Spatially Correlated Chirality in Chiral Two-Dimensional Perovskites Revealed by Second-Harmonic-Generation Circular Dichroism Microscopy.

Understanding the chiral mechanism of chiral hybrid perovskites is a prerequisite for developing relevant chiroptoelectronic applications. Although conventional circular dichroism (CD) spectroscopy can be used to characterize chirality in chiral perovskites, it has a low signal-to-noise ratio and can provide only information about macroscopic chirality. Herein, with the aim of revealing the microscopic chiral mechanism in chiral perovskites, we utilize a spacer cation alloying strategy to construct chiral two-dimensional perovskites. For the first time, we demonstrate second-harmonic-generation CD microarea imaging in chiral perovskite thin films to unveil their spatially correlated chirality. In combination with theoretical calculations, it is revealed that the spatially correlated chirality is caused by localized out-of-plane supramolecular orientations. This work will not only advance the understanding of the mechanism of chiroptical activity in chiral perovskites but also provide inspiration for the rational design and synthesis of perovskites for chirality-related nonlinear optoelectronic devices.

Nonlinear optical properties in chiral copper oxide nanosheets.

Chiral transition metal oxides (TMOs) are in the forefront of research as potential active materials in various optoelectronic applications. However, the nonlinear optical (NLO) properties of the chiral TMOs have not been fully understood. Here, several kinds of copper oxide nanosheets capped with different chiral amino acids are synthesized. Notably, we investigate the NLO activities of these materials, including broadband second harmonic generation and transformation of nonlinear optical properties from saturable absorption to reverse saturable absorption. This work will broaden the use of chiral TMO materials in nonlinear photonic devices.

Regulating Optical Activity and Anisotropic Second-Harmonic Generation in Zero-Dimensional Hybrid Copper Halides.

Structural engineering permits the introduction of chirality into organic-inorganic hybrid metal halides (HMHs), which creates a promising and exclusive material for applications in various optoelectronics. However, the optical activity regulation of chiral HMHs remains largely unexplored. In this work, we have synthesized two pairs of lead-free chiral HMHs with a zero-dimensional tetrahedral arrangement, i.e., (R- and S-1-(1-naphthyl)ethylammonium)2CuCl4 and (R- and S-1-(2-naphthyl)ethylammonium)2CuCl4. The magnitude of optical activity in these HMHs can be efficiently modulated as a result of the different magnetic transition dipole moments. Furthermore, these HMHs exhibited effective second-harmonic generation (SHG) and distinct SHG-circular dichroism (CD), with (R-1-(1-naphthyl)ethylammonium)2CuCl4 having an anisotropy factor (gSHG-CD) of up to 0.41. This work not only provides insights into regulating the optical activity and anisotropic SHG effect of lead-free chiral HMHs but also confirms the feasibility of SHG-CD spectroscopy as a promising tool for characterizing the intrinsic optical activity of chiral materials.

Chiral Hybrid Germanium(II) Halide with Strong Nonlinear Chiroptical Properties.

Due to the pronounced anisotropic response to circularly polarized light, chiral hybrid organic-inorganic metal halides have been regarded as promising candidates for the application in nonlinear chiroptics, especially for the second-harmonic generation circular dichroism (SHG-CD) effect. However, designing novel lead-free chiral hybrid metal halides with large anisotropy factors and high laser-induced damage thresholds (LDT) of SHG-CD remains challenging. Herein, we develop the first chiral hybrid germanium halide, (R/S-NEA)3 Ge2 I7 ⋅H2 O (R/S-NGI), and systematically investigated its linear and nonlinear chiroptical properties. S-NGI and R-NGI exhibit large anisotropy factors (gSHG-CD ) of 0.45 and 0.48, respectively, along with a high LDT of 38.46 GW/cm2 ; these anisotropy factors were the highest values among the reported lead-free chiral hybrid metal halides. Moreover, the effective second-order nonlinear optical coefficient of S-NGI could reach up to 0.86 pm/V, which was 2.9 times higher than that of commercial Y-cut quartz. Our findings facilitate a new avenue toward lead-free chiral hybrid metal halides, and their implementation in nonlinear chiroptical applications.

Chiroptical Transitions of Enantiomeric Ligand-Activated Nickel Oxides.

Ligand-induced chirality in transition-metal oxide (TMO) nanostructures have great potential for designing materials with tunable chiroptical effects. Herein, a facile strategy is reported to prepare chiroptical active nickel-oxide hybrids combined with pH adjustment, and the redox treatment results in ligand transformation, which is attributable to multiple optical transitions in the TMO nanostructures. The theoretical calculation also explains the chiral origins based on their complex models based on empirical analysis. It is also shown that enantiomeric TMO nanoparticles can be used as chiral inducers for chiroptical sensitive polymerization. These results demonstrate that TMO nanostructures can provide rational control over photochemical synthesis and chiral transfer of inorganics nanoarchitecture chirality.

