mJ Cm-2 Research Articles

Control of Aromatic Disinfection Byproducts in Potable Reuse Water by the UV222/H2O2 vs UV254/H2O2 Advanced Oxidation Processes.

Research has demonstrated the difficulty associated with degrading the conventional 1-2 carbon aliphatic halogenated byproducts of disinfectant reactions with organic matter [disinfection byproducts (DBPs)] within advanced oxidation process (AOP) units in potable reuse trains, but the efficacy of AOP units for treating the emerging classes of halogenated aromatic DBPs is unclear. We herein demonstrate more effective removal of 28 halogenated aromatic DBPs in the UV/H2O2 AOP at 222 nm (UV222) than in the conventional UV/H2O2 AOP at 254 nm. Direct photolysis of 28 halogenated aromatic DBPs was greatly enhanced at 222 nm with fluence-based photodecay rate constants of 4.31 × 10-4-1.53 × 10-2 cm2 mJ-1, which was mainly attributed to the higher molar absorption coefficients of halogenated aromatic DBPs at 222 nm than 254 nm. Generally, quantum yields of halogenated aromatic DBPs at both 222 and 254 nm followed the order of halophenols > halohydroxybenzaldehydes > halonitrophenols. All 28 halogenated aromatic DBPs exhibit high reactivity toward HO• with second-order rate constants ranging from 2.18 × 109 to 1.15 × 1010 M-1 s-1 determined by X-ray radiolysis. The UV fluence required to achieve 90% loss of halogenated aromatic DBPs in the UV222/H2O2 AOP was 75-95% lower than that in the UV254/H2O2 AOP, and 90% removal of most tested halogenated aromatic DBPs can be achieved in the UV222/H2O2 AOP within the UV fluence levels commonly applied in potable reuse (700-1000 mJ cm-2).

Solubility Change Behavior of Fluoroalkyl Ether-Tagged Dendritic Hexaphenol under Extreme UV Exposure.

This study focuses on the discovery of a single-component molecular resist for extreme ultraviolet (EUV) lithography by employing the ionizing radiation-induced decomposition of carbon-fluorine chemical bonds. The target material, DHP-L6, was synthesized by bonding perfluoroalkyl ether moieties to amorphous dendritic hexaphenol (DHP) with a high glass transition temperature. Upon exposure to EUV and electron beam irradiation, DHP-L6 films exhibited a decreasing solubility in fluorous developer media, resulting in negative-tone images. The underlying chemical mechanisms were elucidated by Fourier transform-infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy, and nanoindentation experiments. These analyses highlighted the possible electron-induced decomposition of C-F bonds in DHP-L6, leading to molecular network formation via recombination of the resulting C-centered radicals. Subsequent high-resolution lithographic patterning under EUV irradiation showed that DHP-L6 could create stencil patterns with a line width of 26 nm at an exposure dose of 110 mJ cm-2. These results confirm that single-component small molecular compounds with fluoroalkyl moieties can be employed as patterning materials under ionizing radiation. Nonetheless, additional research is required to reduce the relatively high exposure energy for high-resolution patterning and to enhance the line-edge roughness of the produced stencil.

Organic pollutants photodegradation increment with use of TiO2 nanotubes decorated with transition metals after pulsed laser treatment

Among various titanium(IV) oxide (TiO2, titania) structures, 1D nanotubes (TiO2 NTs) produced during the two-electrode anodization process, are extensively utilized in sensors or supercapacitors as well as in photo(electro)catalytic water splitting. However, due to wide bandgap and fast electron-hole recombination additional modifications, mostly concerned on materials surface, are required. According to the recent research, TiO2 NTs photo(electro)catalytic characteristic were markedly improved by the combination of surface decoration with transition metal nanoparticles further treated with the laser beam. Nevertheless, until recently, the photocatalytic ability of laser-treated TiO2 NTs for recalcitrant chemicals degradation were hardly described. In this regard, our work focuses on obtaining long, about 7.3 μm TiO2 NTs (L-TiO2 NTs), together with their photoactivity and physicochemical characteristics, as well as their alterations following surface modification utilizing transition metals (tungsten, chromium and nickel) together with laser treatment. Obtained L-TiO2 NTs are characterized by over 13.5 times larger BET surface area in comparison to reference spaced TiO2 NTs with approximately 2 μm length (0.61 m2 g−1 and 0.05 m2 g−1, respectively). This allowed for increasing of the materials photocatalytic activity in both UV–vis and vis light. Additionally, phenol photodegradation reached up to 34% (0.21·10−2 min−1) for tungsten-modified titania after laser annealing at 20 mJ cm2 fluence. The reaction mechanism research revealed that reduction of organic pollutants concentration was primarily caused by superoxide radical anions •O2−. Furthermore, obtained modified L-TiO2 NTs showed remarkable durability without losing their initial activity over ten photocatalytic cycles.

