用于细胞三维培养的集成微柱阵列的微流控芯片设计与验证

设计并验证了一种用于细胞三维培养的集成微柱阵列的微流控芯片.芯片由一片聚二甲基硅氧烷(PDMS)沟道片和一片玻璃盖片组成, 在PDMS沟道片上集成了一个由两排微柱阵列围成的细胞培养室和两条用于输送培养基的侧沟道.微柱间距直接影响了芯片的使用性能, 是整个芯片设计的关键.基于数值模拟和实验验证, 本研究对微柱间距进行了优化设计.优化后的微流控芯片可以很好地实现细胞与细胞外基质模拟材料混合液的稳定注入、培养基中营养物质向培养室内的快速扩散和细胞代谢物的及时排出.在芯片上进行了神经干细胞的三维培养, 证明了芯片上构建的细胞体外微环境的稳定性.     

疏水表面拓扑结构对其润湿状态影响的粗粒化模拟

采用BMW-MARTINI粗粒化分子动力学模拟方法研究了表面的拓扑结构对疏水性表面润湿状态的影响. 模拟结果表明,对于疏水性表面,增大表面的粗糙度对其疏水性影响不大,而主要是影响其润湿状态. 在一定范围内(柱间距不超过4.7 nm),水珠在微柱结构疏水表面的润湿行为受到柱间距(d)和柱高(h)的双重影响. 柱间距一定时,存在一个临界的柱高,可以使得水珠在表面的润湿状态由Wenzel态向Cassie-Baxter态发生转变,并且该临界高度随着柱间距的增大而增大. 进一步分析发现,本文研究范围内,润湿状态的转变和柱间距与柱高的比值d/h有关,当d/h不超过2时,水珠呈Wenzel态,超过2时则由Wenzel态向Cassie-Baxter态发生转变. 通过能量分析,发现润湿状态的转变主要取决于水珠与表面之间的范德华作用. 本文研究结果可以为开发具有特定功能的疏水性材料提供参考.     

拉伸微模塑制备低密度聚乙烯超疏水表面

以新鲜荷叶为原始模板制备聚二甲基硅氧烷(PDMS)软模板,并用该软模板在真空下热压得低密度聚乙烯(LDPE),冷却剥离得到LDPE超疏水薄膜.场发射扫描电镜(FE-SEM)显示其表面由细长乳突(长约30 μm)构成,接触角为154°±3.5°,水滴极易滚落,而常压下热压得到的薄膜表面乳突则短而粗(长约8～10μm),接触角仅137°±2.7°,短粗的乳突高度接近模板微坑的深度,证明细长乳突是在微模塑脱模时拉伸形成的.     

反应离子刻蚀和自组装分子膜构建硅基底疏水与超疏水表面

采用反应离子刻蚀技术在Si(100)表面加工微米级圆柱阵列, 采用自组装技术分别制备了3种硅烷自组装分子膜. 结果表明, 采用反应离子刻蚀构建出的4种微米级圆柱阵列结构规整, 其直径为5 μm, 高度为10 μm, 间距为15~45 μm. 沉积自组装分子膜后, 试样表面的水接触角显著增大, 其中沉积1H,1H,2H,2H-全氟癸基三氯硅烷(FDTS)自组装分子膜接触角最大, 1H,1H,2H,2H-全氟辛烷基三氯硅烷(FOTS)次之, 三氯十八硅烷(OTS)最小. 测得的接触角大于150°时接近Cassie方程计算的接触角, 而小于150°时接近Wenzel方程计算的接触角. 改变圆柱阵列的间距和选择不同的自组装分子膜, 可以控制表面接触角的大小. 原子力显微镜(AFM)观测结果显示, 沉积自组装分子膜可以产生纳米级的团簇. 由微米级圆柱阵列和纳米级自组装分子膜构成的表面结构使Si试样表面接触角最大可达156.0°.     

