Photochemical Reaction Enabling the Engineering of Photonic Spin-Orbit Coupling in Organic-Crystal Optical Microcavities.

The control and active manipulation of spin-orbit coupling (SOC) in photonic systems are fundamental in the development of modern spin optics and topological photonic devices. Here, we demonstrate the control of an artificial Rashba-Dresselhaus (RD) SOC mediated by photochemical reactions in a microcavity filled with an organic single crystal of photochromic phase-change character. Splitting of the circular polarization components of the optical modes induced by photonic RD SOC is observed experimentally in momentum space. By applying an ultraviolet light beam, we control the spatial molecular orientation through a photochemical reaction, and with that we control the energies of the photonic modes. This way, we realize a reversible conversion of spin splitting of the optical modes with different energies, leading to an optically controlled switching between circularly and linearly polarized optical modes in our device. Our strategy of in situ and reversible engineering of SOC induced by a light field provides a promising approach to actively design and manipulate synthetic gauge fields toward future on-chip integration in photonics and topological photonic devices.

Spin-Valley-Locked Electroluminescence for High-Performance Circularly Polarized Organic Light-Emitting Diodes.

Circularly polarized (CP) organic light-emitting diodes (OLEDs) have attracted attention in potential applications, including novel display and photonic technologies. However, conventional approaches cannot meet the requirements of device performance, such as high dissymmetry factor, high directionality, narrowband emission, simplified device structure, and low costs. Here, we demonstrate spin-valley-locked CP-OLEDs without chiral emitters but based on photonic spin-orbit coupling, where photons with opposite CP characteristics are emitted from different optical valleys. These spin-valley-locked OLEDs exhibit a narrowband emission of 16 nm, a high external quantum efficiency of 3.65%, a maximum luminance of near 98,000 cd/m2, and a gEL of up to 1.80, which are among the best performances of active single-crystal CP-OLEDs, achieved with a simple device structure. This strategy opens an avenue for practical applications toward three-dimensional displays and on-chip CP-OLEDs.

Quasi-Homogeneous Photocatalysis in Ultrastiff Microporous Polymer Aerogels.

The development of efficient and low-cost catalysts is essential for photocatalysis; however, the intrinsically low photocatalytic efficiency as well as the difficulty in using and recycling photocatalysts in powder morphology greatly limit their practical performance. Herein, we describe quasi-homogeneous photocatalysis to overcome these two limitations by constructing ultrastiff, hierarchically porous, and photoactive aerogels of conjugated microporous polymers (CMPs). The CMP aerogels exhibit low density but high stiffness beyond 105 m2 s-2, outperforming most low-density materials. Extraordinary stiffness ensures their use as robust scaffolds for scaled photocatalysis and recycling without damage at the macroscopic level. A challenging but desirable reaction for direct deaminative borylation is demonstrated using CMP aerogel-based quasi-homogeneous photocatalysis with gram-scale productivity and record-high efficiency under ambient conditions. Combined terahertz and transient absorption spectroscopic studies unveil the generation of high-mobility free carriers and long-lived excitonic species in the CMP aerogels, underlying the observed superior catalytic performance.

Dual-Stimuli-Responsive Modulation Organic Afterglow Based on N─H Proton Migration Mechanism.

Organic afterglow materials have significant applications in information security and flexible electronic devices with unique optical properties. It is vital but challenging to develop organic afterglow materials possessing controlled output with multi-stimuli-responsive capacity. Herein, dimethyl terephthalate (DTT) is introduced as a strong proton acceptor. The migration direction of N─H protons on two compounds Hs can be regulated by altering the excitation wavelength (Ex) or amine stimulation, thereby achieving dual-stimuli-responsive afterglow emission. When the Ex is below 300 nm, protons migrate to S1-2 DTT, where strong interactions induce phosphorescent emission of Hs, resulting in afterglow behavior. Conversely, when the Ex is above 300 nm, protons interact with the S0 DTT weakly and the afterglow disappears. In view of amine-based compounds with higher proton accepting capabilities, it can snatch proton from S1-2 DTT and redirect the proton flow toward amine, effectively suppressing the afterglow but obtaining a new redshifted fluorescence emission with Δλ over 200 nm due to the high polarity of amine. Moreover, it is successfully demonstrated that the applications of dual-stimuli-responsive organic afterglow materials in information encryption based on the systematic excitation-wavelength-dependent (Ex-De) behavior and amine selectivity detection.

