Influence of charge distribution on the conformation of neutral polyampholytes

Summary Two polyampholyte copolymers based on sodium-2-acrylamido-2-methylsulfonate (NaAMPS) and methacryloyloxyethyltrimethylammonium chloride (MADQUAT) have been prepared either in homogeneous solution or by an inverse microemulsion polymerization technique. The copolymer microstructure was shown to depend on the method of preparation. The microemulsion polymerization yields copolymers with a monomer sequence distribution not far from random while those obtained by polymerization in solution have a strong tendency to alternation. The aqueous-solution properties of the two samples have been investigated by viscometry. The results show that the charge distribution along the copolymer chain affects considerably its conformation, in good agreement with recent theoretical studies. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994     

Phase separation in dilute solutions of poly (N-isopropylacrylamide)

The appearance of spherical particles resulting from phase separation in dilute solutions of poly(N-isopropylacrylamide) has been observed by dynamic light scattering (DLS). The particles have a relatively narrow size distribution. The size of particles increases with increasing concentration of polymer, and decreasing heating speed. Electron microscopy confirms the existence of spherical particles with size and polydispersity in agreement with DLS.     

Glass transition of the two distinct single-chain particles of poly(N-isopropylacrylamide)

Two distinct single-chain particles of poly(N-isopropylacrylamide) (PNIPAM) in the state of loose coil and compact globule, have been prepared successfully below and above the lower critical solution temperature (LCST) in extreme dilute aqueous solution by the freeze-drying method, respectively. During the preparation of the compact globular single-chain sample, the surfactant of sodium n-dodecyl sulfate (SDS) was added into the system to prevent aggregation of globular single chains formed at a temperature above the LCST. After all the coil has been transformed into the compact globular particle, the SDS molecules were removed by dialysis. The glass transition temperature (T_g) of the two single-chain samples has been measured by differential scanning calorimetery (DSC) in comparison with that of bulk polymer. It was found that the T_g of the single-chain sample in compact-globule state was very near to that of the bulk polymer, whereas the T_g of the single-chain sample in loose-coil state was approximately 6 K lower than that of the bulk polymer. After treating the sample with repeated DSC cycles, the T_g of the single-chain sample in loose-coil state rose up successively near to that of the bulk polymer. These results have been explained in terms of the effect of entanglement on the mobility of the polymer segments in the two distinct single-chain samples.     

The phase transition of poly(N-isopropylacrylamide): the effect of aging

We study the effect of temporal and thermal aging of linear and hydrogel samples of poly(N-isopropylacrylamide) (PNIPAM). For this purpose, we designed a simple and inexpensive experimental device able to measure the optical density as a function of temperature. The samples were aged from 4 to 14 days at two temperatures: 24 and 37°C. We found that the phase transitions of linear PNIPAM samples shift to lower or higher temperatures, depending on the storage conditions, while the phase transitions of hydrogels always shift to higher temperatures. Structural differences between linear and hydrogel PNIPAMs and the formation of additional hydrogen bonds are behind these shifts.     

Temperature-sensitive poly(N-Isopropyl-Acrylamide) microgel particles: A light scattering study

We present a light scattering study of aqueous suspensions of microgel particles consisting of poly(N-Isopropyl-Acrylamide) cross-linked gels. The solvent quality for the particles depends on temperature and thus allows tuning of the particle size. The particle synthesis parameters are chosen such that the resulting high surface charge of the particles prevents aggregation even in the maximally collapsed state. We present results on static and dynamic light scattering (SLS/DLS) for a highly diluted sample and for diffuse optical transmission on a more concentrated system. In the maximally collapsed state the scattering properties are well described by Mie theory for homogenous hard spheres. Upon swelling we find that a radially inhomogeneous density profile develops.     

利用微悬臂梁表面应力研究聚N-异丙基丙烯酰胺分子的构象转变

提出了一种基于微悬臂梁传感技术研究大分子折叠/构象转变的新方法.通过分子自组装的方法将热敏性的聚N-异丙基丙烯酰胺(PNIPAM)分子链修饰到微悬臂梁的单侧表面,用光杠杆技术检测温度在20-40 ℃之间变化时由于微悬臂梁上的PNIPAM分子在水中的构象转变所引起的微悬臂梁变形.实验结果显示:在升温过程中,微悬臂梁的表面应力发生了变化并且导致微悬臂梁产生了弯曲变形,这个过程对应着微悬臂梁上的PNIPAM分子从无规线团构象到塌缩小球构象的构象转变.在降温过程中,微悬臂梁发生了反方向的弯曲变形,这对应着PNIPAM分子从塌缩小球构象向无规线团构象的构象转变.整个温度变化过程中构象转变是连续进行的,而在低临界溶解温度(约32 ℃)附近转变幅度较大,这与自由水溶液中PNIPAM分子的无规线团-塌缩小球构象转变相对应.实验结果还显示:由于PNIPAM分子在塌缩过程中氢键的形成和链段间可能的缠结效应,整个温度循环过程中微悬臂梁的变形是不可逆的且有明显的迟滞效应.     

