Microemulsion-Assisted Self-Assembly of Indium Porphyrin Photosensitizers with Enhanced Photodynamic Therapy.

Designing and constructing supramolecular photosensitizer nanosystems with highly efficient photodynamic therapy (PDT) is vital in the nanomedical field. Despite recent advances in forming well-defined superstructures, the relationship between molecular arrangement in nanostructures and photodynamic properties has rarely been involved, which is crucial for developing stable photosensitizers for highly efficient PDT. In this work, through a microemulsion-assisted self-assembly approach, indium porphyrin (InTPP) was used to fabricate a series of morphology-controlled self-assemblies, including nanorods, nanospheres, nanoplates, and nanoparticles. They possessed structure-dependent 1O2 generation efficiency. Compared with the other three nanostructures, InTPP nanorods featuring strong π-π stacking, J-aggregation, and high crystallinity proved to be much more efficient at singlet oxygen (1O2) production. Also, theoretical modeling and photophysical experiments verified that the intermolecular π-π stacking in the nanorods could cause a decreased singlet-triplet energy gap (ΔEST) compared with the monomer. This played a key role in enhancing intersystem crossing and facilitating 1O2 generation. Both in vitro and in vivo experiments demonstrated that the InTPP nanorods could trigger cell apoptosis and tumor ablation upon laser irradiation (635 nm, 0.1 W/cm2) and exhibited negligible dark toxicity and high phototoxicity. Thus, the supramolecular self-assembly strategy provides an avenue for designing high-performance photosensitizer nanosystems for photodynamic therapy and beyond.

Smart Home Sleep Respiratory Monitoring System Based on a Breath-Responsive Covalent Organic Framework.

A smart home sleep respiratory monitoring system based on a breath-responsive covalent organic framework (COF) was developed and utilized to monitor the sleep respiratory behavior of real sleep apnea patients in this work. The capacitance of the interdigital electrode chip coated with COFTPDA-TFPy exhibits thousands-level reversible responses to breath humidity gases, with subsecond response time and robustness against environmental humidity. A miniaturized printed circuit board, an open-face-mask-based respiratory sensor, and a smartphone app were constructed for the wearable wireless smart home sleep respiratory monitoring system. Leveraging the sensitive and rapid reversible response of COFs, the COF-based respiratory monitoring system can effectively record normal breath, rapid breath, and breath apnea, enabling over a thousand cycles of hour-level continuous monitoring during daily wear. Next, we took the groundbreaking step of advancing the humidity sensor to the clinical trial stage. In clinical experiments on real sleep apnea patients, the COF-based respiratory monitoring system successfully recorded hour-level sleep respiratory data and differentiated the breathing behavior characteristics and severity of sleep apnea patients and subjects with normal sleep function and primary snoring patients. This work successfully advanced humidity sensors into clinical research for real patients and demonstrated the enormous application potential of COF materials in clinical diagnosis.

Compliance with the EAT-Lancet diet and risk of colorectal cancer: a prospective cohort study in 98,415 American adults.

Background: The EAT-Lancet diet (ELD) is a recommended dietary pattern for achieving simultaneous improvements in both individual health and environmental sustainability. While research on the association between ELD and colorectal cancer (CRC) remains scarce, the potential impact of nutrition on CRC prevention and progression is a topic of growing interest. This study aims to investigate the relationship between adherence to the ELD and the risk of CRC, shedding light on the role of nutrition in CRC prevention. Methods: A total of 98,415 participants were included. A Diet History Questionnaire (DHQ) was used to collect dietary information, and an ELD score was used to assess adherence to ELD. Higher scores indicated greater adherence. Cox hazard regression analyses were conducted to examine whether there were associations between the ELD score and CRC risk. The restricted cubic spline (RCS) model was used to further explore the dose-response association between the ELD score and CRC incidence. Subgroup analyses were conducted to identify potential modifiers that interacted with ELD on CRC incidence, and sensitivity analyses were performed to evaluate the robustness of the established association. Results: During a mean follow-up of 8.82 years, a total of 1,054 CRC cases were documented. We found a statistically significant correlation between the ELD score and CRC risk (Q4 vs. Q1: HR 0.81, 95% CI 0.67-0.98; P for trend = 0.034) after adjusting for potential confounders. No statistically significant associations were discovered between ELD adherence and CRC by anatomical site. Subgroup analyses found no interactional factor, sensitivity analyses, and the RCS model showed a robustness and linearity association (P-linearity >0.05). Conclusion: We concluded that adherence to ELD contributes to the prevention of CRC.