Multiple Electron Transfer in Semiconductive Ternary D-D'-A Metal-Organic Framework for Enhanced X-Ray Detection and Imaging.

Semiconductive metal-organic frameworks (MOFs) with donor-acceptor (D-A) characteristics have garnered attractive attention due to their capacity for separating and transferring photogenerated charges, making them promising candidates for high-performance X-ray detectors. However, the low charge transfer efficiency between the metal nodes and organic ligands limits the X-ray-to-electricity conversion efficiency of these materials. Herein, an additional photoactive donor (D') is introduced by incorporating a heavy atom-containing polyoxometalate (POM) [α-SiW12O40]4- into a binary {[Ni·bcbp·(H2O)2]·(H2O)4·Cl}n (Ni-bcbp, bcbp: H2bcbp·2Cl = 1,1'-bis(4-carboxyphenyl)(4,4'-bipyridinium) dichloride) MOF, resulting in a semiconductive ternary D-D'-A framework {[Ni2(bcbp)2·(H2O)4·(DMA)]·(SiW12O40)}n (SiW@Ni-bcbp, DMA: dimethylacetamide). The obtained material features an unprecedented porous 8-connected bcu-net structure that accommodates nanoscale [α-SiW12O40]4- counterions, displaying uncommon optoelectronic responses. In contrast to binary Ni-bcbp, the SiW@Ni-bcbp framework exhibits distinctive photochromism and robust X-ray responsiveness, which can be attributed to the synergistic effects of the electron reservoir and multiple photoinduced electron transfer originating from the POMs. As a result, the X-ray detector based on SiW@Ni-bcbp demonstrates a sensitivity of 5741.6 µC Gyair -1 cm-2 with a low detection limit of 0.49 µGyair s-1. Moreover, the devices demonstrated the capability of producing clearness X-ray images, providing a feasible and stable solution for constructing high-performance direct X-ray detectors.

Spectral multiplexing based on multi-distance lensless imaging.

We have demonstrated the capability of spectral multiplexing in multi-distance diffractive imaging, enabling the reconstruction of samples with diverse spectral responses. While previous methods such as ptychography utilize redundancy in radial diffraction data to achieve information multiplexing, they typically require capturing a substantial amount of diffraction data. In contrast, our approach effectively harnesses the redundancy information in axial diffraction data. This significantly reduces the amount of diffraction data required and relaxes the stringent requirements on optical path stability.

Dual Orthogonally Polarized Lasing Assisted by Imaginary Fermi Arcs in Organic Microcavities.

The polarization control of micro- and nanolasers is an important topic in nanophotonics. Up to now, the simultaneous generation of two distinguishable orthogonally polarized lasing modes from a single organic microlaser remains a critical challenge. Here, we demonstrate simultaneously orthogonally polarized dual lasing from a microcavity filled with an organic single crystal exhibiting selective strong coupling. We show that the non-Hermiticity due to polarization-dependent losses leads to the formation of real and imaginary Fermi arcs with exceptional points. Simultaneous orthogonally polarized lasing becomes possible thanks to the eigenstate mixing by the photonic spin-orbit coupling at the imaginary Fermi arcs. Our work provides a novel way to develop linearly polarized lasers and paves the way for the future fundamental research in topological photonics, non-Hermitian optics, and other fields.

Is precarious employment an occupational hazard? Evidence from Ontario, Canada.

