Visible-light-excited robust room-temperature phosphorescence of dimeric single-component luminophores in the amorphous state.

Organic room temperature phosphorescence (RTP) has significant potential in various applications of information storage, anti-counterfeiting, and bio-imaging. However, achieving robust organic RTP emission of the single-component system is challenging to overcome the restriction of the crystalline state or other rigid environments with cautious treatment. Herein, we report a single-component system with robust persistent RTP emission in various aggregated forms, such as crystal, fine powder, and even amorphous states. Our experimental data reveal that the vigorous RTP emissions rely on their tight dimers based on strong and large-overlap π-π interactions between polycyclic aromatic hydrocarbon (PAH) groups. The dimer structure can offer not only excitons in low energy levels for visible-light excited red long-lived RTP but also suppression of the nonradiative decays even in an amorphous state for good resistance of RTP to heat (up to 70 °C) or water. Furthermore, we demonstrate the water-dispersible nanoparticle with persistent RTP over 600 nm and a lifetime of 0.22 s for visible-light excited cellular and in-vivo imaging, prepared through the common microemulsion approach without overcaution for nanocrystal formation.

Stable and ultralong room-temperature phosphorescent copolymers with excellent adhesion, resistance, and toughness.

Developing stable room-temperature phosphorescence (RTP) emission without being affected by moisture and mechanical force remains a great challenge for purely organic systems, due to their triplet states sensitive to the infinitesimal motion of phosphors and the oxygen quencher. We report a kind of highly robust phosphorescent systems, by doping a rigid phosphor into a copolymer (polyvinyl butyral resin) matrix with a balance of mutually exclusive features, including a rigidly hydrophilic hydrogen bond network and elastically hydrophobic constituent. Impressively, these RTP polymeric films have superior adhesive ability on various surfaces and showed reversible photoactivated RTP with lifetimes up to 5.82 seconds, which can be used as in situ modulated anticounterfeit labels. They can maintain a bright afterglow for over 25.0 seconds under various practical conditions, such as storage in refrigerators, soaking in natural water for a month, or even being subjected to strong collisions and impacts. These findings provide deep insights for developing stable ultralong RTP materials with desirable comprehensive performance.

Can the establishment of state-level urban agglomeration stimulate enterprise innovation?-Taking Yangtze River Delta and Pearl River Delta as an example.

This study uses a quasi-experimental method, Geographic Regression Discontinuity Design (GRDD), to evaluate the actual effect of establishing Yangtze River Delta and Pearl River Delta urban agglomerations on enterprise innovation. GRDD is a design in which a geographic boundary splits the units into treated and control areas in an as-if random fashion, and the shortest distances from each enterprise's location to the boundary of urban agglomeration calculated by ArcGIS are considered as the running variable. The actual effect can be identified by the probability of receiving treatment jumps discontinuously at the known cutoff. It is shown that the establishment of Yangtze River Delta and Pearl River Delta urban agglomerations can significantly improve the enterprise innovation, and this outcome is verified by rigorous robustness tests including the placebo test with pseudo-boundary, the bandwidth sensitivity test, the parametric test with different functional forms and the extreme value test. Further, the influence mechanisms of state-level urban agglomerations promoting enterprise innovation are explored by Staggered DID. It is confirmed that the urban agglomeration construction can promote enterprise innovation through financial support and regional coordination channels.

Catalytically Controlled Ring-Opening Polymerization of 2-Oxo-15-crown-5 for Degradable and Recyclable PEG-Like Polyesters.

Poly(ethylene glycol) (PEG) has been extensively used in diverse applications. However, it is not biodegradable and shows abnormal immune responses. Herein, a fast, controlled, ring-opening polymerization (ROP) of 2-oxo-15-crown-5 (O-15C5) is reported to prepare well-defined PEG-like polyesters, poly(O-15C5). This approach relies on a coordination between the macrocyclic monomer and Na+ that increases the electrophilicity of the carbonyl group of O-15C5 and leads to a fast controlled ROP (dispersity, DM < 1.2). Both computational and mechanistic studies show that the selective Na+ binding to the monomer over poly(O-15C5) allows the ring-opening initiation and propagation to be more energetically favorable than side transesterifications. This is the key to control the challenging entropy-driven ROP of O-15C5. Moreover, with the aid of Na+ and organic base, poly(O-15C5) depolymerized readily into O-15C5 in 2 h. Also, it degraded in a buffer of pH 7.4 by hydrolysis.