SARS-CoV-2 Inactivation on Hard Non-porous Airplane Cabin Material Surfaces was Limited After Exposure to Far UV-C (222 nm) Radiation.

To test the efficacy of 222 nm Far UV-C for surface disinfection of SARS-CoV-2 on inanimate surfaces from airplane cabins. Two far ultraviolet (UV-C) irradiation light systems were evaluated for disinfection of SARS-CoV-2. Materials used for carriers (test surfaces) included polished stainless steel and used airplane materials including seatbelt latches, window dust covers, sidewall laminates, and tray tables. While demonstrating reasonable efficacy under some experimental conditions, the data indicated that 222 nm Far UV-C disinfection alone does not reliably provide a 3 log10 or 99.9% reduction of SARS-CoV-2 on inanimate surfaces from an airplane cabin. An Ushio (Cypress, CA) 1.7" x 2.3" Care222® 12W 222nm BI lamp module tested in triplicate at a low (⁓ 1.5 mJ cm-2), medium (⁓ 3.0 mJ cm-2), and high (⁓ 6 to 9 mJ cm-2) fluence did not provide a ≥ 3 log10 or 99.9% reduction of SARS-CoV-2. The reduction of SARS-CoV-2 was greatest on stainless steel. The result was a log10 reduction of 2.83, 1.33, 2.58, and 2.21 logs for virus samples containing saline, saline with 2.5 mg BSA, saline with 0.25 mg BSA, and artificial saliva respectively at a dosage of 5 to 9 mJ cm-2. The log10 reduction of SARS-CoV-2 in saline with 2.5 mg bovine serum albumin was lowest with 1.33 for stainless steel, 0.93 for belt latch, and 0.61 for tray table at a dosage of 5 to 6 mJ cm-2.The second UV lighting system tested was a prototype mobile wand with a built-in short-pass filtered krypton-chloride cylindrical lamp. One pass of the wand over a tray holding carriers inoculated with SARS-CoV-2 in artificial saliva at a rate of approximately 1 foot (1') per second (sec) exposed the carriers to 7.3 mJ cm-2. The log10 reductions determined for the single pass were 2.97, 3.75, 1.78, 1.91, and 1.28 logs for stainless steel, belt latch, dust cover, sidewall, and tray table respectively. Two passes of the wand generated 17.2 mJ cm-2 and resulted in log10 reductions of 4.04, 3.74, 4.24, 3.68, and 1.66 logs for stainless steel, belt latch, dust cover, sidewall, and tray table respectively. The combination of higher fluence from multiple passes of the wand, the close proximity (10 cm wand to the carrier), the exposure to elevated temperatures up to 35°C, and ozone from the bulb being blown directly onto the carriers contributed to effective viral inactivation on all surfaces except the airplane tray table. The impact of temperature and ozone on viral inactivation should be determined for future testing of the 222 nm UV-C wand.

Highly hydroxylated hafnium clusters are accessible to high resolution EUV photoresists under small energy doses.

