01-24.

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.

A co-assembling system composed of a nonchiral metal-free dye and chiral-molecular-assembly template can be a promising candidate for circularly-polarized luminescent materials with both a high luminescence dissymmetry factor and strong emission.

We hypothesize that there is a risk of ipsilateral breast tumor recurrence (IBTR) in surgical margin-free invasive ductal carcinoma (IDC) in the presence of ductal carcinoma in situ (DCIS) component affecting surgical margins in early stage. From 1990 to 2014, 343 patients with IDC in which the DCIS component constitute have received radiotherapy (RT) following breast-conserving surgery (BCS). All patients received whole breast irradiation with a prescribed dose of 50 Gy in 20 fractions (four times a week). This one-arm cohort with boost RT (253 patients) was compared for IBTR with a non-cohort group receiving no boost RT because of freedom from positive margins (90 patients). Median observation months were 98 (boost group) vs 119 (no boost group), respectively. The 15-year local recurrence-free survival (LRFS) rates were 98.5% and 85.6% in the boost and no boost groups, respectively (Cox proportional hazards model univariate analysis; p = 0.013, HR 0.13). Similarly, for other background factors, there was a significant difference in the LRFS between age groups. The 15-year LRFS rate was 91.8% in patients aged 45 years or younger and 94.6% in patients older than 46 years (p = 0.031, HR 0.21), respectively. Only these two factors were independently significant in Cox proportional hazards model multivariate analysis. IBTR risk in margin-free IDC with DCIS component was independently decreased by boost RT in the cohort setting. Tumor size, extensive intraductal component (EIC), boost dose, the presence of lymph node (LN) metastasis and hormonal therapy were not IBTR risk factors in this study.

Hybrid nanometric helical structures formed by the molecular assemblies of dicationic gemini surfactants with tartrate counterions covered with helical silica walls interact differently with matching or mismatching enantiomers of the tartrate. The difference of the interaction is based on the cooperativity between the chiral crystalline gemini surfactant molecular organization/conformation and the rigid chiral nanospace formed by the helical silica wall.

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.

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.

International audience; 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.

International audience; Hybrid silica-organic nanohelices are used to organize a large variety of nonchiral small organic molecules or inorganic anions to nanometer-sized assemblies. Such chiral organization of achiral molecules induces chiroptical properties as detected by vibrational or electronic circular dichroism (CD), as well as from circularly polarized luminescence (CPL).

Converting non-polarized visible light (natural light) into circular polarized (CP) light is currently an important issue because of the attractive properties of CP light such as acceleration of photosynthesis and enhancement of conversion efficiency of photovoltaics[1,2]. Until now, various methods for creating CP visible light, such as filtration by circular polarizer, selective reflection by chiral liquid crystal structures, and circular polarized luminescence (CPL) from chiral luminophores[3], have been reported. However, creation of highly-pure CP visible light with high light intensity is still considered as challenging issue. In this presentation, we propose an approach for creating highly-pure CP visible light with high light intensity by converting linearly polarized luminescence (LPL) using quarter-wave plate. In this work, we put spotlight on colloidal semiconductor quantum rods (QRs) because of its unique advantages described as follows: (1) Absorption coefficient and emission quantum yield are relatively high. (2) Sharp emission peaks are expected. (3) Variety of QRs with different emission colors can be excited by irradiation of single-wavelength light. We selected CdSe/CdS core/shell QRs as LPL generating 1D nanostructure. CdSe/CdS core/shell QRs were synthesized by hot-injection method. As shown in Figure 1a, the obtained suspension showed orange-colored strong emission under UV light irradiation. TEM image of the dried sample of the QRs toluene suspension indicates that the average length, average width of the obtained rod-like nanostructures were about 30 nm and 4.5 nm, respectively. After QRs/toluene suspension was mixed with poly(ethylene-co-vinyl acetate) (EVA)/toluene solution, the mixture was casted on glass slide and dried it under air. Then, the prepared composite polymer film was stretched in one direction and was attached on glass slide. When the luminescence from the QRs/EVA stretched film was observed under the linear polarizer placed in parallel direction to the stretching direction, the observed light was brighter than that of perpendicular direction (Figure 1c). By measuring the photoluminescence of parallel (I//) and perpendicular (I⊥) components under depolarized excitation at 450 nm, the QRs/EVA stretched film showed clear LPL property with constant ratio (CR) = 5.4, defined as CR = I// / I⊥ (Figure 1b). Furthermore, when the QRs/EVA stretched film was combined with a quarter-wave plate placed at 45° to the stretching direction and was observed through the right-handed (RH) or left-handed (LH) circular polarizer, brighter light was observed through LH circular polarizer (Figure 1d). By quantitative evaluation of RH- and LH-CP light components, total emission includes 82% of LH-CP light and 18% of RH-CP light (Figure 1e). These results indicate that the combination of the QRs/EVA stretched film and quarter-wave plate generate highly-pure CP light which can be distinguished by the naked eye (Figure 2d). Interestingly, the handedness of CP light can be switched by simply changing the angle between fast axis of the quarter-wave plate and stretching direction of LPL films (Figure 1f). In this presentation, we will also discuss about multiplexing of optical information by using CP light conversion. [1] W. Qin et. al., J. Phys. Chem., 2018, 122, 12566-12571. [2] B. Hu et. al., ACS Photonics, 2017, 4, 2821-2827. [3] P. Duan, M. Liu et. al., Adv. Mater. 2020, 32, 1900110. Figure 1