OBJECTIVES: To examine the association between precarious employment and risk of occupational injury or illness in Ontario, Canada. METHODS: We combined accepted lost-time compensation claims from the Workplace Safety and Insurance Board with labour force statistics to estimate injury and illness rates between January 2016 and December 2019. Precarious employment was imputed using a job exposure matrix and operationalised in terms of temporary employment, low wages, irregular hours, involuntary part-time employment and a multidimensional measure of 'low', 'medium', 'high' and 'very high' probabilities of exposure to precarious employment. Negative binomial regression models examined exposure to precarious employment in relation to risk of occupational injury or illness. RESULTS: After adjusting for age, sex and year, all indicators of precarious employment were associated with increased risk of injury or illness. Workers with 'high' and 'very' high' exposure to precarious employment presented a nearly threefold risk of injury or illness (rate ratio (RR): 2.81, 95% CI 2.73 to 2.89; RR: 2.82, 95% CI 2.74 to 2.90). Further adjustment for physical demands and workplace hazards attenuated associations, though a statistically and substantively significant exposure-outcome relationship persisted for workers with 'high' and 'very high' exposures to precarious employment (RR: 1.65, 95% CI 1.58 to 1.72; RR: 2.00, 95% CI 1.92 to 2.08). CONCLUSIONS: Workers exposed to precarious employment are more likely to sustain a lost-time injury or illness in Ontario, Canada. Workplace health and safety strategies should consider the role of precarious employment as an occupational hazard and a marker of work injury risk.

Variation in occupational exposure risk for COVID-19 workers' compensation claims across pandemic waves in Ontario.

OBJECTIVES: To understand rates of work-related COVID-19 (WR-C19) infection by occupational exposures across waves of the COVID-19 pandemic in Ontario, Canada. METHODS: We combined workers' compensation claims for COVID-19 with data from Statistics Canada's Labour Force Survey, to estimate rates of WR-C19 among workers spending the majority of their working time at the workplace between 1 April 2020 and 30 April 2022. Occupational exposures, imputed using a job exposure matrix, were whether the occupation was public facing, proximity to others at work, location of work and a summary measure of low, medium and high occupational exposure. Negative binomial regression models examined the relationship between occupational exposures and risk of WR-C19, adjusting for covariates. RESULTS: Trends in rates of WR-C19 differed from overall COVID-19 cases among the working-aged population. All occupational exposures were associated with increased risk of WR-C19, with risk ratios for medium and high summary exposures being 1.30 (95% CI 1.09 to 1.55) and 2.46 (95% CI 2.10 to 2.88), respectively, in fully adjusted models. The magnitude of associations between occupational exposures and risk of WR-C19 differed across waves of the pandemic, being weakest for most exposures in period March 2021 to June 2021, and highest at the start of the pandemic and during the Omicron wave (December 2021 to April 2022). CONCLUSIONS: Occupational exposures were consistently associated with increased risk of WR-C19, although the magnitude of this relationship differed across pandemic waves in Ontario. Preparation for future pandemics should consider more accurate reporting of WR-C19 infections and the potential dynamic nature of occupational exposures.

ECHO OEM virtual community of learning for primary care.

BACKGROUND: Health issues caused and/or exacerbated by work are common in patients seeking primary health care. Yet, primary care providers generally receive little or no training in the assessment and management of occupational injuries and illnesses. AIMS: To conduct a pilot project to develop, implement and evaluate a programme to teach occupational and environmental medicine to primary healthcare providers. METHODS: We followed the Extensions for Community Healthcare Outcomes (ECHO) model to connect primary healthcare providers with experts in Occupational and Environmental Medicine (OEM). We employed an observational pre-post study design to assess changes in self-efficacy, knowledge, attitudes and beliefs towards OEM. RESULTS: From September 2021 to June 2022, we offered two cycles of 12 sessions each. Participants came from medicine, nursing, psychology, occupational and physical therapy, chiropractic, kinesiology, social work, and pharmacy. Sixty-seven participants completed both pre- and post-ECHO questionnaires. Self-efficacy and knowledge ratings significantly increased after attendance at ECHO compared to the pre-ECHO responses. Attitudes and beliefs were unchanged in most of the items assessed. Participants rated their satisfaction with ECHO between 59% and 97%. CONCLUSIONS: Our pilot study demonstrated the challenges in implementing the first ECHO OEM in Canada. Findings show acceptability and satisfaction, improved self-efficacy, and small increases in knowledge, but not overall attitudes and beliefs. There is a need to understand barriers to participation and to target participants with less knowledge and experience in occupational and environmental medicine.

