Radiation-Assisted Assembly of a Highly Dispersed Nanomolybdenum-Functionalized Covalent Organic Framework.

Two-dimensional covalent organic frameworks (2D COFs), featuring a large surface area and 1D pore structure, serve as promising scaffolds for anchoring functional guest compounds, which can significantly enhance their performance and thus expand their potential applications. Postsynthetic strategy for COFs functionalization is versatile but challenging because of their tedious procedure with high time and energy consumption, generation of excess reaction waste, and damage to COF crystallinity. We report in this work a general strategy for the synthesis of inorganic nanocompound-functionalized COF composites in a one-pot way. Specifically, a high-crystallinity nanoscale molybdenum compound is successfully introduced into a COF skeleton with high dispersion in situ during the crystallization process of the COF induced by gamma ray radiation under ambient conditions. The obtained COF@Mo composites exhibit remarkable sorption performance for methylene blue and many other organic dyes in aqueous solution with the advantages of ultrarapid uptake dynamics and high removal efficiency.

Record High Iodate Anion Capture by a Redox-Active Cationic Polymer Network.

As a critical radioactive anionic contaminant, traditional adsorbents primarily remove iodate (IO3 -) through ion exchange or hard acid-hard base interactions, but suffer from limited affinity and capacity. Herein, employing the synergistic effect of ion exchange and redox, we successfully synthesized a redox-active cationic polymer network (SCU-CPN-6, [C9H10O2N5 ⋅ Cl]n) by merging guanidino groups with ion-exchange capability and phenolic groups with redox ability via a Schiff base reaction. SCU-CPN-6 exhibits a groundbreaking adsorption capacity of 896 mg/g for IO3 -. The inferior adsorption capacities of polymeric networks containing only redox (~0 mg/g) or ion exchange (232 mg/g) fragments underscore the synergistic "1+1>2" effect of the two mechanisms. Besides, SCU-CPN-6 shows excellent uptake selectivity for IO3 - in the presence of high concentrations of SO4 2-, Cl-, and NO3 -. Meanwhile, a high distribution coefficient indicates its exemplary deep-removal performance for low IO3 - concentration. The synergic strategy not only presents a breakthrough solution for the efficient removal of IO3 - but also establishes a promising avenue for the design of advanced adsorbents for diverse applications.

Label-Free Single Microparticles and Cell Aggregates Sorting in Continuous Cell-Based Manufacturing.

There is a paradigm shift in biomanufacturing toward continuous bioprocessing but cell-based manufacturing using adherent and suspension cultures, including microcarriers, hydrogel microparticles, and 3D cell aggregates, remains challenging due to the lack of efficient in-line bioprocess monitoring and cell harvesting tools. Herein, a novel label-free microfluidic platform for high throughput (≈50 particles/sec) impedance bioanalysis of biomass, cell viability, and stem cell differentiation at single particle resolution is reported. The device is integrated with a real-time piezo-actuated particle sorter based on user-defined multi-frequency impedance signatures. Biomass profiling of Cytodex-3 microcarriers seeded with adipose-derived mesenchymal stem cells (ADSCs) is first performed to sort well-seeded or confluent microcarriers for downstream culture or harvesting, respectively. Next, impedance-based isolation of microcarriers with osteogenic differentiated ADSCs is demonstrated, which is validated with a twofold increase of calcium content in sorted ADSCs. Impedance profiling of heterogenous ADSCs-encapsulated hydrogel (alginate) microparticles and 3D ADSC aggregate mixtures is also performed to sort particles with high biomass and cell viability to improve cell quality. Overall, the scalable microfluidic platform technology enables in-line sample processing from bioreactors directly and automated analysis of cell quality attributes to maximize cell yield and improve the control of cell quality in continuous cell-based manufacturing.

Hydrogen Isotope Effect Endows a Breakthrough in Photoluminescent Covalent Organic Frameworks.

