Spatiotemporal-Dependent Confinement Effect of Bubble Swarms Enables a Fractal Hierarchical Assembly with Promoted Chirality.

The submarine-confined bubble swarm is considered an important constraining environment for the early evolution of living matter due to the abundant gas/water interfaces it provides. Similarly, the spatiotemporal characteristics of the confinement effect in this particular scenario may also impact the origin, transfer, and amplification of chirality in organisms. Here, we explore the confinement effect on the chiral hierarchical assembly of the amphiphiles in the confined bubble array stabilized by the micropillar templates. Compared with the other confinement conditions, the assembly in the bubble scenario yields a fractal morphology and exhibits a unique level of the chiral degree, ordering, and orientation consistency, which can be attributed to the characteristic interfacial effects of the rapidly formed gas/water interfaces. Thus, molecules with a balanced amphiphilicity can be more favorable for the promotion. Not limited to the pure enantiomers, chiral amplification of the enantiomer-mixed assembly is observed only in the bubble scenario. Beyond the interfacial mechanism, the fast formation kinetics of the confined liquid bridges in the bubble scenario endows the assembly with the tunable hierarchical morphology when regulating the amphiphilicity, aggregates, and confined spaces. Furthermore, the chiral-induced spin selectivity (CISS) effect of the fractal hierarchical assembly was systematically investigated, and a strategy based on photoisomerization was developed to efficiently modulate the CISS effect. This work provides insights into the robustness of confined bubble swarms in promoting a chiral hierarchical assembly and the potential applications of the resulting chiral hierarchical patterns in solid-state spintronic and optical devices.

Narrowband Blue Circularly Polarized Luminescence Emitter based on BN-Doped Benzo[6]helicene with Stimuli-Responsive Properties.

Boron-doped helicenes, known for their unique electronic and photophysical properties, are of great interest for numerous applications. This research introduces two new azabora[6]helicenes, H[6]BN1 and H[6]BN2, synthesized through an efficient method. These molecules have boron and nitrogen atoms in opposing positions, enhancing their distinctive attributes. Both helicenes show excellent emission properties, with H[6]BN1 and H[6]BN2 exhibiting narrowband blue fluorescence and circularly polarized luminescence (CPL), achieving glum values of 4~5 ×10-4 which is beneficial for chiroptical applications. The addition of a donor group, 3, 6-di-tert-butyl-9H-carbazole, in H[6]BN2 improves luminescence, likely due to enhanced molecular orbital overlap and electron delocalization. H[6]BN1's needle-like single crystals exhibit mechanochromism, changing luminescent color from yellow to green under mechanical stress, which is promising for stimulus-responsive materials. In conclusion, this study presents a novel class of BN[6]helicenes with superior chiroptical properties. Their combination of electronic features and mechanochromism makes them ideal for advanced chiroptical materials, expanding the potential of helicene-based compounds and offering new directions for the synthesis of molecules with specific chiroptical characteristics.

Grafting of Poly(ionic liquid) Brushes through Fe0-Mediated Surface-Initiated Atom Transfer Radical Polymerization for Marine Antifouling.

Surface-tethered poly(ionic liquid) brushes have attracted considerable attention in widespread fields, from bioengineering to marine antifouling. However, their applications have been constrained due to the poor polymerization efficiency and sophisticated operation process. In this work, we efficiently synthesized the poly(ionic liquid) brushes with unparalleled speed (up to 98 nm h-1) through Fe0-mediated surface-initiated atom transfer radical polymerization (Fe0 SI-ATRP) while consuming only microliter of monomer solution under ambient conditions. We also demonstrated that poly(ionic liquid) brushes with gradient thickness and wettability were easily accessible by regulating the distance between the opposite plates of Fe0 SI-ATRP. Moreover, the resultant poly(ionic liquid) brushes presented excellent antibacterial activities against Escherichia coli (99.2%) and Bacillus subtilis (88.1%) after 24 h and low attachment for proteins and marine algae (≤5%) for over 2 weeks. This research provided pathways to the facile and controllable fabrication of poly(ionic liquid) materials for marine antifouling applications.