Strong two-photon absorption induced by energy funneling in chiral quasi-2D perovskites.

Quasi-2D Ruddlesden-Popper-type perovskites (RPPs) exhibit excellent nonlinear optical properties due to their multiple quantum well structures with large exciton binding energy. Herein, we introduce chiral organic molecules into RPPs and investigate their optical properties. It is found that the chiral RPPs possess effective circular dichroism in the ultraviolet to visible wavelengths. Two-photon absorption (TPA)-induced efficient energy funneling from small- to large-n domains is observed in the chiral RPP films, which induces strong TPA with a coefficient up to 4.98 cm MW-1. This work will broaden the application of quasi-2D RPPs in chirality-related nonlinear photonic devices.

Enhanced Performance of Two-Photon Excited Amplified Spontaneous Emission by Cd-Alloyed CsPbBr3 Nanocrystals.

It has been demonstrated that the alloyed perovskite nanocrystals (NCs) with a small amount of Cd element may passivate the inherent halide vacancies in perovskite NCs and improve their stability. However, the study of the optical properties of such alloyed perovskite NCs still remains essentially untouched, which will seriously hinder relevant applications. Herein, using different amounts of CdBr2 as an alloyed metal precursor, a series of CsPbxCd1-xBr3 NCs (x = 1, 0.93, and 0.88) were synthesized. Compared with bare CsPbBr3 NCs, the Cd-alloyed NCs exhibited a near-unity photoluminescence quantum yield (99%), efficiently improved stability, and enhanced electron-phonon coupling strength. As the Cd-alloyed amount was increased, their hot-carrier cooling time became faster and the exciton-biexciton interaction decreased, causing a decreased threshold of two-photon excited amplified spontaneous emission (ASE) from 1.58 to 1.23 mJ cm-2. In addition, the Cd-alloying method can also improve the photostability of ASE, resulting in the initial ASE intensity remaining at 90% even after 7.5 × 105 pulse shots. This work implies that the Cd-alloyed CsPbBr3 NCs will be promising for application in a laser gain medium.

All-optical high spatial-temporal resolution photography with raster principle at 2 trillion frames per second.

A novel single-shot ultrafast all-optical photography with raster principle (OPR) that can capture real-time imaging of ultrafast phenomena is proposed and demonstrated. It consists of a sequentially timed module (STM), spectral-shaping module (SSM), and raster framing camera (RFC). STM and SSM are used for linearly encoding frequency-time mapping and system calibration, respectively. The function of the RFC is sampling the target by microlens arrays and framing on the basis of frequency-time-spatial positions conversion. We demonstrated the recording of transient scenes with the spatial resolution of ∼90lp/mm, the frame number of 12 and the frame rate of 2 trillion frames per second (Tfps) in single-shot. Thanks to its high spatial-temporal resolution, high frame rate (maximum up to 10 Tfps or more) and sufficient frame number, our OPR can observe the dynamic processes with complex spatial structure at the atomic time scale (10 fs∼1ps), which is promising for application in plasma physics, shock waves in laser-induced damage, and dynamics of condensed matter materials.

Giant Optical Activity and Second Harmonic Generation in 2D Hybrid Copper Halides.

Hybrid organic-inorganic metal halides have emerged as highly promising materials for a wide range of applications in optoelectronics. Incorporating chiral organic molecules into metal halides enables the extension of their unique optical and electronic properties to chiral optics. By using chiral (R)- or (S)-methylbenzylamine (R-/S-MBA) as the organic component, we synthesized chiral hybrid copper halides, (R-/S-MBA)2 CuCl4 , and investigated their optical activity. Thin films of this material showed a record anisotropic g-factor as high as approximately 0.06. We discuss the origin of the giant optical activity observed in (R-/S-MBA)2 CuCl4 by theoretical modeling based on density functional theory (DFT) and demonstrate highly efficient second harmonic generation (SHG) in these samples. Our study provides insight into the design of chiral materials by structural engineering, creating a new platform for chiral and nonlinear photonic device applications of the chiral hybrid copper halides.

Ultrathin Single-Crystalline 2D Perovskite Photoconductor for High-Performance Narrowband and Wide Linear Dynamic Range Photodetection.

