Boron Cluster Renders Organic Radicals Water-Stable for Photothermal Anti-Infections.

Water-stable organic radicals are promising photothermal conversion candidates for photothermal therapy (PTT). However, organic radicals are usually unstable in biological environments, which greatly hinders their wide application. Here, we have developed a chaotropic effect-based and photoinduced water-stable supramolecular radical (MB12-2) for efficient antibacterial PTT. The supramolecular radical precursor MB12-1 was constructed by the chaotropic effect between closo-dodecaborate cluster (B12H122-) and N,N'-dimethylated dipyridinium thiazolo [5,4-d] thiazole (MPT2+). Subsequently, with triethanolamine (TEOA) serving as an electron donor, MB12-1 could transform to its radical form MB12-2 through photoinduced electron transfer (PET) under 435-nm laser irradiation. The N2 adsorption-desorption analysis confirmed that MB12-2 was tightly packed through the introduction of B12H122-, which effectively enhanced its stability via a spatial site-blocked effect. Moreover, the half-life of MB12-2 in water was calculated through ultraviolet-visible light (UV-vis) absorption spectra results for periods as long as 20 days. In addition, in the skin infection model, MB12-2, as a wound dressing, showed remarkable photothermal antibacterial activity (>97%) under 660-nm laser irradiation and promoted wound healing. This study presents a simple method for designing long-term water-stable supramolecular radicals, offering a novel avenue for noncontact treatments for bacterial infections.

Chaotropic Effect-Induced Sol-Gel Transition and Radical Stabilization for Bacterially Sensitive Near-Infrared Photothermal Therapy.

Deep-seated bacterial infections (DBIs) are stubborn and deeply penetrate tissues. Eliminating deep-seated bacteria and promoting tissue regeneration remain great challenges. Here, a novel radical-containing hydrogel (SFT-B Gel) cross-linked by a chaotropic effect was designed for the sensing of DBIs and near-infrared photothermal therapy (NIR-II PTT). A silk fibroin solution stained with 4,4',4″-(1,3,5-triazine-2,4,6-triyl)tris(1-methylpyridin-1-ium) (TPT3+) was employed as the backbone, which could be cross-linked by a closo-dodecaborate cluster (B12H122-) through a chaotropic effect to form the SFT-B Gel. More interestingly, the SFT-B Gel exhibited the ability to sense DBIs, which could generate a TPT2+• radical with obvious color changes in the presence of bacteria. The radical-containing SFT-B Gel (SFT-B★ Gel) possessed strong NIR-II absorption and a remarkable photothermal effect, thus demonstrating excellent NIR-II PTT antibacterial activity for the treatment of DBIs. This work provides a new approach for the construction of intelligent hydrogels with unique properties using a chaotropic effect.

Supramolecular coordination platinum metallacycle-based multilevel wound dressing for bacteria sensing and wound healing.

The exploitation of novel wound healing methods with real-time infection sensing and high spatiotemporal precision is highly important for human health. Pt-based metal-organic cycles/cages (MOCs) have been employed as multifunctional antibacterial agents due to their superior Pt-related therapeutic efficiency, various functional subunits and specific geometries. However, how to rationally apply these nanoscale MOCs on the macroscale with controllable therapeutic output is still challenging. Here, a centimeter-scale Pt MOC film was constructed via multistage assembly and subsequently coated on a N,N'-dimethylated dipyridinium thiazolo[5,4-d]thiazole (MPT)-stained silk fabric to form a smart wound dressing for bacterial sensing and wound healing. The MPT on silk fabric could be used to monitor wound infection in real-time through the bacteria-mediated reduction of MPT to its radical form via a color change. The MPT radical also exhibited an excellent photothermal effect under 660 nm light irradiation, which could not only be applied for photothermal therapy but also induce the disassembly of the Pt MOC film suprastructure. The highly ordered Pt MOC film suprastructure exhibited high biosafety, while it also showed improved antibacterial efficiency after thermally induced disassembly. In vitro and in vivo studies revealed that the combination of the Pt MOC film and MPT-stained silk can provide real-time information on wound infection for timely treatment through noninvasive techniques. This study paves the way for bacterial sensing and wound healing with centimeter-scale metal-organic materials.

Chaotropic Effect-Induced Self-Assembly of the Malachite Green and Boron Cluster for Toxicity Regulation and Photothermal Therapy.