Multiscale Bayes Adaptive Threshold Wavelet Transform Geomagnetic Basemap Denoising Taking Residual Constraints into Account.

To achieve high-precision geomagnetic matching navigation, a reliable geomagnetic anomaly basemap is essential. However, the accuracy of the geomagnetic anomaly basemap is often compromised by noise data that are inherent in the process of data acquisition and integration of multiple data sources. In order to address this challenge, a denoising approach utilizing an improved multiscale wavelet transform is proposed. The denoising process involves the iterative multiscale wavelet transform, which leverages the structural characteristics of the geomagnetic anomaly basemap to extract statistical information on model residuals. This information serves as the a priori knowledge for determining the Bayes estimation threshold necessary for obtaining an optimal wavelet threshold. Additionally, the entropy method is employed to integrate three commonly used evaluation indexes-the signal-to-noise ratio, root mean square (RMS), and smoothing degree. A fusion model of soft and hard threshold functions is devised to mitigate the inherent drawbacks of a single threshold function. During denoising, the Elastic Net regular term is introduced to enhance the accuracy and stability of the denoising results. To validate the proposed method, denoising experiments are conducted using simulation data from a sphere magnetic anomaly model and measured data from a Pacific Ocean sea area. The denoising performance of the proposed method is compared with Gaussian filter, mean filter, and soft and hard threshold wavelet transform algorithms. The experimental results, both for the simulated and measured data, demonstrate that the proposed method excels in denoising effectiveness; maintaining high accuracy; preserving image details while effectively removing noise; and optimizing the signal-to-noise ratio, structural similarity, root mean square error, and smoothing degree of the denoised image.

Galvanic-Replacement-Assisted Synthesis of Nanostructured Silver-Surface for SERS Characterization of Two-Dimensional Polymers.

Surface-enhanced Raman scattering (SERS) spectroscopy is a powerful technology in trace analysis. However, the wide applications of SERS in practice are limited by the expensive substrate materials and the complicated preparation processes. Here we report a simple and economical galvanic-replacement-assisted synthesis route to prepare Ag nanoparticles on Cu(0) foil (nanoAg@Cu), which can be directly used as SERS substrate. The fabrication process is fast (ca. 10 min) and easily scaled up to centimeters or even larger. In addition, the morphology of the nanoAg@Cu (with Ag particles size from 30 nm to 160 nm) can be adjusted by various additives (e.g., amino-containing ligands). Finally, we show that the as-prepared nanoAg@Cu can be used for SERS characterization of two-dimensional polymers, and ca. 298 times relative enhancement of Raman intensity is achieved. This work offers a simple and economical strategy for the scalable fabrication of silver-based SERS substrate in thin film analysis.

Precise Preparation of Triarylboron-Based Graphdiyne Analogues for Gas Separation.

A series of triarylboron-based graphdiyne analogues (TAB-GDYs) with tunable pore size were prepared through copper mediated coupling reaction. The elemental composition, chemical bond, morphology of TAB-GDYs were well characterized. The crystallinity was confirmed by selected area electron diffraction (SAED) and stacking modes were studied in combination with high resolution transmission electron microscope (HRTEM) and structure simulation. The absorption and desorption isotherm revealed relatively high specific surface area of these TAB-GDYs up to 788 m2 g-1 for TMTAB-GDY, which decreased as pore size enlarged. TAB-GDYs exhibit certain selectivity for CO2 /N2 (21.9), CO2 /CH4 (5.3), CO2 /H2 (41.8) and C2 H2 /CO2 (2.3). This work has developed a series of boron containing two-dimensional frameworks with clear structures and good stability, and their tunable pore sizes have laid the foundation for future applications in the gas separation field.

Unraveling Triplet Formation Mechanisms in Acenothiophene Chromophores.

