Protein-based bioactive coatings: from nanoarchitectonics to applications.

Protein-based bioactive coatings have emerged as a versatile and promising strategy for enhancing the performance and biocompatibility of diverse biomedical materials and devices. Through surface modification, these coatings confer novel biofunctional attributes, rendering the material highly bioactive. Their widespread adoption across various domains in recent years underscores their importance. This review systematically elucidates the behavior of protein-based bioactive coatings in organisms and expounds on their underlying mechanisms. Furthermore, it highlights notable advancements in artificial synthesis methodologies and their functional applications in vitro. A focal point is the delineation of assembly strategies employed in crafting protein-based bioactive coatings, which provides a guide for their expansion and sustained implementation. Finally, the current trends, challenges, and future directions of protein-based bioactive coatings are discussed.

USP14 inhibition promotes DNA damage repair and represses ovarian granulosa cell senescence in premature ovarian insufficiency.

BACKGROUND: Premature ovarian insufficiency (POI) is a condition characterized by a substantial decline or loss of ovarian function in women before the age of 40. However, the pathogenesis of POI remains to be further elucidated, and specific targeted drugs which could delay or reverse ovarian reserve decline are urgently needed. Abnormal DNA damage repair (DDR) and cell senescence in granulosa cells are pathogenic mechanisms of POI. Ubiquitin-specific protease 14 (USP14) is a key enzyme that regulates the deubiquitylation of DDR-related proteins, but whether USP14 participates in the pathogenesis of POI remains unclear. METHODS: We measured USP14 mRNA expression in granulosa cells from biochemical POI (bPOI) patients. In KGN cells, we used IU1 and siRNA-USP14 to specifically inhibit USP14 and constructed a cell line stably overexpressing USP14 to examine its effects on DDR function and cellular senescence in granulosa cells. Next, we explored the therapeutic potential of IU1 in POI mouse models induced by D-galactose. RESULTS: USP14 expression in the granulosa cells of bPOI patients was significantly upregulated. In KGN cells, IU1 treatment and siUSP14 transfection decreased etoposide-induced DNA damage levels, promoted DDR function, and inhibited cell senescence. USP14 overexpression increased DNA damage, impaired DDR function, and promoted cell senescence. Moreover, IU1 treatment and siUSP14 transfection increased nonhomologous end joining (NHEJ), upregulated RNF168, Ku70, and DDB1, and increased ubiquitinated DDB1 levels in KGN cells. Conversely, USP14 overexpression had the opposite effects. Intraperitoneal IU1 injection alleviated etoposide-induced DNA damage in granulosa cells, ameliorated the D-galactose-induced POI phenotype, promoted DDR, and inhibited cell senescence in ovarian granulosa cells in vivo. CONCLUSIONS: Upregulated USP14 in ovarian granulosa cells may play a role in POI pathogenesis, and targeting USP14 may be a potential POI treatment strategy. Our study provides new insights into the pathogenesis of POI and a novel POI treatment strategy.

Predicted effects of image acquisition and analysis conditions on DTMRI tractography-based muscle architecture estimates.

PURPOSE: To quantify the effects of the intrinsic signal pattern, image acquisition conditions, and data analysis conditions on diffusion-tensor MRI (DTMRI) tractography-based muscle architecture estimates using a sampling-reconstruction assessment framework. METHODS: Numerical models of muscles were constructed with realistic architectural properties. DTMRI signals were computed at signal-to-noise ratio (SNR) of 24-96 and common voxel sizes. Fiber tracking was performed, and the results were compared with the known architectural properties. RESULTS: SNR exerted the most significant impact on the outcome. The outcome variables approached asymptotes at SNR ≈ 54. Large in-plane voxel dimensions reduced the similarity between reconstructed fibers and the known architectural properties. Higher order polynomials helped reconstruct fibers with more complicated geometry but overfit noise for less complex geometries. The intrinsic fiber curvature also affected the robustness of polynomial smoothing to SNR. Other conditions, such as the fiber dimensionality, voxel aspect ratio, and slice thickness, did not affect the outcomes. CONCLUSION: SNR ≥ 54 is recommended for accurate muscle architecture characterization using DTMRI. Averaged across all simulated conditions, the greatest percent errors under SNR = 54 were -5.6% and -4.0% for the pennation angle and fiber-tract length estimates, respectively. For fiber tracts with intermediate intrinsic curvature, the greatest percent error for the curvature estimate was 9.8% for SNR = 54. Smaller in-plane voxel size (≤1.5 mm) is preferred to minimize the estimation error in architectural properties. If necessary, slice thickness may be adjusted within typical ranges to achieve sufficient SNR when slices are aligned near the fiber direction. Third-order polynomial fitting is appropriate for smoothing fiber tracts.