This work reports the success in accessing high-resolution negative-tone EUV photoresists without radical chain growth in the aggregation mechanism. The synthesis of a highly hydroxylated Hf6O4(OH)8(RCO2)8 cluster 3 (R = s-butyl or s-Bu) is described; its EUV performance enables high resolution patterns HP = 18 nm under only 30 mJ cm-2. This photoresist also achieves high resolution patterns for e-beam lithography. Our new photoresist design to increase hydroxide substitutions of carboxylate ligands in the Hf6O4(OH)4(RCO2)12 clusters improves the EUV resolution and also greatly reduces EUV doses. Mechanistic analysis indicates that EUV light not only enables photolytic decomposition of carboxylate ligands, but also enhances the Hf-OH dehydration. One additional advantage of cluster 3 is a very small loss of film thickness (ca. 13%) after the EUV pattern development.

Amplified spontaneous emission from a liquid crystalline phase: anisotropic property and active modulation.

Amplified spontaneous emission (ASE) is considered to be a primary indication of optical gain in active media without an external resonator. Molecular materials with ASE are expected to be one of the suitable light sources for specific applications such as optical coherent tomography owing to their low coherence and flexible tunability. Concentration quenching of emissive excited states has been a critical issue to boost the quantum efficiency of molecular materials in their condensed phases. The rod-like design of molecules with excited state intramolecular proton transfer (ESIPT) has been demonstrated to overcome this issue in highly-concentrated molecularly-doped systems, as represented by C4alkyne-HBT (2-(4-(1-hexynyl)-2-hydroxyphenyl)-benzothiazole). We designed an ESIPT molecule-doped liquid crystalline (LC) system for optical amplification via the ASE regime with its wide tunability of emission intensity. Detailed ASE behaviour and optical gain of a LC blend of C4alkyne-HBT and 4-pentyl-4'-cyano biphenyl (5CB) was evaluated to afford a maximum optical gain of 16.5 cm-1 with an estimated ASE threshold of optical pumping at 0.6-0.7 mJ cm-2. Although most ASE studies focus on homogeneous solutions, solids, or crystalline states, ASE from a soft-flexible LC phase is quite limited and advantageous for the design of an external optical resonator/cavity structure. Optical excitation parallel and perpendicular to the director resulted in the strong modulation of the ASE. By using the benefits of a LC phase, the ASE was actively modulated under the external electric field by the reorientation of the molecular dipole moment.

Advanced oxidative degradation of monoethanolamine in water using ultraviolet light and hydrogen peroxide.

This study aims to develop a benign and commercially viable method for the degradation of monoethanolamine (MEA) in the aqueous phase via an ultraviolet/hydrogen peroxide (UV/H2O2) advanced oxidation process (AOP). The current investigation is novel in terms of detailed kinetic analysis and degradation mechanisms; the impact of pH and UV light intensity on MEA degradation was thoroughly examined. pH 9 was identified as the optimal condition, achieving a degradation efficiency of 76.28%, while the highest UV light intensity of 59.055 mJ cm-2 resulted in an 85.13% degradation efficiency. A comprehensive kinetic study highlighted the reaction rates under varying conditions, providing valuable insights and dynamics of the degradation. The mechanistic pathway of MEA breakdown, identified using Liquid Chromatography Mass Spectrometry (LCMS) analysis revealed ethylene glycol, glycolaldehyde, glycine aldehyde, glycine, carbon dioxide, and ammonium ions as the primary degradation products. These results provide both operational insights and a greater understanding of the degradation mechanism, demonstrating that UV/H2O2 AOP offers an effective and environmentally benign solution for MEA degradation. The findings make a substantial contribution to the development of MEA treatment methods that are both economically viable and sustainable.

The TR-icOS setup at the ESRF: time-resolved microsecond UV-Vis absorption spectroscopy on protein crystals.

