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Microcapsule formulations have been widely developed and used in agriculture to improve pesticide utilization and reduce environmental pollution. However, commercial formulations of chlorantraniliprole (CAP) are only traditional formulations due to poor solubility of CAP in organic solvents. Here, adopting a solid in oil in water (S/O/W) double-emulsion method combined with premix membrane emulsion, we successfully constructed CAP microcapsule formulations with a high loading content. The microcapsule formulations with good light and thermal stability showed a significantly sustained release for a long period, which could be optimally regulated by tuning the surface porosity and size of the porous microcapsules. Bioassay studies showed that control efficacy of the porous microcapsule formulations against Plutella xylostella was superior to that of the commercial formulation. These results demonstrated that such a porous microcapsule delivery system should have great potential for further exploration as a commercial CAP formulation.

Currently, the major issues in the treatment of osteoarticular tuberculosis (TB) after implant placement are low drug concentration at the infected focus and drug resistance resulting from the long-term chemotherapy. The application of drug-loaded polymeric multilayers on implantable devices offers a promising solution to the problems. Herein, a poly(ethylene glycol)-based hydrogel film embedded with isoniazid (INH)-loaded alginate microparticles was fixed to Ti implants via adhesive polydopamine, subsequently capped by poly(lactic-co-glycolic acid) membranes for the sustained and localized delivery of the anti-TB drug. The antibacterial efficacy of the released INH was confirmed by a 4.5 ± 0.8 cm inhibition zone formed in the fourth week after inoculation of Mycobacterium tuberculosis. The INH-loaded Ti implants showed no toxicity to the osteoblast cell and provided a consistent drug release for nearly one week in vitro. The release profile in vivo showed a high local concentration and low systemic exposure. The local INH concentration could be kept higher than its minimum inhibitory concentration over a period of 8 weeks, which proves that it is a promising strategy to improve the severe osteoarticular TB treatment.

A series of brush block copolymers (BBCPs) with polynorbornene backbones containing poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS, which is a rigid chain) and poly(ethylene oxide) (PEO) side chains were synthesized by tandem ring-opening metathesis polymerizations. The weight fractions of PEO in BBCPs are similar, and the degrees of polymerization (DPs) of PEO side chains are the same while the DPs of PMPCS are different. The bulk self-assembling behaviors were studied by small-angle X-ray scattering (SAXS). The neat BBCPs cannot form ordered nanostructures. However, after the doping of lithium salt, the BBCPs self-assemble into lamellar (LAM) structures. When the DPs of the PEO and PMPCS side chains are similar, the LAM structure is more ordered, which is attributed to the more flat interface between PMPCS and PEO phases. The ionic conductivity (σ) values of the BBCP/lithium salt complex with the most ordered LAM structure at different temperatures were measured. The σ value increases with increasing temperature in the range of 40-200 °C, and the relationship between σ and T fits the Vogel-Tamman-Fulcher (VTF) equation. The σ value at 200 °C is 1.58 × 10

Though many responsive polymers have been prepared, none of them can both self-immolate and self-cross-link via responding to the changes of the environment. Here, we introduce a new responsive hyperbranched polymer, which not only can self-immolate but also can self-cross-link via responding to the external stimuli. Moreover, the obtained polymer can form a bioreducible nanogel in its aqueous solution simply via heating, and the formed nanogel can self-immolate via UV irradiation.

The compound of hydroxyapatite-poly(lactide-co-glycolide) (HA-PLGA) was prepared by ionic bond between HA and PLGA. HA-PLGA was more stable than the simple physical blend of hydroxyapatite and poly(lactide-co-glycolide) (HA/PLGA). The surface of HA-PLGA microsphere fabricated by an emulsion–solvent evaporation method was rougher than that of HA/PLGA microspheres. Moreover, surface HA content of HA-PLGA microspheres was more than that of HA/PLGA microspheres. In vitro mouse OCT-1 osteoblast-like cell culture results showed that the HA-PLGA microspheres clearly promoted osteoblast attachment, proliferation and alkaline phosphatase activity. It was considered that surface rich HA component and rough surface of HA-PLGA microsphere enhanced cell growth and differentiation. The good cell affinity of the HA-PLGA microspheres indicated that they could be used as an injectable scaffold for bone tissue engineering.

Disulfide-exchange was found to cross-link the polyplex of disulfide-containing poly(amido amine) and pDNA with heating of the polyplex solution over a short time. The cross-linked polyplexes based on disulfide-containing poly(amido amine) have excellent stability under physiological salt conditions, and have significantly enhanced transfection activity in the serum media compared to non-cross-linked polyplexes. In vivo, ICR mice were injected with the polyplex through the tail vein, the results show that the transfection efficiency of the cross-linked polyplex is higher than that of the non-cross-linked variety. Furthermore, the polyplex containing Cy5 labelled DNA was also injected into the mice to illustrate the stability and distribution of the polyplex, cross-linked polyplexes show a much brighter luminescence than the non-cross-linked ones. This method does not need a cross-linker or catalyst, and there are no impurities produced, it may be an elegant approach to resolve the dilemma of in vivo application of a DNA polyplex, with excellent stability whilst in circulation and a rapid unpacking of the polyplex inside the cells.

