New pH sensitive network: Combination of an amphiphilic degradable polyester with a β-cyclodextrin copolymer

A novel hydrophobic monomer, ethyladamantyl malolactonate, has been synthesized and copolymerized with benzyl malolactonate by anionic ring-opening polymerization. The ratio of adamantyl monomer varied from 0 to 100 mol%. Deprotection of benzyl groups leads to a water soluble copolyester with carboxylic acid lateral functions which give a polyelectrolyte character to the corresponding polymers. The mixture of a copolyester containing 10% of adamantyl groups and a β-cyclodextrin/epichlorohydrin copolymer in aqueous solution leads to a new pH-dependant associating system. The solution behavior of this system was studied by viscosimetry as a function of pH, concentration and ratio of both copolymers. At the initial solution pH (pH=2), the copolyester adopts a coiled structure as a result of hydrophobic interactions between the pendant adamantyl groups. Consequently, no network formation is observed as shown by a very low viscosity. As the pH increase, the viscosity of the medium increases and reaches a maximum at pH=5. At this pH, the copolyester expands because of electrostatic repulsions between the carboxylate pendant functions. Consequently, the adamantyl groups are accessible and can be encapsulated into the β-cyclodextrin cavities resulting in a significant increase of the viscosity.     

Synthesis of microsequential methylvinylsiloxane–dimethylsiloxane copolymers by nonequilibrium copolymerization

Nonequilibrium anionic ring-opening copolymerization of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (V₄) with hexamethylcyclotrisiloxane (D₃) was examined as a route to methylvinyl–dimethylsiloxane microsequential copolymers. The copolymerization was carried out in toluene and was initiated with Me₃SiCH₂Li using DMSO as the promoter. Distribution of siloxane units obtained from kinetic analysis based on first-order Markovian statistics was compared with that found from analysis by ²⁹Si NMR spectroscopy. Results showed that although chain transfer and back-biting play some role in this system, the kinetics of copolymerization may be described to a reasonable approximation by the first-order Markov model. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 137–145, 1998     

Simulation of conversion profiles and temperature distributions within dimethacrylate thick material during photopolymerization

Photoinitiated polymerization of multifunctional monomers is an usual method to prepare highly crosslinked networks which have a wide variety of applications. This method leads to high reaction rates and the resulting exothermic effect of this reaction can be the cause of defects in the final material. The heterogeneities alter greatly the physical properties of ultimate products, particularly the optical ones, what causes problems in the design of thick and optically perfect materials. The knowledge of the conversion profile and the temperature distribution within the material during the photopolymerization is useful for the process optimization. Unfortunately, these parameters cannot be measured during the process. Thus, we decided to simulate them. Firstly, the necessary parameters (like conversion and reaction rate) were measured on thin material in isothermal conditions by photocalorimetry. Secondly, these kinetic data were used in a computational calculation to obtain the conversion profile and the temperature distribution within dimethacrylate thick material. The calculated temperature and conversion-time curves are in good agreement with the experimental curves determined under the same conditions.     

聚氧乙烯-镧系金属盐(Ln3+)的络合对聚氧乙烯形态结构的影响

采用偏光显微镜(POM)、差示扫描量热(DSC)和X 射线衍射,对聚氧乙烯(PEO)的形态结构和热物理行为随6种镧系盐对PEO的摩尔比变化的规律进行了系统的探讨.结果表明,随六合水氯化镧系盐摩尔比的增加,PEO球晶行为、熔点和熔融热均逐渐减弱,当盐对PEO的摩尔比达到一定值时(如YbCl3·6H2 O :PEO =2 0 ) ,则PEO完全不结晶.不同的镧系盐对PEO结晶的影响程度不同.X 射线衍射分析的结果也表明PEO晶面衍射峰随Ln3+ 盐摩尔比的增加而下降,与POM和DSC结果一致的.结果还表明较高的干燥温度(6 0℃)对PEO与Ln3+ 的相互作用有促进作用.对比二次降温的试样与原始试样的结晶行为,降温后结晶试样的特征表明络合在降温结晶后还存在.红外结果表明PEO与Ln3+ 的相互作用是络合作用.     

One-pot synthesis of oxazoles using isocyanide surrogates

We wish to present herein a simple one-pot synthesis of 2,5-disubstituted oxazoles, starting from benzyl halides and acyl chlorides. The in situ formation of isocyanides, followed by the addition of an acyl chloride in the presence of a base leads to the desired oxazoles in good yields.     

Three-component Ugi-Smiles couplings of cyclic imines

Cyclic imines react with isocyanides and electron-deficient phenols to afford N-aryl piperidines and pyrrolidines in good yields (Ugi-Smiles couplings of cyclic imines). The starting imines were formed by oxidation with N-chlorosuccinimide followed by a base-induced dehydrochlorination.     

Intramolecular Alkynylogous Mukaiyama Aldol Reaction Starting from Bicyclic Alkanones Tethered to Alkynyl Esters: Formal Total Synthesis of (±)‐Hamigeran B

Selecting the ring : tert‐Butyldimethylsilyltriflate (TBSOTf)/NEt₃ treatment of alkynyl esters tethered to bicycloalkanones leads to the formation of tricyclic allenoates with total diasteroselectivity at the ring junction. An intramolecular alkynylogous Mukaiyama aldol reaction promoted by a TBSOTf/NEt₃ dual activation is involved. This novel methodology was illustrated by a formal total synthesis of (±)‐hamigeran B.

     

Solid state nuclear magnetic resonance as a tool to explore solvent-free MALDI samples

Solid-state Nuclear magnetic resonance (NMR) was used here to explore structural characteristics of samples to be subjected to matrix-assisted laser desorption/ionization (MALDI) and prepared without the use of any solvent. The analytical systems scrutinized in NMR were mixtures of a 2,5-dihydroxybenzoic acid (2,5-DHB) matrix and caesium fluoride (CsF), used as the cationization agent in synthetic polymer MALDI mass analysis, at different molar ratios (1:1, 5:1, and 10:1). Complementary information could be obtained from ¹³C, ¹³³Cs, and ¹⁹F NMR spectra. Grinding the matrix together with the salt in the solid state was shown to induce a strong modification in the molecular organization within the MALDI sample. The evidenced mechano-induced reactions allow strong interactions between the matrix and the cation, up to the formation of a salt, and only occur in the presence of some water molecules. Addition of a poly(ethylene oxide) polymer as the analyte did not further modify the observed molecular organizations. Although relative matrix and salt concentrations in the scrutinized samples were unusual for MALDI analysis, mass spectra of good quality could be obtained and revealed that cation attachment on polymers during the MALDI process is not a matrix-independent event since a lower ionization efficiency was obtained from highly organized solid samples, mostly consisting of 2,5-DHB caesium salt species.