We demonstrate that lanthanide ions doped in nanometrical silica helices with a chirally arranged siloxane network without any organic mediates show induced chiroptical properties such as circular dichroism and circularly polarized luminescence.

International audience; Very slow kinetic evolution (days) of chiral nanoribbons based on amphiphilic molecular assemblies is investigated for various enantiomeric excess. In the early stage of ribbon formation, those formed for low enantiomeric excess (0

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 CsPbBr

We report that platinum-assisted chemical etching formed self-organized helical pores in silicon substrates can be utilized as platforms for the electrochemical production of nanohelices of conducting polymers (polypyrrole) and metals (gold). Surprisingly, the nanohelices thus created are tubes although the polymerization and deposition were carried out by anodic and cathodic reactions, respectively. Based on our results, we propose a common mechanism for the formation of tubular nanohelices by both anodic polymerization and cathodic deposition through the accumulation of reactants in microporous silicon which covers the wall surface of the helical pores. Keywords: Helical pore, Nanohelices, Conducting polymers, Metals, Tubes

International audience; The assembling behaviors of non-chiral dicationic amphiphilic molecules (gemini) in the presence of the mixture of chiral anionic nucleotides and non-chiral anions are investigated. We demonstrate that subtle balance of various physico-chemical parameters and the competition between chiral and non-chiral anions at the interface of gemini assemblies influences the expression of molecular chirality at the micrometer scale through the hierarchical molecular assembly.

Cyanine dye or porphyrin are part of an important family of fluorophores, which have been widely used for photosensitization and optical recording materials. We compared herein the aggregation behaviors of two types of cationic dyes of cyanine or porphyrin in the presence of hyaluronic acid, which contains D-glucuronic acid as anionic helical polysaccharide. UV–Vis absorption and photoluminescence spectra of those aqueous solutions revealed that fluorescent dyes of cyanine form H- and J-aggregates in the presence of hyaluronic acid. In particular, photoluminescent quenching through the H- and J-aggregates was observed in the mixture of anionic hyaluronic acid and the cationic cyanine dyes. On the contrary, increment of the intensities of the emission was confirmed in the mixture of porphyrin-hyaluronic acid through the effective interaction between the cationic porphyrin and anionic hyaluronic acid, which was confirmed by remarkable split-Cotton effects of induced circular dichroism in the visible region, though the UV-Vis spectra of porphyrin with hyaluronic acid did not show any sign of aggregation of porphyrin itself. Further addition of hyaluronic acid resulted in the decrease of the extent of the induced circular dichroism, though photoluminescent intensity was kept without quenching. It was also confirmed that the light scattering could be detected only when the remarkable split-Cotton effects were observed. Therefore, cationic porphyrin and anionic hyaluronic acid form complex and the complex might assemble to show the light scattering, though the single molecule of porphyrin was surrounded by polysaccharides and isolated without dye-aggregation.

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 p...

International audience; We demonstrate the direct induction of chirally arranged organic dye-linked polysilsesquioxane through a sol–gel transcription using a chiral supramolecular template. The chiral arrangement was confirmed by using electronic and vibrational circular dichroism and circularly polarized luminescence spectroscopies.

We have newly developed a next-generation portable pulse wave analysis platform that can measure both radial augmentation index (rAI) and aortic PWV (aoPWV) with a smartphone/tablet to prevent future disease.