An ultrasound contrast agent (UCA) plays a key role in ultrasound imaging to precisely diagnose coronary heart disease. Microcapsules composed of inner gas and shell materials are most commonly employed as ultrasound contrast agents. The ultrasonic properties of the microcapsules are significantly dependent on their size and size distribution. Herein, we prepared several uniform sized biodegradable polylactone microcapsules by combining a premix membrane emulsification technique and W/O/W method. We investigated various size-dependent factors to optimize the size and size distribution of the microcapsules. After evaluation for ultrasound imaging, ∼4 μm PLLA (poly(L-lactide)) microcapsules generated more intense ultrasound signals than PLGA7030 or PLGA5050 (poly(lactic-co-glycolic acid), the molar ratio of lactic acid and glycolic acid being 70:30 or 50:50), PEG-b-PLGA7030 (poly(ethylene glycol)-block-poly(lactic-co-glycolic acid)), PLC5050 (poly(L-lactide-co-caprolactone), the molar ratio of lactide and caprolactone being 50:50) and PEG-b-PLLA microcapsules. The signal duration of the PLLA and PEG-PLLA microcapsules could reach ca. 3 and 3.5 min continuously. The ultrasound signal intensity and duration of the signals of PLLA microcapsules were considerably stronger and longer than those of commercially available UCAs, showing that the PLLA microcapsules have a great potential as more efficient UCAs for biomedical imaging.

Inspired by the highly ordered nanostructure of bone, nanodopant composite biomaterials are gaining special attention for their ability to guide bone tissue regeneration through structural and biological cues. However, bone malformation in orthopedic surgery is a lingering issue, partly due to the high surface energy of traditional nanoparticles contributing to aggregation and inhomogeneity. Recently, carboxyl-functionalized synthetic polymers have been shown to mimic the carboxyl-rich surface motifs of non-collagenous proteins in stabilizing hydroxyapatite and directing intrafibrillar mineralization in-vitro. Based on this biomimetic approach, it is herein demonstrated that carboxyl functionalization of poly(lactic-co-glycolic acid) can achieve great material homogeneity in nanocomposites. This ionic colloidal molding method stabilizes hydroxyapatite precursors to confer even nanodopant packing, improving therapeutic outcomes in bone repair by remarkably improving mechanical properties of nanocomposites and optimizing controlled drug release, resulting in better cell in-growth and osteogenic differentiation. Lastly, better controlled biomaterial degradation significantly improved osteointegration, translating to highly regular bone formation with minimal fibrous tissue and increased bone density in rabbit radial defect models. Ionic colloidal molding is a simple yet effective approach of achieving materials homogeneity and modulating crystal nucleation, serving as an excellent biomimetic scaffolding strategy to rebuild natural bone integrity.

Redox-responsive hyperbranched poly(amido amine)s (PAAs) with tertiary amino cores and amine, poly(ethylene glycol) (PEG) and hydroxyl terminal groups were prepared for DNA delivery respectively. The DNA condensation capability of PAAs was investigated using gel electrophoresis, and the results showed that PAA terminated with 1-(2-aminoethyl)piperazine (AEPZ) (BAA) is the most efficient in binding plasmid DNA (pDNA). The diameter and zeta-potential of polyplexes from PAAs were characterized using dynamic light scattering (DLS), and the morphology of the polyplexes was obtained using atomic force microscopy (AFM). All the PAAs were able to condense pDNA into nanoparticles with diameters between 50 and 200 nm with a positive surface charge when the weight ratio of polymer/DNA was higher than 20. Glutathione (GSH)-induced DNA release from polyplexes and the buffering capability of PAAs were investigated as well. Cytotoxicity of PAAs and in vitro gene transfection of polyplexes were evaluated in HEK293, COS-7, MCF-7 and Hep G2 cell lines, respectively. The results reflect that PAAs show remarkably low or even no cytotoxicity, and that PAA with amino terminal groups mediates the most efficient gene transfection with the transfection efficiency comparable to that of 25 kDa polyethylenimine. Further the effects of the presence of buthionine sulfoximine (BSO) on the transfection efficiency and cytotoxicity of BAA polyplexes were investigated.

A general approach is proposed to synthesize Janus polymer/inorganic composite nanosheets. Onto the amine-group-terminated side of the Janus inorganic nanosheets, initiators are covalently bonded. By a favorable grafting from initiator-terminated side, responsive polymers, for example PDEAEMA and PNIPAM, are synthesized by controlled polymerization for example ATRP or RAFT polymerization. Stable emulsions are easily formed in the presence of the Janus nanosheets, which can be easily de-emulsified by subtle changing physicochemical parameters, for example temperature and pH.

