Electron Localization in Rationally Designed Pt1Pd Single-Atom Alloy Catalyst Enables High-Performance Li-O2 Batteries.

Li-O2 batteries (LOBs) are considered as one of the most promising energy storage devices due to their ultrahigh theoretical energy density, yet they face the critical issues of sluggish cathode redox kinetics during the discharge and charge processes. Here we report a direct synthetic strategy to fabricate a single-atom alloy catalyst in which single-atom Pt is precisely dispersed in ultrathin Pd hexagonal nanoplates (Pt1Pd). The LOB with the Pt1Pd cathode demonstrates an ultralow overpotential of 0.69 V at 0.5 A g-1 and negligible activity loss over 600 h. Density functional theory calculations show that Pt1Pd can promote the activation of the O2/Li2O2 redox couple due to the electron localization caused by the single Pt atom, thereby lowering the energy barriers for the oxygen reduction and oxygen evolution reactions. Our strategy for designing single-atom alloy cathodic catalysts can address the sluggish oxygen redox kinetics in LOBs and other energy storage/conversion devices.

High-performance Ge-on-insulator lateral p-i-n waveguide photodetectors for electronic-photonic integrated circuits at telecommunication wavelengths.

We report high-performance germanium-on-insulator (GeOI) waveguide photodetectors (WGPDs) for electronic-photonic integrated circuits (EPICs) operating at telecommunication wavelengths. The GeOI samples were fabricated using layer transfer and wafer-bonding techniques, and a high-quality Ge active layer was achieved. Planar lateral p-i-n WGPDs were fabricated and characterized, and they exhibited a low dark current of 0.1 µA. Strain-induced alterations in the optical properties were observed, resulting in an extended photodetection range up to λ = 1638 nm. This range encompasses crucial telecommunication bands. The WGPDs exhibited a high responsivity of 0.56 A/W and a high detectivity of D ∗ = 1.87 ×109cmHz1/2W - 1 at 1550 nm. A frequency-response analysis revealed that increasing the bias voltage from -1 to -9 V enhances the 3-dB bandwidth from 31 to 49 MHz. This study offers a comprehensive understanding of GeOI WGPDs, fostering high-performance EPICs with implications for telecommunications and beyond.

Dissolved LiO2 or adsorbed LiO2? The reactive superoxide during discharging process in lithium-oxygen batteries.

Lithium-oxygen batteries are promising but have many challenges. Unlike lithium-ion batteries, they are usually discharge-charge cycled with capacity cutoff instead of potential cutoff, which brings controversy. Additionally, which superoxide intermediate, the dissolved or the adsorbed superoxide, is more reactive and leads to cell premature death and unsatisfactory discharge capacity? These questions puzzle researchers and impede the development of lithium-oxygen batteries. Herein, on one hand, we tried to decouple the influence of discharging potential and discharging current density on the discharge products and side reactions. We found that the electrode potential has more impact on the side reactions than the current density. The low potential leads to a high ratio of Li2CO3 to Li2O2 in the discharge product and hence more surface passivation. On the other hand, to identify the more reactive and aggressive species that cause surface passivation, a flow cell setup was applied to suppress the solution route and maximize the products from the surface route. Results show that more Li2CO3 was identified under a large flow rate and thus the intermediates in surface route appear to be more reactive than that in solution route.

Development of mixed pitch grating for the optical addressing of trapped Sr+ ion with data analysis techniques.

Mixed pitch gratings are developed for the optical addressing of trapped 88Sr+ ion by means of simulation and experimental measurement approaches. Meanwhile, Python-based data analysis techniques were developed to analyze simulated and measured beam profiles. A fixed pitch grating with a pitch of 1.2 µm was used as a reference, and a mixed pitch grating with pitches of 1.1/1.2 µm of various ratios are investigated. The Python-based data analysis codes demonstrates highly automated capability in processing both simulated and measured beam profile data to compute key parameters, including beam waist and Gaussian fitting. Mixed pitch grating delivers light beam with smaller beam waist (17.4 µm) compared to the fixed pitch grating (26.4 µm), exhibiting ∼34% beam waist reduction.

Long wavelength mid-infrared multi-gases spectroscopy using tunable single-mode slot waveguide quantum cascade laser.

Single-mode tunable quantum cascade lasers (QCLs) are promising for high-resolution and highly sensitive trace gases sensing across the mid-infrared (MIR) region. We report on the development of a tunable single-mode slot waveguide QCL array in the long wavelength part of the MIR regime (>12 µm). This laser array exhibits a tuning range of around 12 cm-1, from 735.3 to 747.3 cm-1. Using this developed single-mode tunable QCL, we demonstrate individual gas sensing, yielding the detection limit of 940 ppb and 470 ppb for acetylene and o-xylene, respectively. To verify the potential of the developed QCL array in multi-species gas detection, laser absorption measurements of two mixed gases of acetylene and o-xylene were conducted, showing the absorption features of the corresponding gases agree well with the theoretical predictions.