The evolution of molecular platforms for singlet fission (SF) chromophores has fueled the quest for new compounds capable of generating triplets quantitatively at fast time scales. As the exploration of molecular motifs for SF has diversified, a key challenge has emerged in identifying when the criteria for SF have been satisfied. Here, we show how covalently bound molecular dimers uniquely provide a set of characteristic optical markers that can be used to distinguish triplet pair formation from processes that generate an individual triplet. These markers are contained within (i) triplet charge-transfer excited state absorption features, (ii) kinetic signatures of triplet-triplet annihilation processes, and (iii) the modulation of triplet formation rates using bridging moieties between chromophores. Our assignments are verified by time-resolved electron paramagnetic resonance (EPR) measurements, which directly identify triplet pairs by their electron spin and polarization patterns. We apply these diagnostic criteria to dimers of acenothiophene derivatives in solution that were recently reported to undergo efficient intermolecular SF in condensed media. While the electronic structure of these heteroatom-containing chromophores can be broadly tuned, the effect of their enhanced spin-orbit coupling and low-energy nonbonding orbitals on their SF dynamics has not been fully determined. We find that SF is fast and efficient in tetracenothiophene but that anthradithiophene exhibits fast intersystem crossing due to modifications of the singlet and triplet excited state energies upon functionalization of the heterocycle. We conclude that it is not sufficient to assign SF based on comparisons of the triplet formation kinetics between monomer and multichromophore systems.

Synthesis and Structure-Property Relationships in Regioisomeric Alternating Borane-Terthiophene Polymers.

Main-chain boron-containing π-conjugated polymers are attractive for organic electronic, sensing, and imaging applications. Alternating terthiophene-borane polymers were prepared and the effects of regioisomeric attachment of the conjugated linker and variations in the electronic effect of the pendent aryl groups (2,4,6-tri-tert-butylphenyl, Mes*; 2,4,6-tris(trifluoromethyl)phenyl, FMes) examined. Pd2 dba3 /P(t-Bu)3 -catalyzed Stille polymerization of arylbis(2-thienyl)borane and arylbis(3-thienylborane) with 2,5-bis(trimethylstannyl)thiophene at 120 °C gave polymers with appreciable molecular weight but MALDI-TOF MS analyses showed evidence of unusually prominent homocoupling. These defects could be suppressed by using brominated rather than iodinated monomers, more hindered 2,5-bis(tri-n-butylstannyl)thiophene as comonomer, and Pd2 dba3 /P(o-tol)3 as the catalyst at 100 °C. Under these conditions, macrocyclic species with n=3-10 repeating units formed preferentially according to MALDI-TOF MS analyses. Photophysical studies revealed a prominent effect of the regiochemistry and the nature of the pendent aryl groups on the absorption and emission, giving rise to orange, yellow-green, blue-green, and blue emissive materials respectively. The electronic effects were rationalized through DFT calculations on bis(terthiophene) model systems.

Fluorenylidene-Cyclopentadithiophene Based Asymmetric Bistricyclic Aromatic Ene Compounds: Synthesis and Substituents Effects.

Low band gap materials have always been a focus of attention due to their potential applications in various fields. In this work, a series of asymmetric bistricyclic aromatic ene (BAE) compounds with fluorenylidene-cyclopentadithiophene (FYT) skeleton were facially synthesized, which were modified with different substituents (-OMe, -SMe). The FYT core exhibit twisted C=C bond with dihedral angles around 30°, and the introduction of -SMe group can provide additional S⋅⋅⋅S interaction between molecules, which is conducive to the charge transporting. The UV-Vis spectra, electrochemistry and photoelectron spectroscopy revealed that these compounds have relatively narrow band gaps, particularly, the -SMe modified compounds have slightly lower HOMO and Fermi energy levels than that of the -OMe modified compounds. Furthermore, PSCs devices were fabricated with the three compounds as HTMs, and FYT-DSDPA exhibit the best performance among them, revealing the fine-tuning band structure could influence properties of HTMs.

