Two-dimensional radial-π-stacks in solution.

Highly organized π-aggregate architectures can strongly affect electronic couplings, leading to important photophysical behaviors. With the escalating interest in two-dimensional (2D) materials attributed to their exceptional electronic and optical characteristics, there is growing anticipation that 2D radial-π-stacks built upon radial π-conjugation nanorings, incorporating intra- and inter-ring electronic couplings within the confines of a 2D plane, will exhibit superior topological attributes and distinct properties. Despite their immense potential, the design and synthesis of 2D π-stacks have proven to be a formidable challenge due to the insufficient π-π interactions necessary for stable stacking. In this study, we present the successful preparation of single-layer 2D radial-π-stacks in a solution. Pillar-shaped radially π-conjugated [4]cyclo-naphthodithiophene diimide ([4]C-NDTIs) molecules were tetragonally arranged via in-plane intermolecular π-π interactions. These 2D π-stacks have a unique topology that differs from that of conventional 1D π-stacks and exhibit notable properties, such as acting as a 2D template capable of absorbing C60 guest molecules and facilitating the formation of 2D radial-π-stacks comprising [4]C-NDTI-C60 complexes, rapid exciton delocalization across the 2D plane, and efficient excitation energy funneling towards a trap.

Frustrated π-stacking.

The properties of functional materials based on organic π-conjugated systems are governed extensively by intermolecular interactions between π-molecules. To establish clear relationships between supramolecular structures and functional properties, it is essential to attain structurally well-defined π-stacks, particularly in solution, as this enables the collection of valuable spectroscopic data. However, precise control and fine-tuning of π-stacks pose significant challenges due to the weak and bidirectional nature of π-π stacking interactions. This article introduces the concept of "frustrated π-stacking," strategically balancing attractive (π-π interaction) and repulsive (steric hindrance) forces in self-assembly to exert control over the sizes, sequences of π-stacks, and slip-stacked structures. These research efforts contribute to a deeper understanding of the correlation between π-stacks and their properties, thereby providing useful insights for the development of molecular materials with the desired performance.

Unusual Kinetics Induced by Ligands in Rhodium(III)-Catalyzed Dehydrogenative Olefination Reactions.

In this study, we investigate the effects of ligands on C-H activation during rhodium(III)-catalyzed C-H bond olefination reactions using well-defined [CpXRhIII] catalytic systems with three representative CpX (Cp (η5-C5H5), CpCF3 (η5-C5Me4CF3), and Cp* (η5-C5Me5)) ligands. Our results demonstrate that C-H activation as the rate-limiting step is significantly influenced by the steric properties of the CpX ligands. Moreover, we observe a dramatic acceleration of the simple [CpRhIII]-catalyzed C-H olefination reaction with acid coproducts such as HOAc, implying an autocatalytic C-H activation process.

Extended Paraumbilical Perforator Flap Pedicled With the Inferior Epigastric Artery for Coverage of Type III Circumferential Electrical Burns of the Wrist.

Type III electrical burns on the wrist are characterized by circumferential wounds, three dimensional with sandwich-like necrosis, and progressive blood circulation disturbances. Limb salvage is challenging, and success in meeting this challenge depends on vascular reconstruction and wound coverage. This article is intended for the following purposes: to investigate the principles of wound debridement, the management of involved blood vessels, and the clinical effects of the extended paraumbilical perforator flap pedicled with the inferior epigastric artery for coverage of type III circumferential electrical burns of the wrist. A total of 13 male patients (age, 20 to 43 years; average, 29 years) were enrolled in the study. After early escharotomy, debridement, and vascular reconstruction, all wounds were repaired with the extended paraumbilical perforator flap pedicled with the inferior epigastric artery. Flap survival was achieved in all 13 patients. Subcutaneous liquefaction necrosis and infection beneath the flap occurred in three patients. Radial or ulnar artery reconstruction via the great saphenous vein (GSV) graft was performed in 12 cases. All patients had a mean follow-up of 6 to 36 months, and the flaps demonstrated satisfactory flexibility and texture. Hand function was preserved in eight patients, and no patients developed abdominal hernia. Thorough debridement, early vascular reestablishment, and wound coverage are essential for the overall limb salvage effort for type III circumferential electrical burns of the wrist. The extended paraumbilical perforator flap may provide a new and appropriate option for the primary repair of extensive soft tissue defects.