For next-generation Internet-of-Everything applications, for example, artificial-neural-network image sensors, artificial retina, visible light communication, on-chip light interconnection, and flexible devices, etc., high-performance microscale photodetectors are in urgent demands. 2D material (2DM) photodetectors have been researched and demonstrated impressive performances. However, they have not met the demands in filterless narrowband photoresponse, wide linear dynamic range (LDR), ultralow dark current, and large on/off ratio, which are key performances for these applications. 2D Ruddlesden-Popper perovskites (2D-RPPs) are recently highlighted photovoltaic and optoelectronic materials. Embedding ultrathin 2D-RPPs into 2DM photodetectors holds potentials to improve these performances. Herein, a single-crystalline ultrathin (PEA)2 PbI4 is integrated into a vertical-stacked graphene-(PEA)2 PbI4 -graphene micro photoconductor (V-PEPI-PC). V-PEPI-PC exhibits narrowband photoresponses at 517 nm with a full-width-at-half-maximum of 15 nm and a wide LDR of 122 dB. Due to the multiple quantum wells in (PEA)2 PbI4 , V-PEPI-PC demonstrates an ultralow dark current of 1.1 × 10-14 A (44 pA mm-2 ), a high specific detectivity of 1.2 × 1013 Jones, and a high on/off ratio of 1.6 × 106 . Owing to the short vertical channel, V-PEPI-PC shows a fast response rise time of 486 µs. Therefore, the vertical-stacked photodetectors based on hybrid 2D-RPPs and 2DMs may have great potentials in future optoelectronics.

Comparison studies of excitonic properties and multiphoton absorption of near-infrared-I-emitting Cu-doped InP and InP/ZnSe nanocrystals.

Cu-doped InP (Cu:InP) and InP/ZnSe nanocrystals (NCs) with near-infrared-I (NIR-I) emission were prepared and characterized. Femtosecond transient absorption spectra revealed that the epitaxial growth of a ZnSe diffusion barrier onto the Cu:InP core can amplify its exciton-dopant coupling strength, with the energy transfer times of $\sim{220}\;{\rm ps}$∼220ps for Cu:InP NCs and $\sim{183}\;{\rm ps}$∼183ps for Cu:InP/ZnSe NCs. Importantly, the Cu:InP/ZnSe NCs exhibit much larger two- and three-photon absorption cross sections, reaching $\sim{10162}$∼10162 GM at 1030 nm and $\sim{1.06} \times {{10}^{ - 77}}\;{{\rm cm}^6}\,{{\rm s}^2}\,{{\rm photon}^{ - 2}}$∼1.06×10-77cm6s2photon-2 at 1600 nm, compared with Cu:InP NCs.

Few-layer metal monochalcogenide saturable absorbers for high-energy Q-switched pulse generation.

Two-dimensional layered materials have been widely utilized as nonlinear absorption materials to transfer continue-wave into pulse trains in fiber laser systems. Here, we prepare robust GaSe/GeSe composites with high power bearing capacity as saturable absorbers (SAs) and then investigate their nonlinear optical properties via broadband Z-scan measurement at 800 nm and 1550 nm, respectively. The modulation depths of GaSe/GeSe based SAs are measured to be 11.97% and 7.69% at 1550 nm. After incorporating the GaSe/GeSe SAs into an Erbium-doped fiber laser cavity, passively Q-switched pulse trains could be obtained with repetition rates changing from 83.58 to 136.78 kHz (70.41 to 161.65 kHz). The maximum output power and pulse energy are 52.1 mW/370.67 nJ (GaSe) and 21.6 mW/133.74 nJ (GeSe) under the maximum pump power of 600 mW. The results indicate that GaSe and GeSe possess outstanding thermal stability and could be employed as remarkable saturable absorption materials for high-energy pulses generation.

A new method with an explant culture of the utricle for assessing the influence of exposure to low-frequency noise on the vestibule.

Health risks attributed to low-frequency noise (LFN) exposure are a serious global issue. Therefore, the development of a method for a prevention based upon risk assessments for LFN is important. Previously in vivo exposure of mice to LFN at 100 Hz, 95 dB for 1 hr produced imbalance with breakage of the otoconial membrane, which covers hair cells as well as impaired activity of hair cells in the vestibule. However, methods for inhibition of LFN-mediated imbalance have not been developed. At present, there are no apparent techniques available with in vitro or ex vivo assessments to evaluate LFN-mediated imbalance by direct administration of preventive chemicals into the vestibule. Our findings demonstrated the usefulness of an explant culture of the utricle with a fluorescent styryl dye, FM1-43FX. In addition, examination of the morphology of the otoconial membrane with explant cultures of utricles was conducted to determine the risk of LFN. Ex vivo exposure of the utricle to LFN at 100 Hz, 95 dB for 1 hr induced breaks in the otoconial membrane as well as decreased uptake of FM1-43FX in hair cells. Taken together, the results of this study provide a novel technique for assessing the risk of LFN exposure using an ex vivo experiment.

