Water molecule switching heterogeneous proton-coupled electron transfer pathway.

Figuring out the specific pathway of semiconductor-mediated proton-coupled electron transfer (PCET) driven by light is essential to solar energy conversion systems. In this work, we reveal that the amount of adsorbed water molecules determines the photo-induced PCET pathway on the TiO2 surface through systematic kinetic solvent isotope effect (KSIE) experiments. At low water content (<1.7 wt%), the photo-induced single-proton/single-electron transfer on TiO2 nanoparticles follows a stepwise PT/ET pathway with the formation of high-energy H+/D+-O[double bond, length as m-dash]C or H+/D+-O-C intermediates, resulting in an inverse KSIE (H/D) ∼0.5 with t Bu3ArO· and KSIE (H/D) ∼1 with TEMPO in methanol-d 0/d 4 systems. However, at high water content (>2 wt%), the PCET reaction follows a concerted pathway with a lower energy barrier, leading to normal KSIEs (H/D) ≥ 2 with both reagents. In situ ATR-FTIR observation and DFT calculations suggest that water molecules' existence significantly lowers the proton/electron transfer energy barrier, which coincides with our experimental observations.

Mechanism of traditional Chinese medicine in treating overactive bladder.

Overactive bladder syndrome (OAB) has made increasing progress in mechanism and treatment research. Traditional Chinese medicine (TCM) is a common complementary therapy for OAB, and it has been found to be effective. However, the intervention mechanism of TCM in the treatment of OAB is still unclear. The aim of this review is to consolidate the current knowledge about the mechanism of TCM: acupuncture, moxibustion, herbs in treating OAB, and the animal models of OAB commonly used in TCM. Finally, we put forward the dilemma of TCM treatment of OAB and discussed the insufficiency and future direction of TCM treatment of OAB.

Dopamine-derived nanoparticles for the protection of irradiation-induced intestinal injury by maintaining intestinal homeostasis.

Radiotherapy of abdominal and pelvic tumors almost inevitably injures the intestine by oxidative stress and causes inflammation. Regrettably, traditional radioprotective agents for irradiation (IR) induced intestinal injury suffer from challenges such as poor solubility, unsatisfactory bioactivity and undesired adverse reactions, which significantly limit their usefulness. Polydopamine nanoparticles (PDA-NPs) have shown promising potential in scavenging reactive oxygen species (ROS) and suppressing inflammation. In this study, PDA-NPs were prepared by a simple method and their physical properties were characterized. Mice received two doses of PDA-NPs by oral gavage 22 h apart, and were irradiated with X-rays 2 h after the last gavage. The protective effect of PDA-NPs and possible mechanisms of protection against IR-induced intestinal injury were explored. The results showed that PDA-NPs were spherical and well dispersed, with good shape uniformity, compact structure, good colloid dispersion stability, concentration-dependent light absorption, and accurate quantification. Importantly, PDA-NPs reduced mortality and prolonged the average survival time of mice after IR. Furthermore, PDA-NPs protected mice from IR-induced injury to crypt-villus units and maintained intestinal barrier function in the intestine. In particular, PDA-NPs significantly inhibited the depletion of Lgr5+ intestinal stem cells (ISCs) and promoted cell regeneration after IR, which indicated that the regeneration ability of ISCs was maintained and the repair of intestinal structure and function was promoted. Finally, PDA-NPs significantly suppressed the apoptosis, inflammatory pyroptosis and DNA damage of intestinal cells induced by ionizing radiation. Altogether, our study suggested that PDA-NPs may have great potential in protecting the intestines from ionizing radiation damage.

Dual-imprinted mixed matrix membranes for selective recognition and separation: A synergetic imprinting strategy based on complex initiation system.

Molecularly imprinted membranes (MIMs) with sufficient and even-distributed recognition sites that can break the permeability-selectivity trade-off phenomenon are desirable in chemical field of selective separation. Herein graphene oxide (GO)/TiO2-loaded nanocomposite fibrous membranes were prepared by developing two kinds of tetracycline (TC)-imprinted systems in the same MIMs-based material. Thereinto, polydopamine-based and sol-gel-based imprinting processes were applied to the synthesis of GO/TiO2-loaded dual-imprinted mixed matrix membranes (GT-DIMs). The as-prepared GT-DIMs encompassed innovative GO/TiO2-based nanocomposite fibrous channels and two kinds of TC-imprinted systems, and critical comparisons regarding the fluxes, rebinding capacities and permselectivity were provided and studied. Importantly, dual-imprinted system of GT-DIMs could not only allow for largely enhanced rebinding result (70.63 mg/g) and fast adsorption equilibrium rate within 30 min, but also facilitate the high permselectivity of TC in complex separation systems and lab-simulated wastewater samples. The permselectivity factors were all around 5.0, which strongly demonstrated the efficiently selective recognition and separation performance of GT-DIMs. Overall, based on testing results of practical separation and scalability, excellent structural stability and separation continuity had been successfully obtained for selective separation applications of pollutants.