[Distribution Characteristics and Pollution Assessment of Heavy Metals in Soils of a Testing Range].

Heavy metal pollution in testing ranges is one of the most widely concerning environmental problems. The ammunition static detonation test area, the bomb falling area, and the living area of a testing range in Jilin were selected as the study objects. The contents of heavy metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) in 112 topsoil samples and two soil profiles were analyzed, and their distribution characteristics and sources were analyzed in detail. After that, the pollution degree and potential ecological risk of heavy metals were investigated using multiple pollution index assessment methods. The results showed that the average contents of As, Cd, Cu, Ni, and Zn in the soil of the ammunition static detonation test area were higher than the soil background values in Jilin province, and the contents of Cu, Zn, As, and Cd showed strong spatial heterogeneity. The average concentrations of As, Cd, and Ni in the soil of the bomb falling area exceeded their background values. The average contents of As and Cd in the soil of the living area were higher than the background values, and the variation coefficients of Pb, Cd, Zn, and Cr were relatively high, indicating that they may have been affected by human activities. In different test areas, the contents of As, Cr, Cu, Ni, and Zn in the soil samples were significantly different (P<0.05). The ammunition static detonation test area was more strongly affected by the test activities than the bomb falling area, and the heavy metal contents in the surface layer of the soil profile were significantly higher. There was no obvious vertical migration of heavy metals in the soil profiles. The results of multivariate statistics and source identification analysis using absolute principal component score-multiple linear regression (APCS-MLR) showed that Zn, Pb, and Cd were mainly affected by pollution sources related to test activities; Cr and Ni were mainly affected by natural sources of soil forming materials; and the sources of As and Cu were more complicated. The geo-accumulation index showed that Cd in the three areas and Ni in the bomb falling area belonged to pollution level 1 (uncontaminated to moderately contaminated). The Nemerow comprehensive pollution index showed that the pollution levels among the different functional areas were:living area>ammunition static detonation test area>bomb falling area, and the three functional areas were slightly polluted. The potential ecological risk index showed that the study area was at moderate ecological risk level, and Cd was considered to be the main soil pollution factor.

Unequal Perylene Diimide Twins in a Quadruple Assembly.

Natural light-harvesting (LH) systems can divide identical dyes into unequal aggregate states, thereby achieving intelligent "allocation of labor". From a synthetic point of view, the construction of such kinds of unequal and integrated systems without the help of proteinaceous scaffolding is challenging. Here, we show that four octatetrayne-bridged ortho-perylene diimide (PDI) dyads (POPs) self-assemble into a quadruple assembly (POP)4 both in solution and in the solid state. The two identical PDI units in each POP are compartmentalized into weakly coupled PDIs (P520) and closely stacked PDIs (P550) in (POP)4 . The two extreme pools of PDI chromophores were unambiguously confirmed by single-crystal X-ray crystallography and NMR spectroscopy. To interpret the formation of the discrete quadruple assembly, we also developed a two-step cooperative model. Quantum-chemical calculations indicate the existence of multiple couplings within and across P520 and P550, which can satisfactorily describe the photophysical properties of the unequal quadruple assembly. This finding is expected to help advance the rational design of dye stacks to emulate functions of natural LH systems.

The role of resilience in diabetes stigma among young and middle-aged patients with type 2 diabetes.

AIM: To explore the prevalence and related factors influencing diabetes stigma among Chinese young and middle-aged patients with type 2 diabetes. DESIGN: A cross-sectional, quantitative study was conducted through questionnaires. METHODS: A total of 453 young and middle-aged patients with type 2 diabetes were recruited. Questionnaire survey was conducted with convenience sampling from September 2019 to December 2020. This included demographic questionnaire, Type 2 Diabetes Stigma Assessment Scale (DSAS-2) and Connor-Davidson Resilience Scale (CD-RISC). The STROBE checklist was applied as the reporting guideline for this study. RESULTS: The scores of diabetes stigma and resilience of patients were 48.18 ± 14.52 and 66.02 ± 7.18, respectively. Diabetes stigma was negatively correlated with resilience, the correlation coefficient was -0.581. The results showed that the complications, diabetes year, monthly income and insulin treatment are important factors affecting stigma. In addition, it is resilience that was a protective factor of diabetes stigma, explaining 27.2% of the variance in diabetes stigma.

