A Versatile Strategy toward Donor-Acceptor Nanofibers with Tunable Length/Composition and Enhanced Photocatalytic Activity.

Living crystallization-driven self-assembly (CDSA) has emerged as an efficient strategy to generate nanofibers of π-conjugated polymers (CPNFs) in a controlled fashion. However, reports of donor-acceptor (D-A) heterojunction CPNFs are extremely rare. The preparation of these materials remains a challenge due to the lack of rational design guidelines for the D-A π-conjugated units. Herein, we report a versatile CDSA strategy based upon carefully designed D-A-co-oligomers in which electron-deficient benzothiadiazole (BT) or dibenzo[b,d]thiophene 5,5-dioxide (FSO) units are attached to the two ends of an oligo(p-phenylene ethynylene) heptamer [BT-OPE7-BT, FSO-OPE7-FSO]. This arrangement with the electron-deficient groups at the two ends of the oligomer enhances the stacking interaction of the A-D-A π-conjugated structure. In contrast, D-A-D structures with a single BT in the middle of a string of OPE units disrupt the packing. We employed oligomers with a terminal alkyne to synthesize diblock copolymers BT-OPE7-BT-b-P2VP and BT-OPE7-BT-b-PNIPAM (P2VP = poly(2-vinylpyridine), PNIPAM = poly(N-isopropylacrylamide)) and FSO-OPE7-FSO-b-P2VP and FSO-OPE7-FSO-b-PNIPAM. CDSA experiments with these copolymers in ethanol were able to generate CPNFs of controlled length by both self-seeding and seeded growth as well as block comicelles with precisely tunable length and composition. Furthermore, the D-A CPNFs with a BT-OPE7-BT-based core demonstrate photocatalytic activity for the photooxidation of sulfide to sulfoxide and benzylamine to N-benzylidenebenzylamine. Given the scope of the oligomer compositions examined and the range of structures formed, we believe that the living CDSA strategy with D-A-based co-oligomers opens future opportunities for the creation of D-A CPNFs with programmable architectures as well as diverse functionalities and applications.

A Versatile Platform to Generate Shell-Cross-Linked Uniform Π-Conjugated Nanofibers with Controllable Length, High Morphological Stability, and Facile Surface Tailorability.

Living crystallization-driven self-assembly (CDSA) has emerged as an efficient route to generate π-conjugated-polymer-based nanofibers (CPNFs) with promising applications from photocatalysis to biomedicine. However, the lack of efficient tools to endow CPNFs with morphological stability and surface tailorability becomes a frustrating hindrance for expanding application spectrum of CPNFs. Herein, a facile strategy to fabricate length-controllable OPV-based (OPV = oligo(p-phenylenevinylene)) CPNFs containing a cross-linked shell with high morphological stability and facile surface tailorability through the combination of living CDSA and thiol-ene chemistry by using OPV5 -b-PNAAM32 (PNAAM = poly(N-allyl acrylamide)) as a model is reported. Uniform fiber-like micelles with tunable length can be generated by self-seeding of living CDSA. By taking advantage of radical thiol-ene reaction between vinyls of PNAAM corona and four-arm thiols, the shell of micelles can be cross-linked with negligible destruction of structure of vinylene-containing OPV core. The resulting micelles show high morphological stability in NaCl solution and PBS buffer, even upon heating at 80 °C. The introduced extra thiol groups in the cross-linked shell can be further employed to install extra functional moieties via convenient thiol-Michael-type reaction. Given the negligible cytotoxicity of resulting CPNFs, this strategy opens an avenue to fabricate various CPNFs of diverse functionalities for biomedicine.

Hypoxaemia risk in pediatric flexible bronchoscopy for foreign body removal: a retrospective study.