Concurrent and Mechanochemical Activation of Two Distinct and Latent Fluorophores via Retro-Diels-Alder Reaction of an Anthracene-Aminomaleimide Adduct.

Generally, a typical mechanochromophore produces color change through chemical transformation into one or two identical new chromophores/fluorophores under applied mechanical force. Herein, we introduce a novel mechanophore based on an anthracene-aminomaleimide Diels-Alder (DA) adduct featuring two distinct and latent fluorophores. This nonfluorescent mechanophore undergoes retro-DA reaction upon mechanochemical activation in solution and the solid state, generating the respective anthracene and aminomaleimide fragments simultaneously, both of which are highly emissive with different fluorescent colors. In addition, the aminomaleimide fluorophore exhibits sensitive fluorescence on-off response to protic solvents or polar solvents, which enables dual-color mechanochromism from this single mechanophore.

Stepwise Energy Transfer: Near-Infrared Persistent Luminescence from Doped Polymeric Systems.

Organic near infrared (NIR) persistent-luminescence systems with bright and long-lived emission are highly valuable for applications in communication, imaging, and sensors. However, realizing these materials (especially lifetime over 0.1 s) is a challenge, mainly because of non-radiative quenching of their long-lived excitons. Herein, a universal strategy of stepwise Förster resonance energy transfer (FRET) for a bright NIR system with remarkable persistent luminescence (up to 0.2 s at 810 nm) is presented, based on a new triphenylene-dye-doped polymer (triphenylene-2-ylboronic acid@poly(vinyl alcohol) (TP@PVA)) with a persistent blue phosphorescence of 3.29 s. This persistent NIR luminescence is demonstrated for application not only in NIR anti-counterfeiting but also NIR bioimaging with penetrating a piece of skin as thick as 2.0 mm. By co-doping a red dye (such as Nile red) and an NIR dye Cyanine 7 (Cy7) into this doped PVA film, the shortage of spectral overlap between TP emission and Cy7 absorbance is successfully solved, through a stepwise FRET process involving triplet to singlet (TS)-FRET from TP to the intermediate red dye and then singlet to singlet (SS)-FRET to Cy7. It is noted that the efficiency of the upper TS-FRET is enhanced significantly by the lower SS-FRET, leading to high efficiencies for the continuous FRETs.

Tadpole-like Unimolecular Nanomotor with Sub-100 nm Size Swims in a Tumor Microenvironment Model.

Inspired by the natural motors capable of performing multiple tasks in complex living environments, synthetic nanomotors emerge as a potential vehicle for revolutionizing biomedical processes. Yet current motors suffer from decreased and even completely hindered motion in a complex physiological environment, shadowing the future of this booming field. To address this problem, a unimolecular nanomotor based on molecular bottlebrush (MBB) of sub-100 nm size is reported. This motor is constructed precisely via controlled radical polymerization and click chemistry and propelled with biocompatible catalase. Such a molecular nanomotor possesses tadpole-like asymmetry and is able to overcome Brownian motion, and demonstrates strong directional propulsion (linear and coiled cyclic trajectories) in a viscous tumor microenvironment gel model at an ultralow hydrogen peroxide level of 2 mM (0.006%). In addition, the molecular nanomotor exhibits superior stability in serum containing cell medium and good biocompatibility in blood. Such molecular bottlebrush based nanomotors may represent a unique platform for overcoming the tissue penetration barrier.

Molecular Bottlebrushes Featuring Brush-on-Brush Architecture.

