Long-Lasting Antibacterial PDMS Surfaces Constructed from Photocuring of End-Functionalized Polymers.

A challenge remains in the development of anti-infectious coatings for the inert surfaces of biomedical devices that are prone to bacterial colonization and biofilm formation. Here, a facile photocuring method to construct functionalized polymeric coatings on inert polydimethylsiloxane (PDMS) surfaces, is developed. Using atom transfer radical polymerization (ATRP) initiator bearing thymol group, hydrophilic DMAEMA and benzophenone (BP)-containing monomers are copolymerized to form polymers with end functional groups. An end-functionalized biocidal coating is then constructed on the inert PDMS surface in one step using a photocuring reaction. The functionalized PDMS surfaces show excellent antibacterial and antifouling properties, are capable of completely eradiating MRSA within ≈6 h, and effectively inhibit the growth of biofilms. In addition, they have good stability and long-lasting antibacterial activity in body fluid environments such as 0.9% saline and urine. According to bladder model experiments, the catheter's lifespan can be extended from ≈7 to 35 days by inhibiting the growth and migration of bacteria along its inner surface. The photocuring technique is therefore very promising in terms of surface functionalization of inert biomedical devices in order to minimize the spread of infection.

Self-Assembled Borneol-Guanidine-Based Amphiphilic Polymers as an Efficient Antibiofilm Agent.

Biofilm-associated infections remain a tremendous obstacle to the treatment of microbial infections globally. However, the poor penetrability to a dense extracellular polymeric substance matrix of traditional antibacterial agents limits their antibiofilm activity. Here, we show that nanoaggregates formed by self-assembly of amphiphilic borneol-guanidine-based cationic polymers (BGNx-n) possess strong antibacterial activity and can eliminate mature Staphylococcus aureus (S. aureus) biofilms. The introduction of the guanidine moiety improves the hydrophilicity and membrane penetrability of BGNx-n. The self-assembled nanoaggregates with highly localized positive charges are expected to enhance their interaction with negatively charged bacteria and biofilms. Furthermore, nanoaggregates dissociate on the surface of biofilms into smaller BGNx-n polymers, which enhances their ability to penetrate biofilms. BGNx-n nanoaggregates that exhibit superior antibacterial activity have the minimum inhibitory concentration (MIC) of 62.5 µg·mL-1 against S. aureus and eradicate mature biofilms at 4 × MIC with negligible hemolysis. Taken together, this size-variable self-assembly system offers a promising strategy for the development of effective antibiofilm agents.

Bacteria-targeted photothermal therapy for combating drug-resistant bacterial infections.

Photothermal therapy is an ideal non-invasive treatment for bacterial infections. However, if photothermal agents are unable to target bacteria, they can also cause thermal damage to healthy tissue. This study describes the fabrication of a Ti3C2Tx MXene-based photothermal nanobactericide (denoted as MPP) that targets bacteria by modifying MXene nanosheets with polydopamine and the bacterial recognition peptide CAEKA. The polydopamine layer blunts the sharp edges of MXene nanosheets, preventing their damage to normal tissue cells. Furthermore, as a constituent of peptidoglycan, CAEKA can recognize and penetrate the bacterial cell membrane based on similar compatibility. The obtained MPP exhibits superior antibacterial activity and high cytocompatibility compared to the pristine MXene nanosheets. In vivo studies showed that MPP colloidal solution under 808 nm NIR light can effectively treat a subcutaneous abscess caused by multi-drug resistant bacterial infection without adverse effects.

Citronellol-Based Long-Lasting Antibacterial Cotton Fabrics without Bacterial Resistance.

Antibacterial cotton helps prevent the growth and spread of harmful microorganisms, reduces the risk of infection, and has a prolonged service life by reducing bacterial degradation. However, most antibacterial agents used are toxic to humans and the environment. Citronellol-poly(N,N-dimethyl ethyl methacrylate) (CD), a highly effective antibacterial polymer, is synthesized from natural herbal essential oils (EOs). CD exhibited efficient, rapid bactericidal activity against Gram-positive, Gram-negative, and drug-resistant bacteria. Citronellol's environmental benignity makes CDs less hemolytic. Notably, negligible drug resistance developed after 15 bacterial subcultures. The CD-treated cotton fabric displayed better antibacterial performance than AAA-grade antibacterial fabric, even after repeated washing. This study extends the practical application of EOs to antibacterial surfaces and fabrics, which is promising for use in personal care products and medical settings.

Evaluation on the Risk of Water Inrush Due to Roof Bed Separation Based on Improved Set Pair Analysis-Variable Fuzzy Sets.