Enhanced light emission of germanium light-emitting-diode on 150 mm germanium-on-insulator (GOI).

Germanium-on-insulator (GOI) has emerged as a novel platform for Ge-based electronic and photonic applications. Discrete photonic devices, such as waveguides, photodetectors, modulators, and optical pumping lasers, have been successfully demonstrated on this platform. However, there is almost no report on the electrically injected Ge light source on the GOI platform. In this study, we present the first fabrication of vertical Ge p-i-n light-emitting diodes (LEDs) on a 150 mm GOI substrate. The high-quality Ge LED on a 150-mm diameter GOI substrate was fabricated via direct wafer bonding followed by ion implantations. As a tensile strain of 0.19% has been introduced during the GOI fabrication process resulting from the thermal mismatch, the LED devices exhibit a dominant direct bandgap transition peak near 0.785 eV (∼1580 nm) at room temperature. In sharp contrast to conventional III-V LEDs, we found that the electroluminescence (EL)/photoluminescence (PL) spectra show enhanced intensities as the temperature is raised from 300 to 450 K as a consequence of the higher occupation of the direct bandgap. The maximum enhancement in EL intensity is a factor of 140% near 1635 nm due to the improved optical confinement offered by the bottom insulator layer. This work potentially broadens the GOI's functional variety for applications in near-infrared sensing, electronics, and photonics.

Tensile strained direct bandgap GeSn microbridges enabled in GeSn-on-insulator substrates with residual tensile strain.

Despite having achieved drastically improved lasing characteristics by harnessing tensile strain, the current methods of introducing a sizable tensile strain into GeSn lasers require complex fabrication processes, thus reducing the viability of the lasers for practical applications. The geometric strain amplification is a simple technique that can concentrate residual and small tensile strain into localized and large tensile strain. However, the technique is not suitable for GeSn due to the intrinsic compressive strain introduced during the conventional epitaxial growth. In this Letter, we demonstrate the geometrical strain amplification in GeSn by employing a tensile strained GeSn-on-insulator (GeSnOI) substrate. This work offers exciting opportunities in developing practical wavelength-tunable lasers for realizing fully integrated photonic circuits.

Enhanced second-harmonic generation in strained germanium-on-insulator microdisks for integrated quantum photonic technologies.

Quantum photonic circuits have recently attracted much attention owing to the potential to achieve exceptional performance improvements over conventional classical electronic circuits. Second-order χ(2) nonlinear processes play an important role in the realization of several key quantum photonic components. However, owing to their centrosymmetric nature, CMOS-compatible materials including silicon (Si) and germanium (Ge) traditionally do not possess the χ(2) response. Recently, second-harmonic generation (SHG) that requires the χ(2) response was reported in Ge, but no attempts at enhancing the SHG signal have been conducted and proven experimentally. Herein, we demonstrate the effect of strain on SHG from Ge by depositing a silicon nitride (Si3N4) stressor layer on Ge-on-insulator (GOI) microdisks. This approach allows the deformation of the centrosymmetric unit cell structure of Ge, which can further enhance the χ(2) nonlinear susceptibility for SHG emission. The experimental observation of SHG under femtosecond optical pumping indicates a clear trend of enhancement in SHG signals with increasing strain. Such improvements boost conversion efficiencies by 300% when compared to the control counterpart. This technique paves the way toward realizing a CMOS-compatible material with nonlinear characteristics, presenting unforeseen opportunities for its integration in the semiconductor industry.

Br-Doped BiOCl Nanosheet Exposed (001) Facet: Surface Oxygen Vacancy and Directed Electron Flow Boosting the Photocatalytic Performance.

The defective BiOCl nanosheet exposed (001) facet with favorable photocatalytic performance was designed. The surface microstructure analysis and theoretical calculation certified the dominant exposed (001) facet and rich surface oxygen defects of Br--doped BiOCl (B-6) nanosheets. The energy level structure analysis indicates that the band gap can be narrowed and the light absorption range can be widened by introducing Br- to BiOCl, and the presence of defective energy levels increases the photogenerated carrier transfer efficiency. Moreover, the doping of Br- in BiOCl promotes the directional flow of electrons to the surface of B-6, which improves the photocatalytic performance of the sample. Thus, the Br--doped BiOCl can degrade 96.5% RhB within 6 min under visible-light irradiation with high apparent reaction rate constants of 0.51 min-1, exhibiting the strongest photocatalytic degradation performance. This work provides guidance for the preparation of Bi-based photocatalysts with excellent performance.

