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PNAS Nexus · 2023 ·Vol. 2 ·期 11 · IF 0

Prebiotic synthesis of mineral-bearing microdroplet from inorganic carbon photoreduction at air–water interface

Ge Qiuyue,Liu Yangyang,You Wenbo,Wang Wei,Li Kejian,Ruan Xuejun,Xie Lifang,Wang Tao,Zhang Liwu

The origin of life on Earth is an enigmatic and intricate conundrum that has yet to be comprehensively resolved despite recent significant developments within the discipline of archaeology and geology. Chemically, metal-sulfide minerals are speculated to serve as an important medium for giving birth in early life, while yet so far direct evidence to support the hypothesis for the highly efficient conversion of inorganic carbon into praxiological biomolecules remains scarce. In this work, we provide an initial indication that sphalerite, employed as a typical mineral, shows its enormous capability for promoting the conversion of inorganic carbon into elementary biomolecule formic acid (HCOOH) in airborne mineral-bearing aerosol microdroplet, which is over two orders of magnitude higher than that of the corresponding conventional bulk-like aqueous phase medium in the environment (e.g. river, lake, sea, etc.). This significant enhancement was further validated by a wide range of minerals and clays, including CuS, NiS, CoS, CdS, MnS, elemental sulfur, Arizona Test Dust, loess, nontronite, and montmorillonite. We reveal that the abundant interface of unique physical–chemical features instinct for aerosol or cloud microdroplets reduces the reaction energy barrier for the reaction, thus leading to extremely high HCOOH production (2.52 × 1014 kg year−1). This study unfolds unrecognized remarkable contributions of the considered scheme in the accumulation of prebiotic biomolecules in the ancient period of the Earth.

研究领域: 化学 · 生物学 · 地球科学
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2016 · IF 2.822

Voltammetric and microscopical investigation of the properties and behaviors of individual mercury micro-droplets

Cheng Liu,Wenxue Cheng,Qiang Zeng,Xinjian Huang,Lishi Wang

Mercury film modified electrode based stripping voltammetry has become a rapid and low cost method in routine trace element environmental analysis . However, the understanding of the physical and chemical properties of the plated mercury film still needs to be enhanced till now. It has been recognized that the so-called mercury film actually consists of numerous micro mercury droplets, so it is of significant importance to directly investigate the properties and behaviors associated with the individual droplet. Thus, a platinum ultramicroelectrode was used as the substrate for mercury plating, and only one mercury droplet is formed under this condition. Herein, Fourier Transformed Sinusoidal Voltammetry (FTSV) was employed to investigate both the growth process of a mercury droplet and the behaviors of the droplet after plating. Meanwhile, an optical microscope was used to provide direct visual observation. Investigation suggests that: (a) Both the gradual growth process and the fast coalescence event of individual mercury droplet can be resolved with FTSV; (b) The plated mercury droplet can be partially oxidized immediately after the disconnection between the working electrode and the potentiostat in some circumstances, e.g. the presence of trace amount of chloride ion . The present study not only sheds new light on the properties of mercury film electrode but also demonstrates the feasibility of employing FTSV as a new tool for the characterization of micrometer or even nanometer sized particles.

CAS / MDL: 10045-94-0
研究领域: 分析化学 · 环境科学
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Analytical Methods · 2024 · IF 2.7

NIR light-triggered bursting of double-emulsion drop (DED) for micro-droplets generation

