Assessment of lung ultrasound for early detection of respiratory complications in thoracic surgery.

BACKGROUND AND OBJECTIVES: To assess lung ultrasound for the diagnosis and monitoring of respiratory complications in thoracic surgery. METHODS: Prospective observational study in a University hospital, single institution. Adult patients scheduled for pulmonary resection surgery excluding pneumonectomy. An ultrasound follow-up was performed from the day before the surgery to the third day after surgery with calculation of B-line and lung score (reaeration and loss of aeration scores). Respiratory complications were collected throughout the hospitalization period. RESULTS: Fifty-six patients were included. Eighteen patients presented a respiratory complication (32%), and they presented significantly higher BMI and ASA scores. Patients operated by videothoracoscopy were less at risk of complications. At day 3, a reaeration score ≤ 2 on the ventilated side or ≤ -2 on the operated side, and a B-line score>6 on the operated side were in favor of a complication. CONCLUSION: Lung ultrasound can help in the diagnosis of respiratory complications following pulmonary resection surgery.

Insight into the Alcohol-Free Ring-Opening Polymerization of TMC Catalyzed by TBD.

We report herein a study on the alcohol-free, ring-opening polymerization of trimethylene carbonate (TMC) in THF, catalyzed by 1,5,7-triazabicyclo [4.4.0] ec-5-ene (TBD) with ratios nTBD/nTMC ranging between 1/20 and 1/400. In all cases, the reaction proceeds very rapidly, even faster than in the presence of alcohol initiators, and provides PTMC with molecular weights up to Mn = 34,000 g mol-1. Characterization of the obtained PTMC samples by MALDI-TOF mass spectrometry, triple detection size exclusion chromatography and 1H NMR spectroscopy reveals the presence of both linear and cyclic polymer chains.

Tunable vegetable oil/silica hybrid microparticles for poorly water-soluble drug delivery.

To encapsulate and deliver poorly water-soluble drugs, castor oil/silica hybrid microparticles (HMP)s were synthesized. Green chemistries were used to silylate the oil and further cross-link it into solid microparticles by sol-gel reaction. Silylated castor oils (ICO)s at various silylation ratios were prepared and allowed the solubilization of ibuprofen at several concentrations up to 16 wt%. The HMPs were formulated by ThermoStabilized Emulsion (TSE) process which permits to "freeze" the oil-in-water emulsion while the sol-gel reaction occurs. The hybrid mineral/organic composition and the morphology (spherical shape and micrometric size) of these HMPs were determined by complementary technics (SEM, TGA, EDX, 29Si NMR and FTIR spectroscopies). The HMPs reached a good ibuprofen loading efficiency regardless to the formulation used while the release kinetics in simulated oral administration exhibited a tunable release during 3 h according to the silylation ratio. The ibuprofen rate also influenced its own amorphous or crystalline character within the HMPs. For subcutaneous conditions, ibuprofen release took place over 15 days. Finally, biodegradability assays in simulated digestion medium suggested a surface-limited hydrolysis of the particles and cytocompatibility studies on NIH-3T3 and Caco-2 cells demonstrated an excellent cellular viability.

Fatty Acid-Based Radically Polymerizable Monomers: From Novel Poly(meth)acrylates to Cutting-Edge Properties.

The increasing price of barrels of oil, global warming, and other environmental problems favor the use of renewable resources to replace the petroleum-based polymers used in various applications. Recently, fatty acids (FAs) and their derivatives have appeared among the most promising candidates to afford novel and innovative bio-based (co)polymers because of their ready availability, their low toxicity, and their high versatility. However, the current literature mostly focused on FA-based polymers prepared by condensation polymerization or oxypolymerization, while only a few works have been devoted to radical polymerization due to the low reactivity of FAs through radical process. Thus, the aim of this Review is to give an overview of (i) the most common synthetic pathways reported in the literature to provide suitable monomers from FAs and their derivatives for radical polymerization, (ii) the available radical processes to afford FA-based (co)polymers, and (iii) the different applications in which FA-based (co)polymers have been used since the past few years.