BACKGROUND: Hypoxemia represents the most prevalent adverse event during flexible bronchoscopy procedures aimed at foreign body retrieval in pediatric patients; if not expeditiously managed, it carries the potential for cardiac or respiratory arrest. The specific risk factors contributing to the occurrence of hypoxemia during foreign body FB removal via bronchoscopy have yet to be definitively established. METHODS: This retrospective study included a cohort of 266 pediatric subjects from January 1, 2015, to December 31, 2022, who underwent flexible bronchoscopy for the purpose of FB extraction. In this cohort, the supraglottic airway was used to connect the anesthesia apparatus during the removal procedure. RESULTS: In total, 45 of the pediatric patients (16.9%) experienced episodes of hypoxemia during the FB removal procedure. Multivariate analysis revealed that the following factors were significantly associated with the occurrence of hypoxemia: an operation time exceeding 60 min (odds ratio [OR] 8.55; 95% confidence interval [CI] 3.82-19.13), a maximum diameter exceeding 7 mm (OR 5.03; 95% CI, 2.24-11.29), and the presence of radiological evidence indicating pneumonia (OR 2.69; 95% CI, 1.27-5.69). CONCLUSION: During flexible bronchoscopy procedures aimed at FB removal in pediatric patients, there is an increased susceptibility to hypoxemia. Factors including extended operation duration, larger FB dimensions, and radiographic evidence suggestive of pneumonia significantly contribute to a heightened risk of hypoxemia.

Combined use of intranasal Dexmedetomidine and an oral novel formulation of Midazolam for sedation of young children during brain MRI examination: a prospective, single-center, randomized controlled trial.

BACKGROUND: To evaluate the safety and effectiveness of different dosages of intranasal Dexmedetomidine (DEX) in combination with oral midazolam for sedation of young children during brain MRI examination. METHODS: Included in this prospective single-blind randomized controlled trial were 156 children aged from 3 months to 6 years and weighing from 4 to 20 Kg with ASA I-II who underwent brain MRI examination between March 2021 and February 2022. Using the random number table method, they were divided into group A (using 3 ug/kg intranasal DEX plus 0.2 mg/Kg oral midazolam) and group B (using 2 ug/kg intranasal DEX plus 0.2 mg/Kg oral Midazolam). The one-time success rate of sedation, sedation onset time, recovery time, overall sedation time, and occurrence of adverse reactions during MRI examination were compared between the two groups. The heart rate (HR), mean arterial pressure (MAP), and percutaneous SpO2before and after drug administration were observed in both groups. Differences in sedation scores between the two groups were compared before intranasal drug administration (T0), 10 min after drug administration (T1), at the time of falling asleep (T2), at the end of examination (T3), and at the time of recovery (T4). RESULTS: The one-time success rate of sedation in group A and B was 88.31% and 79.75% respectively, showing no significant difference between the two groups (P>0.05). The sedation onset time in group A was 24.97±16.94 min versus 27.92±15.83 min in group B, and the recovery time was 61.88±22.18 min versus 61.16±28.16 min, both showing no significance difference between the two groups (P>0.05). Children in both groups exhibited good drug tolerance without presenting nausea and vomiting, hypoxia, or bradycardia and hypotension that needed clinical interventions. There was no significant difference in the occurrence of abnormal HR, MAP or other adverse reactions between the two groups (P>0.05). CONCLUSION: 3 ug/kg or 2 ug/kg intranasal DEX in combination with 0.2 mg/kg oral Midazolam both are safe and effective for sedation of children undergoing MRI examination with the advantages of fast-acting and easy application. TRIAL REGISTRATION: It was registered at the Chinese Clinical Trial Registry ( ChiCTR1800015038 ) on 02/03/2018.

Risk factors associated with reintubations in children undergoing foreign body removal using flexible bronchoscopy: a single-center retrospective cross-sectional study.