The technique of time-resolved macromolecular crystallography (TR-MX) has recently been rejuvenated at synchrotrons, resulting in the design of dedicated beamlines. Using pump-probe schemes, this should make the mechanistic study of photoactive proteins and other suitable systems possible with time resolutions down to microseconds. In order to identify relevant time delays, time-resolved spectroscopic experiments directly performed on protein crystals are often desirable. To this end, an instrument has been built at the icOS Lab (in crystallo Optical Spectroscopy Laboratory) at the European Synchrotron Radiation Facility using reflective focusing objectives with a tuneable nanosecond laser as a pump and a microsecond xenon flash lamp as a probe, called the TR-icOS (time-resolved icOS) setup. Using this instrument, pump-probe spectra can rapidly be recorded from single crystals with time delays ranging from a few microseconds to seconds and beyond. This can be repeated at various laser pulse energies to track the potential presence of artefacts arising from two-photon absorption, which amounts to a power titration of a photoreaction. This approach has been applied to monitor the rise and decay of the M state in the photocycle of crystallized bacteriorhodopsin and showed that the photocycle is increasingly altered with laser pulses of peak fluence greater than 100 mJ cm-2, providing experimental laser and delay parameters for a successful TR-MX experiment.

A High Temperature Harvestorer Based on a Photovoltaic Cell and an Oxygen Ion Battery

A High Temperature Harvestorer Based on a Photovoltaic Cell and an Oxygen Ion Battery

Rapid Inactivation of Fungal Spores in Drinking Water by Far-UVC Photolysis of Free Chlorine.

Effective and affordable disinfection technology is one key to achieving Sustainable Development Goal 6. In this work, we develop a process by integrating Far-UVC irradiation at 222 nm with free chlorine (UV222/chlorine) for rapid inactivation of the chlorine-resistant and opportunistic Aspergillus niger spores in drinking water. The UV222/chlorine process achieves a 5.0-log inactivation of the A. niger spores at a chlorine dosage of 3.0 mg L-1 and a UV fluence of 30 mJ cm-2 in deionized water, tap water, and surface water. The inactivation rate constant of the spores by the UV222/chlorine process is 0.55 min-1, which is 4.6-fold, 5.5-fold, and 1.8-fold, respectively, higher than those of the UV222 alone, chlorination alone, and the conventional UV254/chlorine process under comparable conditions. The more efficient inactivation by the UV222/chlorine process is mainly attributed to the enhanced generation of reactive chlorine species (e.g., 6.7 × 10-15 M of Cl•) instead of hydroxyl radicals from UV222 photolysis of chlorine, which is verified through both experiments and a kinetic model. We further demonstrate that UV222 photolysis damages the membrane integrity and benefits the penetration of chlorine and radicals into cells for inactivation. The merits of the UV222/chlorine process over the UV254/chlorine process also include the more effective inhibition of the photoreactivation of the spores after disinfection and the lower formation of chlorinated disinfection byproducts and toxicity.

Pilot-scale study of UVC-based AOPs towards implementation at the outlet of domestic WWTPs.

The degradation of a mixture of ibuprofen, naproxen, and diclofenac in various effluents by UVC/H2O2 or UVC/S2O82- was studied to assess the impact of the matrix composition and of the oxidant precursor on process efficiency. Experiments were carried out in a 20-L laboratory pilot (a scaled-down version of a full-scale pilot). In effluents collected during dry weather, the rural constructed wetland effluent allowed faster degradation than the urban conventional WWTP effluent, regardless of the nature of the targets or of the oxidant precursor. This was mainly attributed to a three-times higher chemical oxygen demand in the urban effluent, likely to quench the oxidative species. UV fluences to reach 90% degradation of the three compounds were 3,800 and 5,500 mJ cm-2 in the rural effluent, whereas they were 6,600 and 6,100 mJ cm-2 in the urban effluent with H2O2 and S2O82-, respectively. After a rainfall event, the rural effluent composition was not significantly affected compared to that of the urban effluent that underwent the dilution effect. Therefore, the stability of the rural effluent composition allowed comparable degradation efficiency, whereas the dilution effect led to a significant increase in the degradation rate constants in the urban effluent (up to four times higher).

Seawater pearl hydrolysate inhibits photoaging via decreasing oxidative stress, autophagy and apoptosis of Ultraviolet B-induced human skin keratinocytes.