Molecular bottlebrushes featuring brush-on-brush (BoB) architecture were prepared by combining azide-alkyne click chemistry, ring-opening polymerization (ROP), and atom transfer radical polymerization (ATRP). Primary side chains of diblock copolymers with a poly(ε-caprolactone) (PCL) block and a poly(α-bromo-ε-caprolactone) (P(CL-Br)) block were synthesized by ROP and then grafted onto PCL backbone by the click reaction. Then the secondary side chains of poly(oligo(ethylene glycol) acrylate) (POEGA) were grafted from the P(CL-Br) block by ATRP, yielding an amphiphilic core/shell structure. Imaging of individual macromolecules by atomic force microscopy (AFM) demonstrated dramatically thickened wormlike formation with distinct hairy side chains. Interestingly, for the BoB molecular bottlebrushes with enough long primary and secondary side chains, sufficient tension can be generated along the backbone and thus lead to its cleavage.

Production of optically pure 2,3-butanediol from Miscanthus floridulus hydrolysate using engineered Bacillus licheniformis strains.

2,3-Butanediol (2,3-BD) can be produced by fermentation of natural resources like Miscanthus. Bacillus licheniformis mutants, WX-02ΔbudC and WX-02ΔgldA, were elucidated for the potential to use Miscanthus as a cost-effective biomass to produce optically pure 2,3-BD. Both WX-02ΔbudC and WX-02ΔgldA could efficiently use xylose as well as mixed sugars of glucose and xylose to produce optically pure 2,3-BD. Batch fermentation of M. floridulus hydrolysate could produce 21.6 g/L D-2,3-BD and 23.9 g/L meso-2,3-BD in flask, and 13.8 g/L D-2,3-BD and 13.2 g/L meso-2,3-BD in bioreactor for WX-02ΔbudC and WX-02ΔgldA, respectively. Further fed-batch fermentation of hydrolysate in bioreactor showed both of two strains could produce optically pure 2,3-BD, with 32.2 g/L D-2,3-BD for WX-02ΔbudC and 48.5 g/L meso-2,3-BD for WX-02ΔgldA, respectively. Collectively, WX-02ΔbudC and WX-02ΔgldA can efficiently produce optically pure 2,3-BD with M. floridulus hydrolysate, and these two strains are candidates for industrial production of optical purity of 2,3-BD with M. floridulus hydrolysate.

Molecular bottlebrush as a unimolecular vehicle with tunable shape for photothermal cancer therapy.

Morphology of delivery nanovehicle plays a significant role in bioavailability of drug. Molecular bottlebrush (MBB)-based unimolecular micelle, with tunable morphologies including sphere, rod, and worm, offers a new aspect to uncover the relationship between morphology and bio-behaviors. In this study, a series of MBB as unimolecular micelle with core-shell structures were tailor-made through controlled/living polymerization and click chemistry, and served as carriers of IR780 photothermal agent. With an excellent IR780 loading content of up to ca. 25%, these molecular nanovehicles still maintained their molecular morphologies and did not aggregate in cell culture medium. Among three MBB, the rodlike one exhibited best performance in cell uptake in the 2D and also in spheroid penetration in 3D cell culture. Furthermore, this rodlike system had preferential accumulation in tumor in vivo and excellent effect on photothermal cancer therapy which effectively inhibited tumor growth. These results demonstrated an important role of nanoparticle shape on bio-behaviors and the unimolecular micelle could be a promising nanovehicle with precisely defined structure for biomedicine applications.

Scalable fabrication of size-controlled chitosan nanoparticles for oral delivery of insulin.

Controlled delivery of protein would find diverse therapeutic applications. Formulation of protein nanoparticles by polyelectrolyte complexation between the protein and a natural polymer such as chitosan (CS) is a popular approach. However, the current method of batch-mode mixing faces significant challenges in scaling up while maintaining size control, high uniformity, and high encapsulation efficiency. Here we report a new method, termed flash nanocomplexation (FNC), to fabricate insulin nanoparticles by infusing aqueous solutions of CS, tripolyphosphate (TPP), and insulin under rapid mixing condition (Re > 1600) in a multi-inlet vortex mixer. In comparison with the bulk-mixing method, the optimized FNC process produces CS/TPP/insulin nanoparticles with a smaller size (down to 45 nm) and narrower size distribution, higher encapsulation efficiency (up to 90%), and pH-dependent nanoparticle dissolution and insulin release. The CS/TPP/insulin nanoparticles can be lyophilized and reconstituted without loss of activity, and produced at a throughput of 5.1 g h-1 when a flow rate of 50 mL min-1 is used. Evaluated in a Type I diabetes rat model, the smaller nanoparticles (45 nm and 115 nm) control the blood glucose level through oral administration more effectively than the larger particles (240 nm). This efficient, reproducible and continuous FNC technique is amenable to scale-up in order to address the critical barrier of manufacturing for the translation of protein nanoparticles.