Luminescent covalent organic frameworks (LCOFs) have emerged as indispensable candidates in various applications due to their greater tunable emitting properties and structural robustness compared to small molecule emitters. An unsolved issue in this area is developing highly luminescent LCOFs of which the nonradiative quenching pathways were suppressed as much as possible. Here, a robust aminal-linked COF (DD-COF) possessing perdeuterated light-emitting monomers was designed and synthesized. The solid-state photoluminescence quantum yield of the DD-COF reaches 81%, significantly outcompeting all state-of-the-art LCOFs reported so far. The exceptional luminescent efficiency is attributed to the inhibition of different pathways of nonradiative decay, especially from bond vibrations where only substitution by a heavier isotope with a lower zero-point vibration frequency works. Furthermore, the prepared deuterated COF not only boosts higher photostability under UV irradiation but also enables superior fluorescence sensing performance for iodine detection compared to nondeuterated COF.

Radiation-Induced De Novo Defects in Metal-Organic Frameworks Boost CO2 Sorption.

Defects in metal-organic frameworks (MOFs) can significantly change their local microstructures, thus notably leading to an alteration-induced performance in sorption or catalysis. However, achieving de novo defect engineering in MOFs under ambient conditions without the scarification of their crystallinity remains a challenge. Herein, we successfully synthesize defective ZIF-7 through 60Co gamma ray radiation under ambient conditions. The obtained ZIF-7 is defect-rich but also has excellent crystallinity, enhanced BET surface area, and hierarchical pore structure. Moreover, the amount and structure of these defects within ZIF-7 were determined from the two-dimensional (2D) 13C-1H frequency-switched Lee-Goldburg heteronuclear correlation (FSLG-HETCOR) spectra, continuous rotation electron diffraction (cRED), and high-resolution transmission electron microscopy (HRTEM). Interestingly, the defects in ZIF-7 all strongly bind to CO2, leading to a remarkable enhancement of the CO2 sorption capability compared with that synthesized by the solvothermal method.

An Aryl-ether-linked Covalent Organic Framework Modified with Thioamide Groups for Selective Extraction of Palladium from Strong Acid Solutions.

Efficient adsorption of palladium ions from acid nuclear waste solution is crucial for ensuring the safety of vitrification process for radioactive waste. However, the limited stability and selectivity of most current adsorbents hinder their practical applications under strong acid and intense radiation conditions. Herein, to address these limitations, we designed and synthesized an aryl-ether-linked covalent organic framework (COF-316-DM) grafted dimethylthiocarbamoyl groups on the pore walls. This unique structure endows COF-316-DM with high stability and exceptional palladium capture capacity. The robust polyarylether linkage enables COF-316-DM to withstand irradiation doses of 200 or 400 kGy of ß/γ ray. Furthermore, COF-316-DM demonstrates fast adsorption kinetics, high adsorption capacity (147 mg g-1 ), and excellent reusability in 4 M nitric acid. Moreover, COF-316-DM exhibits remarkable selectivity for palladium ions in the presence of 17 interference ions, simulating high level liquid waste scenario. The superior adsorption performance can be attributed to the strong binding affinity between the thioamide groups and Pd2+ ions, as confirmed by the comprehensive analysis of FT-IR and XPS spectra. Our findings highlight the potential of COFs with robust linkers and tailored functional groups for efficient and selective capture of metal ions, even in harsh environmental conditions.

Identification of ferroptosis-related genes in the progress of NASH.

Background: Non-alcoholic steatohepatitis (NASH) is becoming more widespread, and some similarities exist between its etiology and ferroptosis. However, there are limited investigations on which ferroptosis-related genes (FRGs) are regulated in NASH and how to regulate them. We screened and validated the pivotal genes linked to ferroptosis in NASH to comprehend the function of ferroptosis in the development of NASH. Methods: Two mRNA expression data were obtained from the Gene Expression Omnibus (GEO) as the training set and validation set respectively. FRGs were downloaded from FerrDb. The candidate genes were obtained from the intersection between differentially expressed genes (DEGs) and FRGs, and further analyzed using the Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG). The hub genes were identified by the protein-protein interaction (PPI) network and Cytoscape. Then, FRGs closely related to the severity of NASH were identified and further confirmed using the validation set and mouse models. Ultimately, based on these genes, a diagnostic model was established to differentiate NASH from normal tissues using another data set from GEO. Results: A total of 327 FRGs in NASH were acquired and subjected to GSEA. And 42 candidate genes were attained by overlapping the 585 FRGs with 2823 DEGs, and enrichment analysis revealed that these genes were primarily engaged in the fatty acid metabolic, inflammatory response, and oxidative stress. A total of 10 hub genes (PTGS2、IL1B、IL6、NQO1、ZFP36、SIRT1、ATF3、CDKN1A、EGR1、NOX4) were then screened by PPI network. The association between the expression of 10 hub genes and the progress of NASH was subsequently evaluated by a training set and verified by a validation set and mouse models. CDKN1A was up-regulated along with the development of NASH while SIRT1 was negatively correlated with the course of the disease. And the diagnostic model based on CDKN1A and SIRT1 successfully distinguished NASH from normal samples. Conclusion: In summary, our findings provide a new approach for the diagnosis, prognosis, and treatment of NASH based on FRGs, while advancing our understanding of ferroptosis in NASH.