Switching from Thermally Activated Delayed Fluorescence in Single Crystals for Low-Threshold Laser to Room-temperature Phosphorescence in Amorphous-Film for Highly Efficient OLEDs.

Metal-organic phosphorescent complexes containing Ir or Pt are work horse in organic light-emitting diode (OLED) technology, which can harvest both singlet and triplet excitons in electroluminescence (EL) owing to strong heavy-atom effect. Recently, organic room-temperature phosphorescence (ORTP) have achieved high photoluminescence quantum yield (PLQY) in rigid crystalline state, which, however, is unsuitable for OLED fabrication, therefore leading to an EL efficiency far low behind those of metal-organic phosphorescent complexes. Here, we reported a luminescence mechanism switch from thermally activated delayed fluorescence (TADF) in single crystal microwires to ORTP in amorphous thin-films, based on a tert-butylcarbazole difluoroboron ß-diketonate derivative of DtCzBF2. Tightly packed and well-faceted single-crystal microwires exhibit aggregation induced emission (AIE), enabling TADF microlasers at 473 nm with an optical gain coefficient as high as 852 cm-1 . In contrast, loosely packed dimers of DtCzBF2 formed in guest-host amorphous thin-films decrease the oscillator strength of fluorescence transition but stabilize triplets for ORTP with a PLQY up to 61 %, leading to solution-processed OLEDs with EQE approaching 20 %. This study opens possibilities of low-cost ORTP emitters for high performance OLEDs and future low-threshold electrically injected organic semiconductor lasers (OSLs).

Host Surface-Induced Excitation Wavelength-Dependent Organic Afterglow.

The design and construction of organic afterglow materials is an attractive but formidably challenging task due to the low intersystem crossing efficiency and nonradiative decay. Here, we developed a host surface-induced strategy to achieve excitation wavelength-dependent (Ex-De) afterglow emission through a facile dropping process. The prepared PCz@dimethyl terephthalate (DTT)@paper system exhibits a room-temperature phosphorescence afterglow, with the lifetime up to 1077.1 ± 15 ms and duration time exceeding 6 s under ambient conditions. Furthermore, we can switch the afterglow emission on and off by adjusting the excitation wavelength below or above 300 nm, showing a remarkable Ex-De behavior. Spectral analysis demonstrated that the afterglow originates from the phosphorescence of PCz@DTT assemblies. The stepwise preparation process and detailed experiments (XRD, 1H NMR, and FT-IR analysis) proved the presence of strong intermolecular interactions between the carbonyl groups on the surface of DTT and the entire frame of PCz, which can inhibit the nonradiative processes of PCz to achieve afterglow emission. Theoretical calculations further manifested that DTT geometry alteration under different excitation beams is the main reason for the Ex-De afterglow. This work discloses an effective strategy for constructing smart Ex-De afterglow systems that can be fully exploited in a range of fields.

Room-Temperature Electrical Field-Enhanced Ultrafast Switch in Organic Microcavity Polariton Condensates.

Integrated electro-optical switches are essential as one of the fundamental elements in the development of modern optoelectronics. As an architecture for photonic systems exciton polaritons, hybrid bosonic quasiparticles that possess unique properties derived from both excitons and photons, have shown much promise. For this system, we demonstrate a significant improvement of emitted intensity and condensation threshold by applying an electric field to a microcavity filled with an organic microbelt. Our theoretical investigations indicate that the electric field makes the excitons dipolar and induces an enhancement of the exciton-polariton interaction and of the polariton lifetime. Based on these electric field-induced changes, a sub-nanosecond electrical field-enhanced polariton condensate switch is realized at room temperature, providing the basis for developing an on-chip integrated photonic device in the strong light-matter coupling regime.

Detecting Active Deconjugating Enzymes with Genetically Encoded Activity-Based Ubiquitin and Ubiquitin-like Protein Probes.