Zhaoze Lu,Jian Yu,Kaihua Wang,Wei Cheng,Likai Hou

Micro-droplets have significant applications in microbiologies, pharmaceuticals, cosmetics, and synthetic materials. Here, we present for the first time a near-infrared (NIR) light-triggered double-emulsion drop (DED) bursting method for generating a large number of micro-droplets in several micron. Under the irradiation of NIR light, the inner water phase of the DED containing a trace amount of Prussian blue (PB) rapidly heats up and evaporates rapidly to generate microbubbles due to the photothermal property of PB. By controlling the light intensity, the DED can inflate itself by coalescing these constant microbubbles to burst immediately and tear the middle oil phase to form a large number of micro-droplets. The performance of micro-droplets generated by NIR light-triggered DED bursting is investigated at different oil shell thickness (HO), oil phase viscosity (ηO) and oil type. HO and ηO are both key factors affecting the generation of micro-droplets. DED with lower HO and ηO can generate lower polydispersity and large quantity of micro-droplets by NIR-triggered DEDs bursting. The proportion of micro-droplets below 10 μm can reach up to 95%. Furthermore, camellia oil, as middle oil phase of DEDs, also can be used to generate lower polydispersity and large quantity of micro-droplets in several micron. The presented bursting method has a great potential to generate micro-droplets for micro/nano and biotechnology applications.

CAS / MDL: 38215-36-0
研究领域: 微生物学 · 药学 · 合成材料科学 · 生物技术
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SENSORS AND ACTUATORS B-CHEMICAL · 2017 · IF 5.401

Detecting enzymatic reactions in penicillinase via liquid crystal microdroplet-based pH sensor

Yan Wang,Liyuan Zhao,Aojie Xu,Lei Wang,Lingli Zhang,Shuangqiang Liu,Yongjun Liu,Hanyang Li

We report a liquid crystal (LC) microdroplet-based pH sensor and explore its application for detecting enzymatic reactions in penicillinase. Nematic LC 4-cyano-4'-pentylbiphenyl (5CB) microdroplet, doped with 4'-pentyl-biphenyl-4-carboxylic acid (PBA), is produced in phosphate buffer solution (PBS) with a tapered capillary microtube connected to a syringe pump. The PBA-doped 5CB microdroplets exhibit configuration transitions from bipolar to radial as PBS pH values increase from 5.7 to 6.0. These pH-induced changes in optical appearance are experimentally verified and attributed to the deprotonation of PBA at the aqueous/LC interface. We also examine the feasibility of the PBA-doped 5CB microdroplets as optical microcavities of whispering gallery modes (WGMs). Typical WGM lasing emission is observed in micrometer-sized microdroplets under a pulse laser pump. The WGM spectrum from the microdroplet responds to pH variations, reflecting as a spectral redshift as the pH decreases. The PBA-doped 5CB microdroplet can be successfully exploited accordingly for detecting enzymatic reactions in penicillinase. We demonstrate that the detectable shifts in WGM spectra associated with the microdroplet configuration transitions can serve as an indicator of the H + released from the enzymatic reaction.

研究领域: 生物化学 · 分析化学 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Ultrasound enhancing the mass transfer of droplet microreactor for the synthesis of AgInS2 nanocrystals

Zongbo Zhang,Kai Wang,Changbin Xu,Yu Zhang,Wenting Wu,Changhe Lu,Wengang Liu,Yunlong Rao,Chen Jiang,Chunling Xu,Shiliang Song

Droplet microreactors are powerful tools for synthesizing chemicals, nano materials and biomolecules, but traditional methods, such as mechanical stirring, are hard to enhance the internal mass transfer of droplet microreactor due to its small reaction space. In this study, we propose a novel ultrasonic-enhancing method for droplet microreactor, and report the effect of bubbles inside micro-droplets for the first time. On this basis, the synthesis of AgInS 2 nanocrystals is selected as model reaction to study the enhancement mechanism. It is discovered that the flow field in micro-droplet is significantly improved owing to acoustic streaming and cavitation microstreaming. Benefiting from them, the mass transfer coefficient is enhanced by 72.5 %, and AgInS 2 nanocrystals are successfully synthesized with smaller, more uniform particle size, as well as more adjustable performance compared with no ultrasonic radiation condition. This work provides a new method and a deep insight of ultrasound enhancing droplet microreactor, enabling the continuous production of fine chemical synthesis.