Michael addition polymerizations of amines and acrylic monomers are versatile approaches to biomaterials for various applications. A combinatorial library of poly(β-amino ester)s and diverse poly(amido amine)s from diamines and diacrylates or bis(acrylamide)s have been reported, respectively. Furthermore, novel linear and hyperbranched polymers from Michael addition polymerizations of trifunctional amines and acrylic monomers significantly enrich this category of biomaterials. In this Review, we focus on the biomaterials from Michael addition polymerizations of trifunctional amines and acrylic monomers. First we discuss how the polymerization mechanisms, which are determined by the reactivity sequence of the three types of amines of trifunctional amines, i.e., secondary (2°) amines (original), primary (1°) amines, and 2° amines (formed), are affected by the chemistry of monomers, reaction temperature, and solvent. Then we update how to design and synthesize linear and hyperbranched polymers based on the understanding of polymerization mechanisms. Linear polymers containing 2° amines in the backbones can be obtained from polymerizations of diacrylates or bis(acrylamide)s with equimolar trifunctional amine, and several approaches, e.g., 2A

Here we have demonstrated a facile method for construction of self-assembled nanoparticles with excellent fluorescent properties by the synergetic combination of unique AIE effects and tadpole-shaped polymers. The introduction of acid-sensitive Schiff base bonds furnished the polymeric vesicles and micelles with unique pH responsiveness that can possess maximal drug-release controllability inside tumor cells upon changes in physical and chemical environments, but present good stability under physiological conditions. Having benefited from the efficient fluorescence resonance energy transfer (FRET), the DOX-loaded fluorescent aggregates were employed for intracellular imaging and self-localization in surveillance of systemic DOX delivery. Cytotoxicity assay of the DOX-loaded aggregates indicated a fast internalization and a high cellular proliferation inhibition to MCF-7 cells while the PEG-POSS-(TPE)7 nanoparticles displayed no cytotoxicity, exhibiting excellent biocompatibility and biological imaging properties. These results indicated that these biodegradable nanoparticles, as a class of effective pH-responsive and visible nanocarriers, have the potential to improve smart drug delivery and enhance the antitumor efficacy for biomedical applications.

Cationic polymer vectors have received increasing attention for gene delivery in biotechnology over the past 2 decades, but few polymer vectors were used in clinical applications due to their low gene transfection efficacy. One of the major reasons is that the conventional cationic polymers can induce the increasing of intracellular reactive oxygen species (ROS) concentration and oxidative stress, which reduces the gene transfection efficacy. Here, we create a novel class of thioether dendron-branched polymer conjugate and self-assemble this conjugate into bioreducible cationic nanomicelles with disulfide bond connecting the thioether core to the cationic shell. The obtained nanomicelles have a unique ROS self-scavenging ability, thereby dramatically improving gene transfection efficacy.

We demonstrate a facile approach to constructing aggregation induced emission (AIE) fluorescent vesicles assembled using a PEG–POSS–(TPE)7 polymer. The narrow wall thickness provides an ideal confined space for creating fluorescence resonance energy transfer (FRET) systems between TPE donors and encapsulated FITC or DOX acceptors.

Here we demonstrate a type of pH and reduction dual-sensitive biodegradable micelles, which were self-assembled by a cationic polymer in an aqueous solution. Due to tumor cells or tissues showing low pH and high reduction concentration, these micelles possessed specific tumor targetability and maximal drug-release controllability inside tumor cells upon changes in physical and chemical environments, but presented good stability at physiological conditions. CCK-8 assay showed that the DOX-loaded micelles had a similar cytotoxicity for MCF-7 tumor cells as free DOX, and blank micelles had a very low cytotoxicity to the cells. Fluorescent microscopy observation revealed that the drug-loaded micelles could be quickly internalized by endosomes to inhibit cancer cell growth. These results indicated these biodegradable micelles, as a novel and effective pH- and redox-responsive nanocarrier, have a potential to improve drug delivery and enhance the antitumor efficacy.

Three types of azobenzene-based telechelic guest polymers, PEG-azo, azo-PEG-azo, and PEG-azo4, were synthesized by a facile method. Subsequently, a series supramolecular amphiphiles with three distinct topological structures (hemitelechelic, ditelechelic, and quadritelechelic) were constructed through coupling with host polymer β-cyclodextrin-poly(l-lactide) (β-CD-PLLA) by combined host-guest complexation. Research on the self-assembly behavior of these amphiphiles demonstrated that the variation in self-assembly was tuned by the synergistic interaction of hydrophilicity and the curvature of the polymer chains, and very importantly, the topological structure of amphiphiles demonstrated effective control of the self-assembly behavior.