Post-translational modification of proteins by Ubiquitin (Ub) and Ubiquitin-like proteins (Ubls) can be reversed by deconjugating enzymes, which have been implicated in different pathways and associated with various human diseases. To understand the activity and dynamics of deconjugating enzymes, multiple synthetic and semi-synthetic Ub/Ubl probes have been developed, and some of them have been applied to screen inhibitors of deconjugating enzymes. Since these Ub/Ubl probes are generally not cell-permeable, different strategies have been developed to deliver Ub/Ubl probes to live cells. However, till now, no Ub/Ubl probes can be expressed in live cells to directly report on the activities of deconjugating enzymes in the most relevant cellular environment. Here, we genetically encoded cross-linkable Ub/Ubl probes in live E. coli and HEK293T cells. These probes can cross-link with deconjugating enzymes in vitro and in vivo. Using these Ub probes combined with mass spectrometry, we have successfully identified endogenous deconjugating enzymes in live cells. We believe that these genetically encoded Ub/Ubl probes are valuable for investigating biological functions of deconjugating enzymes in physiological environments.

Novel Semiconductive Ternary Hybrid Heterostructures for Artificial Optoelectronic Synapses.

Synaptic devices that mimic biological synapses are considered as promising candidates for brain-inspired devices, offering the functionalities in neuromorphic computing. However, modulation of emerging optoelectronic synaptic devices has rarely been reported. Herein, a semiconductive ternary hybrid heterostructure is prepared with a D-D'-A configuration by introducing polyoxometalate (POM) as an additional electroactive donor (D') into a metalloviologen-based D-A framework. The obtained material features an unprecedented porous 8-connected bcu-net that accommodates nanoscale [α-SiW12 O40 ]4- counterions, displaying uncommon optoelectronic responses. Besides, the fabricated synaptic device based on this material can achieve dual-modulation of synaptic plasticity due to the synergetic effect of electron reservoir POM and photoinduced electron transfer. And it can successfully simulate learning and memory processes similar to those in biological systems. The result provides a facile and effective strategy to customize multi-modality artificial synapses in the field of crystal engineering, which opens a new direction for developing high-performance neuromorphic devices.

Capturing Protein-Protein Interactions with Acidic Amino Acids Reactive Cross-Linkers.

Acidic residues (Asp and Glu) have a high prevalence on protein surfaces, but cross-linking reactions targeting these residues are limited. Existing methods either require high-concentration coupling reagents or have low structural compatibility. Here a previously reported "plant-and-cast" strategy is extended to develop heterobifunctional cross-linkers. These cross-linkers first react rapidly with Lys sidechains and then react with Asp and Glu sidechains, in a proximity-enhanced fashion. The cross-linking reaction proceeds at neutral pH and room temperature without coupling reagents. The efficiency and robustness of cross-linking using model proteins, ranging from small monomeric proteins to large protein complexes are demonstrated. Importantly, it is shown that this type of cross-linkers are efficient at identifying protein-protein interactions involving acidic domains. The Cross-linking mass spectrometry (XL-MS) study with p53 identified 87 putative binders of the C-terminal domain of p53. Among them, SARNP, ZRAB2, and WBP11 are shown to regulate the expression and alternative splicing of p53 target genes. Thus, these carboxylate-reactive cross-linkers will further expand the power of XL-MS in the analysis of protein structures and protein-protein interactions.

idenPC-MIIP: identify protein complexes from weighted PPI networks using mutual important interacting partner relation.

Protein complexes are key units for studying a cell system. During the past decades, the genome-scale protein-protein interaction (PPI) data have been determined by high-throughput approaches, which enables the identification of protein complexes from PPI networks. However, the high-throughput approaches often produce considerable fraction of false positive and negative samples. In this study, we propose the mutual important interacting partner relation to reflect the co-complex relationship of two proteins based on their interaction neighborhoods. In addition, a new algorithm called idenPC-MIIP is developed to identify protein complexes from weighted PPI networks. The experimental results on two widely used datasets show that idenPC-MIIP outperforms 17 state-of-the-art methods, especially for identification of small protein complexes with only two or three proteins.