Ultraviolet (UV) is the main reason to cause photoaging skin which not only hinders beauty, brings the patients with psychological burden, but also pathologically leads to the occurrence of tumors in skin. This study goes into the inhibitory effect and mechanism of seawater pearl hydrolysate (SPH) to address human skin keratinocytes photoaging induced by UVB. The photoaging model of Hacat cell was constructed by UVB irradiation, the levels of oxidative stress, apoptosis, aging, autophagy and autophagy-related protein and signal pathway expression were assessed to characterize the inhibitory effect and mechanism of SPH on photoaging Hacat cell. Seawater pearl hydrolysate significantly accelerated (p < 0.05) the activities of superoxide dismutase, catalase, and glutathione peroxidase, and markedly reduced (p < 0.05) the contents of reactive oxygen species (ROS), malondialdehyde, protein carbonyl compound and nitrosylated tyrosine protein, aging level, apoptosis rate in Hacat cell induced by 200 mJ cm-2 UVB after 24 and 48 h of culture; high dose SPH significantly raised (p < 0.05) relative expression level of p-Akt, p-mTOR proteins, and markedly decreased (p < 0.05) relative expression level of LC3II protein, p-AMPK, and autophagy level in Hacat cell induced by 200 mJ cm-2 UVB, or in combination with the intervention of PI3K inhibitor or AMPK overexpression after 48 h of culture. Seawater pearl hydrolysate can effectively inhibit 200 mJ cm-2 UVB-induced photoaging of Hacat cells. The mechanism indicates removing the excessive ROS through increasing the antioxidation of photoaging Hacat cells. Once redundant ROS is eliminated, SPH works to reduce AMPK, increase PI3K-Akt pathway expression, activate mTOR pathway to lowdown autophagy level, and as a result, inhibit apoptosis and aging in photoaging Hacat cells.

Enhancement of a pyroelectric body energy harvesting scheme employing pulsed electric fields.

This research utilizes waste heat energy as a sustainable energy source to enhance pyroelectric power output by combining pyroelectric nanogenerators with an external pulsed electric field. When the surface temperature of the pyroelectric body varies, applying different pulses of the external electric field results in maximum power accumulation. A novel power-generating experimental setup was developed to measure and compute pyroelectric power generation. A standard Fuji ceramic C-9 sample was used to generate pyroelectric energy in a 20 °C temperature range from 120 to 140 °C. The continuous temperature variation frequency was 0.05Hz, and the pulsed electric field was applied when the temperature rose. Pulses of the electric field with widths of 10, 50, 100, and 200ms were applied to the sample under different pulse amplitudes, and the amplitude of each pulse was 250, 500, 1000, or 1500 V/mm. The maximum power generated through the application of an external pulsed electric field under the above-mentioned conditions was evaluated. This system had the highest power density of 0.204 mJ cm-2 °C-1kV-1. In addition, for the lowest input power, the maximum power generation condition was a 10ms pulse width and an amplitude of 250Vmm-1 in the applied electric field. This state might power smart sensor modules, IoT devices, automobiles, and other waste heat energy applications. Nano-pulse electric field applications may reduce input power to its lowest level, dependent on net-producing power. Therefore, new researchers can use net-generation power efficiency to create a large-scale power source using multiple pyroelectric arrays.

Resolving the Heat Generated from ZrO2 Atomic Layer Deposition Surface Reactions.

In situ pyroelectric calorimetry and spectroscopic ellipsometry were used to investigate surface reactions in atomic layer deposition (ALD) of zirconium oxide (ZrO2 ). Calibrated and time-resolved in situ ALD calorimetry provides new insights into the thermodynamics and kinetics of saturating surface reactions for tetrakis(dimethylamino)zirconium(IV) (TDMAZr) and water. The net ALD reaction heat ranged from 0.197 mJ cm-2 at 76 °C to 0.155 mJ cm-2 at 158 °C, corresponding to an average of 4.0 eV/Zr at all temperatures. A temperature dependence for reaction kinetics was not resolved over the range investigated. The temperature dependence of net reaction heat and distribution among metalorganic and oxygen source exposure is attributed to factors including growth rate, equilibrium surface hydroxylation, and the extent of the reaction. ZrO2 -forming surface reactions were investigated computationally using DFT methods to better understand the influence of surface hydration on reaction thermodynamics.