12-year LIDAR observations of tropospheric aerosol vertical distribution using a Mie scattering LIDAR in Hefei (31.9°N, 117.2°E) from 1998 to 2009 are presented and analyzed in this paper. Characters of temporal variation and vertical distribution of tropospheric aerosol over Hefei are summarized from the LIDAR measurements. The impacts of natural source and human activities on the aerosol vertical distribution over Hefei could be seen clearly. Dust particles from the north in spring could affect the aerosol distributions below about 12 km over Hefei, and aerosol scale height in April reaches 2.29±0.68 km. Both LIDAR measurements and surface visibility imply that aerosols in the lower troposphere have been increasing since about 2005.

A turn-key Raman–Mie lidar system for water vapor and aerosol detection is described, which is placed in a boxcar and can be operated both at night and daytime. The operation of the lidar is very simple, especially, it does not need readjustment after road transit. The effective detection range of the system can reach tropopause for aerosol, and the improved system can obtain water vapor profile in boundary layers during daytime. Some experimental results and validations are presented.

The traditional approach to inverting aerosol extinction makes use of the assumption of a constant LIDAR ratio in the entire Mie-LIDAR signal profile using the Fernald method. For the large uncertainty in the cloud optical depth caused by the assumed constant LIDAR ratio, an not negligible error of the retrieved aerosol extinction below the cloud will be caused in the backward integration of the Fernald method. A new algorithm to determine aerosol extinction below a cirrus cloud from Mie-LIDAR signals, based on a new cloud boundary detection method and a Mie-LIDAR signal modification method, combined with the backward integration of the Fernald method is developed. The result shows that the cloud boundary detection method is reliable, and the aerosol extinction below the cirrus cloud found by inverting from the modified signal is more efficacious than the one from the measured signal including the cloud-layer. The error due to modification is less than 10% taken in our present example.

A 'living' controlled hydrogel formation method was first reported to create loose and compact in situ biodegradable hydrogels. The method executed under mild reaction conditions can conveniently tailor the hydrogel properties, and it has the potential to develop into a powerful tool for the design, synthesis, and self-assembly of novel tailor-made biomaterials and drug delivery systems.

A series of polymerization-induced self-assembly (PISA) formulations are developed based on reversible addition-fragmentation chain-transfer (RAFT) dispersion polymerization of semi-fluorinated methacrylates. Alcoholic RAFT dispersion polymerization of 2-(perfluorobutyl)ethyl methacrylate (FBEMA), 2-(perfluorohexyl)ethyl methacrylate (FHEMA), and 2-(perfluorooctyl)ethyl methacrylate (FOEMA) is systematically evaluated to extend the general usability of semi-fluorinated methacrylates to PISA. The nanostructure of the assemblies is correlated to the side-chain length of the monomer: RAFT dispersion polymerization of FBEMA produces spherical micelles, wormlike micelles, and vesicles depending on its degree of polymerization (DP), while only spheres are generated for the PISA of FHEMA. PISA of FOEMA generates liquid crystalline cylindrical micelles, whose diameter increases with the DP of FOEMA. These results demonstrate the general feasibility of semi-fluorinated methacrylates to PISA. Besides, PISA of FHEMA is also realized in a variety of solvents, including iso-propanol, toluene, dioxane, and dimethyl formamide, exhibiting the superior solvent serviceability of the PISA formulations based on semi-fluorinated methacrylates.

In recent years, starch microparticles have gained interest in many fields. However, low production, uncontrollable size, and varying size distribution hinder their practical application. Here, we adopt a premix membrane emulsification (PME) method to prepare starch microcapsules at high production rates. The process conditions were optimized to fabricate uniform microcapsules with controllable sizes and narrow size distribution (PDI < 0.1). Through encapsulating avermectin (Av), a kind of water-insoluble pesticide, into the shell of the microcapsules in situ during the process, we developed a pesticide delivery system that enabled a controlled and consistent release of Av over a period of 2 weeks. Kinetic analysis indicated that the mechanisms of Av release involved non-Fickian and Case-II transport. The diameters (0.70-4.8 mu m) of the microcapsules and Av contents (16-47%) were adjusted to achieve suitable release profiles. The results will lay the foundation for further field experiments. (C) 2015 Elsevier Ltd. All rights reserved.

Recent research has indicated that polydopamine and synthetic eumelanins are optoelectronic biomaterials in which one-dimensional aggregates composed of ordered-stacking oligomers have been proposed as unique organic semiconductors. However, improving the ordered-stacking of oligomers in polydopamine nanostructures is a big challenge. Herein, we first demonstrate how folic acid molecules influence the morphology and nanostructure of polydopamine via tuning the π–π interactions of oligomers. MALDI-TOF mass spectrometry reveals that porphyrin-like tetramers are characteristic of folic acid–polydopamine (FA–PDA) nanofibers. X-ray diffraction combined with simulation studies indicate that these oligomers favour aggregation into graphite-like ordered nanostructures via strong π–π interactions. High-resolution TEM characterization of carbonized FA–PDA hybrids show that in FA–PDA nanofibers the size of the graphite-like domains is over 100 nm. The addition of folic acid in polydopamine enhances the ordered stacking of oligomers in its nanostructure. Our study steps forward to discover the mystery of the structure–property relationship of FA–PDA hybrids. It paves a way to optimize the properties of PDA through the design and selection of oligomer structures.