Enhancing the performance of mode-pairing quantum key distribution by wavelength division multiplexing.

Mode-pairing quantum key distribution (MP-QKD) holds great promise for the practical implementation of QKD in the near future. It combines the security advantages of measurement device independence while still being capable of breaking the Pirandola-Laurenza-Ottaviani-Banchi bound without the need for highly demanding phase-locking and phase-tracking technologies for deployment. In this work, we explore optimization strategies for MP-QKD in a wavelength-division multiplexing scenario. The simulation results reveal that incorporation of multiple wavelengths not only leads to a direct increase in key rate but also enhances the pairing efficiency by employing our novel pairing strategies among different wavelengths. As a result, our work provides a new avenue for the future application and development of MP-QKD.

Accuracy improvement of two-dimensional shape reconstruction based on OFDR using first-order differential local filtering.

The accuracy of two-dimensional (2D) shape reconstruction is highly susceptible to fake peaks in the strain distribution measured by optical frequency domain reflectometry (OFDR). In this paper, a post-processing method using first-order differential local filtering is proposed to suppress fake peaks and further improve the accuracy of shape reconstruction. By analyzing the principles of 2D shape reconstruction, an explanation of how fake peaks lead to shape reconstruction errors is provided, along with the introduction of an error evaluation standard. The principle of first-order differential local filtering is presented, and its feasibility is verified by simulation. An OFDR 2D shape reconstruction system is built, with three groups of 2D shape reconstruction experiments carried out, including up bending, down bending and arch bending. The experimental results show that the end errors of the three groups of shape reconstruction are respectively reduced from 2.33%, 2.97%, and 1.07% to 0.25%, 0.78%, and 0.20%, at the shape reconstruction length of 0.5 m. The research demonstrates that the accuracy of OFDR 2D shape reconstruction can be improved by using first-order differential local filtering.

The impact of diffusion tensor imaging tractography settings on muscle fascicle architecture and diffusion parameter estimates: Tract length, completion, and curvature are most sensitive to tractography settings.

Diffusion-tensor (DT)-MRI tractography provides information about properties relevant to muscle health and function, including estimates of architectural properties such as fascicle length, pennation angle, and curvature and diffusion properties such as mean diffusivity (MD) and fractional anisotropy (FA). Tractography settings, including integration algorithms, thresholds for early tract termination, and tract smoothing approaches, impact the accuracy of the muscle property estimates. However, muscle DT-MRI tractography is performed using a variety of these settings, complicating comparisons between different studies. The effects of different tractography settings on muscle architecture estimates have not been fully explored, and optimized settings for muscle tractography have not yet been determined. We examined the influence of integration algorithm and termination check settings combined with a range of step sizes, termination criteria, and smoothing polynomial orders on tract characteristics, completion/reason for termination, and goodness of fit between fiber tracts and smoothing polynomials using 3-T DT-MR images of the lower leg muscles of seven healthy adults. We found that tract length and completion were highly sensitive to strict FA and intersegment angle thresholds (25%-69% reduction in complete fiber tracts from lowest to highest minimum FA threshold and 11%-36% reduction from highest to lowest intersegment angle threshold). Higher order polynomials (third and fourth order vs. second order) better fit the muscle fiber trajectories, but curvature estimates were highly sensitive to smoothing polynomial order (3.9-6.6 m-1 increase for second- vs. fourth-order fitting polynomials). Step size impacted curvature estimates, albeit to a lesser degree. Integration algorithm had little impact, and mean pennation angle, and tract-based FA and MD, were relatively insensitive to all parameters. The results demonstrate which muscle diffusion measures and architectural estimates are most sensitive to varying tractography settings and support the need for consistent reporting of tractography details to aid interpretation and comparison of results between studies.