Flap failure prediction in microvascular tissue reconstruction using machine learning algorithms.

BACKGROUND: Microvascular tissue reconstruction is a well-established, commonly used technique for a wide variety of the tissue defects. However, flap failure is associated with an additional hospital stay, medical cost burden, and mental stress. Therefore, understanding of the risk factors associated with this event is of utmost importance. AIM: To develop machine learning-based predictive models for flap failure to identify the potential factors and screen out high-risk patients. METHODS: Using the data set of 946 consecutive patients, who underwent microvascular tissue reconstruction of free flap reconstruction for head and neck, breast, back, and extremity, we established three machine learning models including random forest classifier, support vector machine, and gradient boosting. Model performances were evaluated by the indicators such as area under the curve of receiver operating characteristic curve, accuracy, precision, recall, and F1 score. A multivariable regression analysis was performed for the most critical variables in the random forest model. RESULTS: Post-surgery, the flap failure event occurred in 34 patients (3.6%). The machine learning models based on various preoperative and intraoperative variables were successfully developed. Among them, the random forest classifier reached the best performance in receiver operating characteristic curve, with an area under the curve score of 0.770 in the test set. The top 10 variables in the random forest were age, body mass index, ischemia time, smoking, diabetes, experience, prior chemotherapy, hypertension, insulin, and obesity. Interestingly, only age, body mass index, and ischemic time were statistically associated with the outcomes. CONCLUSION: Machine learning-based algorithms, especially the random forest classifier, were very important in categorizing patients at high risk of flap failure. The occurrence of flap failure was a multifactor-driven event and was identified with numerous factors that warrant further investigation. Importantly, the successful application of machine learning models may help the clinician in decision-making, understanding the underlying pathologic mechanisms of the disease, and improving the long-term outcome of patients.

C- and S-Shaped Perylene Diimide Heterohelicenes: Modular Synthesis and Spiral-Stair-Like π-Stacking.

A number of C- and S-shaped perylene diimide (PDI) heterohelicenes with high dipole moments were synthesized from simple perylene tetrabutylester (PTE). Taking advantage of the weak coordination ability of the sterically crowded peri ester groups in PTE, efficient Rh(III)-catalyzed 2,8- and 2,11-bisiodinations of the perylene core were realized. The 2,8- and 2,11-diiodinated PTEs and PDIs represent key synthons for further ortho-π-extensions. In contrast to most helical π-skeletons that feature loose molecular packings, enantiomerically pure C-shaped PDI azahelicenes adopt unique spiral-stair-like π-stacking superstructures.

RNA-Seq Analysis of the Key Long Noncoding RNAs and mRNAs Related to the Regulation of Acute Heat Stress in Rainbow Trout.

As the global climate warms, more creatures are threatened by high temperatures, especially cold-water fish such as rainbow trout. Evidence has demonstrated that long noncoding RNAs (lncRNAs) play a pivotal role in regulating heat stress in animals, but we have little understanding of this regulatory mechanism. The present study aimed to identify potential key lncRNAs involved in regulating acute heat stress in rainbow trout. lncRNA and mRNA expression profiles of rainbow trout head kidney were analyzed via high-throughput RNA sequencing, which exhibited that 1256 lncRNAs (802 up-regulation, 454 down-regulation) and 604 mRNAs (353 up-regulation, 251 down-regulation) were differentially expressed. These differentially expressed genes were confirmed to be primarily associated with immune regulation, apoptosis, and metabolic process signaling pathways through Gene Ontology and Kyoto Encyclopedia of Genes and Genomes pathway enrichment analysis and coding-noncoding co-expression network analysis. These results suggested that 18 key lncRNA-mRNA pairs are essential in regulating acute heat stress in rainbow trout. Overall, these analyses showed the effects of heat stress on various physiological functions in rainbow trout at the transcriptome level, providing a theoretical basis for improving the production and breeding of rainbow trout and the selection of new heat-resistant varieties.