Association of diabetes risk reduction diet with renal cancer risk in 101,755 participants: a prospective study.

BACKGROUND: There is little prospective evidence exists about whether adherence to a diabetes risk reduction diet (DRRD) is related to a significant reduction in renal cancer risk. We sought to clarify whether adherence to DRRD was associated with a reduced risk of renal cancer in a US population. METHODS: A population-based cohort of 101,755 American adults was identified from the Prostate, Lung, Colorectal, and Ovarian Cancer Screening Trial. A DRRD score was calculated to assess adherence to this dietary pattern, where increased scores indicated greater adherence. The relationship between DRRD score and risk of renal cancer was assessed based on the hazard ratios (HRs) and 95% confidence intervals (CIs), which were both calculated using Cox regression. Non-linear association was determined through restricted cubic spline regression. Potential effect modifiers were identified through subgroup analyses. RESULTS: Over a mean follow-up of 8.8 years, 446 renal cancers were detected. In this analysis, the fully adjusted model depicted a notable 29% reduction in the risk of renal cancer among individuals in the highest quartile of DRRD score in comparison with the lowest quartile individuals (HRQ4 vs. Q1: 0.71; 95% CI = 0.54, 0.94; Ptrend = 0.008). This association remained consistent across a series of sensitivity analyses. A non-linear inverse dose-response association between renal cancer risk with DRRD score was observed (Pnonlinearity = 0.026). Subgroup analyses showed that this favorable link was more prominent in participants with low Healthy Eating Index-2015 (Pinteraction = 0.015). Regarding the individual components of DRRD, a decrease in the risk of renal cancer was linked to increased intake of cereal fiber and whole fruit, and lower sugar-sweetened beverage consumption (all Ptrend < 0.05). CONCLUSIONS: Our findings indicate that individuals adhering to DRRD are associated with a reduction in the risk of renal cancer.

Association between sulfur microbial diet and the risk of colorectal cancer precursors in older adults.

Background: Sulfur microbial diet (SMD), related to the enrichment of sulfur-metabolizing gut bacteria, has been confirmed to be linked to an elevated risk of early-onset colorectal adenoma in young females. However, it remains unclear whether SMD is associated with the risk of colorectal adenoma in older people, who are at greater risk for colorectal cancer. Methods: All data on participants in this study were retrieved from the intervention arm of the Prostate, Lung, Colorectal, and Ovarian (PLCO) cancer screening test. Participants' adherence to this dietary pattern was assessed using SMD score. Hazard ratios (HR) and 95% confidence intervals (CI) were adopted in Cox proportional hazards regression models to assess the link between SMD score and the incidence of colorectal adenoma in participants included in the study. Specific stratified analyses were constructed to assess whether this association changed in different conditions, whereas the robustness of the association was examined through sensitivity analyses. Results: The mean baseline age of participants was 62.1 (SD 5.2) years (range 54.0-75.0 years). During 19,468,589 person-years of follow-up, 992 colorectal adenoma cases were documented in a total of 17,627 included participants. In a fully adjusted model, an increased risk of colorectal adenoma was determined in participants in the highest quartile of SMD score in comparison with those in the lowest quartile (HRquartile4 vs. HRquartile1 = 1.23; 95% CI: 1.02, 1.47; p = 0.017 for trend). This positive association between SMD score and adenoma risk was more evident in participants who were current or former smokers (p = 0.029 for interaction). Conclusion: In this study, our results support a role for the SMD in the carcinogenicity of colorectal cancer precursors among older adults. Nevertheless, these results require validation through more research.

The Synergistic Mechanisms of AIE, ESIPT and ICT in the α-cyanostilbene-based Derivative: A Red-fluorescence Probe With a Large Stokes' Shift for Copper (II) Ion Determination and Reversible Response to Amine/acid Vapor.