Vegetable oil hybrid films cross-linked at the air-water interface: formation kinetics and physical characterization.

Vegetable oil based hybrid films were developed thanks to a novel solvent- and heating-free method at the air-water interface using silylated castor oil cross-linked via a sol-gel reaction. To understand the mechanism of the hybrid film formation, the reaction kinetics was studied in detail by using complementary techniques: rheology, thermogravimetric analysis, and infrared spectroscopy. The mechanical properties of the final films were investigated using nano-indentation, whereas their structure was studied using a combination of wide-angle X-ray scattering, electron diffraction, and atomic force microscopy. We found that solid and transparent films form in 24 hours and, by changing the silica precursor to castor oil ratio, their mechanical properties are tunable in the MPa-range by about a factor of twenty. In addition to that, a possible optimization of the cross-linking reaction with different catalysts was explored, and finally cytotoxicity tests were performed on fibroblasts proving the absence of film toxicity. The results of this work pave the way to a straightforward synthesis of castor-oil films with tunable mechanical properties: hybrid films cross-linked at the air-water interface combine an easy and cheap spreading protocol with the features of their thermal history optimized for possible future micro/nano drug loading, thus representing excellent candidates for the replacement of non-environmentally friendly petroleum-based materials.

UV-responsive amphiphilic graft copolymers based on coumarin and polyoxazoline.

A series of amphiphilic photo-responsive heterografted copolymers have been successfully synthesized. The random copolymers were composed of a methacrylate backbone, with various compositions of hydrophilic oligomeric 2-methyl-2-oxazoline side chains (OMOx) and hydrophobic long alkyl chains terminated by a coumarin moiety (Cm). Using dynamic (DLS) and static light scattering (SLS), and transmission electron microscopy (TEM), their self-assembling behavior was studied in water using the nanoprecipitation method. Depending on the system, one, two or three particle size distributions co-exist in solution. However, DLS measurements showed that monomodal and slightly polydisperse self-assemblies were obtained with the more hydrophobic copolymers (i.e., 85% of hydrophobic monomers with a long alkyl chain terminated by a coumarin moiety (MCm) per molecule) with hydrodynamic diameters ranging from ca. 130 to 300 nm. Morphological information on these self-assembly structures was obtained using SLS: a Gaussian behavior has thus been evidenced. Finally, these heterografted copolymers were illuminated using UV light at λ = 350 nm inducing photo-crosslinking of the coumarin units. The influence of UV illumination on the thus-formed nanoparticles was investigated by carrying out complementarily DLS-measurements and UV spectroscopy.

Synthesis and self-assembly of carbamoylmethylphosphonate acrylamide-based diblock copolymers: new valuable thermosensitive materials.

We report the synthesis by RAFT polymerization of well-defined diblock copolymers bearing carbamoylmethylphosphonate moieties which proved to sorb gadolinium. These poly(diethyl-6-(acrylamido)hexylcarbamoylmethylphosphonate-b-acrylic acid) (P(CPAAm6C-b-AA)) copolymers were able to self-assemble as a function of temperature, above their cloud point value.

Improvement of the interfacial compatibility between cellulose and poly(L-lactide) films by plasma-induced grafting of L-lactide: the evaluation of the adhesive properties using a peel test.