Linagliptin's impact on lymphatic barrier and lymphangiogenesis in oral cancer with high glucose.

OBJECTIVES: Uncertainties remain regarding the effect of elevated glucose levels on lymphatic metastasis of cancer cells. Our study elucidated the mechanisms linking high glucose to lymphangiogenesis and lymphatic barrier-related factors and investigated the protective role of linagliptin against lymphatic barrier dysfunction. MATERIALS AND METHODS: A CAL-27-LEC co-culture system was established. Sodium fluorescein permeability assay observed lymphatic endothelial cell permeability. Western blotting and RT-qPCR detected protein and mRNA expression under different conditions, respectively. CCK-8, scratch wound healing, and transwell assays revealed cell migration and proliferation. Tube formation experiment tested capacity for endothelial tube formation. Immunohistochemical staining analyzed tissue sections from 43 oral cancer individuals with/without diabetes. RESULTS: In high-glucose co-culture system, we observed increased lymphatic barrier permeability and decreased expression of ZO-1 and occludin, two tight-junction proteins; conversely, the expression of PAR2, a high permeability-related protein, was increased. Following linagliptin treatment, the expression levels of VEGF-C, VEGFR-3, and PAR2 decreased, while those of ZO-1 and occludin increased. Considerably higher levels of LYVE-1 expression in individuals with diabetes than in those without diabetes. CONCLUSIONS: By ameliorating the high glucose-induced disruption of the lymphatic endothelial barrier, linagliptin may reduce lymphangiogenesis and exhibit an inhibitory effect on lymphatic metastasis in oral cancer patients with diabetes.

Association between polypharmacy and 2-year outcomes among Chinese older inpatients: a multi-center cohort study.

BACKGROUND: The escalating global prevalence of polypharmacy presents a growing challenge to public health. In light of this issue, the primary objective of our study was to investigate the status of polypharmacy and its association with clinical outcomes in a large sample of hospitalized older patients aged 65 years and over. METHODS: A two-year prospective cohort study was carried out at six tertiary-level hospitals in China. Polypharmacy was defined as the prescription of 5 or more different medications daily, including over-the-counter and non-prescription medications. Baseline polypharmacy, multimorbidity, and other variables were collected when at admission, and 2-year outcomes were recorded by telephone follow-up. We used multivariate logistic regression analysis to examine the associations between polypharmacy and 2-year outcomes. RESULTS: The overall response rate was 87.2% and 8713 participants were included in the final analysis. The mean age was 72.40 years (SD = 5.72), and women accounted for 42.2%. The prevalence of polypharmacy among older Chinese inpatients is 23.6%. After adjusting for age, sex, education, marriage status, body mass index, baseline frailty, handgrip strength, cognitive impairment, and the Charlson comorbidity index, polypharmacy is significantly associated with frailty aggravation (OR 1.432, 95% CI 1.258-1.631) and mortality (OR 1.365, 95% CI 1.174-1.592), while inversely associated with readmission (OR 0.870, 95% CI 0.764-0.989). Polypharmacy was associated with a 35.6% increase in the risk of falls (1.356, 95%CI 1.064-1.716). This association weakened after adjustment for multimorbidity to 27.3% (OR 1.273, 95%CI 0.992-1.622). CONCLUSIONS: Polypharmacy was prevalent among older inpatients and was a risk factor for 2-year frailty aggravation and mortality. These results highlight the importance of optimizing medication use in older adults to minimize the risks associated with polypharmacy. Further research and implementing strategies are warranted to enhance the quality of care and safety for older individuals exposed to polypharmacy. TRIAL REGISTRATION: Chinese Clinical Trial Registry, ChiCTR1800017682, registered 09/08/2018.

