Design,synthesis and anti-influenza virus activities of terminal modified antisense oligonucleotides

Four novel terminal modified antisense oligonucleotides (ODNs) were designed, synthesized and tested for their anti-influenza virus activity. Initial biological studies indicated that lipophilic and rimantadin emodificated Flutide exhibited more potent anti-H1N1 activity than Flutide. Among them, lipophilic modificated ODN (Flutide-I) showed the most antiviral activity. The EC₅₀ value of Flutide-I for inhibiting H1N1 induced cytopathic effect (CPE) and H1N1 RNA were respectively (0.26 ± 0.16) μM and (0.11 ± 0.03) μM. The cytotoxicity of these compounds has also been assessed. No significant cytotoxicities were found for any of these compounds with the concentrations up to 20 μM.     

Interaction of the low-molecular weight salts with cationic polyelectrolytes

The interaction of several mono-, di-, and trivalent anions with cationic polyelectrolytes having different contents in N,N-dimethyl-2-hydroxypropylen ammonium chloride units (polymer A) or tertiary amine N-atoms and PEG (polymer PEGA) in the main chain was studied by viscosimetric and conductometric measurements. Both methods have shown a stronger interaction for tri- and bi- than for univalent counterions. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2571–2581, 1997     

Structural and adhesion properties of surfaces functionalized with polyelectrolytes and polystyrene particles

Surfaces functionalized with polystyrene particles and polyelectrolytes were used to investigate the morphological and adhesion properties of composite substrates. Atomic force microscopy (AFM) studies showed that surfaces with non-homogeneous topography have non-homogeneous adhesion properties. In addition, the homogeneity of the adhesion properties is dependent upon the chemical species used to functionalize the surface. Force volume (FV) imaging was utilized to map the adhesion of the fabricated substrates with high-resolution. The FV studies revealed that the hydrophobicity of the surface is not uniform despite the fact that the surface was functionalized with the same polyelectrolyte. The analysis methodology we report here opens the possibility to design better surfaces for future tissue engineering applications.     

多组分聚合物体系中的相容和络合

在含可控特殊相互作用的多组分聚合物体系中，随着体系中的相互作用密度的增强，体系在本体中可经历由不相容到相容直至络合的不同物理状态。本文概述了相容、络合研究的进展，着重讨论了相容和络合的区别和联系，提出了含氢键相互作用的高分子共混体系中相容－络合转变存在的普遍性。     

Characterization of complexes formed by polypropylene imine dendrimers and anti-HIV oligonucleotides

Current anti-HIV therapies are capable of controlling viral infection but do not represent a definitive cure. They rely on the administration of antiretroviral nucleoside analogues, either alone or in combination with vectors. Dendrimers are branched, synthetic polymers with layered architectures, promising non-viral vectors in gene therapy. The aim of the paper was to study the interactions between three anti-HIV antisense oligonucleotides (ODNs): SREV, ANTI TAR, GEM91 and different generation polypropylene imine dendrimers (PPI) by monitoring changes in the fluorescence polarization of fluorescein attached to the ends of the ODNs when increasing concentrations of dendrimers were added. Laser Doppler electrophoresis, dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to characterize, respectively, zeta potential, particle size and morphology of dendriplexes formed in different molar ratios. Antisense oligonucleotides interacted with polypropylene imine dendrimers in different molar ratios depending on generation. Zeta potential of dendriplexes varied from (-25 to -21) mV to -5 mV (for PPIG3 and PPIG4 complexes) and to zero (for PPIG2 complexes). The structures presented a polydisperse size from about 50 nm to even 700-800 nm by TEM and about 250 nm by DLS. It means that besides single dendriplexes, aggregates were also present.     

非共轭单体的活性自由基聚合进展

活性自由基聚合经过十多年的发展,已成为一种有效的高分子设计手段.代表性的活性自由基聚合技术包括氮氧调控自由基聚合(NMP),原子转移自由基聚合(ATRP)和可逆加成-断裂链转移(RAFT)聚合或通过黄原酸酯交换法设计大分子(MADIX).这些技术已成功应用到多数共轭单体上,但对非共轭单体的聚合控制还不太成功.本文总结了几类适合非共轭单体的活性自由基(共)聚合方法,主要有RAFT/MADIX体系,某些ATRP体系,碘退化转移体系及近年新出现的有机碲调控自由基聚合(TERP)和有机锑调控自由基聚合(SBRP)体系,其中,TERP和SBRP的独特性值得关注.     