A High-Radical-Yield Advanced Oxidation Process Coupling Far-UVC Radiation with Chlorinated Cyanurates for Micropollutant Degradation in Water.

Increasing the radical yield and reducing energy consumption would enhance the sustainability and competitiveness of advanced oxidation processes (AOPs) for micropollutant degradation in water. We herein report a novel AOP coupling far-UVC radiation at 222 nm with chlorinated cyanurates (termed the UV222/Cl-cyanurates AOP) for radical generation and micropollutant abatement in water. We experimentally determined the concentrations of HO•, Cl•, and ClO• in the UV222/Cl-cyanurates AOP in deionized water and swimming pool water. The radical concentrations are 10-27 times and 4-13 times, respectively, higher than those in the UV254/Cl-cyanurates AOP and the well-documented UV254/chlorine AOP under comparable conditions (e.g., same UV fluence and oxidant dosing). We determined the molar absorption coefficients and innate quantum yields of two chlorine species and two Cl-cyanurates at 222 nm and incorporated these parameters into a kinetic model. The model enables accurate prediction of oxidant photodecay rates as well as the pH impact on radical generation in the UV222/Cl-cyanurates AOP. We predicted the pseudo-first-order degradation rate constants of 25 micropollutants in the UV222/Cl-cyanurates AOP and demonstrated that many micropollutants can be degraded by >80% with a low UV fluence of 25 mJ cm-2. This work advances the fundamental photochemistry of chlorine and Cl-cyanurates at 222 nm and offers a highly effective engineering tool in combating micropollutants in water where Cl-cyanurates are suitable to use.

222 nm Far-UVC from filtered Krypton-Chloride excimer lamps does not cause eye irritation when deployed in a simulated office environment.

Far-UVC, from filtered Krypton-Chloride lamps, is promising for reducing airborne transmission of disease. While significant research has been undertaken to investigate skin safety of these lamps, less work has been undertaken on eye safety. There is limited data on human eye safety or discomfort from the deployment of this germicidal technology. In this pilot study, immediate and delayed eye discomfort were assessed in a simulated office environment with deployment of Krypton-Chloride lamps, located on the ceiling and directed downwards into the occupied room. Discomfort was assessed immediately postexposure and several days after exposure using validated, Standard Patient Evaluation Eye Dryness (SPEED) and Ocular Surface Disease Index (OSDI) questionnaires. Our results show no significant eye discomfort or adverse effects from the deployment of Far-UVC in this simulated office environment, even when lamps were operated continuously with participants receiving head exposures of up to 50 mJ cm-2 . In addition, a statistically significant reduction in bacteria and fungi of 52% was observed. Far-UVC in this simulated office environment did not cause any clinically significant eye discomfort and was effective at reducing pathogens in the room. These results contribute an important step to further investigation of the interaction of Far-UVC with the human eye.

Centralized Excited States and Fast Radiation Transitions Reduce Laser Threshold in Carbon Dots.

As a new type of solution-processed nano-laser material, carbon dots (CDs) have shown considerable potential in optical communication, laser displays, micro/nano processing, and biomedicine. Reducing the laser threshold of the gain material is of considerable significance for further development of CDs' applications in the field of micro/nano lasers. A series of blue-emissive CDs (B-CDs) are synthesized by changing the molar ratios of the precursors (citric acid (CA): L-Cysteine (L-Cys)). B-CDs have a structure of carbon nanoparticles with their surface being modified with 5-oxo-3,5-dihydro-2Hthiazolo [3,2-a]pyridine-7-carboxylic acid (TPCA). The laser can only be generated when the molar ratio of the precursors is between 1:1 and 2:1. With an increase in this ratio, the laser threshold decreases from 341.6 to 165.5 mJ cm-2 . The decrease in the laser threshold is attributed to the increase in the radiation transition rate and centralized sp3 -related excited state levels, which are favorable for light amplification and population inversion. These results will be instructional for the reasonably design of CDs-based laser materials and prompt their potential use in practical photonics.

Field Study and Evaluation of KrCl* Far UV-C Device Capability for Inactivation of Phi6 Bacteriophage.

