Droplet Precise Self-Splitting on Patterned Adhesive Surfaces for Simultaneous Multidetection

Precise separation and localization of microdroplets are fundamental for various fields, such as high-throughput screening, combinatorial chemistry, and the recognition of complex analytes. We have developed a droplet self-splitting strategy to divide an impacting droplet into predictable microdroplets and deposit them at preset spots for simultaneous multidetection. No matter exchange was observed between these microdroplets, so they could be manipulated independently. Droplet self-splitting was attributed to anisotropic liquid recoiling on the patterned adhesive surface, as influenced by the droplet Weber number and the width of the low-adhesive stripe. A quantitative criterion was also developed to judge the droplet self-splitting capability. The precise separation and distribution of microdroplets enabled simultaneous arrayed reactions and multiple analyte detection using one droplet of sample.     

Determinants for Fusion Speed of Biomolecular Droplets

Biomolecular droplets formed through phase separation have a tendency to fuse. The speed with which fusion occurs is a direct indicator of condensate liquidity, which is key to both cellular functions and diseases. Using a dual-trap optical tweezers setup, we found the fusion speeds of four types of droplets to differ by two orders of magnitude. The order of fusion speed correlates with the fluorescence of thioflavin T, which in turn reflects the macromolecular packing density inside droplets. Unstructured protein or polymer chains pack loosely and readily rearrange, leading to fast fusion. In contrast, structured protein domains pack more closely and have to break extensive contacts before rearrangement, corresponding to slower fusion. This molecular interpretation for disparate fusion speeds provides mechanistic insight into the assembly and aging of biomolecular droplets.     

Probe-Free Direct Identification of Type I and Type II Photosensitized Oxidation Using Field-Induced Droplet Ionization Mass Spectrometry

While Type I and Type II photosensitizers are often carefully tailored to achieve their respective advantages in treating different cancers, the identifications of the Type I and II mechanisms as such, the key reaction intermediates, and the consequent oxidation products of the substrates have never been easy. Using our unique home-built field-induced droplet ionization mass spectrometry (FIDI-MS) method that selectively samples molecules at the air–water interface, here we show the facile determination of both Type I and II mechanisms of a poster-child photosensitizer, temoporfin, without the addition of any probes. The unstable doublet radical resulting from the hydrogen abstraction by the triplet temoporfin through the Type I mechanism is captured, manifesting the in situ advantage of FIDI-MS. We anticipate that the method developed in this study can be widely utilized in the future designs of novel photosensitizers and the screening of their photosensitization mechanisms.     

Elemental analysis of silicon based minerals by ultrasonic slurry sampling electrothermal vaporisation ICP-MS

Ultrasonic slurry sampling electrothermal vaporisation inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) was applied to the elemental analysis of silicate based minerals, such as talc or quartz, without any pre-treatment except the grinding of the sample. The electrothermal vaporisation device consists of a tungsten coil connected to a home-made power supply. The voltage program, carrier gas flow rate and sonication time were optimised in order to obtain the best sensitivity for elements determined. The relationship between the amount of sample in the slurry and the signal intensity was also evaluated. Unfortunately, in all cases, quantification had to be carried out by the standard additions method owing to the strong matrix interferences. The global precision of the proposed method was always better than 12%. The limits of detection, calculated as three times the standard deviation of the blank value divided by the slope of the calibration curve, were between 0.5 ng/g for As and 3.5 ng/g for Ba. The method was validated by comparing the concentrations found for Cu, Mn, Cr, V, Li, Pb, Sn, Mg, U, Ba, Sr, Zn, Sb, Rb and Ce using the proposed methodology with those obtained by conventional nebulisation ICP-MS after acid digestion of the samples in a microwave oven. The concentration range in the solid samples was between 0.2 μg/g for Cr and 60 μg/g for Ba. All results were statistically in agreement with those found by conventional nebulisation.     

基于液滴微流控接口的高效液相色谱-毛细管电泳二维分离平台初探

蛋白质组体系的高度复杂性需要更高分辨率的多维分离技术。近年兴起的液滴技术在微纳尺度样品操控方面具有微体积、低扩散、无返混等独特优势,有望为多维分离平台的接口提供解决方案。通过采用不同结构的液滴微流控芯片可以实现“液滴生成”与“油相排除”功能,进行样品由连续流-非连续流-连续流的高效转移,将不同的分离模式进行二维耦联。本研究利用液滴作为接口技术耦联高效液相色谱与毛细管电泳构建二维分离系统,以蛋白质降解的复杂多肽混合物为样品,考察了液滴接口二维分离平台的可行性和有效性,并获得3000以上的峰容量,初步展示了该接口技术在多维分离分析领域的应用潜力。     

Pickering乳滴模板法制备超粒子结构有机/无机杂化微球

Pickering乳滴模板法制备有机/无机杂化的核壳微球越来越引起人们的关注,主要因为该方法制备出的微球具有以无机粒子为壳层的超粒子结构(supracolloidal structure),能够赋予微球独特的功能.胶体粒子在乳滴表面自组装形成有序的球面胶体壳,得到稳定Pickering乳液,固定乳滴表面的胶体粒子来制备核壳结构的微球或者以胶体粒子为壳层的微胶囊(colloidosome).本文综述了我们课题组以Pickering乳滴模板法制备超粒子结构有机/无机杂化微胶囊包括实心微球方面的工作.我们选择具有不同性能、种类的胶体粒子以及具有不同性质和功能的核材料,采用Pickering乳滴模板法,对吸附在乳滴表面的胶体粒子用不同的固定方法制备具有不同结构和性能的微球和微胶囊,利用基于多重Pickering乳液的聚合技术制备双纳米复合的超粒子结构多核聚合物微球.     