Hyperbranched poly(amino ester)s containing tertiary amines in the core and primary, secondary, and tertiary amines in the periphery, respectively, were evaluated for DNA delivery in vitro. The same core structure facilitated the investigation on the effects of the terminal amine type on the properties of hyperbranched poly(amino ester)s for DNA delivery. The hydrolysis of the poly(amino ester)s was monitored using (1)H NMR. The results reflected that the terminal amine type had negligible effects on the hydrolysis rate but was much slower than that of linear poly(amino ester)s, probably due to the compact hyperbranched spatial structure preventing the accessibility of water. In comparison with PEI 25 K, the hyperbranched poly(amino ester)s showed much lower cytotoxicity in Cos7, HEK293, and HepG2 cells. Gel electrophoresis indicated that poly(amino ester)s could condense DNA efficiently, and the zeta potentials and sizes of the complexes formed with different weight ratios of hyperbranched poly(amino ester)s and DNA were measured. Remarkably, all the hyperbranched poly(amino ester)s showed DNA transfection efficiency comparable to PEI 25 K in Cos7, HEK293, and HepG2 cells regardless of the terminal amine type. Therefore, the terminal amine type had insignificant effects on the hydrolysis rate, cytotoxicity, DNA condensation capability, and in vitro DNA transfection efficiency of the hyperbranched poly(amino ester)s.

The poly lactic-co-glycolic acid (PLGA) bio-scaffold is a biodegradable scaffold commonly used for tissue repair. However, implanted PLGA scaffolds usually cause serious inflammatory responses around grafts. To improve PLGA scaffold-based tissue repair, it is important to control the PLGA-mediated inflammatory responses. Recent evidence indicated that PLGA induce dendritic cell (DC) maturation in vitro, which may initiate host immune responses. In the present study, we explored the modulatory effects of mesenchymal stem cells (MSC) on PLGA-induced DCs (PLGA-DC). We found that mouse MSCs inhibited PLGA-DC dendrite formation, as well as co-stimulatory molecule and pro-inflammatory factor expression. Functionally, MSC-educated PLGA-DCs promoted Th2 and regulatory T cell differentiation but suppressed Th1 and Th17 cell differentiation. Mechanistically, we determined that PLGA elicited DC maturation via inducing phosphorylation of p38/MAPK and ERK/MAPK pathway proteins in DCs. Moreover, MSCs suppressed PLGA-DCs by partially inactivating those pathways. Most importantly, we found that the MSCs were capable of suppressing DC maturation and immune function in vivo. Also, the proportion of mature DCs in the mice that received MSC-PLGA constructs greatly decreased compared with that of their PLGA-film implantation counterparts. Additionally, MSCs co-delivery increased regulatory T and Th2 cells but decreased the Th1 and Th17 cell numbers in the host spleens. Histological analysis showed that MSCs alleviated the inflammatory responses around the grafted PLGA scaffolds. In summary, our findings reveal a novel function for MSCs in suppressing PLGA-induced host inflammatory response and suggest that DCs are a new cellular target in improving PLGA scaffold-based tissue repair.

A Dual-wavelength Mie Polarization Raman Lidar has been developed for cloud and aerosol optical properties measurement. This idar system has built in Hefei and passed the performance assessment in 2012, and then moved to Jinhua city to carry out the long-term continuous measurements of vertical distribution of regional cloud and aerosol. A double wavelengths (532 and 1064 nm) Nd-YAG laser is employed as emitting source and four channels are used for detecting back-scattering signals from atmosphere aerosol and cloud including 1064 nm Mie, 607 nm N2 Raman, two 532 nm Orthogonal Polarization channels. The temporal and spatial resolutions for this system, which is operating with a continuing mode (24/7) automatically, are 30s and 7.5m, respectively. The measured data are used for investigating the aerosol and cloud vertical structure and cloud phase from combining of cloud signal intensity, polarization ratio and color ratio.

Bone tuberculosis (TB) is one of the most common extrapulmonary TB. Effective integration of chemotherapy and bone regeneration is an optimal solution for bone TB therapy. Herein, we produce a composite scaffold drug delivery system fabricated with an isoniazid conjugated star poly(lactide-coglycolide) (PLGA-INH4) and beta-TCP. The cytological assay indicated the composite system possesses good biocompatibility. The in vitro and in vivo drug release evaluations showed that the composite system can intactly release the pristine INH and maintain effective INH concentration in a controlled manner for more than 100 days, and achieve high localized drug concentration and low systemic drug concentration. The rabbit radius repair experiment testified the scaffold has good bone regeneration capacity. Our work demonstrate the composite system can simultaneously achieve localized long-term drug controlled release and bone regeneration, which provides a promising route for improved bone TB treatment. (C) 2015 Elsevier Ltd. All rights reserved.