"Far UV-C" is an effective disinfection method that can be deployed in occupied areas. Commercially available Krypton Chloride (KrCl*) excimer lamps filtered to emit at 222 nm are effective in disinfecting pathogens and safe for human exposure up to an allowable threshold exposure, which is much longer than for conventional UV lamps emitting at 254 nm. Laboratory and controlled field testing of a filtered KrCl* excimer lamp for disinfection of a virus suspended in a thin film aqueous solution in an occupied office setting was conducted. Complete inactivation of almost 6 log (99.9999%) of Phi6 bacteriophage virus was achieved in ~20 min of exposure time in a field setting, equivalent to a dose of about 10 mJ cm-2 . The Phi6 inactivation rate constant for the field test results were not statistically different from laboratory values (P > 0.05, paired t-test). When positioned at 1 m distance from possible human exposure, this device can be used safely for almost 4.5 h of continuous direct exposure without any acute or long-term adverse health effects. This study illustrates the applicability and deployment of Far UV-C for pathogen reduction and can help in decision making for implementation of Far UV-C for disinfection in human-occupied environments.

Highly Anisotropic Second-Order Nonlinear Optical Effects in the Chiral Lead-Free Perovskite Spiral Microplates

Chiral metal halide perovskites with intrinsic asymmetric structures have drawn increased research interest for the application of second-order nonlinear optics (NLO). However, designing chiral perovskites with the features of a large NLO coefficient, high laser-induced damage thresholds (LDT), and environmental friendliness remains a major challenge. Herein, we have synthesized two chiral hybrid bismuth halides: (R/S-MBA)4Bi2Br10 spiral structure microplates, templated by chiral (R/S)-methylbenzylamine (R/S-MBA). The as-grown chiral lead-free perovskite spiral microplates exhibit a recorded second harmonic generation (SHG) effect with a large effective second-order NLO coefficient (deff) of 11.9 pm V-1 and a high LDT of up to 59.2 mJ cm-2. More importantly, the twisted screw structures show competitive circular polarization sensitivity at 1200 nm with an anisotropy factor (gSHG-CD) of 0.58, which is about 3 times higher than that of reported Pb-based chiral perovskites. These findings provide a new platform to design multifunctional lead-free chiral perovskites for nonlinear photonic applications.

Nanodroplet vaporization with pulsed-laser excitation repeatedly amplifies photoacoustic signals at low vaporization thresholds.

Nanodroplets' explosive vaporization triggered by absorption of laser pulses produces very large volume changes. These volume changes are two orders of magnitude higher than those of thermoelastic expansion generated by equivalent laser pulses, and should generate correspondingly higher photoacoustic waves (PAW). The generation of intense PAWs is desirable in photoacoustic tomography (PAT) to increase sensitivity. The biocompatibility and simplicity of nanodroplets obtained by sonication of perfluoropentane (PFP) in an aqueous solution of bovine serum albumin (BSA) containing a dye make them particularly appealing for use as contrast agents in clinical applications of PAT. Their usefulness depends on stability and reproducible vaporization of nanodroplets (liquid PFP inside) to microbubbles (gaseous PFP inside), and reversible condensation to nanodroplets. This work incorporates porphyrins with fluorinated chains and BSA labelled with fluorescent probes in PFP nanodroplets to investigate the structure and properties of such nanodroplets. Droplets prepared with average diameters in the 400-1000 nm range vaporize when exposed to nanosecond laser pulses with fluences above 3 mJ cm-2 and resist coalescence. The fluorinated chains are likely responsible for the low vaporization threshold, ∼2.5 mJ cm-2, which was obtained from the laser fluence dependence of the photoacoustic wave amplitudes. Only ca. 10% of the droplets incorporate fluorinated porphyrins. Nevertheless, PAWs generated with nanodroplets are ten times higher than those generated by aqueous BSA solutions containing an equivalent amount of porphyrin. Remarkably, successive laser pulses result in similar amplification, indicating that the microbubbles revert back to nanodroplets at a rate faster than the laser repetition rate (10 Hz). PFP nanodroplets are promising contrast agents for PAT and their performance increases with properly designed dyes.