Multifunctional Core/Shell Nanoparticles Self‐Assembled from pH‐Induced Thermosensitive Polymers for Targeted Intracellular Anticancer Drug Delivery

Core/shell nanoparticles that display a pH‐sensitive thermal response, self‐assembled from the amphiphilic tercopolymer, poly(N‐isopropylacrylamide‐co‐N,N‐dimethylacrylamide‐co‐10‐undecenoic acid) (P(NIPAAm‐co‐DMAAm‐co‐UA)), have recently been reported. In this study, folic acid is conjugated to the hydrophilic segment of the polymer through the free amine group (for targeting cancer cells that overexpress folate receptors) and cholesterol is grafted to the hydrophobic segment of the polymer. This polymer also self‐assembles into core/shell nanoparticles that exhibit pH‐induced temperature sensitivity, but they possess a more stable hydrophobic core than the original polymer P(NIPAAm‐co‐DMAAm‐co‐UA) and a shell containing folate molecules. An anticancer drug, doxorubicin (DOX), is encapsulated into the nanoparticles. DOX release is also pH‐dependent. DOX molecules delivered by P(NIPAAm‐co‐DMAAm‐co‐UA) and folate‐conjugated P(NIPAAm‐co‐DMAAm‐co‐UA)‐g‐cholesterol nanoparticles enter the nucleus more rapidly than those transported by P(NIPAAm‐co‐DMAAm)‐b‐poly(lactide‐co‐glycolide) nanoparticles, which are not pH sensitive. More importantly, these nanoparticles can recognize folate‐receptor‐expressing cancer cells. Compared to the nanoparticles without folate, the DOX‐loaded nanoparticles with folate yield a greater cellular uptake because of the folate‐receptor‐mediated endocytosis process, and, thus, higher cytotoxicity results. These multifunctional polymer core/shell nanoparticles may make a promising carrier to target drugs to cancer cells and release the drug molecules to the cytoplasm inside the cells.     

Influence of Temperature on the Colloidal Stability of Polymer‐Coated Gold Nanoparticles in Cell Culture Media

The temperature‐dependence of the hydrodynamic diameter and colloidal stability of gold‐polymer core‐shell particles with temperature‐sensitive (poly(N‐isopropylacrylamide)) and temperature‐insensitive shells (polyallylaminine hydrochloride/polystyrensulfonate, poly(isobutylene‐alt‐maleic anhydride)‐graft‐dodecyl) are investigated in various aqueous media. The data demonstrate that for all nanoparticle agglomeration, i.e., increase in effective nanoparticle size, the presence of salts or proteins in the dispersion media has to be taken into account. Poly(N‐isopropylacrylamide) coated nanoparticles show a reversible temperature‐dependent increase in size above the volume phase transition of the polymer shell when they are dispersed in phosphate buffered saline or in media containing protein. In contrast, the nanoparticles coated with temperature‐insensitive polymers show a time‐dependent increase in size in phosphate buffered saline or in medium containing protein. This is due to time‐dependent agglomeration, which is particularly strong in phosphate buffered saline, and induces a time‐dependent, irreversible increase in the hydrodynamic diameter of the nanoparticles. This demonstrates that one has to distinguish between temperature‐ and time‐induced agglomerations. Since the size of nanoparticles regulates their uptake by cells, temperature‐dependent uptake of thermosensitive and non‐thermosensitive nanoparticles by cells lines is compared. No temperature‐specific difference between both types of nanoparticles could be observed.     

Grafting of titanium dioxide microspheres with a temperature‐responsive polymer via surface‐initiated atom transfer radical polymerization without the use of silane coupling agents

Titania microspheres with narrow size distribution and diameters of about 1 µm were prepared and subsequently functionalized using surface‐initiated atom transfer radical polymerization (ATRP) of N‐isopropylacrylamide. The ATRP initiator was immobilized on the particle surface via acylation of surface hydroxyl groups with α‐bromoisobutyryl bromide. Subsequently, an established ATRP reaction system was used for the preparation of titania surface‐grafted poly(N‐isopropylacrylamide) (PNiPAAm). Characterization was performed with electron microscopies, X‐ray diffraction, infrared spectroscopy and dynamic light scattering. It was found that the particle size in aqueous dispersions changed reversibly with temperature as expected for a shell of PNiPAAm, a polymer with a lower critical solution temperature at 32 °C. This confirmed the successful preparation of functional, stimuli‐responsive TiO₂ microparticles via a straightforward controlled surface‐initiated polymerization method.     