Parental Monitoring, Parent-Adolescent Communication, and Adolescents' Trust in Their Parents in China.

PURPOSE: Trust is an important aspect of interpersonal relationships, but little is known about adolescents' interpersonal trust. The aim of the present study was to examine the associations among parental monitoring, parent-adolescent communication, and adolescents' trust in their parents in China. METHODS: Data in this study were collected as part of the cross-sectional study of children in China. 3349 adolescents (female 48.6%, age range of 12-15 years) were randomly selected from 35 secondary schools in April, 2009 and administered to the Adolescent Interpersonal Trust Scale, the Parental Monitoring Scale, and the Parent-Adolescent Communication Scale. RESULTS: Adolescents' trust in their parents was positively related to parental monitoring and parent-adolescent communication. Furthermore, parent-adolescent communication mediated the association between parental monitoring and adolescents' trust in their parents. The mediation model fit data of both genders and three age groups equally well. CONCLUSIONS: Parental monitoring and parent-adolescent communication play an importance role in fostering adolescents' trust in their parents.

Study of multi-functional electrospun composite nanofibrous mats for smart wound healing.

Composite nanofibers derived from synthetic and natural polymers normally show desirable characteristics in biomedical applications. In this study, composite nanofibrous mats (denoted as CNMs) with diameters of around 300 nm were fabricated facilely using blends of chitosan, gelatin and shape memory polyurethane (SMPU) by electrospinning and subsequent post-treatment with a silver nitrate solution. The obtained CNMs have shape memory effect and show desirable water vapor transmission ratio, surface wettability, satisfactory biological properties including antibacterial activity against the common Gram-negative and Gram-positive bacteria, cytocompatibility demonstrated to fibroblast, and the hemostatic property through a whole-blood clotting test. In addition, such CNMs can possibly benefit the wound healing through shape fixation-assisted easy processing and shape recovery-assisted closure of cracked wounds, which can be fine-tuned by pre-programming. Therefore, the CNMs presented in this study can be used as potential smart wound dressings.

Shape-memory biopolymers based on ß-sheet structures of polyalanine segments inspired by spider silks.

The molecular structural design learned from natural materials enables synthetic polymers with desirable and unique features to be fabricated. Inspired by spider silks, short-chain polyalanine (PA) is introduced into multiblock biopolymers with poly(ε-caprolactone) segments via a coupling reaction. As a result, PA segments in biopolymers form similar ß-sheet crystals to that of natural spidroins. These new biopolymers are found to exhibit nearly complete shape recovery and high shape fixity, along with significantly improved thermal stability due to the strong ß-sheet structures as netpoints. This work provides new insight for the design of novel shape-memory polymers with potential use in biomedical applications.

Active noise attenuation in ventilation windows.

The feasibility of applying active noise control techniques to attenuate low frequency noise transmission through a natural ventilation window into a room is investigated analytically and experimentally. The window system is constructed by staggering the opening sashes of a spaced double glazing window to allow ventilation and natural light. An analytical model based on the modal expansion method is developed to calculate the low frequency sound field inside the window and the room and to be used in the active noise control simulations. The effectiveness of the proposed analytical model is validated by using the finite element method. The performance of the active control system for a window with different source and receiver configurations are compared, and it is found that the numerical and experimental results are in good agreement and the best result is achieved when the secondary sources are placed in the center at the bottom of the staggered window. The extra attenuation at the observation points in the optimized window system is almost equivalent to the noise reduction at the error sensor and the frequency range of effective control is up to 390 Hz in the case of a single channel active noise control system.