Internal B ← O Bond Facilitated Photo/Thermal Isomerization of Tetra-Coordinated Boranes.

A new series of O∧C-chelate tetra-coordinated boranes with naphtha-aldehyde as the chelate backbone have been synthesized. Their photophysical and photochemical properties have been examined, which show that all of the compounds can undergo both photo and thermal transformations, generating aryl-migrated [1,2]oxaborinine derivatives as the major products. 1,3-Sigmatropic shifts and an intramolecular nucleophilic addition mechanism are proposed for the photochemical and thermal conversion pathways, respectively.

Exosomes-derived miR-548am-5p promotes colorectal cancer progression.

Exosomes are vital modulators in intercellular communication and microRNAs (miRNAs) are enriched within exosomes. MiRNAs are important participants in affecting colorectal cancer (CRC) progression, but the influence and latent mechanism of cancer-secreted exosomal miRNAs in colorectal cancer are not fully understood. miR-548am-5p has been reported to be differentially expressed in colon cancer and is indicated as a biomarker for colon cancer diagnosis at the early stage. In this study, we aimed to explore the role of exosomes-derived miR-548am-5p in CRC development. ISH and FISH were implemented to assess miR-548am-5p expression and location in CRC. CRC cells-secreted exosomes were identified via transmission electron microscopy and western blot. Colony formation, sphere formation and flow cytometry assessed the changes in proliferation, stemness and apoptosis of CRC cells. Bioinformatic analyses and mechanical experiments verified the binding of miR-548am-5p and RAR-related orphan receptor A (RORA). Our study identified miR-548am-5p was highly expressed in CRC tissues and cells. Tumor-derived exosomes expedited CRC cell proliferation and stemness along with secreted miR-548am-5p. Moreover, miR-548am-5p inhibition suppressed CRC cell proliferation and stemness while promoting cell apoptosis. RORA was the target mRNA of miR-548am-5p. Down-regulation of RORA was discovered in CRC and its expression was repressed by CRC cell-derived exosomes. As a result, our work elucidated that tumor-derived exosomal miR-548am-5p promoted CRC cell proliferation and stemness via targeting RORA, providing a valuable sight for CRC therapy.

Comparing Safety Profiles: Low-Temperature Plasma Excision vs. Traditional Adenoidectomy for Adenoid Hypertrophy.

Objective: This study compares the efficacy of low-temperature plasma excision and adenoidectomy performed under a nasal endoscope (NE) to treat adenoid hypertrophy (AH). The goal is to offer valuable insights and guidance for future treatments. Methods: We selected a cohort of 83 children diagnosed with AH admitted to our hospital between August 2019 and August 2022. The observation group included 45 children treated with low-temperature plasma excision under NE, while the control group consisted of 38 children treated with adenoidectomy under NE. We compared various parameters, including operative time, intraoperative bleeding, the time for white film disappearance, and the duration of hospitalization between the two groups. Additionally, we assessed levels of superoxide dismutase (SOD), malondialdehyde (MDA), glutathione peroxidase (GSH-Px), C-reactive protein (CRP), tumor necrosis factor-alpha (TNF-α), interleukin-6 (IL-6), nasal pharyngeal volume (NPV), total inspiratory resistance (TIR), and total expiratory resistance (TER). Pain and sleep were evaluated using the Visual Analogue Scale (VAS) and the Pittsburgh Sleep Quality Index (PSQI). Finally, we recorded perioperative complications in both groups. Results: No significant difference was observed in the time of albuginea regression between the two groups (P > .05). However, the observation group demonstrated shorter operative time, quicker dietary recovery, and reduced hospital stay compared to the control group (P < .05). After treatment, the two groups had no significant differences in NPV, TIR, and TER (P > .05). Nevertheless, the observation group exhibited higher levels of SOD and GSH-Px, while MDA, CRP, TNF-α, IL-6, VAS, and PSQI scores were lower (P < .05). Furthermore, the incidence of complications in the observation group was significantly lower than in the control group (P < .05). Conclusions: Low-temperature plasma excision performed under NE for AH demonstrates superior outcomes and improved surgical safety and is strongly recommended for the treatment of adenoid hypertrophy.