HYPOTHESIS: The interfacial compatibility between hydrophilic cellulose and hydrophobic poly(L-lactide) film surfaces is dependent on the interactions and interlocking of the macromolecular chains of the uppermost layers of both polymers. Grafting or coating the cellulose surface with molecular structures similar to the lactide monomer or oligomer is expected to improve the compatibility. Therefore, it should be possible to enhance the adhesive properties. EXPERIMENTS: Cellulose films were oxygen plasma treated and immersed in a L-lactide solution. The grafting was performed under various conditions (power, pressure, time). The treated cellulose and poly(L-lactide) films were hot-pressed, and the resulting bi-layer laminates were subjected to a peel test. Comparative experiments were performed with the bi-layer laminates prepared from the cellulose films coated with poly(L-lactide-graft-vinyl alcohol) copolymers. FINDINGS: X-ray photoelectron spectroscopy, infra-red analyses and wettability measurements revealed that chains bearing ester groups similar to that of lactide were covalently grafted onto the cellulose. The possible grafting mechanism that was initiated by the ionic species from the surface is discussed. As a result, the peel strength to separate the cellulose and the poly(L-lactide) films increased significantly. A comparison with data in the literature highlights the formation of entanglements inside the interfacial zone showing the efficiency of the plasma treatment.

Self-assembly of phosphorous containing oligomers: morphological features and pH-sensitiveness in suspension.

Methacrylamide-based oligomers bearing phosphonate pending groups at the end of a long alkyl chain and originating from undecylenic acid synthons were subjected to direct oligomer dissolution. Size improvement towards much smaller objects was reached using the nanoprecipitation method: the oligomers were first dissolved in an organic solvent, and then precipitated in water using a syringe pump. Dynamic light scattering (DLS) showed phosphorous containing monomodal and quite narrow-sized self-assemblies in water with hydrodynamic diameters (DH) ranging from 80 to 280 nm (depending on the oligomer system). Direct visualization using transmission electron microscopy (TEM) and atomic force microscopy (AFM) showed filled and almost individual particles with spherical shape. They were considerably shrunk, suggesting the highly swollen character of the self-assemblies in suspension. Morphological information on the multi-scale self-assembled structures was complementarily obtained using static light scattering (SLS). Thus, at a low length-scale, highly segregated sub-units having sharp boundaries surrounded by water (Porod behaviour) were observed, whereas at a high length-scale random non-compact organization of these sub-units via weak interactions was found, forming a chaplet-like structure (Gaussian behaviour). Furthermore, the pH-sensitiveness of the suspensions obtained after the nanoprecipitation method was studied. Particularly, at pH = 12, the characteristic size drastically increased within few hours from typically ∼280 nm to 2 µm due to electrostatic repulsion between deprotonated hydroxyl groups. At longer times, the observed peculiar behaviour corresponded to the model of diffusion-limited cluster aggregation (DLCA) where the particles stuck easily together upon contact [continuation of the article by C. Bouilhac, C. Travelet, A. Graillot, S. Monge, R. Borsali and J.-J. Robin, Polym. Chem., 2014, 5, 2756-2767].

Grafting of poly-L-lysine dendrigrafts onto polypropylene surface using plasma activation for ATP immobilization - Nanomaterial for potential applications in biotechnology.

The present work describes a new environmental friendly strategy for the development of surfaces with high amine density via the grafting of native or modified poly-L-lysine dendrigraft (DGL G3) onto plasma activated polypropylene (PP), polystyrene (PS), polyimide, and polytetrafluoroethylene (PTFE) surface. Modified DGL G3 was prepared by replacement of few peripheral amines by various functionalities. Grafting efficiency was determined by wettability measurements, IRTF, XPS, AFM, and by colorimetry using optimized Coomassie Brilliant Blue method tailored for surface analysis. It was shown that a 4-7nm DGL G3 monolayer with 4×10(14)aminecm(-)(2) was covalently grafted onto various surfaces. Immobilization of adenosine triphosphate on the DGL-g-PP material from dilute solution was studied by bioluminescence and proved the ability of the material to interact with polyanionic biological compounds: 1 ATP complex with 5 amine groups. So, this material has a potential use in diagnostic and more widely for biotechnology due to its high capacity for biomolecule immobilization.

Sorption properties of a new thermosensitive copolymeric sorbent bearing phosphonic acid moieties in multi-component solution of cationic species.