To study and prevent bed separation water inrush accidents in coal mines, it is necessary to evaluate the risk according to the limited geological data correctly. In this work, based on hydrogeological and mining conditions, we established a risk evaluation model and selected seven important factors, including the aquifer thickness, aquifer water abundance, hydraulic pressure of the aquifer, effective aquifuge thickness, mining failure ratio, mining height of the working face, and advancing distance as evaluation indexes. The intuitionistic fuzzy analytic hierarchy process (IFAHP) and entropy weight method (EWM) were used to analyze the weights of the original data, and the minimum information entropy principle was used to further integrate the abovementioned calculation results. With the weight results, set pair analysis-variable fuzzy set (SPA-VFS) theory was applied to determine the risk grade of each working face, which provided scientific guidance for the safe mining of coal mines. For the working face where water inrush may occur, the risk of bed separation water inrush can be reduced by optimizing the parameters or changing the mining conditions through the model analysis.

N-alkylation briefly constructs tunable multifunctional sensor materials: Multianalyte detection and reversible adsorption.

A series of N-alkyl-substituted polybenzimidazoles (SPBIs), synthesized by simple condensation and N-alkylation, act as functional materials with tunable microstructures and sensing performance. For their controllable morphologies, the formation of nano-/microspheres is observed at the n(RBr)/n(PBI) feed ratio of 5:1. Products with different degrees of alkylation can recognize metal ions and nitroaromatic compounds (NACs). For example, SPBI-c, obtained at the feed ratio of 1:1, can selectively detect Cu2+, Fe3+, and NACs. By contrast, SPBI-a, obtained at the feed ratio of 0.1:1, can exclusively detect Cu2+ with high sensitivity. Their sensing mechanisms have been studied by FT-IR spectroscopy, SEM, XPS, and DFT calculations. Interestingly, the SPBIs can adsorb Cu2+ in solution and show good recyclability. These results demonstrate that polymeric materials with both sensing and adsorption applications can be realized by regulating the alkylation extent of the main chain, thus providing a new approach for the facile synthesis of multifunctional materials.

Preparation of Large Conjugated Polybenzimidazole Fluorescent Materials and Their Application in Metal Ion Detection.

A new type of conjugated polybenzimidazole (CPBI) was synthesized through a simple polycondensation reaction without metal catalysis, and N-alkylation modification was carried out to solve the problems of solubility and fluorescence properties. A series of nano-microsphere polymers CPBIn with large conjugation, good solubility, and strong fluorescence has been successfully used as "turn-off" fluorescent probes for the first time. The results show that, under suitable N-alkylation conditions, the obtained CPBIn can be used as a highly sensitive and selective fluorescent probe for the detection of Cu2+ and Zn2+ at the same time, and their detection limits are both nM levels. In addition, CPBI2 can be designed as an ultra-sensitive IMPLICATION logic gate at the molecular level, cyclically detecting Cu2+. With the test paper containing CPBI2, easy and quick on-site detection can be achieved. This research provides a new idea for the brief synthesis of multifunctional materials.

Quick construction of a C-N bond from arylsulfonyl hydrazides and Csp2-X compounds promoted by DMAP at room temperature.

An efficient approach for C-N bond construction by the coupling reaction of arylsulfonyl hydrazides and Csp2-X compounds is described for the first time with good yields at room temperature. The reaction promoted by the simple base DMAP displays excellent regioselectivity as well as high functional group tolerance with 41 examples. Even for inactive Csp2-Cl compounds, the metal-free transformation also affords a satisfactory yield after prolonging the reaction time, which is comparable to that of the corresponding Csp2-Br compound. The good effect of DMAP and its action mechanism are confirmed by the competitive experiments of reactivity between Cl-substituted and Br-substituted substrates and the single-crystal X-ray analysis of the key intermediate quaternary ammonium salt. Importantly, the application of this method for a gram-scale (even over 10 g) preparation can be accomplished.

Disproportionate Coupling Reaction of Sodium Sulfinates Mediated by BF3·OEt2: An Approach to Symmetrical/Unsymmetrical Thiosulfonates.

The BF3·OEt2-mediated disproportionate coupling reaction of sodium sulfinates was found for the first time. In this reaction, various S-S(O)2 bonds can be formed, efficiently giving thiosulfonates in moderate to excellent yields. As a convenient protocol for the synthesis of symmetrical and unsymmetrical thiosulfonates, its reaction mechanism involves the formation of a thiyl radical and sulfonyl radical via a sulfinyl radical disproportionation. What is more, this transformation can also be applied practically as a gram-scale reaction and to the two-step synthesis of sulfone and sulfonamide in one pot in situ using thiosulfonate as an intermediate.