BACKGROUND: Reintubation is a severe complication during foreign body (FB) removal that uses flexible bronchoscopy. OBJECTIVE: To investigate the incidence and risk factors for reintubations in children undergoing FB extraction by flexible bronchoscopy in a single center. DESIGN: A retrospective cross-sectional study. SETTING: All children with foreign body aspiration at Fujian Maternity and Child Health Hospital, Affiliated Hospital of Fujian Medical University from January 2015 to December 2020. PATIENTS: Children with FB removal using a flexible bronchoscopy were enrolled in the trial according to the inclusion criteria. MEASUREMENTS: Both multivariable and logistic regression analyses were used to analyze the association between characteristic data and reintubations. The results were presented as odds ratios (ORs) with 95% confidence intervals (CIs). RESULTS: In total, 244 patients met with the inclusion criteria and were included in the analysis. Among those participants, 28 children (11.5%) underwent reintubations after FB removal by flexible bronchoscopy. Independent factors associated with reintubations were identified as operative time ≥ 60 min [OR: 3.68, 95% CI (1.64-8.82)] and ASA ≥ III [OR: 5.7, 95% CI (1.23-26.4)]. CONCLUSIONS: Children undergoing FB removal by a flexible bronchoscopy may encounter with a high incidence of postoperative reintubations. Both long operative duration and a severe physical status cause a growing risk of reintubations.

Uniform Nanowires Containing a Heterogeneousπ-Conjugated Core of Controlled Length, Composition and Morphology.

In this work, it is demonstrated for the first time that heterojunction nanowires, consisting of a gradient and segmented-like heterogeneous π-conjugated core with controllable length, composition and morphology, can be generated by co-self-seeding of oligo(p-phenylene vinylene) (OPV)- and oligo(p-phenylene ethynylene) (OPE)-containing block copolymers in spite of different chain lengths and molecular conformation for OPE and OPV. More importantly, based on the understanding of the formation of heterogeneous core by the co-self-seeding approach, a "heating/cooling" seeded growth route was developed, by which linear and branched heterojunction nanowires containing a segmented heterogeneous π-conjugated core of controlled length, composition and morphology can be obtained. This work provides a versatile platform to generate heterojunction nanowires with excellent controllability in length, composition, and morphology.

Use of intravenous lidocaine for dose reduction of propofol in paediatric colonoscopy patients: a randomised placebo-controlled study.

BACKGROUND: Propofol, a widely used sedative in endoscopic procedures, sometimes causes cardiopulmonary complications. Intravenous lidocaine can diminish visceral pain and decrease the dose of propofol. The purpose of this study was to assess the efficacy and safety of intravenous lidocaine in reducing propofol dosage during paediatric colonoscopy. METHODS: Forty children who underwent colonoscopy were divided into two groups. Lidocaine hydrochloride (1.5 mg/kg induction and 2 mg/kg/h maintenance) was given intravenously to the lidocaine group, and the same amount of saline was given to the control group after they received lidocaine induction. Propofol initial plasma concentration of 5 µg/mL was targeted, and the procedure was performed after the bispectral index value reached 55. The primary outcome was propofol requirement. RESULTS: The propofol requirement in the lidocaine group was decreased by 35.5% (128.6 ± 30.4 mg vs. 199.4 ± 57.6 mg; p < 0.001; 95%CI: - 100.60, - 41.02). The incidence of involuntary body movements was significantly lower in the lidocaine group (p = 0.028; OR = 0.17; 95%CI: 0.03, 0.92). The awakening time (p < 0.001; 95%CI: - 7.67, - 5.13) and recovery times (p < 0.001; 95%CI: - 7.45, - 4.35) were significantly lower in the lidocaine group. Pain was significantly less at 30 min and 60 min after the procedure in the lidocaine group (0 [0-4] vs. 3 [0-5], p < 0. 001; 0 [0-2] vs. 1 [0-3], p = 0.001). There was no difference in the incidence of bradycardia, hypotension, or hypoxia between the two groups. CONCLUSIONS: For colonoscopy procedures in paediatric patients, intravenous lidocaine reduces the amount of propofol needed, provides better sedation and postprocedural pain management, as well as a reduction in recovery time. TRIAL REGISTRATION: The trial was registered on November 6, 2020 at China Clinical Trials Registration Center ( www.chictr.org.cn ) ref.: ChiCTR 2,000,039,706.