In this paper, original thermosensitive copolymers bearing phosphonic acid groups, namely the poly(N-n-propylacrylamide-stat-2-(methacryloyloxy)methylphosphonic acid) (P(NnPAAm-stat-hMAPC1)) were synthesized, and their sorption properties for three divalent cations (Ni(2+), Ca(2+), Cd(2+)) and one trivalent cation (Al(3+)) have been investigated. The sorption experiments were performed with increasing relative amount of cationic pollution compared to the amount of sorption sites (C(n+)/P ratio) in mono and multi-component solutions to investigate the sorption mechanisms. C(n+)/P proved to strongly affect the sorption capacity and high capacities were obtained for all cations at highest C(n+)/P ratios, reaching one mole of C(sorbed)(n+) per phosphonated moiety. For divalent cations, sorption mechanisms were likely to be described by electrostatic interactions only, whereas for aluminum trivalent cation the sorption not only resulted from electrostatic interactions but also from the formation of coordination binding. The selectivity of the phosphonic acid moieties for aluminum cations was demonstrated, highlighting the interest of P(NnPAAm-stat-(h)MAPC1) for their use for the treatment of metallic pollution from wastewater.

Synthesis of antibacterial surfaces by plasma grafting of zinc oxide based nanocomposites onto polypropylene.

Antibacterial polymer surfaces were designed using ZnO nanoparticles as a bactericide. Mineral encapsulated nanoparticles were grafted onto activated polymer surfaces through their shells. Polypropylene (PP) surfaces were treated using an innovative process coupling core-shell technology and plasma grafting, well-known techniques commonly used to obtain active surfaces for biomedical applications. First, ZnO nanoparticles were encapsulated by (co)polymers: poly(acrylic acid) (PAA) or a poly(methyl methacrylate-co-methacrylic acid) copolymer [P(MMA-MA)]. Second, PP substrates were activated using plasma treatment. Finally, plasma-treated surfaces were immersed in solutions containing the encapsulated nanoparticles dispersed in an organic solvent and allowed to graft onto it. The presence of nanoparticles on the substrates was demonstrated using Fourier-Transform Infrared Spectroscopy (FTIR) analysis, Scanning Electron Microspcopy (SEM)/Energy-Dispersive X-ray (EDX), and Atomic Force Microscopy (AFM) studies. Indeed, the ZnO-functionalized substrates exhibited an antibacterial response in Escherichia coli adhesion tests. Moreover, this study revealed that, surprisingly, native ZnO nanoparticles without any previous functionalization could be directly grafted onto polymeric surfaces through plasma activation. The antibacterial activity of the resulting sample was shown to be comparable to that of the other samples.

Removal of nickel ions from aqueous solution by low energy-consuming sorption process involving thermosensitive copolymers with phosphonic acid groups.

In order to remove metal ions from wastewaters, thermosensitive copolymers bearing sorption properties toward metal cations were prepared by free radical copolymerization between the N-n-propylacrylamide (NnPAAm) and the (dimethoxyphosphoryl)methyl 2-methylacrylate (MAPC1), followed by a hydrolysis of the phosphonated esters into phosphonic diacid groups ((h)MAPC1). The thermosensitivity and the sorption abilities of the resulting poly(NnPAAm-stat-(h)MAPC1) copolymers were studied. Lower Critical Solution Temperatures (LCST) of these copolymers ranged from 22 °C to 26 °C, depending on the molar ratio of phosphonated monomers and were lower than those obtained with usual poly(N-isopropylacrylamide)-based polymers. The influence of both the temperature and the pH on the sorption properties of the copolymers was evaluated for Ni(2+) cations. The most interesting results were obtained for temperatures around the LCST, i.e. when the proximity of the complexing groups favored the sorption of metallic cations. Concerning the pH effect, the maximum sorption capacity was obtained at pH 7, i.e. in the absence of competition between the sorption of H(+) and Ni(2+) ions on the phosphonic acid groups. The influence of the molar ratio of metal ions and phosphonate moieties was also studied and different sorption mechanisms were proposed.

How to modulate the chemical structure of polyoxazolines by appropriate functionalization.