Extensive studies have illustrated the importance of obtaining exact vertical structures of clouds and aerosols for satellite and relevant climate simulations. However, challenging exists, for example, in distinguishing clouds from aerosols at times. Accurate cloud vertical profiles are mainly determined by cloud bases and heights. Based on the ground-based lidar observations in Hefei Radiation Observatory (HeRO), the vertical structures of clouds and aerosols in Hefei area(31.89°N，117.17°E) during May 2012-May 2014 have been investigated. The results show that the cloud fraction in the autumn and winter is less than that in the summer and spring, and is largest in the spring followed by the summer. The cloud fractions in the autumn and winter are comparable. The low cloud accounts for the most portion of the total. Compared with the cloud of the other heights, the high cloud is the least in the winter. Nearly 50% of the total vertical profiles can be detected by lidar as clouds and the proportion of the cloud of different heights seems to be stable annually. The fraction of low cloud is nearly 45%, medium cloud is nearly 35%, and high cloud is nearly 20%. In comparison with the results derived from CALIPSO, it is found that high cloud is usually missed for the ground-based lidar, while low cloud is usually omitted for the satellite observations. A combination of ground-based and space-borne lidar could lead to more reliable results. Further analysis will be performed in future studies.

The functionalization of carbon nanotubes (CNTs) has been carried out in various ways for numerous applications in biotechnology, including for the preparation of sensors, as scaffolds for cell growth, imaging reagents, and transporters for drug delivery. One way is to immobilize DNA onto the surface of CNTs through noncovalent interactions or covalent bonds. Covalent-bond approaches might compromise and even spoil the functions of DNA owing to chemical reactions and the difficulty in releasing DNA. Nevertheless, noncovalent approaches developed to date may only provide metastable immobilization of DNA onto the surface of CNTs. It was reported that the migration of DNA linked covalently to CNTs was retarded in gel electrophoresis but noncovalent interactions between DNA and CNTs did not completely prevent migration. Polyethylenimine (PEI) is a type of polymer with a high density of amines, thus DNA may be immobilized securely onto the surface of multiwalled carbon nanotubes (MWNTs) that have been functionalized with PEI through strong electrostatic interactions arising from these amines. Hence, we have adopted a grafting-from approach to prepare polyethylenimine-graft multiwalled carbon nanotubes (PEIg-MWNTs). DNA has been immobilized securely onto the surface of PEI-g-MWNTs as demonstrated by the total inhibition of the migration of DNA in gel electrophoresis, and PEI-g-MWNTs showed transfection efficiency for delivery of DNA that was similar to or even several times higher than that of PEI (25 K) and several orders of magnitude higher than that of naked DNA. PEI was grafted onto the surface of MWNTs by performing a cationic polymerization of aziridine in the presence of amine-functionalized MWNTs (NH2–MWNTs). NH2– MWNTs were obtained by introducing carboxylic acid groups onto the surface of MWNTs by heating at reflux in 3.0m nitric acid. The carboxylic acid groups were transformed into acyl chloride groups by treatment with thionyl chloride followed by treatment with ethylenediamine. The grafting of PEI was realized through two mechanisms, the activated monomer mechanism (AMM) or the activated chain mechanism (ACM), by which protonated aziridine monomers or the terminal iminium ion groups of propagation chains, respectively, are transferred to amines on the surface of MWNTs. (see Supporting Information.) The relative amount of PEI grafted onto the surface of MWNTs was investigated by thermogravimetric analysis (TGA) performed under nitrogen. MWNTs were thermally stable up to 600 8C (Figure 1A, curve a) whereas pure PEI degraded completely at about 500 8C (Figure 1A, curve d). At 500 8C, pristine MWNTs, NH2–MWNTs, and PEI-g-MWNTs showed negligible, about 2.3%, and 10.5% weight losses, respectively, thus PEI-g-MWNTs contained about 8.2% PEI. Grafting with PEI made PEI-g-MWNTs easy to disperse in water, and the resulting suspension was still stable after six months. However, NH2–MWNTs dispersed poorly in water and precipitation occurred within several hours (see Supporting Information). Transmission electron microscopy (TEM) provides direct evidence of grafting of PEI onto the surface of MWNTs. Figure 1B shows TEM images of PEI-g-MWNTs on a holey carbon film: individually dispersed MWNTs are separated from others. High-resolution TEM (Figure 1B, inset) indicates that PEI was grafted onto the surface of MWNTs as lumps with different sizes instead of as a uniform coating. This clumping results from the carboxylic acid groups, the ethylenediamine, and the PEI adhering preferably to the defects, which are the most active locations for chemical or physical functionalization; these defects tend to cluster at the bends along the surface of MWNTs grown by chemical vapor deposition (CVD). In Figure 1C, the H NMR spectrum of PEI-g-MWNTs in D2O is compared with that of PEI in D2O (pH 7.0). The signal at about d= 3.1 ppm for PEI-g-MWNTs is attributed to grafted PEI, but the significantly decreased mobility of the PEI chains in PEIg-MWNTs leads to broadening of the resonances. Some of the amine groups of PEI were protonated (pKa of PEI is greater than 8.0); we found that protonation or partial protonation of PEI was necessary for the formation of a stable aqueous suspension of PEI-g-MWNTs and neutralizing PEI by adjusting the pH value to 9 or higher led to precipitation of dispersed PEI-graft-MWNTs within several hours. PEI obtained by cationic polymerization of aziridine has a dendritic structure that contains primary, secondary, and tertiary amines with a molar ratio of about 1:2:1. Grafting PEI onto the surface of MWNTs should have a negligible effect on the chemistry. The migration of DNA was totally inhibited in gel electrophoresis when the weight ratio of PEI[*] Dr. Y. Liu, D.-C. Wu, Dr. W.-D. Zhang, Dr. C.-B. He Institute of Materials Research and Engineering 3 Research Link, Singapore 117602 (Singapore) Fax: (+65)6872-7528 E-mail: ye-liu@imre.a-star.edu.sg