PL-search: a profile-link-based search method for protein remote homology detection.

Protein remote homology detection is a fundamental and important task for protein structure and function analysis. Several search methods have been proposed to improve the detection performance of the remote homologues and the accuracy of ranking lists. The position-specific scoring matrix (PSSM) profile and hidden Markov model (HMM) profile can contribute to improving the performance of the state-of-the-art search methods. In this paper, we improved the profile-link (PL) information for constructing PSSM or HMM profiles, and proposed a PL-based search method (PL-search). In PL-search, more robust PLs are constructed through the double-link and iterative extending strategies, and an accurate similarity score of sequence pairs is calculated from the two-level Jaccard distance for remote homologues. We tested our method on two widely used benchmark datasets. Our results show that whether HHblits, JackHMMER or position-specific iterated-BLAST is used, PL-search obviously improves the search performance in terms of ranking quality as well as the number of detected remote homologues. For ease of use of PL-search, both its stand-alone tool and the web server are constructed, which can be accessed at http://bliulab.net/PL-search/.

idenPC-CAP: Identify protein complexes from weighted RNA-protein heterogeneous interaction networks using co-assemble partner relation.

Protein complexes play important roles in most cellular processes. The available genome-wide protein-protein interaction (PPI) data make it possible for computational methods identifying protein complexes from PPI networks. However, PPI datasets usually contain a large ratio of false positive noise. Moreover, different types of biomolecules in a living cell cooperate to form a union interaction network. Because previous computational methods focus only on PPIs ignoring other types of biomolecule interactions, their predicted protein complexes often contain many false positive proteins. In this study, we develop a novel computational method idenPC-CAP to identify protein complexes from the RNA-protein heterogeneous interaction network consisting of RNA-RNA interactions, RNA-protein interactions and PPIs. By considering interactions among proteins and RNAs, the new method reduces the ratio of false positive proteins in predicted protein complexes. The experimental results demonstrate that idenPC-CAP outperforms the other state-of-the-art methods in this field.

SOX9 promotes the invasion and migration of lung adenocarcinoma cells by activating the RAP1 signaling pathway.

OBJECTIVE: SOX9 has been shown to be related to the metastasis of various cancers. Recently, it has been reported that SOX9 plays a regulatory role in lung adenocarcinoma (LUAD) cell metastasis, but the specific mechanism remains to be explored. Therefore, the objective of this study was to observe the effect and mechanism of SOX9 on the invasion and migration of LUAD cells. METHODS: RT-qPCR was applied to observe the expression of SOX9 and RAP1 in tumor tissues and corresponding normal lung tissues collected from LUAD patients. Co-immunoprecipitation and Pearson correlation to analyze the expression correlation of SOX9 with RAP1. To observe the role of SOX9, the invasion and migration levels of LUAD A549 cells in each group were observed by Transwell invasion assay and Scratch migration assay after knocking down or overexpressing SOX9. Besides, the expression levels of RAP1 pathway-related proteins (RAP1, RAP1GAP and RasGRP33) were observed by RT-qCPR or western blot. Subsequently, RAP1 was overexpressed and SOX9 was knocked down in A549 cells, and then the cell invasion/migration level and RAP1 pathway activity were assessed. RESULTS: The expression levels of SOX9 and RAP1 in tumor tissues and A549 cells of LUAD patients were significantly increased and positively correlated. Overexpression of SOX9 or RAP1 alone in A549 cells enhanced the invasion and migration ability of cells, as well as up-regulated the expression levels of RAP1, RAP1GAP and RasGRP33. However, knocking down SOX9 decreased cell invasion and migration levels and weakened the activity of RAP1 pathway. Notably, overexpressing RAP1 while knocking down SOX9 significantly activated RAP1 pathway and promoted cell invasion and migration. CONCLUSION: Overexpression of SOX9 in LUAD can significantly activate the RAP1 signaling pathway and promote cell invasion and migration.