Multifunctional Magnetic Optical Sensor Particles with Tunable Sizes for Monitoring Metabolic Parameters and as a Basis for Nanotherapeutics

Magnetic optical sensor particles with multifunctional cores and shells are synthesized via a facile nanoprecipitation method and the subsequent modification of the particle shell. The hydrophobic particle core includes optical oxygen indicators, a light harvesting system, photosensitizers, and magnetic nanoparticles. Further functionalities are introduced by modifying the shell with enzymes, antibodies, multiple layers of polyelectrolytes, stimuli‐responsive polymers, and luminescent indicator dyes. The hydrodynamic diameter is tunable by varying different precipitation parameters.     

Mechanical and shape‐memory behavior of shape‐memory polymer composites with hybrid fillers

Shape‐memory polymer (SMP) materials have several drawbacks such as low strength, low stiffness and natural insulating tendencies, which seriously limit their development and applications. Much effort has been made to improve their mechanical properties by adding particle or fiber fillers to reinforce the polymer matrix. However, this often leads to the mechanical properties being enhanced slightly, but the shape‐memory effect of reinforced SMP composites being drastically reduced. The experimental results reported here suggested that the mechanical resistive loading and thermal conductivity of a composite (with hybrid filler content of 7.0 wt%) were improved by 160 and 200%, respectively, in comparison with those of pure bulk SMP. Also, the glass transition temperature of the composite was enhanced to 57.28 °C from the 46.38 °C of a composite filled with 5.5 wt% hybrid filler, as determined from differential scanning calorimetry measurements. Finally, the temperature distribution and recovery behavior of specimens were recorded with infrared video in a recovery test, where a 28 V direct current circuit was applied. The effectiveness of carbon black and short carbon fibers being incorporated into a SMP with shape recovery activated by electricity has been demonstrated. These hybrid fillers were explored to improve the mechanical and conductive properties of bulk SMP. Copyright © 2010 Society of Chemical Industry     

Temperature‐responsive polymers with LCST in the physiological range and their applications in textiles

Current academic and industrial research sustains large efforts to synthesize and develop environmentally responsive smart materials. The temperature‐responsive materials with a trigger temperature in the physiological range attract much attention due to their potential biomedical applications. We describe their chemistry and the way to synthesize them, focusing on applications for smart clothing fabrication. Copyright © 2007 Society of Chemical Industry     

Technique for Estimating the Number of Active Flows in High‐Speed Networks

The online collection of coarse‐grained traffic information, such as the total number of flows, is gaining in importance due to a wide range of applications, such as congestion control and network security. In this paper, we focus on an active queue management scheme called SRED since it estimates the number of active flows and uses the quantity to indicate the level of congestion. However, SRED has several limitations, such as instability in estimating the number of active flows and underestimation of active flows in the presence of non‐responsive traffic. We present a Markov model to examine the capability of SRED in estimating the number of flows. We show how the SRED cache hit rate can be used to quantify the number of active flows. We then propose a modified SRED scheme, called hash‐based two‐level caching (HaTCh), which uses hashing and a two‐level caching mechanism to accurately estimate the number of active flows under various workloads. Simulation results indicate that the proposed scheme provides a more accurate estimation of the number of active flows than SRED, stabilizes the estimation with respect to workload fluctuations, and prevents performance degradation by efficiently isolating non‐responsive flows.     

主被动磁悬浮高速转子系统的自动平衡控制

针对主被动磁悬浮转子高速旋转时质量不平衡和被动磁轴承磁中心的偏移导致的同频振动力问题,提出了一种基于位移陷波加前馈补偿的自动平衡控制方法。首先,在转子为零位移控制状态下提取控制电流的同频成分,计算获得与被动磁轴承磁中心偏移相关的参变量;然后,在额定转速下设计通用陷波器以消除同频电流,前馈补偿主动磁轴承、被动磁轴承位移负刚度力和被动磁轴承磁中心偏移力,使主被动磁轴承的同频输出力为零,实现了转子绕惯性中心旋转。对提出的方法进行了仿真和实验验证并与仅补偿质量不平衡的算法进行了对比。仿真结果显示:提出的方法的同频磁轴承力减小到了只进行质量不平衡补偿算法的6%;实验结果显示:同频振动加速度减小到只进行质量不平衡补偿算法的23.3%。仿真和实验验证了该方法的有效性,表明该方法对同频振动抑制效果显著,实现了转子的自动平衡控制。