Hyperbranched poly(amino ester)s were synthesized via a novel 2A2 + BB‘B‘ ‘ approach, represented by the Michael addition polymerization of a trifunctional amine, 1-(2-aminoethyl)piperazine (AEPZ) (BB‘B‘ ‘-type monomer), with a double molar diacrylate, 1,4-butanediol diacrylate (BDA) (A2-type monomer). The formation of B‘ ‘A2-type intermediate via its precursor, B‘B‘ ‘A-type intermediate, was verified by in situ monitoring the polymerizations using NMR and MS (ESI). High molecular weight hyperbranched poly(BDA2-AEPZ1) with vinyl terminal group was obtained from the B‘ ‘A2-type intermediate when the polymerization was performed in DMSO at 70 °C for ca. 101.0 h. Then the terminal vinyl group was tuned to primary, secondary, and tertiary amine, as verified by NMR. The radius of gyration (Rg) and hydrodynamic radius (Rh) of hyperbranched poly(BDA2-AEPZ1)-MPZ were measured using small-angle X-ray scattering (SAXS) and laser dynamic light scattering (LDLS), respectively, and the ratio of Rg/Rh of ca. 1.0 confir...

A self-condensing vinyl polymerization (SCVP) strategy via atom transfer radical polymerization (ATRP) was employed to grow hyperbranched macromolecules on the surfaces of multiwalled carbon nanotubes (MWNTs). The MWNT surface fixed with ATRP initiators [MWNT-COOCH2CH2OCOC(CH3)2Br, MWNT-Br] was prepared by reaction of MWNT-COCl with excess of 2-hydroxyethyl 2‘-bromoisobutyrate. Then, using the MWNT-Br as polyfunctional initiator (B*f), hyperbranched macromolecules were covalently grafted on MWNTs by self-condensing vinyl polymerization of 2-((bromobutyryl)oxy)ethyl acrylate (BBEA, AB* inimer) via the ATRP process. The resultant products were characterized by FT-IR, NMR, and TEM. TGA measurements showed that the weight ratio of the as-grown hyperbranched polymers on the MWNT surfaces reached 80%. The as-prepared MWNTs grafted with hyperbranched polymers exhibit relatively good dispersibility in organic solvents such as THF and chloroform.

The mechanisms of the Michael addition polymerizations of different trifunctional amines with an equimolar 1,4-butanediol diacrylate (BDA) were investigated by using 1H and 13C NMR to in situ monitor the polymerization processes. The trifunctional amine monomers adopted were 1-(2-aminoethyl)piperazine (AEPZ) and 4-(aminomethyl)piperidine (AMPD) and linear aliphatic amines with different steric hindrance on the 2° amines (original), i.e., N-methylethylenediamine (MEDA), N-ethylethylenediamine (EEDA), and N-hexylethylenediamine (HEDA). For AEPZ, AMPD, and MEDA with low steric hindrance on the 2° amines (original), the reactivity sequence of the three types of amines was 2° amines (original) > 1° amines ≫ 2° amines (formed) and linear poly(amino ester)s were formed via AB-type intermediates due to the 2° amines (formed) being kept out of the reaction. However, AB-type intermediates were only formed from the 2° amines (original) for AEPZ and AMPD, but from both the 2° amines (original) and 1° amines due to th...