Herein, α-cyanostilbene-based luminogen with an electron donor-π-electron acceptor (D-π-A) architecture was formylated into the salicylaldehyde-analogue luminogen, followed by the Schiff base reaction with phenylamine, a red-emitting luminogen was elaborately designed and successfully synthesized in a high yield of 89%. Its well-defined structure was confirmed by FT-IR, MALDI-TOF-MS, HR-MS and 1H/13C NMR technologies. Based on the synergistic mechanisms of aggregation-induced emission (AIE), excited-state intramolecular proton transfer (ESIPT) and intramolecular charge transfer (ICT), it enjoyed a red-fluorescence emission at 627 nm in THF/water mixtures (fw = 95%) and was used as a probe. Moreover, the TLC-based test strips loaded with the probe not only exhibited the reversible fluorescence response to amine/acid vapor but also showed sensitive and selective fluorescence response towards Cu2+. Furthermore, the fluorescence titration experiment between the probe and Cu2+ in THF/water mixtures (fw = 95%, pH = 7.4) revealed that the detection limit was 1.18 × 10-7 M and the binding constant was 1.59 × 105. Job's plot experiment and HR-MS analysis revealed the 2:1 binding stoichiometry of the probe with Cu2+. The method enabled real-time assessment for Cu2+ in real water samples. This study could offer insightful opinions on the development of long-wavelength emissive luminogens based on α-cyanostilbene.

Polysulfide synthesis via visible-light-induced heteroarene-migratory dithiosulfonylation reaction.

A photocatalyzed heteroarene-migratory dithiosulfonylation of alkene-tethered sulfone using dithiosulfonate (ArSO2-SSR) has been reported, featuring mild conditions, and high atom economy. The resulting products can be converted into dihydrothiophenes and homoallyl disulfides, making the method highly valuable.

Access to Polysulfides through Photocatalyzed Dithiosulfonylation.

In this study, we outline a general method for photocatalyzed difunctionalization of alkenes, a diene, alkynes, 1,3-enynes, and [1.1.1]propellane using dithiosulfonate reagents (ArSO2 -SSR) with improved atom economy. Both "ArSO2 -" and "-SSR" on the dithiosulfonate are transferred under mild conditions with broad substrate scope, high stereoselectivity, and complete regioselectivity. Significantly, the resulting dithiosulfonylated styrene is a general and practical nucleophilic disulfuration reagent, reacting with a variety of electrophiles efficiently. Both reactions can be conducted on gram scale, rendering the approach highly valuable.

A sweat-responsive covalent organic framework film for material-based liveness detection and sweat pore analysis.

Covalent organic frameworks have shown considerable application potential and exceptional properties in the construction of stimulus-responsive materials. Here, we designed a sweat-responsive covalent organic framework film for material-based fingerprint liveness detection. When exposed to human sweat, the COFTPDA-TFPy film can transform from yellow to red. The COFTPDA-TFPy film, when touched by living fingers, can produce the naked-eye-identified fingerprint pattern through the sweat-induced color change, while artificial fake fingerprints cannot. This technique, which we named material-based liveness detection, can thus intuitively discern living fingers from fake fingerprints with a 100% accuracy rate. Additionally, the distribution of sweat pores on human skin can also be collected and analyzed by shortening the contact time. By merely washing them with ethanol, all the samples can be utilized again. This work inventively accomplished material-based liveness detection and naked-eye-identified sweat pore analysis and highlighted their potential for use in clinical research and personal identification.

Multiple heteroatom substitution effect on destructive quantum interference in tripodal single-molecule junctions.

Quantum interference (QI) has been identified as a promising strategy for designing molecular-scale electronic devices. Heteroatom doping can effectively tailor the local structures and electronic states of intrinsic molecules, and endow them with modified electron transport properties. Herein, the impacts of multiple heteroatom substitution on destructive quantum interference (DQI) have been investigated based on tripodal meta-linked phenyl derivatives. Orbital views based on the Hückel method qualitatively predict the meta-anchored molecules with DQI features, while the introduction of nitrogen atoms can alleviate the suppression of DQI at the Fermi level (EF). This is generally consistent with the movement or even removal of the antiresonance dips in transmission spectra. The substituent on position 2 can raise the antiresonance energy, while the substituent on position 4 or 6 can lower the antiresonance energy. When more than one nitrogen atom is incorporated, the impact of the substitution on positions 4 and 6 can be superimposed and the substitution on positions 2 and 4 can be partly cancelled. The experimental single-molecule conductance for tripodal molecules follows the trend of 0N-3SMe < 1N-3SMe < 3N-3SMe < 2N-3SMe, in agreement with the theoretical prediction. Additionally, the regulation is the intrinsic property depending on the position and number of the nitrogen atoms in the backbone and is irrelevant to the number and type of the anchoring groups. Our findings provide qualitative guidance for tuning the electron transport based on DQI in heterocycle molecular devices.

