Boroxine Nanotubes: Moisture‐Sensitive Morphological Transformation and Guest Release

Boroxines, (R‐BO)₃, which can be easily synthesized via a dehydration reaction of boronic acids, R–B(OH)₂, selectively self‐assemble in toluene into nanofibers, nanorods, nanotapes, and nanotubes, depending on the aromatic substituent (R). Spectroscopic measurements show that the nanotube consists of a J‐aggregate of the boroxine. Humidification converts the morphology from the nanotube to a sheet as a result of the hydrolysis of the boroxine components and subsequent molecular‐packing rearrangement from the J‐aggregate to an H‐aggregate. Such a transformation leads to the compulsive release of guest molecules encapsulated in the hollow cylinder of the nanotube. The hydrolysis and the molecular‐packing rearrangement described above are suppressed by coordination of pyridine to the boron atom, with the resulting moiety acting as a Lewis acid of the boroxine component. The pyridine‐coordinated nanotube is transformed into a helical coil by humidification. Guest release during the nanotube‐to‐helical‐coil transformation is much slower than during the nanotube‐to‐sheet transformation, but faster than from a nanotube that did not undergo morphological transformation. The storage and release of guest molecules from the boroxine nanotubes can be precisely controlled by adjusting the moisture level and the concentration of Lewis bases, such as amines.     

NIR驱动MWCNT修饰的超滑PI光热响应膜表面液滴定向输运

目的 制备多壁碳纳米管(MWCNT)修饰的超滑聚酰亚胺(PI)光热响应膜表面,实现近红外光(NIR)驱动液滴定向输运.方法 基于静电纺丝结合喷涂法制备MWCNT修饰的超滑PI光热响应膜表面,分别通过扫描电子显微镜、接触角测量仪、红外热成像仪表征样品的微观形貌、润湿特性及光热特性,分析液滴大小与润滑油黏度对液滴定向输运的影响规律,研究NIR驱动液滴在MWCNT修饰的超滑PI光热响应膜表面定向输运的作用机理.结果 MWCNT修饰PI膜表面的疏水性提高,液滴静态接触角从115°增大至160°.NIR连续照射MWCNT修饰的超滑PI光热响应膜表面90 s,表面温度的最大上升速率为42.6℃/s,表面最大温度达到123.6℃.通过NIR照射超滑PI纳米纤维膜表面,表面局部温度上升,产生润湿梯度力,驱动液滴在表面定向输运.液滴定向输运与润湿梯度力及粘滞阻力有关.超滑PI光热响应膜表面的润滑油黏度相同时,液滴体积越小,粘滞阻力越小,液滴定向输运的速度越快.5μL液滴在润滑油黏度为0.65 mm2/s的超滑PI光热响应膜表面的运动速度最大,运动速度为1.64 mm/s.液滴体积相同时,超滑PI光热响应膜表面的润滑油黏度越大,液滴受到的润湿梯度力越小.5μL液滴在润滑油黏度为100 mm2/s的超滑PI光热响应膜表面的润湿梯度力Fwet-grad最小,润湿梯度力为6.39×10?6 N.结论 MWCNT修饰的超滑PI光热响应膜表面具有良好的光热效应,NIR可精准驱动单液滴及多液滴在表面的定向输运.     

Transparent,Stimuli‐Responsive Films from Cellulose‐Based Organogel Nanoparticles

The use of bio‐based nanoscaled cellulose for the construction of novel functional materials has progressed rapidly over the past years. In comparison to most of studies starting with the hydrophilic nanoscaled cellulose, surface‐stearoylated cellulose nanoparticles (SS‐CNPs) are used in this report for the construction of multifunctional, responsive films. SS‐CNPs with an average size of 115 ± 0.5 nm are obtained after the surface‐modification of cellulose under heterogeneous conditions. Crystalline cellulose core is present within SS‐CNPs according to solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy. SS‐CNPs show excellent dispersibility in nonpolar solvents and form temperature‐responsive organogels in tetrahydrofuran (THF) at low temperature or after long time storage at room temperature. Moreover, transparent and self‐standing films of SS‐CNPs from their THF‐suspension show solvent‐responsive surface wettability and responsive shape‐memory property. SS‐CNPs can also be used for the fabrication of nanocomposite films together with nonpolar compounds, such as (2‐stearoylaminoethyl) rhodamine B. Thus, these novel SS‐CNPs derived from sustainable cellulose fibers are promising candidates for the construction of novel functional materials.     