研究领域: 化学工程 · 纳米材料科学 · 生物技术
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Journal of Energy Chemistry · 2025 · IF 14.9

Nitrate synthesis from charged water microdroplets and dinitrogen

Yingfeng Wu,Zhendong Luo,Yifan Yang,Jianhan Wu,Xiuquan Jia,Feng Wang

Nitrate synthesis is an important process for agriculture and industry, but suffers from energy-intensive steps including the synthesis and subsequent oxidation of ammonia. Herein, we present a selective N 2 transformation to nitrate by guiding the charge neutralization of self-electrified water microdroplets in an artificial cloud generated with the portable ultrasonic atomizer. The electron and ion transfer in the charge neutralization of water microdroplets on metal micromesh enables an up to ∼40-fold increase in the reactivity of nitrate formation reaction driven by ultrasonic energy. A robust semi-continuous N 2 oxidation by a Ni-mesh-screened cloud system was achieved, providing nitrate with ∼12 mM concentration every 20 h. These findings emphasize the potential of harnessing the microdroplet-mediated cloud electrochemistry of N 2 in decentralizing the current mass production of fertilizer.

CAS / MDL: 7440-02-0
研究领域: 化学 · 环境科学 · 农业科学
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ADVANCED FUNCTIONAL MATERIALS · 2018 ·Vol. 28 ·期 10 ·1705699 · IF 13.325

In Situ Self-Assembly of Coacervate Microdroplets into Viable Artificial Cell Wall with Heritability

Dongyue Su,Xiaoman Liu,Lina Liu,Lei Wang,Hui Xie,Hao Zhang,Xianghe Meng,Xin Huang

Creating an intelligent artificial cell wall to endow fabricated cells with more advanced functionalities is highly desirable. Here, an efficient and cytocompatible approach to generate a type of viable artificial cell wall based on direct self-assembly of coacervate microdroplets on individual cellular surface is developed, which can protect the fabricated cell against various external stresses and can then prolong the storage of the fabricated cells over two months. Moreover, as a type of viable artificial cell wall, it can not only help the fabricated cell sequester nutrients or functionalized substances such as catalase, or iron oxide nanoparticles actively from the solution which then makes the fabricated cell more versatile but also allows the fabricated cell proliferate. Significantly, the artificial cell wall also shows heritable behavior that can reserve its protection to as far as the third-generation daughter cell. Undoubtedly, such an illustrated artificial cell wall provides a conceptually new and promising technique toward the cell-based research as well as application of next generation.

研究领域: 合成生物学 · 细胞工程 · 材料科学
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TALANTA · 2019 · IF 4.916

Real-time, quantitative and sensitive detection of urea by whispering gallery mode lasing in liquid crystal microdroplet

Rui Duan,Yanzeng Li,Bojian Shi,Hanyang Li,Jun Yang

In this study, we demonstrate a novel nematic liquid crystal (LC) 4-cyano-4′-pentylbiphenyl (5CB) microdroplet-based biosensor for real-time, quantitative and sensitive detection of urea by whispering gallery mode (WGM) lasing technology. The single stearic acid-doped 5CB microdroplet is taken as both optical resonator and sensing reactor. To the best of our knowledge, this work is the first report of urea detection with WGM lasing. The enzymatic reaction between urea and urease produces hydroxide ions. Deprotonation and self-assembly of stearic acid occur at the aqueous/LC interface with increased pH value, promoting the reorientation of LC molecules. The detectable shift of WGM lasing spectra related to the configuration transition of LC microdroplets can be used as an indicator of enzymatic reaction, and this allows detection of urea molecules by the sensor at a concentration of only 0.1 mM. The proposed sensor also demonstrated the ability to detect urea in real urine samples. Compared with conventional POM observations, monitoring and identification of lasing spectra from LC microdroplets as a versatile method allow for more quantitative and sensitive detection of analyte reactions and can be expected to replace POM imaging technology for current LC-based biosensor systems.