Dynamics of T follicular helper cells in patients with rheumatic diseases and subsequent antibody responses in a three-dose immunization regimen of CoronaVac.

Given increased acceptance of the CoronaVac, there is an unmet need to assess the safety and immunogenic changes of CoronaVac in patients with rheumatic diseases (RD). Here we comprehensively analysed humoral and cellular responses in patient with RD after a three-dose immunization regimen of CoronaVac. RD patients with stable condition and/or low disease activity (n = 40) or healthy controls (n = 40) were assigned in a 1:1 ratio to receive CoronaVac (Sinovac). The prevalence of anti-receptor binding domain (RBD) antibodies and neutralizing antibodies was similar between healthy control (HC) and RD patients after the second and the third vaccination. However, the titers of anti-RBD IgG and neutralizing antibodies were significantly lower in RD patients compared to HCs (p < 0.05), which was associated with an impaired T follicular helper (Tfh) cell response. Among RD patients, those who generated an antibody response displayed a significantly higher Tfh cells compared to those who failed after the first and the second vaccination (p < 0.05). Interestingly, subjects with a negative serological response displayed a similar Tfh memory response to severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2)-derived peptides as their anti-RBD IgG positive counterpart, and all (4/4) of the non-responders in HCs, and 62.5% (5/8) of the non-responders in patients with RD displayed a positive serological response following the third dose. No serious adverse events were observed. In conclusion, our findings support SARS-CoV-2 vaccination in patients with RD with stable and/or low disease activity. The impaired ability in generating vaccine-specific antibodies in patients with RD was associated with a reduction in Tfh cells induction. The window of vaccination times still needs to be explored in future studies. Clinical trial registration: This trial was registered with ChiCTR2100049138.

Predictors and prognostic stratification for lupus low disease activity state: results from a prospective clinical trial.

OBJECTIVE: To identify predictors for lupus low disease activity state (LLDAS), early-achieved LLDAS and long-term disease activity, and to refine a prognostic stratification tool for use in active SLE patients. METHOD: A total of 245 active SLE patients were enrolled, followed up quarterly from 2014 to 2016. LLDAS-50 was defined as the maintenance of LLDAS for ≥50% of the observed time. LLDAS at 3 months after cohort entry (LLDAS-3mo) was considered an early-achieved LLDAS. Multivariate analysis was performed to identify predictors for LLDAS, early-achieved LLDAS and long-term disease activity. Based on the factors associated with LLDAS, a prognostic stratification tool for LLDAS was established. RESULTS: The 2-year probability of achieving LLDAS was 62.9% (154/245). Multivariate analysis-determined renal involvement, haematological involvement and hypocomplementaemia were negative predictors for achieving LLDAS and LLDAS-50. In multivariate logistic analysis, antiphospholipid antibodies positivity, hypocomplementaemia, renal involvement and haematological involvement were identified as negative predictors for achieving LLDAS-3mo. LLDAS-3mo (P < 0.0001; risk ratio: 47.694; 95% CI: 13.776, 165.127) was a strong predictor for LLDAS-50. The probability of achieving LLDAS, LLDAS-50 and LLDAS-3mo were 88.9% (32/36), 69.4% (25/36) and 41.7% (15/36) in the low-risk group, 65% (65/100), 51.0% (51/100) and 32.0% (32/100) in intermediate-risk group, and 52.8% (57/108), 27.8% (30/108) and 13.0% (14/108) in high-risk group respectively. Significant differences (P < 0.0001) were observed in the LLDAS Kaplan-Meier estimates for the three risk groups based on the identified risk factors. CONCLUSION: Renal involvement, haematological involvement and hypocomplementaemia were negative predictors of LLDAS achievement and maintenance. LLDAS-3mo was a positive predictor for the long-term sustainment of LLDAS.