Emergence of a Lanthanide Chalcogenide as an Ideal Scintillator for a Flexible X-ray Detector.

The development of high-performance X-ray detectors requires scintillators with fast decay time, high light yield, stability, and X-ray absorption capacity, which are difficult to achieve in a single material. Here, we present the first example of a lanthanide chalcogenide of LaCsSiS4 : 1 % Ce3+ that simultaneously integrates multiple desirable properties for an ideal scintillator. LaCsSiS4 : 1 % Ce3+ demonstrates a remarkably low detection limit of 43.13 nGyair s-1 and a high photoluminescence quantum yield of 98.24 %, resulting in a high light yield of 50480±1441 photons/MeV. Notably, LaCsSiS4 : 1 % Ce3+ exhibits a fast decay time of only 29.35±0.16 ns, making it one of the fastest scintillators among all lanthanide-based inorganic scintillators. Furthermore, this material shows robust radiation and moisture resistance, endowing it with suitability for chemical processing under solution conditions. To demonstrate the X-ray imaging capacity of LaCsSiS4 : 1 % Ce3+ , we fabricated a flexible X-ray detector that achieved a high spatial resolution of 8.2 lp mm-1 . This work highlights the potential of lanthanide chalcogenide as a promising candidate for high-performance scintillators.

Label-free microfluidic cell sorting and detection for rapid blood analysis.

Blood tests are considered as standard clinical procedures to screen for markers of diseases and health conditions. However, the complex cellular background (>99.9% RBCs) and biomolecular composition often pose significant technical challenges for accurate blood analysis. An emerging approach for point-of-care blood diagnostics is utilizing "label-free" microfluidic technologies that rely on intrinsic cell properties for blood fractionation and disease detection without any antibody binding. A growing body of clinical evidence has also reported that cellular dysfunction and their biophysical phenotypes are complementary to standard hematoanalyzer analysis (complete blood count) and can provide a more comprehensive health profiling. In this review, we will summarize recent advances in microfluidic label-free separation of different blood cell components including circulating tumor cells, leukocytes, platelets and nanoscale extracellular vesicles. Label-free single cell analysis of intrinsic cell morphology, spectrochemical properties, dielectric parameters and biophysical characteristics as novel blood-based biomarkers will also be presented. Next, we will highlight research efforts that combine label-free microfluidics with machine learning approaches to enhance detection sensitivity and specificity in clinical studies, as well as innovative microfluidic solutions which are capable of fully integrated and label-free blood cell sorting and analysis. Lastly, we will envisage the current challenges and future outlook of label-free microfluidics platforms for high throughput multi-dimensional blood cell analysis to identify non-traditional circulating biomarkers for clinical diagnostics.

Effectiveness and Acceptability of Conversational Agents for Smoking Cessation: A Systematic Review and Meta-analysis.