Lutein delays photoreceptor degeneration in a mouse model of retinitis pigmentosa.

Retinitis pigmentosa is a retinal disease characterized by photoreceptor degeneration. There is currently no effective treatment for retinitis pigmentosa. Although a mixture of lutein and other antioxidant agents has shown promising effects in protecting the retina from degeneration, the role of lutein alone remains unclear. In this study, we administered intragastric lutein to Pde6brd10 model mice, which display degeneration of retinal photoreceptors, on postnatal days 17 (P17) to P25, when rod apoptosis reaches peak. Lutein at the optimal protective dose of 200 mg/kg promoted the survival of photoreceptors compared with vehicle control. Lutein increased rhodopsin expression in rod cells and opsin expression in cone cells, in line with an increased survival rate of photoreceptors. Functionally, lutein improved visual behavior, visual acuity, and retinal electroretinogram responses in Pde6brd10 mice. Mechanistically, lutein reduced the expression of glial fibrillary acidic protein in Müller glial cells. The results of this study confirm the ability of lutein to postpone photoreceptor degeneration by reducing reactive gliosis of Müller cells in the retina and exerting anti-inflammatory effects. This study was approved by the Laboratory Animal Ethics Committee of Jinan University (approval No. LACUC-20181217-02) on December 17, 2018.

Effects of dietary eicosapentaenoic acid and docosahexaenoic acid supplementation on metabolic syndrome: A systematic review and meta-analysis of data from 33 randomized controlled trials.

BACKGROUND & AIMS: Previous randomized controlled trials (RCTs) have compared the effects of pure preparations of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) in reducing metabolic syndrome (MetS) risk factors, but the results were inconsistent. The present study aimed to clarify whether EPA and DHA have differential effects on MetS features in humans. METHODS: A systematic literature search was conducted in CNKI, PubMed, Embase and Scopus updated to February 2021. The mean changes in the characteristics of MetS were calculated as weighted mean differences by using a random-effects model. Thirty-three RCTs were included. RESULTS: The results showed that both EPA and DHA were effective at lowering serum triglycerides (TG) levels. EPA supplementation decreased the serum levels of total cholesterol (TC) (WMD = -0.24 mmol/L; 95% CI, -0.43, -0.05 mmol/L), TG (WMD = -0.77 mmol/L; 95% CI, -1.54, -0.00 mmol/L) and low density lipoprotein-cholesterol (LDL-C) (WMD = -0.13 mmol/L; 95% CI, -0.25, -0.01 mmol/L), while DHA increased the serum levels of TC (WMD = 0.14 mmol/L; 95% CI, 0.03, 0.25 mmol/L), LDL-C (WMD = 0.26 mmol/L; 95% CI, 0.15, 0.38 mmol/L) and high density lipoprotein-cholesterol (HDL-C) (WMD = 0.07 mmol/L; 95% CI, 0.04, 0.09 mmol/L). Moreover, DHA increased the serum levels of insulin compared with EPA, especially in subgroups whose mean age was <60 years (0.43 mU/L; 95% CI: 0.04, 0.81 mU/L) and duration of DHA supplementation < 3 months (0.39 mU/L; 95% CI: 0.01, 0.77 mU/L). CONCLUSIONS: The present meta-analysis provides evidence that EPA and DHA have different effects on risk factors of MetS.

Naphthodithiophene Diimide Based Chiral π-Conjugated Nanopillar Molecules.

The synthesis, structures, and properties of [4]cyclonaphthodithiophene diimides ([4]C-NDTIs) are described. NDTIs as important n-type building blocks were catenated in the α-positions of thiophene rings via an unusual electrochemical-oxidation-promoted macrocyclization route. The thiophene-thiophene junction in [4]C-NDTIs results in an ideal pillar shape. This interesting topology, along with appealing electronic and optical properties inherited from the NDTI units, endows the [4]C-NDTIs with both near-infrared (NIR) light absorptions, strong excitonic coupling, and tight encapsulation of C60 . Stable orientations of the NDTI units in the nanopillars lead to stable inherent chirality, which enables detailed circular dichroism studies on the impact of isomeric structures on π-conjugation. Remarkably, the [4]C-NDTIs maintain the strong π-π stacking abilities of NDTI units and thus adopt two-dimensional (2D) lattice arrays at the molecular level. These nanopillar molecules have great potential to mimic natural photosynthetic systems for the development of multifunctional organic materials.