Novel Tu translation elongation factor, mitochondrial (TUFM) homozygous variant in a consanguineous family with premature ovarian insufficiency.

Premature ovarian insufficiency (POI) is a clinical syndrome of ovarian dysfunction characterized by cessation of menstruation occurring before the age of 40 years. The genetic causes of idiopathic POI remain unclear. Here we recruited a POI patient from a consanguineous family to screen for potential pathogenic variants associated with POI. Genetic variants of the pedigree were screened using whole-exome sequencing analysis and validated through direct Sanger sequencing. A homozygous variant in TUFM (c.524G>C: p.Gly175Ala) was identified in this family. TUFM (Tu translation elongation factor, mitochondrial) is a nuclear-encoded mitochondrial protein translation elongation factor that plays a critical role in maintaining normal mitochondrial function. The variant position was highly conserved among species and predicted to be disease causing. Our in vitro functional studies demonstrated that this variant causes decreased TUFM protein expression, leading to mitochondrial dysfunction and impaired autophagy activation. Moreover, we found that mice with targeted Tufm variant recapitulated the phenotypes of human POI. Thus, this is the first report of a homozygous pathogenic TUFM variant in POI. Our findings highlighted the essential role of mitochondrial genes in folliculogenesis and ovarian function maintenance.

Boosting the performance of loss-tolerant measurement-device-independent quantum key distribution.

Measurement-device-independent quantum key distribution can remove all possible detector side channels, and is robust against state preparation flaws when further combined with the loss-tolerant method. However, the secure key rate in this scenario is relatively low, thus hindering its practical application. Here, we first present a four-intensity decoy-state protocol where the signal intensity is modulated only in Z basis for key generation while the decoy intensities are modulated in both Z and X bases for parameter estimation. Moreover, we adopt collective constraint and joint-study strategy in statistical fluctuation analysis. We have also experimentally demonstrated this protocol and the result indicates high performance and good security for practical applications.

Elevated cell-free mitochondria DNA level of patients with premature ovarian insufficiency.

BACKGROUND: Premature ovarian insufficiency (POI) patients present with a chronic inflammatory state. Cell-free mitochondria DNA (cf-mtDNA) has been explored as a reliable biomarker for estimating the inflammation-related disorders, however, the cf-mtDNA levels in POI patients have never been measured. Therefore, in the presenting study, we aimed to evaluate the levels of cf-mtDNA in plasma and follicular fluid (FF) of POI patients and to determine a potential role of cf-mtDNA in predicting the disease progress and pregnancy outcomes. METHODS: We collected plasma and FF samples from POI patients, biochemical POI (bPOI) patients and control women. Quantitative real-time PCR was used to measure the ratio of mitochondrial genome to nuclear genome of cf-DNAs extracted from the plasma and FF samples. RESULTS: The plasma cf-mtDNA levels, including COX3, CYB, ND1 and mtDNA79, were significantly higher in overt POI patients than those in bPOI patients or control women. The plasma cf-mtDNA levels were weakly correlated with ovarian reserve, and could not be improved by regular hormone replacement therapy. The levels of cf-mtDNA in FF, rather than those in plasma, exhibited the potential to predict the pregnancy outcomes, although they were comparable among overt POI, bPOI and control groups. CONCLUSIONS: The increased plasma cf-mtDNA levels in overt POI patients indicated its role in the progress of POI and the FF cf-mtDNA content may hold the value in predicting pregnancy outcomes of POI patients.

The impact of COVID-19 on online medical education: a knowledge graph analysis based on co-term analysis.