Covalent Organic Frameworks as Electrode Materials for Metal Ion Batteries: A Current Review.

As the world moves toward electromobility, our daily lives are flooded with variety of lithium ion batteries (LIBs), and the concerns of cost, safety and environmental friendliness of LIBs spring up in the minds of scientists. Although organic electrodes have been considered as promising alternatives to their inorganic counterparts, some intrinsic weaknesses still plague scientists, such as high solubility, low conductivity and sluggish ion diffusion. The emergence of covalent organic frameworks (COFs) attracts our attention because of their robust networks and open pores that could facilitate the infiltration of electrolyte ions when used as electrodes for metal-ion batteries (MIBs). In this review, we summarized the recent progress of COFs as electrode materials, and the strategies toward enhancing electrochemical performance of COF-based electrode in MIBs are discussed. Hopefully, this review will provide a fundamental guidance for future development of COF-based electrodes.

Remifentanil patient-controlled versus epidural analgesia on intrapartum maternal fever: a systematic review and meta-analysis.

BACKGROUND: Intravenous remifentanil patient-controlled analgesia (RPCA) is an alternative for epidural analgesia (EA) in labor pain relief. However, it remains unknown whether RPCA is superior to EA in decreasing the risk of intrapartum maternal fever during labor. METHODS: According to the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines, a systematic review and meta-analysis was performed by searching PubMed, EMBASE and the Cochrane Central Register of Controlled Trials from inception to April 2019. All randomized controlled trials (RCTs) investigating the risk of intrapartum maternal fever with RPCA compared with EA alone or EA in combination with spinal analgesia during labor were included. RESULTS: A total of 825 studies were screened, and 6 RCTs including 3341 patients were identified. Compared with EA, RPCA was associated with a significantly lower incidence of intrapartum maternal fever (risk ratio [RR] 0.48, P = 0.02, I2 = 49%) during labor analgesia. After excluding 2 trials via the heterogeneity analysis, there was no difference in the incidence of intrapartum fever between patients receiving RPCA and those receiving EA. Satisfaction with pain relief during labor was lower in the RPCA group than that in the EA group (- 10.6 [13.87, - 7.44], P < 0.00001, I2 = 0%). The incidence of respiratory depression was significantly greater in the RPCA group than that in the EA group (risk ratio 2.86 [1.65, 4.96], P = 0.0002, I2 = 58%). The incidence of Apgar scores < 7 at 5 min in the RPCA group was equivalent to that in the EA group. CONCLUSION: There is no solid evidence to illustrate that the incidence of intrapartum maternal fever is lower in patients receiving intravenous RPCA than in patients receiving EA.

Continuous and Segmented Semiconducting Fiber-like Nanostructures with Spatially Selective Functionalization by Living Crystallization-Driven Self-Assembly.

Fiber-like π-conjugated nanostructures are important components of flexible organic electronic and optoelectronic devices. To broaden the range of potential applications, one needs to control not only the length of these nanostructures, but the introduction of diverse functionality with spatially selective control. Here we report the synthesis of a crystalline-coil block copolymer of oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine) (OPV5 -b-P2VP44 ), in which the basicity and coordinating/chelating ability of the P2VP segment provide a landscape for the incorporation of a variety of functional inorganic NPs. Through a self-seeding strategy, we were able to prepare monodisperse fiber-like micelles of OPV5 -b-P2VP44 with lengths ranging from 50 to 800 nm. Significantly, the exposed two ends of OPV core of these fiber-like micelles remained active toward further epitaxial deposition of OPV5 -b-PNIPAM49 and OPV5 -b-P2VP44 to generate uniform A-B-A and B-A-B-A-B segmented block comicelles with tunable lengths for each block. The P2VP domains in these (co-)micelles can be selectively decorated with inorganic and polymeric nanoparticles as well as metal oxide coatings, to afford hybrid fiber-like nanostructures. This work provides a versatile strategy toward the fabrication of narrow length dispersity continuous and segmented π-conjugated OPV-containing fiber-like micelles with the capacity to be decorated in a spatially selective way with varying functionalities.