微柱高效液相色谱法测定葛根中的几种黄酮类成分

研究了用微柱高效液相色谱法测定葛根中的四种黄酮类成分。样品中的黄酮用甲醇超声振荡提取,然后用WatersXteraTMRP18(50×1.0mm,3.5μm)微柱吸附,以1%的乙酸溶液和甲醇为流动相梯度洗脱分离,用紫外二极管阵列检测器检测,结果满意。     

透明超疏水纳米阵列的构建及露滴自弹跳特性

利用溶胶-凝胶技术制备氧化锌晶种层,再通过化学氧化法在FTO玻璃表面制备了高度垂直取向的氧化锌纳米棒阵列.研究了晶种溶胶浓度和液相化学生长时间对阵列纳米结构形貌的影响规律和作用机理,并进一步分析了表面润湿性和透明性的变化情况.通过氧化锌纳米棒阵列的可控构建,获得了平均透光率可达95%的透明超疏水表面.密集生长的纳米阵列使得该表面在稳态结露条件下,直径约10μm的小尺度球状露滴合并后易发生自驱弹跳,脱附率高,露滴数量密度、覆盖率和平均直径均能保持在恒定范围,显示出优异的抗结露特性.     

基于智能手机摄影的接触角测量实验

建立了一种基于智能手机摄影测量接触角的简便方法，使用附加近摄镜的智能手机对固体表面的液滴进行拍摄，对图片进行测量和计算即可测得其接触角。该方法简单廉价，较为准确，可用于研究表面活性剂对接触角的影响，亲水和疏水表面对接触角的影响等。使用该方法可以在物理化学实验、精细化工实验等课程中引入接触角相关实验，增进学生对接触角概念的理解。     

基于热模塑法制备HDPE仿生超疏水表面

研究了热模塑法在制备超疏水高密度聚乙烯(HDPE)膜中的应用。以高岭土增强的聚二甲基硅氧烷(PDMS)为软模板,采用热模塑技术,将荷叶表面的微结构信息复制到HDPE膜表面。接触角测量结果显示,10%掺杂量的PDMS软模板复制得到的HDPE膜表面,与水的接触角高达156°,呈现超疏水性。扫描电镜照片显示,PDMS软模板具有与荷叶表面互补的"负型结构",而HDPE膜表面则具有与荷叶类似的微米—纳米复合粗糙结构。此法无需溶剂,可推广制备其它热塑性高聚物的超疏水表面。     

聚苯乙烯/聚二甲基硅氧烷嵌段共聚物的表面形态研究

采用原子力显微镜(AFM)和透射电镜(TEM)研究了聚苯乙烯/聚二甲基硅氧烷嵌段共聚物(PS-b-PDMS)薄膜的相形态.结果表明,当采用甲苯作为溶剂,旋转涂膜的薄膜样品呈现网络状的形态分布在表面,而样品所对应的透射电镜照片中,PDMS相作为球状分布在PS的连续相中.退火温度对共聚物表面形态有一定的影响,当退火温度高于PDMS的玻璃化温度,表面中PDMS相增多.PS-b-PDMS嵌段共聚物的表面形态随着所用溶剂的变化而有所不同,当采用甲苯作为溶剂时,样品的PS相形成凹坑分布在PDMS的相区之中,而采用环己烷作为溶剂时,PS相作为突起分布在PDMS相区之中.另外,基底对共聚物薄膜表面形态的有较大的影响,当采用硅晶片作为基底时,样品中的PDMS相和PS相呈现近似平行于表面的层状结构.     

用光学显微术和X-射线衍射法研究焦炭结构

用X-射线衍射测定了具有各种不同光学组织(从各向同性到直径大于60μm 的广域)的24种焦炭。研究了光学组织指数(OTI)与微晶高度和面间距之间的关系。对于光学组织中大于中粒锒嵌(1.5—5.0μm)的焦炭,其OTI 值随X-射线衍射指数的变化很小。对于光学组织中结构很小的焦炭,则微晶高度急剧下降和面间距增加。这些结果可以解释为当生成中粒锒嵌焦炭时,流动中间相融并,消除了缺陷。而光学组织尺寸较小的焦炭则是未经融并,因此缺陷残存于焦炭中,从而降低了结晶化程度。     

Isoelectric focusing in an ordered micropillar array

An original micropillar array dedicated to electrophoretic separations has been developed. It consists of a rectangular zone of PDMS micropillars protruding on a PDMS block. This area has been chosen to mimic a diluted gel structure and remains uncovered to keep the ability to perform an immunoblot after the protein separation for further applications in the field of allergy diagnosis. The micropillar array geometry has been optimized by evaluating the influence of pillar shape, pillar size and interpillar distance on evaporation and IEF separation. The separation conditions namely electrolyte composition, temperature and sample loading have been studied. Finally a protein mixture with pI ranging from 4.7 to 10.6 has been successfully separated within this microdevice by IEF without decreasing the resolving power obtained with conventional minigel. The micropillar array developed for electrophoretic separations leads to much shorter analysis times and can be reused several times while gels are disposable.     