Malachite green (MG), a toxic antibacterial agent, is widely used in the farming industry. Effectively regulating the biotoxicity of this highly water-soluble cationic dye is challenging. Here, we present a novel strategy to reduce the biotoxicity of MG through the self-assembly of MG and the closo-dodecaborate cluster ([B12H12]2-) driven by the chaotropic effect. [B12H12]2- and MG in an aqueous solution can rapidly form an insoluble cubic-type supramolecular complex (B12-MG), and the original toxicity of MG is completely suppressed. Surprisingly, this supramolecular complex, B12-MG, has a strong UV-vis absorption peak at 600-800 nm and significant photothermal conversion efficiency under 660 nm laser irradiation. On this basis, B12-MG, the supramolecular complex, can be used as an efficient photothermal agent for antimicrobial photothermal therapy (PTT) both in vitro and in vivo. As a molecular chaperone of MG, [B12H12]2- not only can be applied as an antidote to regulate the biotoxicity of MG but also provides a novel method for the construction of photothermal agents for PTT based on the chaotropic effect.

Epidemiological characteristics and spatiotemporal analysis of mumps at township level in Wuhan, China, 2005-2019.

The resurgence and outbreaks of mumps occur frequently in many countries worldwide in recent years, even in countries with high vaccination coverage. In this study, a descriptive and spatiotemporal clustering analysis at the township level was conducted to explore the dynamic spatiotemporal aggregation and epidemiological characteristics of mumps in Wuhan. During 2005 and 2019, there were 40 685 cases reported in Wuhan, with an average annual morbidity of 28.11 per 100 000 populations. The morbidity showed a fluctuating tendency, and peaked in 2010 and 2018. Bimodal seasonality was found, with a large peak between May and July, and a mild peak from November to January in the following year. Male students aged 5-9-year-old were the main risk group of mumps infection. Significant global spatial auto-correlation was detected except in 2007, 2009 and 2015. The spatial and temporal scan statistics indicated that the hot-spots mainly located at the western and southern areas of Wuhan with variations almost every year. Our findings could assist the public health authorities to develop and improve targeted health strategies, and allocate health resources rationally.

Supramolecularly assisted chlorhexidine-bacterial membrane interaction with enhanced antibacterial activity and reduced side effects.

Bacterial infection has emerged as a grievous threat to public health, and lots of antibacterial agents were developed to solve this issue. However, enhancing the antibacterial activity of antibacterial agents while reducing their side effects remains a challenge. Herein, a supramolecular antibacterial agent based on the host-guest interaction between cucurbit[7]uril (CB[7]) and chlorhexidine (CHX) was designed. CHX can be encapsulated in the cavity of CB[7] to form a 1:3 host-guest complex (CHX-3CB[7]). It was amazingly found that this supramolecular complex could display higher antibacterial activity than CHX alone. Electrospray mass spectrometry and UV-vis spectra revealed that the introduction of CB[7] promoted the protonation of N-atoms on CHX, resulting in stronger ion interaction with phospholipids and thus enhancing the destruction of the bacterial membrane. Scanning electron microscopy (SEM), surface ζ-potentials and outer/inner membrane integrity assays also reveal that the introduction of CB[7] aggravates the rupture of membrane. What is more, the cytotoxicity and irritation of CHX were decreased by forming the host-guest complex with CB[7]. This work provides a paradigm for enhancing antibacterial activity and reducing side effects of drugs through supramolecular chemistry.

Research Progress on Triarylmethyl Radical-Based High-Efficiency OLED.

Perchlorotrityl radical (PTM), tris (2,4,6-trichlorophenyl) methyl radical (TTM), (3,5-dichloro-4-pyridyl) bis (2,4,6 trichlorophenyl) methyl radical (PyBTM), (N-carbazolyl) bis (2,4,6-trichlorophenyl) methyl radical (CzBTM), and their derivatives are stable organic radicals that exhibit light emissions at room temperature. Since these triarylmethyl radicals have an unpaired electron, their electron spins at the lowest excited state and ground state are both doublets, and the transition from the lowest excited state to the ground state does not pose the problem of a spin-forbidden reaction. When used as OLED layers, these triarylmethyl radicals exhibit unique light-emitting properties, which can increase the theoretical upper limit of the OLED's internal quantum efficiency (IQE) to 100%. In recent years, research on the luminescent properties of triarylmethyl radicals has attracted increasing attention. In this review, recent developments in these triarylmethyl radicals and their derivatives in OLED devices are introduced.