Self-Assembled Helical and Twisted Nanostructures of a Preferred Handedness from Achiral π-Conjugated Oligo( p-phenylenevinylene) Derivatives.

The formation of chiral nanostructures from the self-assembly of achiral building blocks without external symmetry breaking inducing factors is believed to associate with the origin of chirality. Herein, we reported the synthesis and self-assembly of oligo( p-phenylenevinylene)- b-poly(ethylene glycol) (OPV3- b-PEG17, the subscripts represent the number of repeat unit of each block) in solution. We systematically examined the influence of solvent, heating temperature, and concentration of OPV3- b-PEG17 on the self-assembly of OPV3- b-PEG17 by UV/vis absorption and fluorescence spectrometry, circular dichroism technique, and transmission electron and atomic force microscopy. Interestingly, helical and twisted nanoribbons and nanotubes of a preferred handedness can be formed from achiral OPV3- b-PEG17 in the mixture of water/ethanol (v/v = 1/1) and the solution showed an obvious exciton-coupled bisignated signal, which indicated that symmetry breaking occurred during the formation of these nanostructures without external inducing factors. Our results showed that the occurrence of symmetry breaking is subtle to the experimental factors including solvent, heating temperature, and concentration of OPV3- b-PEG17. The directional π-π stacking along with steric repulsion between PEG domains should be the driving force for the formation of these chiral nanostructures. The occurrence of statistical fluctuations in the initial stage of self-assembly led to an accidental excess of helical or/and twisted structures, that is, symmetry breaking. Subsequently, the autocatalysis effect resulted in the formation of helical or/and twisted nanoribbons with a preferred handedness.

Antifouling Surfaces Based on Fluorine-Containing Asymmetric Polymer Brushes: Effect of Chain Length of Fluorinated Side Chain.

The influence of chain length of a fluorinated side chain of an asymmetric polymer brush with poly(ethylene glycol) (PEG) side chains on the antifouling property was systematically investigated so as to obtain more knowledge for deepening our understanding of the structure-(antifouling)-property relationship of asymmetric polymer brush. A series of asymmetric polymer brushes, consisting of hydrophobic poly(pentafluoropropyl methacrylate) (PPTFMA) side chains with the number of repeat units of pentafluoropropyl methacrylate (PTFMA) ranging from 8 to 42 and hydrophilic PEG side chains, was first synthesized by sequential reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP). Subsequently, thin films were prepared by spin-casting the solution of these brushes onto indium tin oxide (ITO) and SiO2 substrates. Water contact angle analysis showed that the hydrophobicity of the film surface increased with the length of PPTFMA side chain. The atomic force microscopy (AFM) measurement demonstrated that these films had a roughness of <3 and <10 nm onto ITO glass and SiO2 substrates, respectively. The antifouling behaviors of these films in bovine serum albumin (BSA) solution were evaluated by quartz crystal microbalance (QCM), which showed that the asymmetric brush surfaces had considerable antifouling performance with less protein adsorption in comparison with the bare surface. In addition, the films made from polymer brushes with shorter PPTFMA side chains exhibited better antifouling and fouling-release behaviors.

Adipose-derived mesenchymal stem cells therapy for acute kidney injury induced by ischemia-reperfusion in a rat model.