Fabrication of a Large-Area Flexible Scintillating Membrane for High-Resolution X-ray Imaging Using an AIEgen-Functionalized Metal-Organic Framework.

With the growing demand for X-ray imaging, especially for three-dimensional objects with curved surfaces, a large-area flexible X-ray imaging membrane based on scintillating materials becomes the focus of vigorous investigation. Among the developed scintillators, metal-organic frameworks (MOFs) featuring tunable photophysical properties and marked luminescence stability hold great promise for serving as ideal X-ray scintillators. Here, we report a flexible composite scintillating membrane with superior imaging performance. The membrane is achieved by embedding an aggregation-induced emission (AIE) luminogen (AIEgen, H4ETTC)-functionalized MOF scintillator (Y-PCN-94) into a polymer matrix (PDMS). Notably, Y-PCN-94 exhibits a strong AIE effect under both ultraviolet (UV) light and X-ray irradiation, which is also the first time that the AIE effect was observed in the MOF system under an ionizing radiation field. This also gives the material promising radioluminescence properties, such as a low X-ray detection limit (1.6 µGy s-1) and high imaging resolution (>14.3 lp mm-1), which can be mainly attributed to the combination of the AIE effect and strong X-ray stopping power. This work demonstrates that incorporating AIEgens into MOFs or other frameworks can offer an alternative approach for producing high-performance X-ray scintillators.

True Reaction Sites on Discharge in Li-O2 Batteries.

In the pursuit of an advanced Li-O2 battery, the true reaction sites in the cathode determined its cell performance and the catalyst design. When the first layer of insulating Li2O2 solid is deposited on the electrode substrate during discharging, the following O2 reduction to Li2O2 could take place either at the electrode|Li2O2 interface or at the Li2O2|electrolyte interface. The mechanism decides the strategies of catalyst design; however, it is still mysterious. Here, we used rotate ring-disk electrode to deposit a dense Li2O2 film and labeled the Li2O2 product with 16O/18O isotope. By identification of the distribution of the Li216O2 and Li218O2 in the Li2O2 film using new characteristic signals of Li216O2 and Li218O2, our results show that O2 is reduced to Li2O2 at both interfaces. A sandwich structure of Li218O2|Li216O2|Li218O2 was identified at the electrode surface when the electrode was discharged under 16O2 and then 18O2. The electrode|Li2O2 interface is the major reaction site, and it contributes to 75% of the overall reaction. This new mechanism raises new challenges and new strategies for the catalyst design of Li-O2 batteries.

Grating and hole-array enhanced germanium lateral p-i-n photodetectors on an insulator platform.

Germanium (Ge) lateral p-i-n photodetectors with grating and hole-array structures were fabricated on a Ge-on-insulator (GOI) platform. Owing to the low threading dislocation density (TDD) in the transferred Ge layer, a low dark current of 0.279 µA was achieved at -1 V. The grating structure enhances the optical absorption by guiding the lateral propagation of normal incident light, contributing to a 3× improved responsivity at 1,550 nm. Compared with the grating structure, the hole-array structure not only guides the lateral modes but also benefits the vertical resonance modes. A 4.5× higher responsivity of 0.188 A/W at 1,550 nm was achieved on the 260 nm Ge absorptive layer. In addition, both the grating and the hole-array structure attribute to a 2× and a 1.6× enhanced 3dB bandwidth at -5 V due to significantly reduced capacitance. The planar configuration of p-i-n photodiodes is favorable for large-scale monolithic integration. The incorporated surface structures offer promising approaches to reinforce the responsivity and bandwidth simultaneously, paving the way for the development of high-performance Ge photodetectors on silicon substrate.

Combined chemotherapy and endoscopic ultrasound-guided intratumoral 32P implantation for locally advanced pancreatic adenocarcinoma: a pilot study.