Multidisciplinary approach to assess the toxicities of arsenic and barium in drinking water.

Well water could be a stable source of drinking water. Recently, the use of well water as drinking water has been encouraged in developing countries. However, many kinds of disorders caused by toxic elements in well drinking water have been reported. It is our urgent task to resolve the global issue of element-originating diseases. In this review article, our multidisciplinary approaches focusing on oncogenic toxicities and disturbances of sensory organs (skin and ear) induced by arsenic and barium are introduced. First, our environmental monitoring in developing countries in Asia showed elevated concentrations of arsenic and barium in well drinking water. Then our experimental studies in mice and our epidemiological studies in humans showed arsenic-mediated increased risks of hyperpigmented skin and hearing loss with partial elucidation of their mechanisms. Our experimental studies using cultured cells with focus on the expression and activity levels of intracellular signal transduction molecules such as c-SRC, c-RET, and oncogenic RET showed risks for malignant transformation and/or progression arose from arsenic and barium. Finally, our original hydrotalcite-like compound was proposed as a novel remediation system to effectively remove arsenic and barium from well drinking water. Hopefully, comprehensive studies consisting of (1) environmental monitoring, (2) health risk assessments, and (3) remediation will be expanded in the field of environmental health to prevent various disorders caused by environmental factors including toxic elements in drinking water.

Giant two- to five-photon absorption in CsPbBr2.7I0.3 two-dimensional nanoplatelets.

CsPbBr2.7I0.3 two-dimensional (2D) nanoplatelets (NPs) with emission wavelengths of 469 nm and 527 nm were synthesized and characterized. Femtosecond transient absorption spectra revealed hot carrier cooling times of ∼368 fs and ∼438 fs for 469 nm and 527 nm 2D NPs, respectively. Importantly, the 2D NPs exhibit giant two-, three-, four-, and five-photon absorption cross-sections, reaching ∼4.1×106 GM at 830 nm, ∼2.3×10-74 cm6 s2 photon-2 at 1300 nm, 2.06×10-104 cm8 s3 photon-3 at 1600 nm, and 1.50×10-136 cm10 s4 photon-4 at 2200 nm, respectively, which are 3-8 orders of magnitude larger, compared to specially designed organic molecules.

Strong multiphoton absorption in chiral CdSe/CdS dot/rod nanocrystal-doped poly(vinyl alcohol) films.

Cysteine-capped cadmium selenide/cadmium sulfide (CdSe/CdS) dot/rod nanocrystals (NCs) were synthesized and then doped in poly(vinyl alcohol) (PVA) films. Compared with an L-/D-cysteine-capped NC solution (10-4), the anisotropic factors of the circular dichroism and circular polarized luminescence in the doped PVA films increased by one order of magnitude, probably because of the enhanced anisotropy degree, crystal orientations, and ordered morphologies. The two- and three-photon absorption coefficients of the doped PVA films were determined as 0.58 cm/GW at 800 nm and 2.3×10-4 cm3/GW2 at 1300 nm, respectively. The chiral NC-doped PVA films are promising for applications in chirality-related nonlinear photonic devices.

Sex-dependent difference in the association between frequency of spicy food consumption and risk of hypertension in Chinese adults.

PURPOSE: The aim of our study was to explore the association between frequency of spicy food consumption and risk of hypertension in Chinese adults. METHODS: Data were extracted from the 2009 wave of the China Health and Nutrition Survey, consisting of 9273 apparently healthy adults. Height, weight, and blood pressure (BP) were measured and diet was assessed with three consecutive 24-h recalls in combination with a weighed food inventory. Frequency of spicy food consumption and degree of pungency in spicy food consumption were self-reported. Hypertension was defined as systolic BP (SBP) ≥ 140 mmHg and/or diastolic BP (DBP) ≥ 90 mmHg, or having known hypertension. Multilevel mixed-effects models were constructed to estimate changes in SBP and DBP levels as well as risk of hypertension. RESULTS: Higher frequency of spicy food consumption was significantly associated with lower SBP and DBP levels and lower risk of hypertension in female participants after adjustment for potential confounders (all P trend < 0.05) and cluster effects at different levels (individual, community, and province). Compared with female participants who did not eat spicy food, the adjusted odds ratios of hypertension were 0.740 (95% CI 0.569, 0.963; P = 0.025) in female participants who consumed usually, and 0.760 (95% CI 0.624, 0.925; P = 0.006) in female participants who ate spicy food with moderate pungency. There was no significant association of spicy food consumption with hypertension in male participants. CONCLUSIONS: Frequency of spicy food consumption was inversely associated with risk of hypertension in female, but not male adults.