Acute kidney injury (AKI) represents a group of complicated syndromes with a high mortality rate. The administration of adipose-derived mesenchymal stem cells (ADMSCs) has been tested as a possible treatment method for AKI. The long-term evaluation of AKI induced by ischemia/reperfusion (IR) and the probable renal protection of ADMSCs are limited. In this study we have established a rat AKI model induced by IR and investigated the possible protective effects of ADMSCs. Adult Sprague-Dawley (SD) rats were divided into three groups (n = 6/each group). The MOCK group was as the normal control. Rats in the IR-AKI and IR-AKI+ADMSCs groups were subjected to IR injury by clamping both renal pedicles for 40 minutes. Rats in the MOCK and IR-AKI groups were injected with PBS via the tail vein as negative treatment controls. Rats in the IR-AKI+ADMSCs group received ADMSCs therapy (2 × 106 cells were injected into the rats via the tail vein). We found that ADMSC transplantation restored the pathologic morphology induced by IR-AKI to normal compared with the MOCK group, suggesting the reparative function of ADMSCs in kidney tissues. Compared with IR-induced AKI alone, ADMSC treatment significantly decreased the number of apoptotic cells, the level of total urinary protein and serum creatinine, the expression of pro-inflammatory cytokines (IL-6, TNF-α, IL-1ß, IFN-γ, TNF-α, IFN-γ, and TGF-ß), and the inflammation-associated proteins (HGF and SDF1), but increased the expression of the anti-inflammatory cytokine, IL-10, and the anti-apoptotic regulator, Bcl-2. Our data have indicated that ADMSC transplantation may protect against IR-induced AKI by anti-apoptotic and anti-inflammatory effects.

Effect of static lung expansion on pulmonary function following cardiopulmonary bypass in children.

Objective: To observe the effect of the lung-protective ventilation strategy, static lung expansion, during cardiopulmonary bypass (CPB) on pulmonary function and tracheal intubation time following cardiac surgery in children. Methods: A total of 48 child patients (aged 1-3) with ventricular septal defect (VSD) were enrolled, and all underwent CPB cardiac surgery for the first time. The patients were divided into two groups using the random number table method: the experimental group (Group A, n = 30) and the control group (Group B, n = 18). After terminating the mechanical ventilation during CPB, the adjustable pressure limiting valve of the anesthesia machine was adjusted in the experimental group to maintain the pressure of the breathing circuit at 5 cmH2O, such that both lungs remained in a static expansion state. In the control group, routine mechanical ventilation was terminated as usual. Results: When static lung expansion with a continuous positive airway pressure of 5 cmH2O was employed in the VSD children during CPB, compared with termination of mechanical ventilation, the partial pressure of oxygen in the arterial blood increased, while the respiratory index decreased and the oxygenation index increased following the surgery. Conclusion: In child patients undergoing VSD reparation under CPB, lung injury occurs following the procedure, and the pulmonary oxygenation function and pulmonary oxygen diffusion function decrease. When static lung expansion of 5 cmH2O is performed during CPB, the improvement in lung function is better than that of apnea without lung expansion pressure.

Risk factors for acute kidney injury in preterm neonates after noncardiac surgery: a single-center retrospective cohort study.