Chaotropic Effect Stabilized Radical-Containing Supramolecular Organic Frameworks for Photothermal Therapy.

Radical-containing frameworks (RCFs) have emerged as promising functional materials in various fields due to the combination of the highly ordered frame structure and the fascinating property of organic radicals. Here, the first example of radical-containing supramolecular organic frameworks (SOFs) fabricated by the chaotropic effect between closo-dodecaborate cluster (B12 H122- ) and 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPT3+ ) is presented. The SOFs can be easily synthesized by stirring the B12 H122- and the TPT3+ in aqueous solution through self-assembly. Upon 435 nm light irradiation, the SOFs exhibits photochromic behavior from slight yellow (SOF-1) to dark purple (SOF-2). Electron paramagnetic resonance spectroscopy also reveals that stable radicals are generated in situ after light irradiation. Powder X-ray diffraction demonstrates the SOFs maintain their structural stabilities upon light irradiation. More interestingly, the radical-containing SOFs exhibit efficient photothermal effect under 660 nm light irradiation, which can be applied as photothermal agent for antibacterial application both in vitro and in vivo. This work highlights the construction of RCFs through supramolecular self-assembly, which may arouse applications in energy, catalysis, photoluminescence, and biomedical fields.

Design, synthesis, and biological evaluation of benzo[b]thiophene 1,1-dioxide derivatives as potent STAT3 inhibitors.

As a member of the signal transducer and activator of transcription (STAT) family, STAT3 plays a critical role in several biological pathways such as cell proliferation, migration, survival, and differentiation. Due to abnormal continuous activation in tumors, inhibition of STAT3 has emerged as an attractive approach for the treatment of various cancer cells. Herein, we report a series of novel STAT3 inhibitors based on benzo[b]thiophene 1,1-dioxide scaffold and evaluated their anticancer potency. Among them, compound 8b exhibited the best activity against cancer cells. Compound 8b induced apoptosis and blocked the cell cycle. Meanwhile, 8b reduced intracellular ROS content and caused the loss of mitochondrial membrane potential. Further research revealed that 8b significantly blocked STAT3 phosphorylation and STAT3-dependent dual-luciferase reporter gene experiments showed that compound 8b has a marked inhibition of STAT3-mediated Firefly luciferase activity. Molecular modeling studies revealed compound 8b occupied the pocket well with the SH2 domain in a favorable conformation.

Factors Affecting Patient Satisfaction with Community Health Service under the Gatekeeper System: A Cross-sectional Study in Nanjing, China.

The gatekeeper policy has been implemented for approximately ten years on a pilot population in China. It is necessary to assess the satisfaction of patients utilizing community health service (CHS) under the gatekeeper system. Our study showed that the cognition of gatekeeper policy was associated with four dimensions including doctor-patient relationships, information and support, organization of care, and accessibility (P < 0.001). One or more factors such as gender and self-perceived health scores also affected their satisfaction. General practitioners must be prepared to focus on these aspects of information and support, organization of care, and accessibility as indicators of potential opportunities for improvement. Additionally, policymakers can improve patients' satisfaction with CHS by strengthening their awareness of the gatekeeper policy.

An activated sludge model based on activated sludge model number 3 for full-scale wastewater treatment plant simulation.

A modified model based on the activated sludge model no. 3 was established to simulate a full-scale municipal wastewater treatment plant in Shanghai, China. The activated sludge model no. 3 was modified to describe the simultaneous storage and growth processes occurring in activated sludge systems under aerobic and anoxic conditions. The mechanism of soluble microbial product formation and degradation by microorganisms was considered in this proposed model. Three months simulation was conducted including soluble chemical oxygen demand, NH4(+)-N, NO(X)(-)-N and T-N parameters, and compared with measured data from the Quyang wastewater treatment plant. Results indicated that the calculated effluent chemical oxygen demand and NH4(+)-N using this proposed model were in good agreement with the measured data. Results also showed that besides inert soluble organic matter contributing to the effluent chemical oxygen demand, soluble microbial products played an important part in the effluent chemical oxygen demand and, therefore, demonstrated that these products composed an important portion of effluent soluble chemical oxygen demand in wastewater treatment plants and should not be neglected.