Cytotoxic evaluation of N-isopropylacrylamide monomers and temperature-sensitive poly(N-isopropylacrylamide) nanoparticles

The objective of this research project is to investigate the biocompatibility of N-isopropylacrylamide (NIPAAm) monomers and poly(N-isopropylacrylamide) (PNIPAAm) nanoparticles in vitro. PNIPAAm nanoparticles of different sizes were synthesized and characterized by transmission electron microscopy and dynamic light scattering. Cytotoxicity studies using MTS assays were conducted on fibroblasts, smooth muscle cells, and endothelial cells. In addition, the concentration of NIPAAm monomers remaining on PNIPAAm nanoparticles was determined using bromination and spectrophotometry. The cytotoxicity results did not show a significant difference in cell survival when cells were exposed to different particle sizes (100, 300, and 500 nm). Dose studies showed that all three cell types exposed to 100 nm PNIPAAm nanoparticles at concentrations less than or equal to 5 mg/mL were compatible, while cells exposed to NIPAAm monomers exhibited toxicity even at very low concentrations. We also found that 1 mg/mL concentration of 100 nm PNIPAAm nanoparticles was cytocompatible for 4 days, whereas NIPAAm monomers were cytotoxic after 24 h of exposure. Photomicrographs showed altered morphology in cells exposed to NIPAAm monomers, while cells exposed to PNIPAAm nanoparticles maintained their normal morphology. Finally, a very low concentration of NIPAAm monomers remained on the PNIPAAm nanoparticles after synthesis and dialysis. Our results demonstrate that NIPAAm monomers are cytotoxic, whereas PNIPAAm nanoparticles are compatible at 5 mg/mL concentration or below for fibrobasts, smooth muscle cells, and endothelial cells.     

Anomalous temperature dependence of speed of sound of bulk poly(N-isopropylacrylamide) hydrogels near the phase transition

Bulk Poly(N-isopropylacrylamide) (PNIPAm) hydrogels are thermally responsive polymers that undergo a sharp volumetric phase transition around its lower critical solution temperature of 33 °C. The physical characteristics of bulk, micro-, and nano-form PNIPAm hydrogel have been well-studied, and have applications ranging from biomedical devices to mechanical actuators. An important physical characteristics which reveals lack of available information is speed of sound. Prior studies have utilized Brillouin scattering, multi-echo reflection ultrasound spectroscopy, the sing-around method, and others in measuring the speed of sound. We use a planar resonant cavity with bulk PNIPAm hydrogel in aqueous solution to determine the temperature dependent speed of sound around the lower critical solution temperature. The results show sharp nonmonotonic behavior of the sound velocity in vicinity of the phase transition.     

Synthesis and spectral-luminescent properties of poly(N-isopropylacrylamide)

The spectral-luminescent characteristics of water and methanol solutions of polymers containing tetraphenylporphyrin substituents were investigated. The water-soluble polymer was obtained by the interaction of poly(N-isopropylamide) containing N-oxysuccinimide substituents with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin. From the synthesized polymer its analog with Zn-porphyrin substituents was obtained. This phenomenon is attributed to the specific features of the conformational behavior of polymeric chains in water solutions. Water solutions of polymers experience a thermally reversible phase transition upon heating, which is accompanied by a considerable enhancement of light scattering. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 483–487, July–August, 2000.     

The bulk dynamics of a compositionally asymmetric diblock copolymer studied using dynamic light scattering

We have studied the bulk dynamics of a compositionally asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) (PEP-PDMS) diblock copolymer in a large temperature range both in the ordered and in the disordered state. The volume fraction of the PEP block is 0.22. Apart from the disordered state, the sample shows three ordered morphologies. Using dynamic light scattering, we have investigated the dynamics in all four phases and combined these results with those obtained using pulsed field gradient NMR. In the disordered state, we find--apart from the slow cluster mode--the heterogeneity mode related to the self-diffusion of single chains. The relaxation time of this mode, reduced by temperature and the zero-shear viscosity , , increases with temperature. In the cubic phase right below the ODT temperature, we observe two diffusive processes, and we attribute the faster one to the mutual diffusion of micelles and block copolymers not bound to micelles (“free chains”) through the PDMS matrix. The slower mode may either be due to the mutual diffusion of free chains and chains bound to PEP micelles or to the cooperative diffusion of micellar aggregates. In the non-cubic ordered state at intermediate temperatures, an additional weak diffusive mode is observed. The low-temperature ordered state is body-centered cubic, and here, only the mutual diffusion of micelles and free chains lies in our experimental time window. Received 19 March 1999 and Received in final form 25 August 1999     