Postoperative acute kidney injury (AKI) is a common complication that is associated with chronic kidney disease, early postsurgical mortality, and prolonged hospital stays. Preterm neonates who undergo surgery are at risk factors for AKI due to underdeveloped kidneys. To date, little is known about the incidence and perioperative risk factors for AKI in preterm neonates undergoing noncardiac surgery. Preterm neonates who underwent noncardiac surgery between January May 1, 2020, and February 28, 2023, were enrolled in the trial according to the inclusion criteria. Both multivariable and logistic regression analyses were used to analyze the associations between characteristic data and AKI. In total, 106 preterm neonates met the inclusion criteria, and 25 preterm neonates (23.6%) developed postoperative AKI. Multivariate analysis revealed that the factors associated with AKI were gestational age < 32 weeks [OR: 4.88; 95% CI (1.23-19.42)], preoperative sepsis [OR: 3.98; 95% CI (1.29-12.28)], and intraoperative hypotension [OR: 3.75; 95% CI (1.26-11.15)]. Preterm neonates who developed AKI were more likely to have longer hospital length of stays (38 [18,69] days vs. 21[12,46]) and higher medical costs (93,181.6 [620450.0,173,219.0] ï¿¥ vs. 58,134.6 [31015.1,97,224,1) ï¿¥ than neonates who did not develop AKI. Preterm neonates who underwent noncardiac surgery had a high incidence of AKI. Independent risk factors for AKI in preterm neonates who underwent noncardiac surgery were low gestational age, preoperative sepsis, and intraoperative hypotension. Preterm neonates who developed AKI were more likely to have longer hospital stays and higher medical costs.

Self-assembly of amphiphilic homopolymers bearing ferrocene and carboxyl functionalities: effect of polymer concentration, ß-cyclodextrin, and length of alkyl linker.

Three new acrylamide monomers containing ferrocene and tert-butyl ester groups were first synthesized via multistep nucleophilic substitution reaction under mild conditions followed by reversible addition-fragmentation chain transfer (RAFT) homopolymerization to give well-defined homopolymers with narrow molecular weight distributions (M(w)/M(n) ≤ 1.36). The target amphiphilic homopolymers were obtained by the acidic hydrolysis of tert-butyoxycarbonyls to carboxyls in every repeating unit using CF3COOH. The self-assembly behaviors of these amphiphilic homopolymers bearing both ferrocene and carboxyl moieties in each repeating unit in aqueous media were investigated by transmission emission microscopy (TEM), dynamic light scattering (DLS), and atomic force microscopy (AFM). Large compound micelles with different morphologies were formed by these amphiphilic homopolymers, which consist of the corona formed by hydrophilic carboxyls and the core containing numerous reverse micelles with hydrophilic islands of carboxyls in continuous hydrophobic phase of ferrocene-based segments. The morphologies of the formed micelles could be tuned by the concentration of amphiphilic homopolymers, pH value of the solution, the length of -CH2 linker between ferrocene group and carboxyl, and the amount of ß-cyclodextrin (ß-CD).

Preparation and cellular uptake behaviors of uniform fiber-like micelles with length controllability and high colloidal stability in aqueous media.

Fragmentation/disassembly of fiber-like micelles generated by living crystalline-driven self-assembly (CDSA) is usually encountered in aqueous media, which hinders the applications of micelles. Herein, we report the generation of uniform fiber-like micelles consisting of a π-conjugated oligo(p-phenylenevinylene) core and a cross-linking silica shell with grafted poly(ethylene glycol) (PEG) chains by the combination of living CDSA, silica chemistry and surface grafting-onto strategy. Owing to the presence of crosslinking silica shell and the outmost PEG chains, the resulting micelles exhibit excellent dispersity and colloidal stability in PBS buffer, BSA aqueous solution and upon heating at 80 °C for 2 h without micellar fragmentation/disassembly. The micelles also show negligible cytotoxicity toward both HeLa cervical cancer and HEK239T human embryonic kidney cell lines. Interestingly, micelles with L n of 156 nm show the "stealth" property with no significant uptake by HeLa cells, whereas some certain amounts of micelles with L n of 535 nm can penetrate into HeLa cells, showing length-dependent cellular uptake behaviors. These results provide a route to prepare uniform, colloidally stable fiber-like nanostructures with tunable length and functions derived for biomedical applications.

π-Conjugated-polymer-based nanofibers through living crystallization-driven self-assembly: preparation, properties and applications.