Nanometric chiral objects such as twisted or helical nanoribbons represent a new class of objects having important potential in a large panel of applications, taking advantage, for example, of electromechanical or optical chirality, local chiral environment for catalysis, and chiral recognition. Supramolecular chemistry has played a central role in the production of such structures through either chiral macromolecules/foldamers or the self-assembly of chiral molecules; the latter can also be used as templates for the sol-gel transcription to silica materials, offering them polymorphisms with further structural stability. Here, we report a totally different and dynamic approach to produce helical mesostructures. This study focuses on helical nanopores that are spontaneously formed in the platinum-assisted chemical etching of silicon by dynamic self-organization under a nonequilibrium state. The symmetry breaking of a helical nanopore formation is achieved by the spatial symmetry breaking of a spatiotemporal pattern at the nanoscale and without incorporation of chiral molecules. Rotational motion of the platinum nanocatalyst, which is regarded as a spatiotemporal pattern at the etching frontier (the platinum/silicon interface), induces precession movement of the nanocatalyst, and movement of the catalyst during etching forms helical nanopores in the silicon. We consider that this study is an important milestone to understand the close relation between spatiotemporal pattern formation and the dynamic emergence of symmetry breaking in chemical reactions.

Synthesis of chiral inorganic or hybrid nanomaterials through sol–gel transcription of chiral organic templates has attracted a great deal of interest for more than a decade. However, the chiral nature of these inorganic matrices has never been directly observed. For the first time, we report a direct evaluation of chirality on noncrystalline silica chiral nanoribbons by vibrational circular dichroism (VCD) measurements. Strong Cotton effect around 1150–1000 cm–1 from Si—O—Si asymmetric stretching vibration was observed. Surprisingly, calcination of these hybrid nanoribbons doubled the intensity of Cotton effects. On the basis of transmission electron microscopy observations, IR, VCD, NMR, and Raman spectroscopies, we demonstrate that the silica chirality originates from twisted siloxane network composed of chiral arrangement of the Si—O—Si bonds. Our findings clearly prove the presence of chiral organization of amorphous silica network, making them very promising chiral platforms for chiral recognition, ...

Hybrid nanohelices were obtained from silicification of self-assemblies of gemini surfactants with tartrate counterions. The chiral arrangement of these non-chiral gemini surfactants was preserved in the silica matrix even after the counterion exchange for a non-chiral bromide, and was capable of inducing the chiral organisation of a non-chiral dye, methyl orange.

International audience; Amyloid fibrils generally display chirality, a feature which has rarely been exploited in the development of therapeutics against amyloid diseases. This study reports, for the first time, the use of mesoscopic chiral silica nanoribbons against the in vivo amyloidogenesis of human islet amyloid polypeptide (IAPP), the peptide whose aggregation is implicated in type 2 diabetes. The thioflavin T assay and transmission electron microscopy show accelerated IAPP fibrillization through elimination of the nucleation phase and shortening of the elongation phase by the nanostructures. Coarse-grained simulations offer complementary molecular insights into the acceleration of amyloid aggregation through their nonspecific binding and directional seeding with the nanostructures. This accelerated IAPP fibrillization translates to reduced toxicity, especially for the right-handed silica nanoribbons, as revealed by cell viability, helium ion microscopy, as well as zebrafish embryo survival, developmental, and behavioral assays. This study has implicated the potential of employing chiral nanotechnologies against the mesoscopic enantioselectivity of amyloid proteins and their associated diseases.

We demonstrate the first example of induced CD of monoatomic anions. This was detected using chirally-arranged molecular assemblies of non-chiral cationic gemini surfactants (16-2-16) with monoatomic anions stabilized with silica-coating. Furthermore, we have also achieved multi-step transfer of a chiral environment through an in situ chemical reaction via chiralized monoatomic anions.

Fabrication of nanostructure in various typed solar cell is of great importance in terms of the improvement of charge carrier collection and junction area. Here, we report that well-aligned nanopillar arrays are spontaneously developed in the process of the spin coating when a polymer is added to specific porphyrin–fullerene complexes. The nanopillars embedded in the polymers are composed of donor–acceptor assembled systems, based on J-type aggregation of a low-molecular zinc porphyrin derivative and subsequent integration of pyridylated fullerene derivative with coordination and orientation. The diameter and the height of the nanopillars can be controlled by the side chain-length and the concentration of the polymer as well as drying time after the spin coating. Structural, optical, and electrical properties of the nanopillar are also investigated. Finally, improved power conversion efficiency in the porphyrin–fullerene nanopillar is experimentally observed compared to that of the planar thin film prepared under similar conditions.