Hydrodynamic chromatography of polystyrene microparticles in micropillar array columns

We report on the possibility to perform HDC in micropillar array columns and the potential advantages of such a system. The HDC performance of a pillar array column with pillar diameter = 5 μm and an interpillar distance of 2.5 μm has been characterized using both a low MW tracer (FITC) and differently sized polystyrene bead samples (100, 200 and 500 nm). The reduced plate height curves that were obtained for the different investigated markers all overlapped very well, and attained a minimum value of about h_min = 0.3 (reduction based on the pillar diameter), corresponding to 1.6 μm in absolute value and giving good prospects for high efficiency separations. The obtained reduced retention time values were in fair agreement with that predicted by the Di Marzio and Guttman model for a flow between flat plates, using the minimal interpillar distance as characteristic interplate distance.     

激光刻蚀硅表面的形貌及其对浸润性的影响

利用脉冲激光在Si表面刻蚀具有不同宽度和深度的微槽形貌, 通过测量接触角的大小研究其浸润特性, 并分析了形貌与浸润性的关系. 结果表明, 在Si表面刻蚀微槽深度一定的条件下, 刻蚀微槽宽度越宽, 接触角越小; 在Si表面刻蚀微槽宽度一定的条件下, 刻蚀微槽越深, 接触角越大, 最高可达165°. 而且Si表面上刻蚀后产生的细微尖峰结构对其浸润特性有显著的影响. 因此, 利用激光刻蚀表面方法可以在一定程度上调控固体表面的润湿性能.     

Hydrodynamic chromatography separations in micro- and nanopillar arrays produced using deep-UV lithography

We report on a series of hydrodynamic chromatography separations conducted in micropillar array columns with an interpillar distance spacing of, respectively, 1.00, 0.70, and 0.47 μm. The columns have been produced using state-of-the-art deep-UV lithography and deep reactive ion etching techniques. Despite the fact that the efficiency was smaller than theoretically possible (due to fabrication limitations and significant injection and detection band broadening), it was nevertheless possible to separate mixtures of fluorescein isothiocyanate (used as the t(0) -marker) and 20- and 40-nm polystyrene beads. With the smallest interpillar distance, a resolution of R(s) = 0.5 between the 20- and 40-nm particles could be obtained in 90s over a column length of 4 cm. The selectivity obtained in the pillar array columns was found to be very similar to that observed in packed-bed columns. By detecting the fluorescent signals in a 90-μm-deep detection groove at the end of the column, the signal-to-noise ratio could be enhanced up to 150 times.     

Photonic rubber sheets with tunable color by elastic deformation

This article describes an elastic silicone sheet with reversible tuning structural color. The sheet has a thin layer of cubic close-packed, ccp, colloidal particles embedded in poly(dimethylsiloxane), PDMS, elastomer. The array of ccp (111) planes diffracts light of selective wavelengths according to Bragg's law. This is responsible for the structural color of the PDMS sheet. Because the sheet was stretched in the horizontal direction, it was reduced in size in the vertical direction. As a result, the lattice distance of ccp (111) planes decreased, and the reflected wavelength of light shifted to shorter wavelengths. For example, the peak of reflection was tuned from 589 to 563 nm as a function of sheet elongation. The peak position decreased linearly with deformation when the deformation was within 20% of its elongation. Accordingly, the color of the PDMS sheet changed from red to green. When the mechanical strain on the PDMS sheet was released, the peak returned to its original position, and the color of the PDMS sheet also changed back to red. Tuning the color of the PDMS sheet is a reversible and repeatable process. The novel PDMS sheet has the potential to be applied to mechanical strain sensing.     

Characterization of watermarks formed in nano-carpet effect

In the spreading of a water droplet on an aligned silicon nanorod array surface, a precursor rim was detected moving ahead of the contact line. In this process, nanorods were bundled by the capillary force to form clusters, and a watermark developed on the surface after water evaporated. The size of the watermark, R(p)max, corresponding to the maximum radius of the precursor rim, followed a simple power law relationship with the volume of water droplet omega, R(p)max proportional to omega(beta). The scaling exponent beta increased when the nanorod height decreased, but all in the vicinity of 1/3. This behavior was attributed to the competition of evaporation and spreading of a water droplet during the spreading process. The size of the bundled nanorod cluster formed by the capillary force not only depended on the nanorod height but also on the location in the watermark. The cluster size almost remained as a constant near the center, and then it decreased with the distance from the center. This phenomenon can be qualitatively interpreted through the change of the total free energy during the precursor invading the nanorod array, by considering the contribution from the mechanical energy change due to the bending and clustering of nanorods.     