π-Conjugated-polymer-based nanofibers (CPNFs) of controlled length, composition and morphology are promising for a broad range of emerging applications in optoelectronics, biomedicine and catalysis, owing to the morphological merits of fiber-like nanostructures and structural attributes of π-conjugated polymers. Living crystallization-driven self-assembly (CDSA) of π-conjugated-polymer-containing block copolymers (BCPs) has emerged as an efficient strategy to prepare CPNFs with precise dimensional and structural controllability by taking advantage of the crystallinity of π-conjugated polymers. In this review, recent advances in the generation of CPNFs have been highlighted. The influence of the structure of π-conjugated-polymer-containing BCPs and experimental conditions on the CDSA behaviors, especially seeded growth and self-seeding processes of living CDSA, has been discussed in detail, aiming to provide an in-depth overview of living CDSA of π-conjugated-polymer-containing BCPs. In addition, the properties of CPNFs as well as their potential applications have been illustrated. Finally, we put forward the current challenges and research directions in the field of CPNFs.

Sulfur dioxide signaling molecule-responsive polymeric nanoparticles.

Stimuli-responsive polymer nano-capsules toward a specific signaling molecule show great potential in the fabrication of smart and efficient controlled/targeted drug vehicles. Herein, we design and synthesize a PEG45-b-PVPOP14 diblock copolymer (PEG = poly(ethylene glycol) and PVPOP = poly(4-vinylphenyl 4-oxopentanoate), the subscripts representing the number of repeat units of each block) with levulinate-protected phenol side groups. The PEG45-b-PVPOP14 diblock copolymer could self-assemble to form large compound micelles in aqueous media. Since the core of the large compound micelles formed contains both hydrophilic PEG and hydrophobic PVPOP domains, this kind of micelle is able to load both hydrophobic and hydrophilic species within the core. The ester moiety of levulinate-protected phenol can be selectively cleaved upon incubation with a sulfite, a derivative of SO2 in aqueous media, to give phenol groups. Thus, the sulfite exhibits the ability to alter the amphiphilicity and further the self-assembled behavior of PEG45-b-PVPOP14. The release of payloads in the core of micelles can be accelerated by triggering of the sulfite. Significantly, the nano-capsule of PEG45-b-PVPOP14 shows specific response to the sulfite (SO2) with slight interference of other bio-species, such as Cys, GSH and Hcy. As far as we are aware, this is the first example of a nano-capsule with sulfite (SO2) specific responsiveness. We envisage that this polymer model could broaden the scope of biological signaling molecule responsive macromolecular systems and provide a new platform to fabricate SO2-responsive biomedicine materials.

Biomimetic Asymmetric Polymer Brush Coatings Bearing Fencelike Conformation Exhibit Superior Protection and Antifouling Performance.

Antifouling surfaces with optimized conformation and compositional heterogeneities are presented with the goal of improving the efficacy of surface protection. The approach exploits the adhesive group (thiol or catechol chain end) to anchor asymmetric polymer brushes (APBs) bearing amphiphilic side chains with synergistic nonfouling and fouling-release abilities onto the surface. The conformation of the APB surface is close to the fencelike structure, which mimics lubricating protein lubricin, endowing the surface with capacity of enhanced protection and antiadhesivity, even facing the high compression of fouling. By utilizing a poly(Br-acrylate-alkyne) macroagent comprising alkynyl and 2-bromopropionate groups, we prepared a series of APB surfaces based on polyacrylate-g-poly(ethylene oxide)/poly(pentafluorophenyl methacrylate) (PA-g-PEO/PPFMA) APBs to explore the influence of the content of the fluorinated segment and bioinspired topological polymer chemistry on their antifouling performance. The APB surfaces can not only provide compositional heterogeneities of PEO and fluorinated segments in each side chain but also give a high surface coverage because of the characteristic of high grafting density of macromolecular brushes. It was found for the first time, as far as we are aware, the fencelike APB surface shows excellent antifouling performance with less protein adsorption (up to 91% off) and cell adhesion (up to 84% off) in comparison with the controlled substrate under relatively long incubation time.