Tuning the through-space charge transfer emission in triarylborane and triarylamine functionalized dipeptide organogels.

We report herein a new class of either carbazolyl or BMes2 (Mes = mesityl) group functionalized Boc-Lys(Z)-Phe-OMe (Z = carbobenzyloxy) dipeptides-Boc-Lys(Z)-Phe-C5-carbazolyl (N2) and Boc-Lys(Z)-Phe-C6-BMes2 (B2). Both of the compounds are able to gel in several common aromatic solvents at low concentration. The photophysical studies reveal the existence of intense through space charge transfer interaction between the donor and acceptor units in the B2 and N2 based dual-component supramolecular organogels. Furthermore, by tuning the B2 : N2 ratios in the binary gels, both the maximum emission wavelength and the morphologies of the dual-component gels can be effectively modulated.

Applying the B/N Lewis Pair Approach to Access Fusion-Expanded Binaphthyl-Based Chiral Analogues.

We herein describe the synthesis of two axially chiral systems (HBN and BBN) by the incorporation of B centers into binaphthyl derivatives (HPy and BPy). Heteroatom-doped chiral polycyclic aromatic hydrocarbons were thus formed by fusion of the azaboroles to binaphthyls with the formation of B-N dative bonds. The resulting B-N Lewis pairs that serve as attractive fluorophores enabled modulation of the chiroptical properties both in solution and in the solid state.

Dipole Effect of BN-Doped Tetrathienonaphthalene on Photo-Physical Properties and Lewis Acidity of the D-π-A Derivatives.

Dimesitylboryl-acceptor (A) and diarylamine-donor (D) substituents are introduced at α positions of BN-doped tetrathienonaphthalene in the same and opposite directions of the B-N bond, namely, B-BN-N and N-BN-B, in order to demonstrate how the substitution patterns influence the photophysical properties. The photophysical and electrochemical properties of these D-π-A molecules have been investigated in detail, aided by UV-vis absorption and fluorescence spectroscopy as well as cyclic voltammetry. We find that both B-BN-N and N-BN-B show the typical intramolecular charge transfer emission. N-BN-B exhibits strong fluorescence with a narrower band gap and stronger Lewis acidity than that of B-BN-N. DFT calculations help give a reasonable explanation that subtle differences in the electronic structure of the host skeleton could also influence the substituents and feed back this effect to the entire molecule.

A New Platform of B/N-Doped Cyclophanes: Access to a π-Conjugated Block-Type B3 N3 Macrocycle with Strong Dipole Moment and Unique Optoelectronic Properties.

We herein describe a new design principle to achieve B/N-doped cyclophane where an electron-donor block of three triarylamines (Ar3 N) and an acceptor block of three triarylboranes (Ar3 B) are spatially separated on opposite sides of the π-extended ring system. DFT computations revealed the distinct electronic structure of the block-type macrocycle MC-b-B3N3 with a greatly enhanced dipole moment and reduced HOMO-LUMO energy gap in comparison to its analogue with alternating B and N sites, MC-alt-B3N3. The unique arrangement of borane acceptor Ar3 B and amine donor Ar3 N components in MC-b-B3N3 induces exceptionally strong intramolecular charge transfer in the excited state, which is reflected in a largely red-shifted luminescence at 612 nm in solution. The respective linear open-chain oligomer L-b-B3N3 was also synthesized for comparison. Our new approach to donor-acceptor macrocycles offers important fundamental insights and opens up a new avenue to unique optoelectronic materials.

Dynamic B/N Lewis Pairs: Insights into the Structural Variations and Photochromism via Light-Induced Fluorescence to Phosphorescence Switching.