Polyoxazolines (POx) are increasingly being studied as polymeric building blocks due to the possibility of affording tunable properties. Additionally, as the biocompatibility and stealth behavior of POx are similar to that of poly(ethylene glycol) (PEG), it has become challenging to develop polyoxazoline-based (co)polymers. Even if POx have a lot of advantages, they also show an important drawback, as it has been impossible, to date, to prepare high-molecular-weight polyoxazolines with a low polydispersity index. Thus, it appears important that they be judiciously functionalized. This review covers the multiple ways that polyoxazolines can be functionalized. The use of functional initiators, functional terminating agents, and 2-R-2-oxazolines with an R functional side group is detailed. In conclusion, some perspectives on POx functionalizations are also reported, with functions permitting selective "click" reactions.

Synthesis and evaluation of triazole-linked poly(ε-caprolactone)-graft-poly(2-methyl-2-oxazoline) copolymers as potential drug carriers.

Well-defined graft copolymers were obtained using a copper-catalysed azide-alkyne Huisgen's cycloaddition click reaction from both biocompatible and non-toxic poly(ε-caprolactone) and poly(2-methyl-2-oxazoline) homopolymers. Resulting amphiphilic copolymers proved to form micelles that could be used as potential drug carriers.

Phosphorus-containing polymers: a great opportunity for the biomedical field.

This Review is focused on the growing interest brought to phosphorus-containing organic materials for applications in the biomedical field, mainly because of their properties such as biocompatibility, hemocompatibility, and protein adsorption resistance. It mainly describes relevant works achieved on these materials for various applications: dentistry, regenerative medicine, and drug delivery. Special attention was given to 2-methacryloyloxyethyl phosphorylcholine (MPC) monomer as the latter appeared of great importance because of its biomimetic structure due to the presence of the phospholipid group on its structure. As a result, much research effort is currently concentrated on the development of phosphorylcholine-containing (co)polymers that represent a promising class of materials.

Self-assembly of poly(ethylene glycol)-poly(alkyl phosphonate) terpolymers on titanium oxide surfaces: synthesis, interface characterization, investigation of nonfouling properties, and long-term stability.

This contribution deals with the self-assembling of a terpolymer on titanium oxide (TiO(2)) surface. The polymer structure was obtained by polymerization of different methacrylates, i.e., alkyl-phosphonated, butyl and PEG methacrylate, in the presence of a chain transfer agent. The resulting PEG-poly(alkyl phosphonate) material, characterized mainly by SEC and NMR, self-organized at the interface of TiO(2). AR-XPS demonstrated the binding of phosphonate groups to TiO(2) substrate and the formation of a PEG-brush layer at the outermost part of the system. The stability of this terpolymer adlayer, after exposure to solutions of pH 2, 7.4, and 9 up to 3 weeks, was evaluated quantitatively by XPS and ellipsometry. We demonstrated an overall stability improvements of this coating against desorption in contact with aqueous solutions in comparison with reference self-assembly systems. Finally, the PEG-terpolymer adlayer proved to impart to TiO(2) substrate antifouling properties when exposed to full blood serum.

Reactivity of wheat gluten protein during mechanical mixing: radical and nucleophilic reactions for the addition of molecules on sulfur.

Mechanical properties of gluten-based biomaterials, such as break stress, were known to be influenced by temperature and shear stresses applied during processing. It is well documented in literature that these processing parameters promoted wheat gluten protein aggregation. Exchange between disulfide bonds and thiol groups oxidation are the postulated mechanisms that lead to gluten protein solubility loss in sodium dodecyl sulfate buffers. Both nucleophilic and radical reactions were postulated to act during gluten aggregation. To graft molecules on gluten, a study was carried out to explore the reactivity of its thiol and disulfide groups during thermomechanical mixing. A range of reactants able to react via radical or nucleophilic pathways with thiol groups were synthesized. Reactivity between gluten and functions was quantified by gluten solubility measurements. This investigation and literature observations allowed proposal of a general gluten aggregation mechanism during mixing.