INTRODUCTION: Conversational agents (CAs; computer programs that use artificial intelligence to simulate a conversation with users through natural language) have evolved considerably in recent years to support healthcare by providing autonomous, interactive, and accessible services, making them potentially useful for supporting smoking cessation. We performed a systematic review and meta-analysis to provide an overarching evaluation of their effectiveness and acceptability to inform future development and adoption. AIMS AND METHODS: PsycInfo, Web of Science, ACM Digital Library, IEEE Xplore, Medline, EMBASE, Communication and Mass Media Complete, and CINAHL Complete were searched for studies examining the use of CAs for smoking cessation. Data from eligible studies were extracted and used for random-effects meta-analyses. RESULTS: The search yielded 1245 publications with 13 studies eligible for systematic review (total N = 8236) and six studies for random-effects meta-analyses. All studies reported positive effects on cessation-related outcomes. A meta-analysis with randomized controlled trials reporting on abstinence yielded a sample-weighted odds ratio of 1.66 (95% CI = 1.33% to 2.07%, p < .001), favoring CAs over comparison groups. A narrative synthesis of all included studies showed overall high acceptability, while some barriers were identified from user feedback. Overall, included studies were diverse in design with mixed quality, and evidence of publication bias was identified. A lack of theoretical foundations was noted, as well as a clear need for relational communication in future designs. CONCLUSIONS: The effectiveness and acceptability of CAs for smoking cessation are promising. However, standardization of reporting and designing of the agents is warranted for a more comprehensive evaluation. IMPLICATIONS: This is the first systematic review to provide insight into the use of CAs to support smoking cessation. Our findings demonstrated initial promise in the effectiveness and user acceptability of these agents. We also identified a lack of theoretical and methodological limitations to improve future study design and intervention delivery.

Metal-Organic Framework@Metal Oxide Heterostructures Induced by Electron-Beam Radiation.

Metal organic frameworks (MOFs) are a distinct family of crystalline porous materials finding extensive applications. Their synthesis often requires elevated temperature and relatively long reaction time. We report here the first case of MOF synthesis activated by high-energy (1.5 MeV) electron beam radiation from a commercially available electron-accelerator. Using ZIF-8 as a representative for demonstration, this type of synthesis can be accomplished under ambient conditions within minutes, leading to energy consumption about two orders of magnitude lower than that of the solvothermal condition. Interestingly, by controlling the absorbed dose in the synthesis, the electron beam not only activates the formation reaction of ZIF-8, but also partially etches the material during the synthesis affording a hierarchical pore architecture and highly crystalline ZnO nanoparticles on the surface of ZIF-8. This gives rise to a new strategy to obtain MOF@metal oxide heterostructures, finding utilities in photocatalytic degradation of organic dyes.

Thermodynamics-Kinetics-Balanced Metal-Organic Framework for In-Depth Radon Removal under Ambient Conditions.

Radon (Rn), a ubiquitous radioactive noble gas, is the main source of natural radiation to human and one of the major culprits for lung cancer. Reducing ambient Rn concentration by porous materials is considered as the most feasible and energy-saving option to lower this risk, but the in-depth Rn removal under ambient conditions remains an unresolved challenge, mainly due to the weak van der Waals (vdW) interaction between inert Rn and adsorbents and the extremely low partial pressure (<1.8 × 10-14 bar, <106 Bq/m3) of Rn in air. Adsorbents having either favorable adsorption thermodynamics or feasible diffusion kinetics perform poorly in in-depth Rn removal. Herein, we report the discovery of a metal-organic framework (ZIF-7-Im) for efficient Rn capture guided by computational screening and modeling. The size-matched pores in ZIF-7-Im abide by the thermodynamically favorable principle and the exquisitely engineered quasi-open apertures allow for feasible kinetics with little sacrifice of sorption thermodynamics. The as-prepared material can reduce the Rn concentration from hazardous levels to that below the detection limit of the Rn detector under ambient conditions, with an improvement of at least two orders of amplitude on the removal depth compared to the currently best-performing and only commercialized material activated charcoal.

Effectiveness and acceptability of conversational agents for sexual health promotion: a systematic review and meta-analysis.

Digital health interventions for sexual health promotion have evolved considerably alongside innovations in technology. Despite these efforts, studies have shown that they do not consistently result in the desired sexual health outcomes. This could be attributed to low levels of user engagement, which can hinder digital health intervention effectiveness, as users do not engage with the system enough to be exposed to the intervention components. It has been suggested that conversational agents (automated two-way communication systems e.g. Alexa) have the potential to overcome the limitations of prior systems and promote user engagement through the increased interactivity offered by bidirectional, natural language-based interactions. The present review, therefore, provides an overview of the effectiveness and user acceptability of conversational agents for sexual health promotion. A systematic search of seven databases provided 4534 records, and after screening, 31 articles were included in this review. A narrative synthesis of results was conducted for effectiveness and acceptability outcomes, with the former supplemented by a meta-analysis conducted on a subset of studies. Findings provide preliminary support for the effectiveness of conversational agents for promoting sexual health, particularly treatment adherence. These conversational agents were found to be easy to use and useful, and importantly, resulted in high levels of satisfaction, use and intentions to reuse, whereas user evaluations regarding the quality of information left room for improvement. The results can inform subsequent efforts to design and evaluate these interventions, and offer insight into additional user experience constructs identified outside of current technology acceptance models, which can be incorporated into future theoretical developments.

