Clickable Polymerization-Induced Emission Luminogens Toward Color-Tunable Modification of Non-Traditional Intrinsic Luminescent Polymers.

Non-traditional intrinsic luminescent (NTIL) polymer is an emerging field, and its color-tunable modification is highly desirable but still rarely investigated. Here, a click chemistry approach for the color-tunable modifications of NTIL polymers by introducing clickable polymerization-induced emission luminogen (PIEgen), is demonstrated. Through Cu-catalyzed azide-alkyne cycloaddition click chemistry, a series of PIEgens is successful prepared, which is further polymerized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Interestingly, after clickable modification, these monomers are nonemissive in both solution and aggregation states; while, the corresponding polymers exhibit intriguing aggregation-induced emission (AIE) characteristics, confirming their PIEgen characteristics. By varying alkynyl substitutions, color-tunable NTIL polymers are achieved with emission wavelength varying from 448 to 498 nm, revealing a series of PIEgens and verifying the importance of modification of NTIL polymers. Further luminescence energy transfer application is carried out as well. This work therefore designs a series of clickable PIEgens and opens a new avenue for the modification of NTIL polymers via click chemistry, which may cause inspirations to the research fields including luminescent polymer, NTIL, click chemistry, AIE and modification.

Pincushion of Tubule Discovery and Tubular Morphology Landscape Establishment of Block Copolymer Self-Assemblies.

Block copolymer (BCP) self-assembly is a versatile technique in the preparation of polymeric aggregates with varieties of morphologies. However, its morphology library is limited. Here, the discovery of pincushion of tubules is reported for the first time, via BCP self-assembly of poly(4-vinylpyridine)-b-polystyrene (P4VP-b-PS) with very high molecular weight (500 kDa) and asymmetry (2 mol% P4VP). The investigation confirms the importance of core-forming block length on morphology control of BCP self-assemblies, especially with respect to tubular structures. The morphology landscape of tubular structures is successfully established, where dumbbell of tubule, tubule, loose clew of tubules, tight clew of tubules, and pincushion of tubules can be prepared by adjusting the core-forming block length. This work therefore expands the structure library of BCP self-assemblies and opens up a new avenue for the further applications of these tubular materials.

Borinic Acid Polymer: Simplified Synthesis and Enzymatic Biofuel Cell Application.

A simplified one-pot and less harmful method has been introduced for the synthesis of borinic acid monomer. The corresponding borinic acid polymer (PBA) has been prepared by reversible addition-fragmentation chain transfer polymerization. Property investigations confirm the characteristics of PBA as a new type of "smart material" in the field of thermo-responsive polymer. The potential application of PBA in the field of enzymatic biofuel cell has been illustrated with a wide open circuit potential of 0.92 V.

RAFT-Polymerization-Induced Self-Assembly and Reorganizations: Ultrahigh-Molecular-Weight Polymer and Morphology-Tunable Micro-/Nanoparticles in One Pot.

A one-pot method is introduced for the successful synthesis of narrow-distributed (D = 1.22) vinyl polymer with both ultrahigh molecular weight (UHMW) (M w = 1.31 × 106 g mol-1 ) and micro-/nanomorphology under mild conditions. The method involves the following four stages: homogeneous polymerization, polymerization-induced self-assembly (PISA), PISA and reorganization, and PISA and multiple reorganizations. The key points to the production of UHMW polystyrene are to minimize radical termination by segregating radicals in different nanoreactors and to ensure sufficient chain propagation by promoting further reorganizations of these reactors in situ. This method therefore endows polymeric materials with the outstanding properties of both UHMW and tunable micro-/nanoparticles under mild conditions in one pot.

Thermo-responsive behavior of borinic acid polymers: experimental and molecular dynamics studies.