pH‐ and NIR Light‐Responsive Micelles with Hyperthermia‐Triggered Tumor Penetration and Cytoplasm Drug Release to Reverse Doxorubicin Resistance in Breast Cancer

The acquisition of multidrug resistance (MDR) is a major hurdle for the successful chemotherapy of tumors. Herein, a novel hybrid micelle with pH and near‐infrared (NIR) light dual‐responsive property is reported for reversing doxorubicin (DOX) resistance in breast cancer. The hybrid micelles are designed to integrate the pH‐ and NIR light‐responsive property of an amphiphilic diblock polymer and the high DOX loading capacity of a polymeric prodrug into one single nanocomposite. At physiological condition (i.e., pH 7.4), the micelles form compact nanostructure with particle size around 30 nm to facilitate blood circulation and passive tumor targeting. Meanwhile, the micelles are quickly dissociated in weakly acidic environment (i.e., pH ≤ 6.2) to release DOX prodrug. When exposed to NIR laser irradiation, the hybrid micelles can trigger notable tumor penetration and cytosol release of DOX payload by inducing tunable hyperthermia effect. In combination with localized NIR laser irradiation, the hybrid micelles significantly inhibit the growth of DOX‐resistant MCF‐7/ADR breast cancer in an orthotopic tumor bearing mouse model. Taken together, this pH and NIR light‐responsive micelles with hyperthermia‐triggered tumor penetration and cytoplasm drug release can be an effective nanoplatform to combat cancer MDR.     

一种磁性介孔硅纳米探针及其对Fe~(3+)的识别和脱除

制备了一种可用于Fe~(3+)检测和脱除的香豆素类磁性介孔硅纳米探针MMS-C,通过TEM、FT-IR、XRD、N2吸附手段表征了其结构。性能测试结果表明,MMS-C在甲醇中对Fe~(3+)表现荧光猝灭的响应和较高的识别选择性。此外,MMS-C对Fe~(3+)具有一定的脱除能力,脱除率为38.9%。     

Application of stimuli responsive polymers for sustainable ion exchange chromatography

Ion exchange processes are widely used in the food, bioprocessing and related industries for the isolation of proteins and other ionic species. Traditional ion exchange resins require salts, acids or bases for releasing adsorbed molecules creating a strong saline waste stream with negative environmental and economic impact. Stimuli responsive polymers (SRPs) with ion exchange functional groups can be used to selectively capture and release charged molecules from a complex mixture using physical stimuli to trigger conformational transitions in the polymer. The structural change of the polymers in response to a stimulus may lead to reduced ligand–target molecule interaction resulting in the release of the captured molecule without the use of chemical reagents, thereby reducing the environmental burden associated with ion exchange processes. The use of temperature responsive polymers has already been demonstrated for such applications at analytical scale. However, little progress has been made to extend these discoveries to the development of materials and methods amenable to industrial scale processing. So far, other SRPs such as, electric, magnetic and light responsive polymers remain largely unexplored for such application. This article discusses the potential of temperature responsive and other SRPs for developing sustainable ion exchange processes. It also highlights the material science and engineering challenges that need to be overcome to bring such processes to industrial application.     

真空磁绝缘线B-dot电流探测器的研制

为了测量阳加速器新真空磁绝缘线的电流,研制并标定了B-dot探测器。2个B-dot的探测器分别安装在磁绝缘线的入口和中部,输出信号与被测电流的微分成正比,经RC积分后获得电流信号。B-dot探测器采用在线标定,当阴阳极短接点数量较少,且位置距离探测器较近时,会因真空绝缘线(MITL)电流密度不均匀导致标定不准确,故需增多短接点。当短接点的位置距离探测器约2m时,即使只设置2个连接点,探测器位置的MITL电流密度近似均匀。加速器实验结果表明:在MITL阴阳极较近的位置,将B-dot探头安装在阳极孔中不影响磁绝缘效果,B-dot探测器测试稳定可靠,其设计和标定方法可行。