关于活性聚合判据的讨论

活性聚合尤其是活性聚合的判据是高分子化学课程中重要的教学内容。本文对活性聚合的判据进行了全面的总结,并深入分析了每种判据的来源,这些教学内容可作为现有教材的补充,有助于学生深刻理解活性聚合的内涵和外延。     

Polarographic Determination of Famotidine through Complexation with Nickel(II) Chloride

The present investigation describes the development of a sensitive, rapid polarographic method for the determination of famotidine in pure form and in certain dosage forms. The proposed method depends upon studying the polarographic activity of Nickel(II)‐famotidine complex in Britton Robinson buffer over the pH range 4–8 and its usefulness in the analysis of famotidine using direct current (DC_t), differential pulse (DPP), and alternating current (AC_t) polarography. The different experimental parameters affecting the cathodic waves were carefully investigated and optimized. Moreover, to check the validity of the proposed method, the standard addition method was applied by adding famotidine to the previously analyzed tablets. The recovery of the drug was calculated by comparing the concentration obtained from the spiked mixtures with those of the pure drug. The results of analysis of commercial tablets and the recovery study suggested that there is no interference from any excipients, which are present in tablets. Statistical comparison of the results was performed with regard to accuracy and precision using student's t‐test and F‐ratio at 95% confidence level. There is no significant difference between the comparison and proposed method with regard to accuracy and precision.     

《高分子化学》课程中“活性自由基聚合”的教学实践

《高分子化学》课程是五大化学基础课程(无机化学、有机化学、分析化学、物理化学、高分子化学)之一,是化学类、高分子材料与工程、材料化学专业的必修课程。"活性"/可控自由基聚合是一种相对较新且重要的聚合物合成技术和方法,针对目前《高分子化学》课程中活性自由基聚合的教学比较薄弱的现状,从教学的角度探讨了活性聚合和可控/"活性"自由基聚合的本质和特点,介绍了本人在这方面的教学实践活动,遵循成果导向教育理念,通过以学为中心的教学方式,打造金课,提高教学质量。     

Two-dimensional ordered arrays of monodisperse silica particles grafted with concentrated polymer brushes

Hybrid particles which have a core of monodisperse silica particle and a shell of well-defined poly(methyl methacrylate) chains end-grafted on the core surface with a surface density as high as 0.8 chains/nm² were prepared by surface-initiated atom transfer radical polymerization of methyl methacrylate with an initiator-fixed silica particle. Monolayers of the hybrid particles were formed at the air-water interface by depositing a defined amount of the particle suspension onto water surface. Transmission electron microscopic and atomic force microscopic observations of these monolayers showed that the hybrid particles formed a two-dimensional hexagonally ordered lattice with a wide controllability of interparticle distance. This lattice structure was utilized as a template for the fabrication of a negatively patterned surface of poly(dimethylsiloxane) elastomer.     

A facile and environment-friendly method for fabrication of polymer brush

A novel environment-friendly system is proposed tofabricate polymer brush, which has the advantages including non-toxic and inexpensive initiator(eosin Y), visible-light exposure(λ= 515 nm), water medium and ambient environment. The experimental results from UV-Vis spectroscopy, AFM-based single molecule force spectroscopy(SMFS) and other measurements indicate thata polymer brush with a living nature is fabricated via free radical polymerization. This polymer brush may find applications incoatings, bio-interfaces and so forth.     

Controlled complexation of plasmid DNA with cationic polymers: effect of surfactant on the complexation and stability of the complexes

The aggregation of the cationic polymer-plasmid DNA complexes of two commonly used polymers, polyethyleneimine (PEI) and poly-l-lysine (PLL) were systematically compared. The complexation was studied in 5% glucose solution at 25 degrees C using dynamic light scattering and isothermal titration calorimetry. The aggregation of the complexes was controlled by addition of the surfactant polyoxyethylene stearate (POES). The stability of the complexes was evaluated using dextran sulphate (DS) as relaxing agent. The relaxation of the complexes in the presence of DS was studied using agarose gel electrophoresis. This study elucidates the role of surfactant in controlling the size of the PEI/pDNA complex and reveals the differences of the two polymers as complexing agents.     