The thermo-responsive properties of borinic acid polymers were investigated by experimental and molecular dynamics simulation studies. The homopolymer poly(styrylphenyl(tri-iso-propylphenyl)borinic acid) (PBA) exhibits an upper critical solution temperature (UCST) in polar organic solvents that is tunable over a wide temperature range by addition of small amounts of H2O. The UCST of a 1 mg mL(-1) PBA solution in DMSO can be adjusted from 20 to 100 °C by varying the H2O content from ∼0-2.5%, in DMF from 0 to 100 °C (∼3-17% H2O content), and in THF from 0 to 60 °C (∼4-19% H2O). The UCST increases almost linearly from the freezing point of the solvent with higher freezing point to the boiling point of the solvent with the lower boiling point. The mechanistic aspects of this process were investigated by molecular dynamics simulations. The latter indicate rapid and strong hydrogen-bond formation between BOH moieties and H2O molecules, which serve as crosslinkers to form an insoluble network. Our results suggest that borinic acid-containing polymers are promising as new "smart" materials, which display thermo-responsive properties that are tunable over a wide temperature range.

One-Pot Synthesis of Stimuli-Responsive Fluorescent Polymers through Polymerization-Induced Emission.

Stimuli-responsive opposite emission (A)/absorption (B) polymer material (A∪B = Ω and A∩B = Ø) represents a novel polymer material that is difficult to prepare. Here, we demonstrate a one-pot strategy for the molecular design of stimuli-responsive opposite emission/absorption polymer material with intriguing properties of opposite emission/absorption and aggregation-induced emission (AIE) type nontraditional intrinsic luminescence (NTIL) in the visible region, through reversible addition-fragmentation chain transfer polymerization-induced emission (PIE) of the N,N-dimethyl-triphenylmethanol moiety. Investigations reveal that NTIL is due to the through-space conjugation effect caused by polymer chain entanglement, when increasing the repeating unit number. The corresponding stimuli-responsive opposite emission/absorption properties are derived from the carbocation-quinoid mechanism, which enables the fluorescence encryption capability. This work therefore demonstrates the proof of concept of a novel opposite emission/absorption polymer material that might cause inspiration in different fields.

Plastic properties affect the composition of prokaryotic and eukaryotic communities and further regulate the ARGs in their surface biofilms.

Plastic wastes are ubiquitous in the offshore and oceans with an increasing quantity, and inevitably, microbial communities colonized the plastics to form biofilms, which have become dispersal vectors for antibiotic resistance genes (ARGs). This study focused on the impact of plastic properties including hardness, wettability, and zeta-potential on the biomass, prokaryotic and eukaryotic communities and ARGs in biofilms formed on specific plastics (polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET)) in an estuarine environment. The results showed that, in comparison to PP, more biomass characterized by more dry weight, chlorophyll a (Chl a) and total organic carbon (TOC) was found in biofilms formed on PE and PET, which may be related to their lower surface wettability. Proteobacteria were the dominant prokaryotic phyla, and they accounted for 53.06%, 81.90%, 37.06%, 76.25%, and 54.27% of the total sequences in biofilms on PE, PP, PET, water and sediment, respectively. Ascomycota were the predominant eukaryotic phyla in biofilms, water, and sediment, and their abundances were elevated in biofilms on PP, which accounted for 34.73%. The biofilms on PP had a higher relative abundance of ARGs (3.13) compared to those on PE (2.59) and PET (0.23). Furthermore, both the plastic-biofilm properties (e.g. dry weight, Chl a, and TOC) and microbial communities (e.g., Fungi and Proteobacteria) may be involved in regulating the abundance of ARGs. Moreover, mobile genetic elements (MGEs) were significantly correlated to both the absolute and relative abundance of ARGs, indicating that MGEs may regulate the migration of ARGs in biofilms. Taken together, this investigation provides the significance of the plastic type, surface properties, and surrounding environments in shaping microbial communities and ARGs in biofilms formed on plastics.

Shell-cross-linked micelles from PNIPAM-b-(PLL)2 Y-shaped miktoarm star copolymer as drug carriers.