Normally-off computing (Noff computing) using a multicontext field programmable gate array (MC-FPGA) consisting of crystalline oxide semiconductor FETs has been developed. The Noff computing discussed in this paper is a control architecture for an MC-FPGA capable of performing fine-grained power gating on each programmable logic element (PLE) whose registers include a volatile register and also a nonvolatile shadow register for storing and loading data in the volatile register. The MC-FPGA performs fine-grained control of power supplied only to PLEs contributing to effective calculation, when context switching happens. With an MC-FPGA fabricated with a hybrid process of a 1.0 µm crystalline oxide semiconductor FET on a 0.5 µm CMOS FET, it has been confirmed that the proposed Noff computing can resume the previous task when a context switches back to it, increases PLE use efficiency, and reduces the power consumption by 27.7% at operating frequencies of 20 MHz with a driving voltage of 2.5 V.

A boosting pass gate (BPG) suitable for a programmable routing switch including a $c$ -axis aligned crystal In-Ga-Zn-O (CAAC-IGZO) field effect transistor (FET) is proposed. The CAAC-IGZO is one of crystalline oxide semiconductors (OS). The proposed BPG (OS-based BPG, OS BPG) has a combination of a pass gate (PG) and a configuration memory (CM) cell utilizing a CAAC-IGZO FET with extremely low OFF-state current and a storage capacitor. This OS BPG achieves a routing switch with fewer transistors than a conventional routing switch having a combination of a PG and an static RAM (SRAM) cell. Owing to the boosting effect, the switching characteristics, at not only positive transition but also negative transition of input signals, of the OS BPG are improved without using overdriving. In circuits fabricated with a hybrid process of a CMOSFET and a CAAC-IGZO FET with gate lengths of 0.5 and 1.0 $\mu $ m, the net delays of the OS BPG, 75 and 58 ns, at driving voltages of 2.0 and 2.5 V have been found to be less than those of the conventional routing switch (SRAM-based PG, SRAM PG) by about 79% and 62%, respectively. It has also been confirmed that a field-programmable gate array (FPGA) chip utilizing the OS BPG as a routing switch reduces the layout areas of routing switches and the whole chip by 61% and 22%, respectively, and increases the maximum operating frequencies at driving voltage of 2.0 and 2.5 V by about 2.8 times and 1.6 times of those of the FPGA chip utilizing the SRAM PG as a routing switch.

This paper proposes a new approach for generating strong circularly polarized luminescence (CPL), based on the complexation of non-chiral, non-functionalized fluorophores with chirally-assembled na...

We demonstrate that the fluorescence emission that originated from a cyanine dye forming H-aggregates with a narrow absorption band and a remarkably large Stokes shift can be induced by symmetry breaking. The H-aggregate formation was successfully induced using chirally assembled cationic gemini surfactants with enantiomeric tartrate counterions as templates in water.

The concept of metamaterials emerged in years 2000 with the achievement of artificial structures enabling non conventional propagation of electromagnetic waves, such as negative phase velocity of negative refraction. The electromagnetic response of metamaterials is generally based on the presence of optically-resonant elements (or meta-atoms) of sub-wavelength size and well designed morphology so as to provide the desired electric and magnetic optical properties. Top-down technologies based on lithography techniques have been intensively used to fabricate a variety of efficient electric and magnetic resonators operating from microwave to visible light frequencies. However, the technological limits of the top-down approach are reached in visible light where a huge number of nanometre sized elements is required. We show here that the bottom-up fabrication route based on the combination of nanochemistry and of the self-assembly methods of colloidal physics provide an excellent alternative for the large scale synthesis of complex meta-atoms, as well as for the fabrication of 2D and 3D samples exhibiting meta-properties in visible light., Comment: 8 pages, 7 figures

Using data retention circuits that include crystalline oxide semiconductor transistors as backup circuits for power gating, a processor system can reduce standby leakage current significantly. This is effective in the Internet of Things (IoT) applications that require standby power reduction. The crystalline oxide semiconductor transistor can constitute a nonvolatile data retention circuit easily because it exhibits significantly lower off-state current than a silicon transistor and is highly compatible with a CMOS logic circuit. The backup circuit can achieve 2-clock-cycle data backup and 4-clock-cycle data restore; thus, the processor system can efficiently perform temporally fine-grained power gating and can achieve longer standby times. Furthermore, area overheads due to the backup circuits are kept very small because the crystalline oxide semiconductor transistors are stacked on silicon transistors.