Real-time monitoring of living cationic ring-opening polymerization of THF and direct prediction of equilibrium molecular weight of polyTHF

A convenient real-time monitoring of monomer concentration during living cationic ring-opening polymerizations of tetrahydrofuran(THF) initiated with methyl triflate(Me OTf) has been developed for kinetic investigation and determination of equilibrium monomer concentration([M]e) via in situ FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance(ATR) immersion probe. The polymerization rate was first order with respect to monomer concentration and initiator concentration from the linear slope of ln([M]0-[M]e)/([M]-[M]e) versus polymerization time at different temperatures in various solvents. [M]e decreased linearly with initial monomer concentration while increased exponentially with increasing polymerization temperature. The equilibrium also strongly depends on solvent polarity and its interaction with monomer. The equilibrium polymerization time(te) decreased with increasing solvent polarity and decreased linearly with increasing [M]0 in three solvents with different slopes to the same point of bulk polymerization in the absence of solvent. Equation of Mn,e = 72.1/(0.14–0.04[M]e) has been established to provide a simple and effective approach for the prediction for the number-average molecular weight of poly THFs at equilibrium state(Mn,e) in the equilibrium living cationic ring-opening polymerization of THF at 0 °C.     

Complexation of decamethylcucurbit[5]uril with alkali metal ions

Four coordination compounds, namely [Na(H₂O)(H₂O)₂⊂C₄₀H₅₀N₂₀O₁₀](C₆H₆O₂)₂Cl·8H₂O (1), [K₂(H₂O)₂(H₂O)⊂C₄₀H₅₀N₂₀O₁₀](C₆H₆O₂)₂Cl₂·7H₂O (2), [Rb₂(H₂O)₂(H₂O)⊂C₄₀H₅₀N₂₀O₁₀](C₆H₆O₂)₂Cl₂·7H₂O (3) and [Cs(H₂O)₂(H₂O⊂C₄₀H₅₀N₂₀O₁₀)](C₆H₆O₂)₂Cl·6H₂O (4), were obtained by the reactions of the corresponding alkali metal salts with decamethylcucurbit[5]uril (Me₁₀Q[5]) in the presence of hydroquinone, and their structures were determined by single-crystal X-ray diffraction. The results revealed that in compounds 1 and 4 each Me₁₀Q[5] ligand coordinates one Na⁺ or Cs⁺ ion to form a molecular bowl structure, while in compounds 2 and 3 each Me₁₀Q[5] ligand coordinates two K⁺ or Rb⁺ ions to form a closed molecular capsule structure, and adjacent molecular capsules bridge each other through water molecules to form 1D coordination polymers. In addition, we found that the coordination distances for the metal ions and the height of the metal ions out-of-portal-plane for the four compounds are in the same order, 1 < 2 < 3 < 4, which is attributed to the fact that the radius of alkali cations is in the order Na⁺ < K⁺ < Rb⁺ < Cs⁺. Although each portal of Q[6] binds with two alkali cations (not including Cs⁺), the Q[6]-based alkali cations complexes display similar structural trends.     

Consequences of the nanoporosity of cellulosic fibers on their streaming potential and their interactions with cationic polyelectrolytes

Electrokinetic tests, based on the streaming potential method, were used to elucidate interactions between cationic polyelectrolytes and cellulosic fibers and to reveal aspects of fibers’ nanoporosity. The fibrillated and nanoporous nature of bleached kraft fibers gave rise to time-dependent changes in streaming potential, following treatment of the wetted fibers with poly-diallyldimethylammonium chloride. Electrokinetic test results were consistent with an expected longer time required for higher-mass polyelectrolytes to diffuse into pore spaces, compared to lower-mass polyelectrolytes. Further evidence of the relative inability of polyelectrolyte molecules to diffuse into the pores of cellulose was obtained by switching back and forth between high and low ionic strength conditions during repeated measurement of streaming potential, after the fibers had been treated with a moderate amount of cationic polymer. By changing the concentration of sodium sulfate it was possible to switch the sign of streaming potential repeatedly from positive to negative and back again. Such results imply that a continuous path for liquid flow exists either in a fibrillar layer or within the cell walls. The same concepts also helped to explain the dosages of high-charge cationic polymer needed to achieve maximum dewatering rates, as well as the results of retention experiments using positively and negatively charged microcrystalline cellulose particles.     