Ultralong afterglow emissions due to room-temperature phosphorescence (RTP) are of paramount importance in the advancement of smart sensors, bioimaging and light-emitting devices. We herein present an efficient approach to achieve rarely accessible phosphorescence of heavy atom-free organoboranes via photochemical switching of sterically tunable fluorescent Lewis pairs (LPs). LPs are widely applied in and well-known for their outstanding performance in catalysis and supramolecular soft materials but have not thus far been exploited to develop photo-responsive RTP materials. The intramolecular LP M1BNM not only shows a dynamic response to thermal treatment due to reversible N→B coordination but crystals of M1BNM also undergo rapid photochromic switching. As a result, unusual emission switching from short-lived fluorescence to long-lived phosphorescence (rad-M1BNM, τRTP =232 ms) is observed. The reported discoveries in the field of Lewis pairs chemistry offer important insights into their structural dynamics, while also pointing to new opportunities for photoactive materials with implications for fast responsive detectors.

Electron-Deficient Conjugated Materials via p-π* Conjugation with Boron: Extending Monomers to Oligomers, Macrocycles, and Polymers.

The extension of conjugated organoboranes from monomeric species to oligomers, macrocycles, and polymers offers access to a plethora of fascinating new materials. The p-π* conjugation between empty orbitals on boron and the conjugated linkers not only affects the electronic structure and optical properties, but also enables mutual interactions between electron-deficient boron centers. The unique properties of these electron-deficient π-conjugated systems are exploited in highly luminescent materials, organic optoelectronic devices, and sensing applications.

Highly Emissive 9-Borafluorene Derivatives: Synthesis, Photophysical Properties and Device Fabrication.

A series of 9-borafluorene derivatives, functionalised with electron-donating groups, have been prepared. Some of these 9-borafluorene compounds exhibit strong yellowish emission in solution and in the solid state with relatively high quantum yields (up to 73.6 % for FMesB-Cz as a neat film). The results suggest that the highly twisted donor groups suppress charge transfer, but the intrinsic photophysical properties of the 9-borafluorene systems remain. The new compounds showed enhanced stability towards the atmosphere, and exhibited excellent thermal stability, revealing their potential for application in materials science. Organic light-emitting diode (OLED) devices were fabricated with two of the highly emissive compounds, and they exhibited strong yellow-greenish electroluminescence, with a maximum luminance intensity of >22 000 cd m-2 . These are the first two examples of 9-borafluorene derivatives being used as light-emitting materials in OLED devices, and they have enabled us to achieve a balance between maintaining their intrinsic properties while improving their stability.

COVID-19 illness and autoimmune diseases: recent insights.

BACKGROUND: The aim of this review is to explore whether patients with autoimmune diseases (AIDs) were at high risk of infection during the COVID-19 epidemic and how severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pandemic affected immune system. METHODS: A systematic literature search was performed using the foreign databases (NCBI, web of science, EBSCO, ELSEVIER ScienceDirect) and Chinese databases (WanFang, CNKI (China National Knowledge Infrastructure), VIP, CBM) to locate all relevant publications (up to January 10, 2021). The search strategies used Medical Search Headings (MeSH) headings and keywords for "COVID-19" or "SARS-CoV-2" or "coronavirus" and "autoimmune disease". RESULTS: This review evaluates the effect of SARS-CoV-2 on the immune system through ACE-2 receptor binding as the main pathway for cell attachment and invasion. It is speculated that SARS-COV-2 infection can activate lymphocytes and inflammatory response, which may play a role in the clinical onset of AIDs and also patients were treated with immunomodulatory drugs during COVID-19 outbreak. Preliminary studies suggested that the risk of developing severe forms of COVID-19 in patients with AIDs treated with immunomodulators or biologics might not increase. A large number of samples are needed for further verification, leading to an excessive immune response to external stimuli. CONCLUSION: The relationship between autoimmune diseases and SARS-CoV-2 infection is complex. During the COVID-19 epidemic, individualized interventions for AIDs should be provided such as Internet-based service.