Analysis of the volatile compounds of Teucrium flavum L. subsp. flavum (Lamiaceae) by headspace solid-phase microextraction coupled to gas chromatography with flame ionisation and mass spectrometric detection

In this study, a headspace solid-phase microextraction (HS-SPME) method, in combination with gas chromatography flame ionisation detector and gas chromatography-mass spectrometry, has been developed for use in the analysis of the volatile compounds of Teucrium flavum L. subsp. flavum, a plant whose particular fragrance is used in the preparation of flavoured wines, bitters and liqueurs, or as a substitute for hops in the flavouring of beer. The tested fibres were 100?μm poly(dimethylsiloxane) (PDMS), the 65?μm PDMS/divinylbenzene (DVB) and 50/30?μm DVB-carboxen-PDMS. The best fibre was found to be PDMS when working in the following conditions: 60°C temperature, 30?min extraction time, 30?mg sample amount, 1?mm sample particle size. The HS-SPME method permitted the identification (95.8-97.8%) of 76 (dry) and 66 (fresh) different volatiles. In addition, we discovered that the presence of water in the sample can enhance the absolute quantity of alcoholic compounds such as 1-octen-3-ol and reduce the presence of esters such as methyl geranate.     

Micro-perforated elastomeric poly(dimethylsiloxane) mask fabricated using high-aspect-ratio micro-pillar arrays for spatially defined surface modification: an unconventional method for establishing a microarray platform

Herein, we introduce the fabrication of a micro-perforated elastomeric poly(dimethylsiloxane) (PDMS) mask and employ it for spatially defined surface modification. To fabricate the micro-perforated PDMS mask, high-aspect-ratio micro-pillar arrays having millimeter scale height were first fabricated via direct photopolymerization using a thiol–ene-based UV-curable adhesive. Square pillars (500 × 500 μm) and 200 μm circular pillars with 5 and 12.5 in the aspect ratios, respectively, were successfully fabricated with high pattern fidelity, reaching 2.5mm in height. Next, using the micro-pillar-array platform as a master mold, PDMS prepolymer was cast and polymerized to form an elastomeric PDMS mask having micro-perforation arrays. Alternating hydrophilic and hydrophobic surfaces were successfully obtained by oxidizing PDMS-covered Si wafer with corona discharge. Spatially defined chemical functionalities obtained by selective oxidation and subsequent silanization were clearly distinguished via colorimetric detection methods employing ninhydrin and toluidine reagents. The micro-perforated elastomeric PDMS mask enables selective modification of a surface without utilizing photoreactive chemicals and a photomask. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

An automated headspace solid-phase microextraction followed by gas chromatography–mass spectrometry method to determine macrocyclic musk fragrances in wastewater samples

A fully automated method has been developed for determining eight macrocyclic musk fragrances in wastewater samples. The method is based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatography–mass spectrometry (GC-MS). Five different fibres (PDMS 7 μm, PDMS 30 μm, PDMS 100 μm, PDMS/DVB 65 μm and PA 85 μm) were tested. The best conditions were achieved when a PDMS/DVB 65 μm fibre was exposed for 45 min in the headspace of 10 mL water samples at 100 °C. Method detection limits were found in the low ng L^?1 range between 0.75 and 5 ng L^?1 depending on the target analytes. Moreover, under optimized conditions, the method gave good levels of intra-day and inter-day repeatabilities in wastewater samples with relative standard deviations (n?=?5, 1,000 ng L^?1) less than 9 and 14 %, respectively. The applicability of the method was tested with influent and effluent urban wastewater samples from different wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed the presence of most of the target macrocyclic musks with, most notably, the maximum concentration of ambrettolide being obtained in WWTP A (4.36 μg L^?1) and WWTP B (12.29 μg L^?1), respectively. The analysis of effluent urban wastewater showed a decrease in target analyte concentrations, with exaltone and ambrettolide being the most abundant compounds with concentrations varying between below method quantification limit (<MQL) and 2.46 μg L^?1.