Thermodynamic Modeling of Actinide Complexation with Acetate and Lactate at High Ionic Strength

The stability constants of NpO ₂ ⁺ , UO ₂ ²⁺ Am³⁺, and Th⁴⁺ with acetate and lactate anions has been measured in 0.3–5.0m NaCl media at 25°C by the solvent extraction technique. For the 1:1 complexation, the values of the stability constants increased in the order: NpO ₂ ⁺ < Am³⁺ < ₂ ²⁺ < Th⁴⁺, in accordance with the actinide charge density and reflecting the strongly ionic bonding of the complexes. The Pitzer ionic interaction parameters were calculated and used to estimate the thermodynamic stability constants at I = 0. Because our data were collected mainly in the high ionic strength region values of ⁽¹⁾ were estimated from values reported in the literature. For all stability constants the Pitzer model gives an excellent representation of the data using three interaction parameters ⁽⁰⁾, ⁽¹⁾, and COn leave from Institute of     

Synthesis of monodisperse zinc sulfide particles grafted with concentrated polystyrene brush by surface-initiated nitroxide-mediated polymerization

Monodisperse zinc sulfide (ZnS) particles of diameters ranging from 120 to 400 nm were prepared and then coated with a thin layer of silica (SiO₂). After the surface modification with an alkoxyamine derivative, polystyrene (PS) brushes of chain lengths ranging from 30,000 to 114,000 in M_n with relatively low polydispersities less than 1.5 in M_w/M_n were successfully grafted by surface-initiated nitroxide-mediated polymerization, where the M_n and M_w are the number- and weight-averaged molecular weights, respectively. The graft density reached a value as high as 0.9 chains nm⁻². These core-shell hybrid particles (ZnS@SiO₂-PS) were highly dispersible, without any aggregation, in various solvents good for PS, also forming a monolayer at the air-water interface by spreading its solution. The transmission electron microscopic observation of the monolayers deposited on a solid support revealed two-dimensionally close-packed arrays of particles. These monolayers exhibited a beautiful structural color dependent on the angle of incident light because of such an ordered array of the ZnS cores with a high refractive index. Hollow spheres constituted of a SiO₂ shell with well-defined, high-density PS brushes were first synthesized by selective dissolution of the ZnS core from the ZnS@SiO₂-PS hybrid particle.     

核苷酸与β-环糊精及硼酸盐的络合作用在高效毛细管电泳分离核苷酸中的应用

核苷酸和β-环糊精(β-CD)及硼酸盐之间存在络合作用，可应用于核苷酸的高效毛细管电泳分离，在10mmol/L β-CD和20mmol/L硼酸盐存在时，实现了8种单磷酸核苷酸的分离测定；讨论了pH值、β-CD浓度、硼酸盐浓度及分离电压对分离和络合作用的影响。     

Synthesis and interfacial properties of novel cationic polyelectrolytes with brush-on-brush structure of poly(ethylene oxide) side chains

Novel cationic polyelectrolytes with a brush-on-brush structure of poly(ethylene oxide) (PEO) side chains and a charge-containing polyacrylate backbone were synthesized. The PEO side chains were not directly attached to the backbone but via polymethacrylate spacers, thus locating the PEO chains a distance away from the charged units of the backbone. The cationic brush-on-brush polyelectrolytes with high density of PEO chains showed a strong affinity to silica surfaces, provided the backbone charge density was high enough. The adsorption of these polymers was studied by QCM-D giving very high sensed mass, 20 mg/m². It was shown by direct force measurements that protective surface layers were formed by the novel polyelectrolytes, generating strongly repulsive steric forces, which provided an effective barrier against flocculation. The adsorbed layer was sufficiently robust to withstand sliding experiments under a pressure of up to 35 MPa. The friction force in water was very low, and the lubrication was characterized by a friction coefficient in the range of 0.02-0.06.