Organic Hollow Mesoporous Silica as a Promising Sandalwood Essential Oil Carrier.

As film-forming agents, fillers and adsorbents, microplastics are often added to daily personal care products. Because of their chemical stability, they remain in the environment for thousands of years, endangering the safety of the environment and human health. Therefore, it is urgent to find an environmentally friendly substitute for microplastics. Using n-octyltrimethoxysilane (OTMS) and tetraethoxysilane (TEOS) as silicon sources, a novel, environmentally friendly, organic hollow mesoporous silica system is designed with a high loading capacity and excellent adsorption characteristics in this work. In our methodology, sandalwood essential oil (SEO) was successfully loaded into the nanoparticle cavities, and was involved in the formation of Pickering emulsion as well, with a content of up to 40% (w/w). The developed system was a stable carrier for the dispersion of SEO in water. This system can not only overcome the shortcomings of poor water solubility and volatility of sandalwood essential oil, but also act as a microplastic substitute with broad prospects in the cosmetics and personal care industry, laying a foundation for the preparation and applications of high loading capacity microcapsules in aqueous media.

Protection of agarwood essential oil aroma by nanocellulose-graft-polylactic acid.

Essential oil products are often volatile, and their aromas cannot be effectively preserved over long periods of time. In this study, nanocellulose crystals were modified, and an amphiphilic copolymer was prepared by ring-opening polymerisation to produce wall materials. A nanocellulose crystal-grafted polylactic acid copolymer was successfully synthesised and characterised using nuclear magnetic resonance spectrometry, Fourier transform infrared spectrometry, X-ray diffraction, and thermogravimetric analysis. Because of the amphiphilic properties of the synthesised copolymer, an agarwood essential oil nanoemulsion system was prepared. Using transmission electron microscopy and dynamic laser light scattering, the nanoemulsion was observed to have an apparent shell-core structure. The nanoemulsion was uniformly distributed, and the system had good stability. Finally, the electronic nose results showed that the nanocellulose crystal-grafted polylactic acid copolymer micelle effectively protected agarwood essential oil aromas.

Multifunctional-imprinted nanocomposite membranes with thermo-responsive biocompatibility for selective/controllable recognition and separation application.

Inspired by the biomimetic modification strategy of dopamine self-polymerization technique, molecularly imprinted nanocomposite membranes (MINCMs) with thermo-responsive rebinding and separation performance were synthesized and evaluated. Herein, the Au/SiO2-based multilevel structure had been successfully obtained onto the polydopamine (pDA) modified membrane surfaces. Afterward, the poly(N-isopropylacrylamide)-based biomolecule-imprinted sites were adequately constructed by developing a photoinitiated atom transfer radical polymerization (pATRP) imprinting strategy using the high-biocompatible ovalbumin (Ova, pI 4.6) as template molecule. Therefore, thermo-responsive 'specific recognition sites' toward Ova were then achieved on the as-prepared MINCMs after the well-designed imprinting process. When the external temperature was set at 37 °C, excellent ovalbumin rebinding capacity (33.26 mg/g), selectivity factor (3.06) and structural stability were obtained. Importantly, as to the controllable biocompatibility research of this work, the bare glass and Ova-bound-MINCMs (the MINCMs were bound with Ova) showed basically the same cell adhesion behaviors and viability, indicating the excellent biocompatibility of the Ova-bound-MINCMs. Additionally, efficient and rapid regulation of cell adhesion/detachment on ovalbumin-bound MINCMs could be still obtained even after 10 cycles of temperature-switch process, which indicated that the as-prepared MINCMs had strong ability to work under high intensity and long continuous operation.

Carbon Monoxide-Releasing Molecule-3 Suppresses Tumor Necrosis Factor-α- and Interleukin-1ß-Induced Expression of Junctional Molecules on Human Gingival Fibroblasts via the Heme Oxygenase-1 Pathway.