Effect of the degree of crosslinking on the interfacial layer structure of poly(vinyl chloride) dispersed with crosslinked poly(n-butyl methacrylate) particles

The interfacial layer structure of a model incompatible polymer blend system was analyzed using ¹H pulse nuclear magnetic resonance (pulse NMR) spectroscopy. Non-crosslinked and crosslinked poly(n-butyl methacrylate) particles with a mean size of ca. 0.9 μm were prepared by seeded emulsion polymerization, and the degree of crosslinking was varied. The particles were powdered using a freeze-dry method and dispersed in poly(vinyl chloride) by melt blending. Dynamic mechanical analysis indicated that the non-crosslinked particles were completely compatible. In contrast, mutual diffusion of the polymer chains in the crosslinked particles was restricted within the particle/matrix interfacial layer. As a result, an incompatible phase structure in which the crosslinked particles were dispersed in the continuous phase was formed. Pulse NMR analysis indicated that the interfacial layer thickness was in the range of 17–98 nm. The thickness decreased with an increase in the degree of crosslinking in the particles. The interfacial layer thickness in the particles was approximately 10 times larger than that for the incompatible polymer pair. Tensile test results indicated that the elongation at break was dependent on the thickness of the interfacial layer. The yield stress was developed for the particles with high hardness that was independent of the interfacial thickness.     

Direct solution of the Hill-Wheeler equations for scattering states (II)

Various methods for directly solving the Hill-Wheeler equations of composite particle scattering are examined. Numerical limitations due to the singular nature of the resolvent kernels are pointed out. Potential scattering and elastic α-α scattering serve as examples to test the reliability of the various methods in actual application.     

后向动态光散射系统的像差分析与校正

针对后向动态光散射颗粒测量系统信噪比较低的问题,从光学系统的像差入手,采用Zemax对其进行了仿真和分析,并提出了校正方案。首先介绍了后向动态光散射颗粒测量系统的基本原理和光学系统,从校正像差的角度出发,采用Zemax对后向动态光散射系统进行仿真,并对其像差进行分析。然后根据仿真结果,提出了校正方案,采用Ze-max设计了方案中的参数,得出了理论上的校正结果。最后采用优化好的结果进行后向动态光实验,得到了实验数据。均值误差和重复性误差分别达到了1.52%和1.24%。满足国标均值误差和重复性误差小于2%的要求。     

Grafting onto poly(ethylene terephthalate) driven by 172 nm UV light

The reactivity of the surface of poly(ethylene terephthalate) (PET) film under 172 nm UV irradiation (xenon excimer lamp) towards nitrogen-borne 1-octene, n-nonane and heptafluorodecene vapor was investigated. Materials receiving from 0 to 24 J/cm² of UV were examined by X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (ToF/SIMS), water and mineral oil contact angle measurement and atomic force microscopy (AFM). A uniform nanoscale layer developed on PET surface attributed to the grafting reaction between photolytically-produced polymer radicals and vapor phase molecules.     

Pion small-angle multiple scattering at energies spanning the (3,3) resonance

The small-angle multiple scattering of positive and negative pions has been measured for C, Al, Cu and Pb targets throughout an energy range spanning the (3, 3) resonance. The measurements were made using two-dimensional multiwire proportional counters placed in the pion beam. All previous multiple scattering data for electrons and protons as well as these new data for pions are used to recalculate the empirical terms in the Moliere theory of multiple scattering. A second-order Born approximation multiple scattering theory has been devised for spin zero particles. Modified Moliere theory gives a better fit to the experimental data than the second-order Born calculation. Because the updated Moliere theory contains much simpler equations and gives closer agreement with experiment, it is recommended in place of the more sophisticated theory for the interpretation of new experimental data.     

A relativistic description of πd scattering in the (3,3) resonance region

We discuss two alternative sets of relativistic (three-dimensional) scattering equations for the coupled {πd, NΔ} systems — including spin and isospin. The equations are solved, and the results compared with experiments in the (3, 3) resonance region. Except for the backward angle region at 256 MeV, the agreement with experiment is good. Specific relativistic effects are isolated, and their importance (for πd as well as π-nucleus scattering) assessed.     

The dynamic angle-limited integrated scattering (DALIS) method for measuring scattering of light from optical surfaces with random roughness

A new and simple dynamic angle limited integrated scattering (DALIS) method is developed to examine optically smooth reflective surfaces with defined surface form. Our experimental results from two systems show advantages over conventional angle resolved scattering measurement (ARS) methods. By collecting scattered light in a given solid angle, our methods do not require a detection unit with an extremely large dynamic range. Unlike in the common ARS measurement method, here we use a simple linear translation stage to scan scattered light. The power spectrum density function and the autocorrelation function of the surface roughness can be recovered from the measured scattering pattern. This method can be applied to in-workshop inspection of optical polishing processes.