Efficient neutron radiation shielding by boron-lithium imidazolate frameworks.

Radiation protective materials are widely applied to avoid occupational hazards from either particle emissions or high-energy electromagnetic waves. Herein, we present a boron imidazolate framework (BIF) as a novel neutron shielding additive with high neutron capture cross-section elements B/Li and H. The BIF1-based epoxy resin matrix (Ep-BIF1) possesses high thermal stability and excellent resistance capacity. The neutron radiation shielding property was characterized using an Am-Be source, in which the thermal neutron shielding efficiency of Ep-BIF1 is notably higher than that of Ep-B4C with equal boron concentration, showing potential applications as an advanced efficient neutron radiation shielding composite.

Can chatbots help to motivate smoking cessation? A study on the effectiveness of motivational interviewing on engagement and therapeutic alliance.

BACKGROUND: Cigarette smoking poses a major threat to public health. While cessation support provided by healthcare professionals is effective, its use remains low. Chatbots have the potential to serve as a useful addition. The objective of this study is to explore the possibility of using a motivational interviewing style chatbot to enhance engagement, therapeutic alliance, and perceived empathy in the context of smoking cessation. METHODS: A preregistered web-based experiment was conducted in which smokers (n = 153) were randomly assigned to either the motivational interviewing (MI)-style chatbot condition (n = 78) or the neutral chatbot condition (n = 75) and interacted with the chatbot in two sessions. In the assessment session, typical intake questions in smoking cessation interventions were administered by the chatbot, such as smoking history, nicotine dependence level, and intention to quit. In the feedback session, the chatbot provided personalized normative feedback and discussed with participants potential reasons to quit. Engagement with the chatbot, therapeutic alliance, and perceived empathy were the primary outcomes and were assessed after both sessions. Secondary outcomes were motivation to quit and perceived communication competence and were assessed after the two sessions. RESULTS: No significant effects of the experimental manipulation (MI-style or neutral chatbot) were found on engagement, therapeutic alliance, or perceived empathy. A significant increase in therapeutic alliance over two sessions emerged in both conditions, with participants reporting significantly increased motivation to quit. The chatbot was perceived as highly competent, and communication competence was positively associated with engagement, therapeutic alliance, and perceived empathy. CONCLUSION: The results of this preregistered study suggest that talking with a chatbot about smoking cessation can help to motivate smokers to quit and that the effect of conversation has the potential to build up over time. We did not find support for an extra motivating effect of the MI-style chatbot, for which we discuss possible reasons. These findings highlight the promise of using chatbots to motivate smoking cessation. Implications for future research are discussed.

Microfluidic Impedance-Deformability Cytometry for Label-Free Single Neutrophil Mechanophenotyping.

The intrinsic biophysical states of neutrophils are associated with immune dysfunctions in diseases. While advanced image-based biophysical flow cytometers can probe cell deformability at high throughput, it is nontrivial to couple different sensing modalities (e.g., electrical) to measure other critical cell attributes including cell viability and membrane integrity. Herein, an "optics-free" impedance-deformability cytometer for multiparametric single cell mechanophenotyping is reported. The microfluidic platform integrates hydrodynamic cell pinching, and multifrequency impedance quantification of cell size, deformability, and membrane impedance (indicative of cell viability and activation). A newly-defined "electrical deformability index" is validated by numerical simulations, and shows strong correlations with the optical cell deformability index of HL-60 experimentally. Human neutrophils treated with various biochemical stimul are further profiled, and distinct differences in multimodal impedance signatures and UMAP analysis are observed. Overall, the integrated cytometer enables label-free cell profiling at throughput of >1000 cells min-1 without any antibodies labeling to facilitate clinical diagnostics.