Glutamate attenuates lipopolysaccharide induced intestinal barrier injury by regulating corticotropin-releasing factor pathway in weaned pigs.

OBJECTIVE: The purpose of this study was to evaluate the protection of glutamate (GLU) against the impairment in intestinal barrier function induced by lipopolysaccharide (LPS) stress in weaned pigs. METHODS: Twenty-four weaned pigs were divided into four treatments containing: i) non-challenged control, ii) LPS-challenged control, iii) LPS+1.0% GLU, and iv) LPS+2.0% GLU. On day 28, pigs were treated with LPS or saline. Blood samples were collected at 0, 2, and 4 h post-injection. After blood samples collection at 4 h, all pigs were slaughtered, and spleen, mesenteric lymph nodes, liver and intestinal samples were obtained. RESULTS: Dietary GLU supplementation inhibited the LPS-induced oxidative stress in pigs, as demonstrated by reduced malondialdehyde level and increased glutathione level in jejunum. Diets supplemented with GLU enhanced villus height, villus height/crypt depth and claudin-1 expression, attenuated intestinal histology and ultrastructure impairment induced by LPS. Moreover, GLU supplementation reversed intestinal intraepithelial lymphocyte number decrease and mast cell number increase induced by LPS stress. GLU reduced serum cortisol concentration at 4 h after LPS stress and downregulated the mRNA expression of intestinal corticotropin-releasing factor signal (corticotrophin-releasing factor [CRF], CRF receptor 1 [CRFR1], glucocorticoid receptor, tryptase, nerve growth factor, tyrosine kinase receptor A), and prevented mast cell activation. GLU upregulated the mRNA expression of intestinal transforming growth factor ß. CONCLUSION: These findings indicate that GLU attenuates LPS-induced intestinal mucosal barrier injury, which is associated with modulating CRF signaling pathway.

Constructing Stable Chromenoquinoline-Based Covalent Organic Frameworks via Intramolecular Povarov Reaction.

Chemically stable chromenoquinoline (CQ)-based covalent organic frameworks (COFs) were constructed by postsynthetic conversion of imine COFs. The key step of an intramolecular Povarov reaction can transform a preintegrated alkyne group to bridge the benzene rings on both sides of the imine linkage via chemical bonds, affording a ladder-type CQ linkage. This novel approach achieves a high cyclization degree of 80-90%, which endows the CQ-COFs with excellent chemical stability toward strong acid, base, and redox reagents. The synthetic approach can be applied to various monomers with different symmetries and functional core moieties. The absorption and fluorescence intensities of CQ-COFs are sensitive to acid, which allows for dual-mode sensing of strongly acidic environments.

Sandmeyer-Type Reductive Disulfuration of Anilines.

A transition metal/ligand-free disulfuration of anilines with disulfur transfer reagents (dithiosulfonate or tetrasulfide) is reported herein. The reaction, which can be considered as a reductive disulfuration variation of the classic Sandmeyer reaction, is performed under mild conditions and exhibits broad scope across the aniline substrate and disulfur transfer reagent classes. The gram-scale synthesis of disulfides is successfully achieved through this method, rendering the approach highly valuable.

Direct Noncovalent Activation of α,ß-Unsaturated Aldehydes for the Stereodivergent Synthesis of Substituted Cyclohexenes.

HOMO-raising noncovalent activation of α-aryl α,ß-unsaturated aldehydes using a bifunctional Brønsted base catalyst is achieved. The catalytically generated dienolate intermediate undergoes all-carbon [4+2] cyclizations with nitroolefins, leading to chiral cyclohexenes with four contiguous stereocenters in high yields and with excellent enantioseletivity. Furthermore, the diastereodivergent synthesis of the products is realized by introducing a second steric control to the bifunctional catalyst; 4 isomers out of 16 possible stereoisomers of the products were selectively produced by simple use of two catalysts and their (pseudo)enantiomers. The results presented here provide new insights into the remote activation of the carbonyl functionality as well as the stereodivergent synthesis of complex chiral molecules with multiple stereocenters.