Enhanced electrochemiluminescence of CdS quantum dots capped with mercaptopropionic acid activated by EDC for Zika virus detection.

Enhanced electrochemiluminescence (ECL) signals of CdS quantum dots capped with 3-mercaptopropionic acid (MPA@CdS QDs) have been observed after using N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) to activate the carboxyl groups. The generated ECL signals are strong enough that their images can be captured using a Huawei mobile phone. A possible mechanism for the generation of enhanced ECL signals has been proposed. Then, a sandwich immunosensor platform for detecting Zika virus (ZIKV) was fabricated with silica microspheres as the carrier and MPA@CdS QDs as ECL signal labels. Due to the dual signal amplification of EDC activation and microsphere enrichment, good linearity from 1.0 fg mL-1 to 1.0 ng mL-1 was exhibited by the QD-based ECL immunosensor for ZIKV detection. The detection limit was 0.3 fg mL-1.

The effect of inhibiting exosomes derived from adipose-derived stem cells via the TGF-ß1/Smad pathway on the fibrosis of keloid fibroblasts.

BACKGROUND: The main mechanism of keloid formation is that keloid fibroblasts (KFs) apoptosis is inhibited, leading to excessive proliferation. Transforming growth factor-ß1 (TGF-ß1) is a key signal molecule in the process of regulating cell fibrosis. This paper discusses the effect of adipose-derived stem cell exosomes (ADSCs-EXO) on the proliferation and apoptosis of KFS and its possible mechanism, in order to provide reference for the clinical intervention of hypertrophic scar. METHODS: ADSCs were isolated and cultured from human adipose tissue, the supernatant was collected, and the exosomes secreted by ADSCs-EXO were extracted by ultracentrifugation. At the same time, KFs were cultured from human keloid tissue to P3 generation, and then divided into four groups: control group, experimental group A, experimental group B and experimental group C. KFs were then cultured with four concentrations of ADSCs-EXO (0, 1, 10, and 100 µg/mL, respectively). After 24 hours, cells in each group were taken to detect the following: proliferation of cells in each group using the cell counting Kit 8 (CCK-8) method, cell migration ability via the Transwell test, cell apoptosis by flow cytometry, collagen synthesis using the hydroxyproline method, messenger ribonucleic acid (mRNA) expression of fibrosis-related genes in each group by real-time fluorescent polymerase chain amplification, and the expression of fibrosis-related proteins in the cells of each group by western blotting. RESULTS: Compared with the control group, the proliferation rate, migration rate, and collagen synthesis levels in the three experimental groups decreased with the increase of ADSCs-EXO concentration, while the apoptosis rate in the three experimental groups increased with the increase of ADSCs-EXO concentration, and the differences were statistically significant (P<0.05). Also, compared with the control group, the relative mRNA and protein expression of alpha-smooth muscle actin (α-SMA), TGF-ß1, and Smad3 in the three groups decreased significantly, while the expression of three kinds of mRNA and protein decreased with the increase of ADSCs-EXO concentration, and the differences were statistically significant (P<0.05). CONCLUSIONS: ADSCs-EXO may inhibit the proliferation and migration, and promote the apoptosis of KFs by inhibiting the expression of the TGF-ß1/Smad pathway.

Luteolin delays photoreceptor degeneration in a mouse model of retinitis pigmentosa.