Task-Specific Tailored Cationic Polymeric Network with High Base-Resistance for Unprecedented 99TcO4 - Cleanup from Alkaline Nuclear Waste.

Direct removal of 99TcO4 - from alkaline nuclear waste is desirable because of the nuclear waste management and environmental protection relevant to nuclear energy but is yet to be achieved given that combined features of decent base-resistance and high uptake selectivity toward anions with low charge density have not been integrated into a single anion-exchange material. Herein, we proposed a strategy overcoming these challenges by rationally modifying the imidazolium unit of a cationic polymeric network (SCU-CPN-4) with bulky alkyl groups avoiding its ring-opening reaction induced by OH- because of the steric hindrance effect. This significantly improves not only the base-resistance but also the affinity toward TcO4 - as a result of enhanced hydrophobicity, compared to other existing anion-exchange materials. More importantly, SCU-CPN-4 exhibits record high uptake selectivity, fast sorption kinetics, sufficient robustness, and promising reusability for removing 99TcO4 - from the simulated high-level waste stream at the U.S. Savannah River Site, a typical alkaline nuclear waste, in both batch experiment and dynamic column separation test for the first time.

Efficient Sr-90 removal from highly alkaline solution by an ultrastable crystalline zirconium phosphonate.

We report here a distinct case of strontium removal under 1 M NaOH solution by an ultrastable crystalline zirconium phosphonate framework (SZ-7) with high adsorption capacity (183 mg g-1) and in-depth removal performance (Kd = 3.9 × 105 mL g-1), demonstrating the potential application of SZ-7 for 90Sr removal in highly alkaline nuclear waste.

Deuterated Covalent Organic Frameworks with Significantly Enhanced Luminescence.

Luminescent covalent organic frameworks (COFs) find promising applications in chemical sensing, photocatalysis, and optoelectronic devices, however, the majority of COFs are non or weakly emissive owing to the aggregation-caused quenching (ACQ) or the molecular thermal motion-based energy dissipation. Here, we report a previously unperceived approach to improve luminescence performance of COFs by introducing isotope effect, which is achieved through substitution of hydrogen from high-frequency oscillators X-H (X=O, N, C) by heavier isotope deuterium. Combining the "bottom-up" and in situ deuteration methods generates the first deuterated COF, which exhibits an impressively 19-fold enhancement in quantum yield over that of the non-deuterated counterpart. These results are interpreted by theoretical calculations as the consequence of slower C/N-D and OD⋅⋅⋅O vibrations that impede the nonradiative deactivation process. The proposed strategy is proved applicable to many other types of emissive COFs.

Calcium phosphate-based composite cement: Impact of starch type and starch pregelatinization on its physicochemical properties and performance in the vertebral fracture surgical models in vitro.

Calcium phosphate cement (CPC) modified with native and pregelatinized normal corn and waxy maize starches was studied. Effects of starch pregelatinization and starch type on the physicochemical properties of CPC were investigated. CPC modified with pregelatinized normal corn starch (CPB-PNC) or pregelatinized waxy maize starch (CPB-PW) was evaluated by two vertebral fracture surgical models in vitro. Both granular and pregelatinized starches significantly improved the setting times and injectability of CPC, but only the pregelatinized starches improved the anti-collapsibility and compressive strength of CPC significantly. CPB-PW, whose micro-structure was compact and uniform, showed the best physicochemical properties. Addition of starch did not inhibit the hydro-reaction of CPC. Unmodified CPC had very poor dispersibility and could not apply in the tests of the surgical models. Pregelatinized starch especially waxy maize starch improved the dispersibility of CPC and showed good dispersion area, volume, improved pull-out force and maximum torque in the Sawbones sponge model. Similarly, in the minimally invasive kyphoplasty model, CPB-PNC and CPB-PW could disperse in the osteoporotic sheep vertebrae and improve the compressive strength of the sheep vertebral body. In conclusion, starch pregelatinization and starch botanical source affect the physicochemical properties of CPC significantly. Bone cements modified by different starches also performed differently in surgical models for osteoporotic vertebral fracture. Pregelatinized waxy maize starch may be a better candidate for CPC modification comparing to the pregelatinized normal corn starch.