BACKGROUND: This study evaluated clinical outcomes of combined chemotherapy and endoscopic ultrasound (EUS)-guided intratumoral radioactive phosphorus-32 (32P) implantation in locally advanced pancreatic adenocarcinoma (LAPC). METHODS: Consecutive patients with newly diagnosed LAPC were recruited over 20 months. Baseline computed tomography and 18F-2-fluoro-2-deoxy-D-glucose (18FDG) positron emission tomography-computed tomography were performed and repeated after 12 weeks to assess treatment response. Following two cycles of conventional chemotherapy, patients underwent EUS-guided 32P implantation followed by six chemotherapy cycles. RESULTS: 12 patients with LAPC (median age 69 years [interquartile range 61.5-73.3]; 8 male) completed treatment. Technical success was 100 % with no procedural complications. At 12 weeks, median reduction in tumor volume was 8.2 cm3 (95 % confidence interval 4.95-10.85; P = 0.003), with minimal or no 18FDG uptake in nine patients (75 %). Tumor downstaging was achieved in six patients (50 %), leading to successful resection in five (42 %), including four R0 resections (80 %). CONCLUSIONS: EUS-guided 32P implantation was feasible, well tolerated, and resulted in a 42 % surgical resection rate. Further evaluation in a larger randomized multicenter trial is warranted.

Introducing Zirconium Organic Gels for Efficient Radioiodine Gas Removal.

Iodine radioisotope, as one of the most important fission products of uranium, may cause severe damage to human health when it is accidentally discharged into the environment. Hence, efficient removal of radioactive iodine is one of the most critical issues for both used nuclear fuel (UNF) reprocessing and environmental remediation. In this work, three metal-organic gels (MOGs) were introduced for iodine removal. The presented zirconium-based MOGs, namely, CWNU, CWNU-NH2, and CWNU-2NH2, were prepared via moderate solvothermal reactions. These MOGs all exhibit excellent chemical stability and reusability, marked iodine sorption capability, and favorable machinability, which can even rival commercial ones. The sorption capacities are determined to be 3.36, 4.10, and 4.20 g/g, respectively. The increased amount of amino group is considered to be responsible for the elevated iodine sorption capacity and kinetics, as confirmed by combined sorption studies and XPS analysis. The presented work sheds light on the utilization of MOGs for radioiodine capture.

Catalytic asymmetric preparation of pyrroloindolines: strategies and applications to total synthesis.

Pyrroloindolines are important and privileged polycyclic indoline motifs that are widely present in natural products and bio-significant molecules. From an organic chemistry perspective, their rigid tricyclic molecular architectures with a fully substituted carbon center at the C3a-position pose a great challenge to synthetic chemists. In a biological context, pyrroloindoline-containing alkaloids display a plethora of promising activities, making them significant in biological sciences and drug development. In the past few decades, pyrroloindoline and its analogues have emerged as appealing synthetic targets, attracting tremendous attention from the synthetic community. In this review, we summarize the state-of-the-art catalytic asymmetric synthesis of pyrroloindolines, as well as the related applications to the total synthesis of natural products.

Synthesis of Axially Chiral CF3 -Substituted 2-Arylpyrroles by Sequential Phosphine-Catalyzed Asymmetric [3+2] Annulation and Oxidative Central-to-Axial Chirality Transfer.

A sequential phosphine-catalyzed asymmetric [3+2] annulation of aldimines with allenoates and oxidative central-to-axial chirality transfer strategy has been developed. This approach is operationally simple, allowing for rapid access to a range of axially chiral CF3 -containing 2-arylpyrroles with high enantiomeric excess. Furthermore, an atroposelective synthesis of esaxerenone is presented, illustrating the practical potential of the reported method.

Facilitators and barriers to medication adherence with adjuvant endocrine therapy in women with breast cancer: a structural equation modelling approach.

PURPOSE: To identify a structure to explain the relationship between socio-clinico factors, necessity-concerns beliefs, and perceived barriers to adherence with adjuvant endocrine therapy (AET) amongst women with breast cancer. METHODS: Participants were 244 patients with early-stage breast cancer recruited from two tertiary hospitals from May 2015 to December 2018 who completed questionnaires on medication adherence (Simplified Medication Adherence Questionnaire), necessity-concerns beliefs (Beliefs about Medicine Questionnaire), and barriers to adherence (Adherence Starts with Knowledge Questionnaire). Socio-clinico variables were collected via interview and medical records review. Structural equation modelling was applied to examine the relationships between these variables and possible mediating effects of necessity-concerns beliefs on adherence to AET. RESULTS: The median age of the study participants was 61 (range 32-80) years and the median duration on AET was 1.6 (IQR 1.2-2.6) years. Adherence was positively associated with age (ß = 0.145, 95% CI: 0.011 to 0.279, p = 0.034) and negatively associated with barriers (ß = - 0.381, 95% CI: - 0.511 to - 0.251, p < 0.001). There was no effect of Necessity (ß = 0.006, 95% CI: - 0.145 to 0.158, p = 0.933) or Concerns (ß = 0.041, 95% CI: - 0.117 to 0.199, p = 0.614) on adherence. Necessity-concerns beliefs were also not significant mediators in the relationship between socio-clinico factors and medication adherence. CONCLUSIONS: Older age and lower barriers to adherence were associated with higher adherence scores. Necessity-concerns beliefs did not have a significant effect on adherence as majority of the patients identified forgetfulness as a reason for non-adherence.