Luteolin is neuroprotective for retinal ganglion cells and retinal pigment epithelial cells after oxidative injury, whereby it can inhibit microglial neurotoxicity. Therefore, luteolin holds the potential to be useful for treatment of retinal diseases. The purpose of this study was to investigate whether luteolin exhibits neuroprotective effects on rod cells in rd10 mice, a slow photoreceptor-degenerative model of retinitis pigmentosa. Luteolin (100 mg/kg) intraperitoneally injected daily from postnatal day 14 (P14) to P25 significantly enhanced the visual performance and retinal light responses of rd10 mice at P25. Moreover, it increased the survival of photoreceptors and improved retinal structure. Mechanistically, luteolin treatment attenuated increases in reactive oxygen species, photoreceptor apoptosis, and reactive gliosis; increased mRNA levels of anti-inflammatory cytokines while lowering that of pro-inflammatory and chemoattractant cytokines; and lowered the ratio of phospho-JNK/JNK. Application of the JNK inhibitor SP600125 exerted a similar protective effect to luteolin, suggesting that luteolin delays photoreceptor degeneration and functional deterioration in rd10 mice through regulation of retinal oxidation and inflammation by inhibiting the JNK pathway. Therefore, luteolin may be useful as a supplementary treatment for retinitis pigmentosa. This study was approved by the Qualified Ethics Committee of Jinan University, China (approval No. IACUC-20181217-02) on December 17, 2018.

π-Extended perylene diimide double-heterohelicenes as ambipolar organic semiconductors for broadband circularly polarized light detection.

Despite great challenges, the development of new molecular structures with multiple and even conflicting characteristics are eagerly pursued for exploring advanced applications. To develop high-performance chiral organic semiconducting molecules, a distorted π-system is required for strong coupling with circularly polarized light (CPL), whereas planar π-stacking systems are necessary for high charge-carrier mobility. To address this dilemma, in this work, we introduce a skeleton merging approach through distortion of a perylene diimide (PDI) core with four fused heteroaromatics to form an ortho-π-extended PDI double-[7]heterohelicene. PDI double helicene inherits a high dissymmetry factor from the helicene skeleton, and the extended π-planar system concurrently maintains a high level of charge transport properties. In addition, ortho-π-extension of the PDI skeleton brings about near-infrared (NIR) light absorption and ambipolar charge transport abilities, endowing the corresponding organic phototransistors with high photoresponsivity of 450 and 120 mA W-1 in p- and n-type modes respectively, along with a high external quantum efficiency (89%) under NIR light irradiations. Remarkably, these multiple characteristics enable high-performance broadband CPL detections up to NIR spectral region with chiral organic semiconductors.

Patterns of Extrathoracic Metastases in Different Histological Types of Lung Cancer.

Lung cancer is the leading cause of cancer-related deaths mainly attributable to metastasis, especially extrathoracic metastasis. This large-cohort research is aimed to explore metastatic profiles in different histological types of lung cancer, as well as to assess clinicopathological and survival significance of diverse metastatic lesions. Lung cancer cases were extracted and enrolled from the Surveillance, Epidemiology, and End Results (SEER) database. χ2-tests were conducted to make comparisons of metastatic distribution among different histological types and odds ratios were calculated to analyze co-occurrence relationships between different metastatic lesions. Kaplan-Meier methods were performed to analyze survival outcomes according to different metastatic sites and Cox regression models were conducted to identify independent prognostic factors. In total, we included 159,241 lung cancer cases with detailed metastatic status and complete follow-up information. In order to understand their metastatic patterns, we elucidated the following points in this research: (1) Comparing the frequencies of different metastatic lesions in different histological types. The frequency of bone metastasis was highest in adenocarcinoma, squamous cell carcinoma, LCLC and NSCLC/NOS, while liver was the most common metastatic site in SCLC. (2) Elaborating the tendency of combined metastases. Bi-site metastases occurred more common than tri-site and tetra-site metastases. And several metastatic sites, such as bone and liver, intended to co-metastasize preferentially. (3) Clarifying the prognostic significance of single-site and bi-site metastases. All single-site metastases were independent prognostic factors and co-metastases ended up with even worse survival outcomes. Thus, our findings would be beneficial for research design and clinical practice.

Ni-Catalyzed Allylic Dearomatization Reaction of ß-Naphthols with Allylic Alcohols.

Ni-catalyzed intermolecular allylic dearomatization reaction of ß-naphthols with allylic alcohols was achieved. By utilizing Ni(cod)2 as a catalyst precursor, DPEphos as a ligand and 4 Å molecular sieves as additives, the dearomatization reaction of ß-naphthols with aryl allylic alcohols proceeded smoothly under mild conditions, affording the desired ß-naphthalenone products bearing a quaternary carbon center in moderate to good yields with excellent linear selectivity.