Well-defined AB2 Y-shaped miktoarm star copolymers of PNIPAM-b-(PZLL)2 and PNIPAM-b-(PLL)2 were synthesized through the combination of atom transfer radical polymerization (ATRP), ring-opening polymerization (ROP), and click chemistry, where PNIPAM, PZLL, and PLL are poly(N-isopropylacrylamide), poly(epsilon-benzyloxy-carbonyl-L-lysine), and poly(L-lysine), respectively. Propargyl amine was employed as ROP initiator for the preparation of alkynyl-terminated PZLL. Diazide-terminated PNIPAM was obtained with an azide-containing ATRP initiator. The subsequent click reaction led to the formation of PNIPAM-b-(PZLL)2. After the removal of the benzyloxycarbonyl group, water-soluble PNIPAM-b-(PLL)2 was obtained. The core-shell micelles of PNIPAM-b-(PLL)2 were formed above lower critical solution temperature of PNIPAM block. At this temperature, the shell cross-linking was performed through the reaction between glutaraldehyde and the primary amine groups of the PLL shell, affording the micelles with the endurance to temperature and pH changes. These shell-cross-linked micelles were used as drug nanocarriers and the release profile was dually controlled by the solution temperature and the cross-linking degree.

Antibiotic resistance genes in biofilms on plastic wastes in an estuarine environment.

Plastic wastes are ubiquitous in aquatic environment. Biofilms, which are often formed on the surface of plastic waste, may contain antibiotic resistance genes (ARGs). This study focused on the occurrence and distribution of ARGs, metal resistance genes (MRGs) and their associated microbial communities in biofilms formed on different types of plastic, in comparison to associated sediment and water samples taken from the Yangtze Estuary. The results showed that polypropylene (PP) and polyethylene (PE) with visible biofilms were highly abundant, and the average absolute abundance of most tested ARGs in the biofilms was higher than that in the sediment and water, indicating that biofilms on plastics can act as a reservoir for ARGs. Moreover, the biofilms on PE had a higher relative abundance of ARGs, compared to those on other plastics, and Firmicutes on PE may be potential hosts for these ARGs. Furthermore, Bacillus, Mycobacterium and Pseudomonas may be multi-resistance genera on plastics, and tetA and tetW may have more potential hosts on PET and PP. Metals, total phosphorus and salinity may be the major environmental factors regulating ARGs in biofilms formed on plastics. The results provide new insights into evaluating the risks caused by plastic wastes and ARGs in biofilms formed on plastics in estuarine environment.

Reinforced Laryngeal Mask in Pediatric Laparoscopic Surgery.

OBJECTIVE: To determine the frequency of reflux and aspiration in children subjected to reinforced laryngeal mask during laparoscopic surgery in the Trendelenburg position, and evaluate its feasibility. STUDY DESIGN: A descriptive study. PLACE AND DURATION OF STUDY: Department of Anesthesiology, Beijing Chaoyang Hospital, Capital Medical University, from January 2017 to May 2018. METHODOLOGY: A total of 300 children, who underwent laparoscopic high ligation of the hernial sac in the Trendelenburg position under general anesthesia, were enrolled into the present study. Reflux and aspiration were assessed by precise saliva pH to determine the pH value at laryngeal mask airway, and at sites on laryngeal mask corresponding to the larynx, face and peripheral area. Then, the presence of food residue was observed at various sites to determine whether there was reflux or aspiration during the operation. RESULTS: Suspected reflux (9.67%) was observed in 29 children and suspected aspiration was observed in nine children (3%). There was no definite reflux or aspiration observed in any of the children. Furthermore, the prevalence of suspected reflux was higher in children who were >3 years and overweight, compared to children with a normal body mass index and an age of <3 years. CONCLUSION: With strict fasting and water deprivation, and strict selection of laryngeal mask indications before selective operation, it is feasible to apply reinforced laryngeal mask in laparoscopic surgery in the Trendelenburg position in children.