Directly suspended droplet microextraction with in injection-port derivatization coupled to gas chromatography-mass spectrometry for the analysis of polyphenols in herbal infusions, fruits and functional foods

A miniaturized liquid-phase extraction procedure based on directly suspended droplet microextraction is proposed for determining different classes of polyphenols. A derivatization reaction by means of in injection-port reaction with bis(trimethylsilyl)trifluoroacetamide is carried out to convert the polar non-volatile polyphenols into volatile derivatives. The separation and detection is carried out by coupling gas chromatography with mass spectrometry in the selected ion monitoring mode. The procedure uses undecanone, a low density organic solvent, and several factors influencing the extraction, collection efficiency and derivatization reaction are optimized. Excellent linearity was obtained for the range studied (0.05-500ngmL(-1)). The limits of detection are between 0.011 and 0.13ngmL(-1), depending on the compound, and the limits of quantification between 0.037 and 0.43ngmL(-1). The sensitivity and detection limits for polyphenols using the DSDME sample pretreatment method were very low. Enrichment factors are between 413 and 578. The recoveries obtained for spiked samples are satisfactory for all the compounds. The coupled miniaturized method is applied to the sensitive determination of both cis- and trans-resveratrol isomers, piceatannol, catechin, epicatechin, quercetin and fisetin in herbal infusions, fruits, juices and functional foods.     

毫秒激光烧蚀镍靶高效率制备NiO纳米立方体

利用长脉宽毫秒激光烧蚀浸没在循环水中的金属镍靶制备了大量的氧化镍(NiO)纳米立方体, 通过透射电子显微镜(TEM)、 选区电子衍射(SAED)、 X射线衍射(XRD)和能量色散谱(EDS)等手段表征了产物的形貌和结构. 结果表明, 高功率密度激光产生的高温高压条件是形成NiO纳米立方体的最重要因素. 激光功率密度高于10⁴ W/cm²时可以生成NiO纳米立方体, 当功率高于该阈值时激光首先将镍靶烧蚀为金属液滴, 高温的金属液体加热周围液体, 并由于液体的限制效应使得压力进一步升高, 最后金属液滴与液体发生表面反应生成NiO纳米立方体.     

Determination of chlorophenols in environmental water samples using directly suspended droplet liquid-liquid-liquid phase microextraction prior to high-performance liquid chromatography

A new sample preparation method named directly suspended droplet liquid-liquid-liquid phase microextraction was used in this research for determination of three chlorophenols in environmental water samples. The analytes (2-chlorophenol, 3-chlorophenol and 4-chlorophenol) were extracted from 4.5?mL acidic donor phase, (pH 2, P1) into an organic phase, 350?µL?of benzene/1-octanol (90?:?10 v/v, P2) and then were back-extracted into a 7?µL droplet of an basic (pH 13) aqueous solution (acceptor phase, P3). In this method, contrary to the ordinary single drop liquid-phase microextraction technique, an aqueous large droplet is freely suspended on the surface of the organic solvent, without using a microsyringe as supporting device. This aqueous microdroplet is delivered at the top-centre position of an immiscible organic solvent which is laid over the aqueous donor sample solution while the solution is being agitated. Then, the acceptor phase containing chlorophenols was withdrawn back into a HPLC microsyringe and neutralised by adding of 7?µL HCl 0.1?M. The total amount was eventually injected into the HPLC system with UV detection at 225?nm for further analysis. Parameters such as the organic solvent, phases volumes, extraction and back-extraction times, stirring rate and pH values were optimised. The calibration graphs are linear in the range of 10–2000?µg?L^?1 with r?≥?0.9973. The enrichment factors were ranged from 115 to 170, and the limit of detection (LOD, n?=?7) varied from 5 to 10?µg?L^?1. The relative standard deviations (RSDs, n?=?5) were found 6.8 to 7.4 at S/N?=?3. All experiments were carried out at room temperature, (22?±?0.5°C).     

Pipette vial dispersive liquid–liquid microextraction combined with high‐performance liquid chromatography for the determination of benzoylurea insecticide in fruit juice

A simple, sensitive, and efficient method of using a pipette vial to perform dispersive liquid–liquid microextraction based on the solidification of floating organic droplets was coupled with high‐performance liquid chromatography (HPLC) and a diode array detector for the preconcentration and analysis of four benzoylurea insecticides in fruit juice. In this method, 1‐dodecanol was used as an extractant, and a snipped pipette was used as an experimental vial to simplify the procedure of collecting and separating solidified extractant. The experimental parameters were optimized using a Plackett–Burman design and one‐factor‐at‐a‐time method. Under the optimal conditions in the water model, the limits of detection for analytes varied from 0.03 to 0.28 μg/L, and the enrichment factors ranged from 147 to 206. Linearity was achieved for diflubenzuron and flufenoxuron in a range of 0.5–500 μg/L, for hexaflumuron in a range of 1–500 μg/L, and for triflumuron in a range of 5–500 μg/L. The correlation coefficients for the analytes ranged from 0.9986 to 0.9994 with recoveries of 91.4–110.9%. Finally, the developed technique was successfully applied to fruit juice samples with acceptable results. The relative standard deviations of the analytes at two spiking levels (50 and 200 μg/L) varied between 0.2 and 4.5%.