Microbial predation accelerates granulation and modulates microbial community composition.

BACKGROUND: Bacterial communities are responsible for biological nutrient removal and flocculation in engineered systems such as activated floccular sludge. Predators such as bacteriophage and protozoa exert significant predation pressure and cause bacterial mortality within these communities. However, the roles of bacteriophage and protozoan predation in impacting granulation process remain limited. Recent studies hypothesised that protozoa, particularly sessile ciliates, could have an important role in granulation as these ciliates were often observed in high abundance on surfaces of granules. Bacteriophages were hypothesized to contribute to granular stability through bacteriophage-mediated extracellular DNA release by lysing bacterial cells. This current study investigated the bacteriophage and protozoan communities throughout the granulation process. In addition, the importance of protozoan predation during granulation was also determined through chemical killing of protozoa in the floccular sludge. RESULTS: Four independent bioreactors seeded with activated floccular sludge were operated for aerobic granulation for 11 weeks. Changes in the phage, protozoa and bacterial communities were characterized throughout the granulation process. The filamentous phage, Inoviridae, increased in abundance at the initiation phase of granulation. However, the abundance shifted towards lytic phages during the maturation phase. In contrast, the abundance and diversity of protozoa decreased initially, possibly due to the reduction in settling time and subsequent washout. Upon the formation of granules, ciliated protozoa from the class Oligohymenophorea were the dominant group of protozoa based on metacommunity analysis. These protozoa had a strong, positive-correlation with the initial formation of compact aggregates prior to granule development. Furthermore, chemical inhibition of these ciliates in the floccular sludge delayed the initiation of granule formation. Analysis of the bacterial communities in the thiram treated sludge demonstrated that the recovery of 'Candidatus Accumulibacter' was positively correlated with the formation of compact aggregates and granules. CONCLUSION: Predation by bacteriophage and protozoa were positively correlated with the formation of aerobic granules. Increases in Inoviridae abundance suggested that filamentous phages may promote the structural formation of granules. Initiation of granules formation was delayed due to an absence of protozoa after chemical treatment. The presence of 'Candidatus Accumulibacter' was necessary for the formation of granules in the absence of protozoa.

Low-power and high-detectivity Ge photodiodes by in-situ heavy As doping during Ge-on-Si seed layer growth.

Germanium (Ge)-based photodetectors have become one of the mainstream components in photonic-integrated circuits (PICs). Many emerging PIC applications require the photodetectors to have high detectivity and low power consumption. Herein, we demonstrate high-detectivity Ge vertical p-i-n photodiodes on an in-situ heavily arsenic (As)-doped Ge-on-Si platform. The As doping was incorporated during the initial Ge-on-Si seed layer growth. The grown film exhibits an insignificant up-diffusion of the As dopants. The design results in a ∼45× reduction on the dark current and consequently a ∼5× enhancement on the specific detectivity (D*) at low reverse bias. The improvements are mainly attributed to the improved epi-Ge crystal quality and the narrowing of the device junction depletion width. Furthermore, a significant deviation on the AsH3 flow finds a negligible effect on the D* enhancement. This unconventional but low-cost approach provides an alternative solution for future high-detectivity and low-power photodiodes in PICs. This method can be extended to the use of other n-type dopants (e.g., phosphorus (P) and antimony (Sb)) as well as to the design of other types of photodiodes (e.g., waveguide-integrated).

Gourd-shaped hole array germanium (Ge)-on-insulator photodiodes with improved responsivity and specific detectivity at 1,550†nm.

Gourd-shaped hole array germanium (Ge) vertical p-i-n photodiodes were designed and demonstrated on a germanium-on-insulator (GOI) substrate with the excellent responsivity of 0.74 A/W and specific detectivity of 3.1 × 1010 cm·Hz1/2/W. It is calculated that the gourd-shaped hole design provides a higher optical absorption compared to a cylinder-shaped hole design. As a result, the external quantum efficiency for the gourd-shaped hole array photodetector was enhanced by ∼2.5× at 1,550 nm, comparing with hole-free array photodetectors. In addition, the extracted specific detectivity is superior to that of commercial bulk Ge photodiodes. The 3-dB bandwidth for the hole array photodetectors is improved by ∼10% due to a lower device capacitance. This work paves the way for low-cost and high-performance CMOS compatible photodetectors for Si-based photonic-integrated circuits.