BACKGROUND: This study aims to identify the characteristics and future directions of online medical education in the context of the novel coronavirus outbreak new through visual analytics using CiteSpace and VOSviewer bibliometric methods. METHOD: From Web of Science, we searched for articles published between 2020 and 2022 using the terms online education, medical education and COVID-19, ended up with 2555 eligible papers, and the articles published between 2010 and 2019 using the terms online education, medical education and COVID-19, and we ended up with 4313 eligible papers. RESULTS: Before the COVID-19 outbreak, Medical students and care were the most frequent keywords and the most cited author was BRENT THOMA with 18 times. The United States is the country with the greatest involvement and research impact in the field of online medical education. The most cited journal is ACAD MED with 1326 citations. After the COVID-19 outbreak, a surge in the number of research results in related fields, and ANXIETY and four secondary keywords were identified. In addition, the concentration of authors of these publications in the USA and China is a strong indication that local epidemics and communication technologies have influenced the development of online medical education research. Regarding the centrality of research institutions, the most influential co-author network is Harvard Medical School in the United States; and regarding the centrality of references, the most representative journal to which it belongs is VACCINE. CONCLUSION: This study found that hey information such as keywords, major institutions and authors, and countries differ in the papers before and after the COVID-19 outbreak. The novel coronavirus outbreak had a significant impact on the online education aspect. For non-medical and medical students, the pandemic has led to home isolation, making it difficult to offer face-to-face classes such as laboratory operations. Students have lost urgency and control over the specifics of face-to-face instruction, which has reduced the quality of teaching. Therefore, we should improve our education model according to the actual situation to ensure the quality of teaching while taking into account the physical and psychological health of students.

Angle-Only Cooperative Orbit Determination Considering Attitude Uncertainty.

In this paper, a novel concept for cooperative orbit determination (OD) using inter-spacecraft angle-only measurements is proposed. Different from the conventional cooperative OD that only estimates orbit states, the attitude of the observer spacecraft is considered by incorporating the attitude into the estimated vector. The observability of a two-spacecraft system is analyzed based on the observability matrix. Observability analysis reveals that inter-spacecraft angle-only measurements are inadequate to estimate both the attitude and the orbit states in two-body dynamics. The observability of the two-spacecraft system can be improved by considering high-order gravitational perturbation or executing an attitude maneuver on the observer spacecraft. This is the first time that we present the observability analysis and orbit estimation results for a two-spacecraft system considering attitude uncertainty for the observer. Finally, simulation results demonstrate the effectiveness of the proposed method. The results in this paper can be potentially useful for autonomous managements of a spacecraft constellation and formation.

Quantitative Muscle Fascicle Tractography Using Brightness-Mode Ultrasound.

A muscle's architecture, defined as the geometric arrangement of its fibers with respect to its mechanical line of action, impacts its abilities to produce force and shorten or lengthen under load. Ultrasound and other noninvasive imaging methods have contributed significantly to our understanding of these structure-function relationships. The goal of this work was to develop a MATLAB toolbox for tracking and mathematically representing muscle architecture at the fascicle scale, based on brightness-mode ultrasound imaging data. The MuscleUS_Toolbox allows user-performed segmentation of a region of interest and automated modeling of local fascicle orientation; calculation of streamlines between aponeuroses of origin and insertion; and quantification of fascicle length, pennation angle, and curvature. A method is described for optimizing the fascicle orientation modeling process, and the capabilities of the toolbox for quantifying and visualizing fascicle architecture are illustrated in the human tibialis anterior muscle. The toolbox is freely available.

Asymmetric Measurement-Device-Independent Quantum Key Distribution through Advantage Distillation.

Measurement-device-independent quantum key distribution (MDI-QKD) completely closes the security loopholes caused by the imperfection of devices at the detection terminal. Commonly, a symmetric MDI-QKD model is widely used in simulations and experiments. This scenario is far from a real quantum network, where the losses of channels connecting each user are quite different. To adapt such a feature, an asymmetric MDI-QKD model is proposed. How to improve the performance of asymmetric MDI-QKD also becomes an important research direction. In this work, an advantage distillation (AD) method is applied to further improve the performance of asymmetric MDI-QKD without changing the original system structure. Simulation results show that the AD method can improve the secret key rate and transmission distance, especially in the highly asymmetric cases. Therefore, this scheme will greatly promote the development of future MDI-QKD networks.