Heat shock protein 70 is a key molecule to rescue imbalance caused by low-frequency noise.

A previous study showed that people living in urban areas are generally exposed to low-frequency noise (LFN) with frequencies below 100 Hz and sound levels of 60-110 dB in daily and occupational environments. Exposure to LFN has been shown to affect balance in humans and mice. However, there is no information about prevention of LFN-mediated imbalance because of a lack of information about the target region based on health risk assessment of LFN exposure. Here, we show that acute exposure to LFN at 100 Hz, 95 dB, but not at 85 dB or 90 dB, for only 1 h caused imbalance in mice. The exposed mice also had decreased cervical vestibular-evoked myogenic potential (cVEMP) with impaired activity of vestibular hair cells. Since imbalance in the exposed mice was irreversible, morphological damage in the vestibules of the exposed mice was further examined. The exposed mice had breakage of the otoconial membrane in the vestibule. LFN-mediated imbalance and breakage of the otoconial membrane in mice were rescued by overexpression of a stress-reactive molecular chaperone, heat shock protein 70 (Hsp70), which has been shown to be induced by exposure of mice to 12 h per day of LFN at 95 dB for 5 days. Taken together, the results of this study demonstrate that acute exposure to LFN at 100 Hz, 95 dB for only 1 h caused irreversible imbalance in mice with structural damage of the otoconial membrane as the target region for LFN-mediated imbalance, which can be rescued by Hsp70.

cVEMP correlated with imbalance in a mouse model of vestibular disorder.

BACKGROUND: Cervical vestibular evoked myogenic potential (cVEMP) testing is a strong tool that enables objective determination of balance functions in humans. However, it remains unknown whether cVEMP correctly expresses vestibular disorder in mice. OBJECTIVE: In this study, correlations of cVEMP with scores for balance-related behavior tests including rotarod, beam, and air-righting reflex tests were determined in ICR mice with vestibular disorder induced by 3,3'-iminodipropiontrile (IDPN) as a mouse model of vestibular disorder. METHODS: Male ICR mice at 4 weeks of age were orally administered IDPN in saline (28 mmol/kg body weight) once. Rotarod, beam crossing, and air-righting reflex tests were performed before and 3-4 days after oral exposure one time to IDPN to determine balance functions. The saccule and utricles were labeled with fluorescein phalloidin. cVEMP measurements were performed for mice in the control and IDPN groups. Finally, the correlations between the scores of behavior tests and the amplitude or latency of cVEMP were determined with Spearman's rank correlation coefficient. Two-tailed Student's t test and Welch's t test were used to determine a significant difference between the two groups. A difference with p < 0.05 was considered to indicate statistical significance. RESULTS: After oral administration of IDPN at 28 mmol/kg, scores of the rotarod, beam, and air-righting reflex tests in the IDPN group were significantly lower than those in the control group. The numbers of hair cells in the saccule, utricle, and cupula were decreased in the IDPN group. cVEMP in the IDPN group was significantly decreased in amplitude and increased in latency compared to those in the control group. cVEMP amplitude had significant correlations with the numbers of hair cells as well as scores for all of the behavior tests in mice. CONCLUSIONS: This study demonstrated impaired cVEMP and correlations of cVEMP with imbalance determined by behavior tests in a mouse model of vestibular disorder.

Stimuli-Responsive Reversible Switching of Intersystem Crossing in Pure Organic Material for Smart Photodynamic Therapy.

Photosensitizers (PSs) with stimuli-responsive reversible switching of intersystem crossing (ISC) are highly promising for smart photodynamic therapy (PDT), but achieving this goal remains a tremendous challenge. This study introduces a strategy to obtain such reversible switching of ISC in a new class of PSs, which exhibit stimuli-initiated twisting of conjugated backbone. We present a multidisciplinary approach that includes femtosecond transient absorption spectroscopy and quantum chemical calculations. The organic structures reported show remarkably enhanced ISC efficiency (ΦISC ), switching from nearly 0 to 90 %, through an increase in the degree of twisting, providing an innovative mechanism to promote ISC. This leads us to propose here and demonstrate the concept of smart PDT, where pH-induced reversible twisting maximizes the ISC rate, and thus enables strong photodynamic action only under pathological stimulus (such as change in pH, hypoxia, or exposure to enzymes). The ISC process is turned off to deactivate PDT ability, when the PS is transferred or metabolized away from pathological region.