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), Raman spectroscopy of adsorbed pyridine molecules (Py-Raman) and in situ Py-IR have been used to investigate the hydroxyl species and acid sites on diatomite surfaces. The Lewis (L) and Bronsted (B) acid sites, and various hydroxyl species, including isolated hydroxyl groups, H-bonded hydroxyl groups and physically adsorbed water, are identified. The L acid sites in diatomite samples are resulted from the clay impurities, and the B acid sites are resulted from some moderate strength H-bonded hydroxyl groups. At room temperature, both of the isolated and H-bonded silanols associate with the physically adsorbed water by hydrogen bond. After calcination treatment, physically adsorbed water will be desorbed from the silanols, and the silanols will condense with the increase of temperature. Generally, the H-bonded silanols condense more easily than the isolated ones. The properties of surface hydroxyl species of diatomaceous silica are more similar to precipitated silica rather than fumed silica.

Mechanical properties are among the most concerned issues for artificial bone grafting materials. The scaffolds used for bone grafts are either too brittle (glass) or too weak (polymer), and therefore composite scaffolds are naturally expected as the solution. However, despite the intensive studies on composite bone grafting materials, there still lacks a material that could be matched to the natural cancellous bones. In this study, nanosized bioactive particles (BP) with controllable size and good colloidal stability were used to composite with gelatin, forming macroporous scaffolds. It was found that the mechanical properties of obtained composite scaffolds, in terms of elastic modulus, compressive strength, and strain at failure, could match to that of natural cancellous bones. This is ascribed to the good distribution of particle in matrix and strong interaction between particle and gelatin. Furthermore, the incorporation of BPs endues the composite scaffolds with bioactivity, forming HA upon reacting with simulated body fluid (SBF) within days, thus stimulating preosteoblasts attachment, growth, and proliferation in these scaffolds. Together with their good mechanical properties, these composite scaffolds are promising artificial bone grating materials.

Generally, it is very difficult to control the size of large compound vesicles. Here, we introduce a novel method for the preparation of biodegradable large compound vesicles with controlled size and narrow size distribution by using aqueous nanodroplets as templates.

Bioactive nanoparticles with controllable size and good colloidal stability were synthesized through surface modification of colloidal silica nanoparticles with Ca(OH)2 as the modifier. These modified nanoparticles showed good bioactivity, showing evidence of hydroxyapatite formation when incubated in simulated body fluid within 3 days. Comparison of bioactivity was made among different sized particles from nanoscale to microscale. It was found the bioactivity of these calcium modified colloidal silica particles generally decreased with particle size in the explored size range (40 nm particles showed bioactivity within 1 day). These particles were also found to be noncytotoxic but promote preosteoblast growth, thus making them promising bioactive additives for bone repair materials.

The bioreducible star-shaped gene vector (POSS-(SS-PDMAEMA)8) with well-defined structure and relatively narrow molecular weight distribution was synthesized via atom transfer radical polymerization (ATRP) of (2-dimethylamino)ethyl methacrylate (DMAEMA) from a polyhedral oligomeric silsesquioxane (POSS) macroinitiator. POSS-(SS-PDMAEMA)8 was composed of a biocompatible POSS core and eight disulfide-linked PDMAEMA arms, wherein the PDMAEMA chain length could be adjusted by controlling polymerization time. POSS-(SS-PDMAEMA)8 can effectively bind pDNA into uniform nanocomplexes with appropriate particle size and zeta potential. The incorporation of disulfide bridges gave the POSS-(SS-PDMAEMA)8 material facile bioreducibility. In comparison with POSS-(PDMAEMA)8 without disulfide linkage, POSS-(SS-PDMAEMA)8 exhibited much lower cytotoxicity and substantially higher transfection efficiency. The present work would provide useful information for the design of new POSS-based drug/gene carriers.

In nature, a sapling can grow into a big tree under irradiation of sunlight. In chemistry, a similar concept that a small molecule only exposing to sunlight grows into a hyperbranched macromolecule has not been realized by now. The achievement of the concept will be fascinating and valuable for polymer synthesis wherein sunlight is inexpensive, abundant, renewable and nonpolluting. Herein, we report a new strategy in which small monomers can directly grow into big hyperbranched macromolecule under irradiation of sunlight without any catalyst.

De-Cheng Wu, Ye Liu,* and Chao-Bin HeInstitute of Materials Research and Engineering, 3 ResearchLink, Singapore 117602ReceiVed NoVember 16, 2007The structures and properties of stimuli-responsive polymerscan change with environmental conditions such as temperature,pH, and ionic strength; therefore, these smart polymers can beexploited for various biomedical applications.

Three alkyl-polypeptide (AP) amphiphiles were prepared using ring-opening polymerization of α-amino acid N-carboxyanhydride. The polypeptide segment was composed of diethylene-glycol-monomethyl-ether-functionalized poly-L-glutamate (poly-L-EG(2)Glu). These AP amphiphiles can spontaneously self-assemble into transparent hydrogels in water. These hydrogels showed shear thinning properties, and their strength can be modulated by hydrophobic alkyl tails. CryoTEM and AFM characterizations suggested that these hydrogels were formed by nanoribbons arising from intermolecular interactions between nonionic poly-L-EG(2)Glu segments.