Topology Abstraction-Based Routing Scheme for Secret-Key Provisioning in Hybrid GEO/LEO Quantum Satellite Networks.

Quantum key distribution (QKD) is a promising technique to resist the threat against quantum computers. However, the high loss of quantum signals over a long-distance optical fiber is an obstacle for QKD in the intercontinental domain. In this context, the quantum satellite network is preferred over the terrestrial quantum optical network. Due to the mobility of satellites, the satellite topology is dynamic in the quantum satellite network, which remains a challenge for routing. In hybrid geostationary-earth-orbit (GEO)/low-earth-orbit (LEO) quantum satellite networks, the lack of an efficient scheduling scheme for GEO/LEO satellites also limits the construction of quantum satellite networks. Therefore, this paper provides a topology abstraction-based routing scheme for secret-key provisioning, where the dynamic physical topology is translated into a quasi-static abstracted topology. This scheme contributes to saving the precious secret key resources. In order to improve the success probability of long-distance QKD requests, three novel resource-scheduling heuristic algorithms are proposed in hybrid GEO/LEO quantum satellite networks. Simulation results indicate that the proposed algorithms can improve the success probability of QKD requests by 47% compared to the benchmark.

Photoswitchable Enantioselective and Helix-Sense Controlled Living Polymerization.

A pair of enantiomeric photoswitchable PdII catalysts, alkyne-PdII /LR-azo and alkyne-PdII /LS-azo , were prepared via the coordination of alkyne-PdII and azobenzene-modified phosphine ligands LR-azo and LS-azo . Owing to the cis-trans photoisomerization of the azobenzene moiety, alkyne-PdII /LR-azo and alkyne-PdII /LS-azo exhibited different polymerization activities, helix-sense selectivities, and enantioselectivities during the polymerization of isocyanide monomers under irradiation of different wavelength lights. Furthermore, the achiral isocyanide monomer A-1 could be polymerized efficiently using alkyne-PdII /LR-azo under dark condition in a living/controlled manner. Further, it generated single right-handed helical poly-A-1m (LR-azo ), confirmed by the circular dichroism spectra and atomic force microscopy images. However, the polymerization of A-1 almost could not be initiated under 420 nm light in identical conditions of dark condition. Moreover, the photoswitchable catalyst alkyne-PdII /LR-azo exhibited high enantioselectivity for the polymerization of the racemates of L-1 and D-1, respectively. D-1 was polymerized preferentially under dark condition with a D-1/L-1 rate ratio of 70, yielding single right-handed polyisocyanides. Additionally, reversible enantioselectivity was observed under 420 nm light using alkyne-PdII /LR-azo , and the calculated polymerization rate ratio of L-1/D-1 was 57 because of the isomerization of the azobenzene moiety of the catalyst. Furthermore, alkyne-PdII /LS-azo showed opposite enantioselectivity and helix-sense selectivity during the polymerization of the racemates of L-1 and D-1.

Breaking the Size Limitation of Directly-Synthesized PbS Quantum Dot Inks Toward Efficient Short-wavelength Infrared Optoelectronic Applications.

PbS quantum dots (QDs) are promising building blocks for solution-processed short-wavelength infrared (SWIR) devices. The recently developed direct synthesis of semi-conductive PbS QD inks has substantially simplified the preparation processing and reduced the material cost, while facing the challenge to synthesize large-size QDs with absorption covering the SWIR region. Herein, we for the first time realize a low-cost, scalable synthesis of SWIR PbS QD inks after an extensive investigation of the reaction kinetics. Finally, based on these PbS SWIR QD inks, the solar cell demonstrates a record-high power conversion efficiency (PCE) of 1.44 % through an 1100 nm cutoff silicon filter and the photodetector device shows a low dark current density of 2×10-6  A cm-2 at -0.8 V reverse bias with a high external quantum efficiency (EQE) of 70 % at ≈1300 nm. Our results realize the direct synthesis of low-cost and scalable SWIR QD inks and may accelerate the industrialization of consumer SWIR technologies.