Human gingival fibroblast barrier dysfunction caused by inflammation contributes to gingivitis and can lead to inflammatory periodontal disease. The disease features include upregulated epithelial permeability, increased inflammatory mediators, and downregulated junctional complex molecules. Carbon monoxide- (CO-) releasing molecule-3 (CORM-3) is a water-soluble compound that has demonstrated anti-inflammatory effects in in vitro and in vivo studies. In this study, we aimed to investigate the effects of CORM-3 on the expression of tight and adherens junction molecules on human gingival fibroblasts (HGFs) stimulated with tumor necrosis factor-α (TNF-α) and interleukin-1ß (IL-1ß). HGFs were cultured from the explants of normal human gingival tissues, which were stimulated in the presence or absence of CORM-3. Epithelial barrier function was evaluated by paracellular permeability and junctional complex molecule expression analyses. The protein and mRNA expression levels of adherens junction molecules (VE-cadherin and ß-catenin) and tight junction molecules (zona occludens-1, ZO-1) were studied using western blot analysis and reverse transcription-quantitative polymerase chain reaction (RT-PCR). The mRNA and protein expression levels of these cytokines were also analyzed in HGFs transiently transfected with HO-1 small interfering RNA (siRNA) in response to TNF-α and IL-1ß stimulation. CORM-3 reduced permeability and enhanced the expression of junctional complex molecules (ZO-1, VE-cadherin, and ß-catenin) in TNF-α- and IL-1ß-induced HGFs. However, these effects of CORM-3 were attenuated when HO-1 siRNA was transiently transfected in HGFs. These findings indicate that CORM-3 exerts anti-inflammatory effects on TNF-α- and IL-1ß-stimulated HGFs via the HO-1 pathway, which suggests the promising potential of CORM-3 in the treatment of inflammatory periodontal disease.

Exploitation of Potentially New Antibiotics from Mangrove Actinobacteria in Maowei Sea by Combination of Multiple Discovery Strategies.

Rediscovery of known antibiotics from actinobacteria, especially Streptomyces, has become a bottleneck issue. Nowadays, more specific identification and dereplication could be acquired by a combination of modern analytic techniques with various databases. In this study, 261 actinobacterial strains were isolated from 8 mangrove soil samples by culture-dependent method. A total of 83 strains were selected to evaluate antibacterial activities and mechanisms by disc diffusion method and a unique double fluorescent protein reporter system (pDualrep2), respectively. Thirty-two strains exhibited antagonistic activity against at least one of the "ESKAPE" pathogens. Four Streptomyces strains (B475, B486, B353, and B98) showed strong inhibitory activity against Gram-positive bacteria and induced DNA damage SOS response. One Micromonospora strain (B704) exhibited inhibitory activity against several pathogens and induced attenuation-based translational inhibitors reporter. Seven members of quinoxaline-type antibiotics including quinomycin A, quinomycin monosulfoxide, and other five putative new analogues were found from the culture broth of strain B475 by a combination of anti-MRSA guide, HPTLC, HPLC-UV, and UPLC-UV-HRESIMS/MS analysis, Chemspider searching, and MS/MS-based molecular networking analysis. In conclusion, this study not only demonstrated that mangrove is a rich source of actinobacteria with the potentially new antibiotics but showed rapid dereplication of known antibiotics in the early stage can improve efficiency for the discovery of new antibiotics.

Ultrasound estimation of female bladder volume based on magnetic resonance modeling.

PURPOSE: We developed a precise method to noninvasively and conveniently measure female bladder volume greater than 100 ml by ultrasound. MATERIALS AND METHODS: Using the proposed method bladder magnetic resonance measurements were made in 7 healthy women to create the volume estimation model. To validate the model for ultrasound application bladder ultrasound images were scanned in 23 healthy women and corresponding volumes were calculated. Calculated and true volumes were compared with the Pearson correlation coefficient and Bland-Altman plots. RESULTS: A total of 51 bladder magnetic resonance images were segmented and reconstructed as 3-dimensional objects. Of the 51 objects 24 had a volume of greater than 100 ml. Based on the 24 objects we regressed the new equation, V = 7.1 x Dl x H - 23, where V represents estimated volume, Dl represents bladder depth and H represents bladder height measured by the proposed method. The estimation was statistically significant (SE 44, r(2) 0.94, p <0.001). A total of 69 ultrasound measurements were made and corresponding volumes were calculated by the equation. The sum of voided and post-void residual volume, when there was any, was considered true volume (range 140 to 995 ml). A significant relationship was found between true and calculated volume (mean difference -3 ml, mean absolute difference 23, r(2) = 0.97, p <0.01). The Bland-Altman 95% limits of agreement were -57 to 51 ml. CONCLUSIONS: The proposed method performs well to estimate female bladder volume greater than 100 ml.