研究领域: 生物传感 · 光学检测 · 分析化学
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ANALYTICAL CHEMISTRY · 2022 · IF 8.008

Defined Ion-Transfer Voltammetry of a Single Microdroplet at a Polarized Liquid/Liquid Interface

Yamin Ma,Cheng Liu,Lishi Wang

A strategy for the fast analysis of ion transfer/facilitated ion transfer toward a tiny (femtoliter) water-in-oil droplet has been established. This scenario is embodied by the fusion of a w/o microdroplet at the micro liquid/liquid (L/L) interface, with the use of Fourier transform fast-scan cyclic voltammetry (FT-FSCV) to express the apparent half-wave potentials of anions or cations encapsulated inside the w/o microdroplet. First, the half-wave potential is in strict accordance with the transfer Gibbs free energy of either cations or anions. Second, the half-wave potential has been found to be positively proportional to the logarithmic concentration of ions, shedding thermodynamic insight into ion transfer. Third, as an instance of multivalent biopolymers, the transfer of protamine inside the single w/o microdroplet has been investigated. Obvious discrepancies in the behaviors of the fusion impacts at different pH, as well as in the absence and presence of the cationic surfactant DNNS–, are revealed. The internal mechanism of protamine transfer has been thoroughly investigated. This work proposes a strategy to sensitively and quickly determine the transfer Gibbs energy and the concentration of ions encapsulated in a single microdroplet, and it provides the possibility of analyzing the interfacial transfer properties of trace biomacromolecules inside an aqueous micro- or nanoscale droplet.

研究领域: 分析化学 · 生物化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2025 · IF 9.7

Real-time probing of fast chemical reactions at the oil/water interface during microdroplet generation

Xiao Liang,Jiyizhe Zhang,Kunlun Gao,Huizhi Wang,Kai Wang,Guangsheng Luo

Hypothesis Probing the interfacial reactions during microdroplet generation is experimentally challenging, limiting the understanding of the reaction dynamics at an early stage. Real-time monitoring of the temporal evolution of interfacial tension offers a quantitative approach for probing interfacial reactions and reveals the reaction rate-control mechanisms governing the interfacial reaction process. Experiments An automated microfluidic platform is developed to monitor the dynamic interfacial tension during microdroplet generation within a second, using oleic acid (HOA) and sodium hydroxide (NaOH) as a representative reaction system. The evolution of interfacial concentration of the reaction product is quantified by experiments using various reactant concentrations and flow rates, allowing for identifying the rate-control mechanisms. Findings The reactions are identified to be mass transfer-controlled or adsorption-controlled at different HOA concentrations with high NaOH/HOA concentration ratios, enabling the determinations of mass transfer boundary layer thickness and adsorption rate constant of HOA. A modified Damköhler number is introduced to characterize the transition between the rate-control mechanisms. Up to one-third of HOA in microdroplets is found to be consumed during the generation stage within one second, and smaller droplets exhibit higher consumption proportions.

研究领域: 化学工程 · 界面科学
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MACROMOLECULAR CHEMISTRY AND PHYSICS · 2016 ·Vol. 218 ·期 2 ·1600422 · IF 2.495

Phase-Separation-Induced Formation of Janus Droplets Based on Aqueous Two-Phase Systems

Hao Yuan,Qingming Ma,Yang Song,Matthew Y. H. Tang,Yau Kei Chan,Ho Cheung Shum

In this study, Janus droplets are fabricated by inducing phase separation of single-phase droplets made up of an aqueous two-phase system (ATPS). The resultant Janus droplets are highly monodisperse in structures and internal morphologies. Due to the affinity partitioning properties of ATPS, encapsulated ingredients can automatically partition into different compartments of the resultant Janus droplets. The use of biocompatible and cytocompatible ATPS also enables the encapsulation of enzymes and cells in the resultant droplets with their activity preserved at a relatively high level.

研究领域: 生物工程 · 材料科学 · 细胞生物学
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FUEL · 2018 · IF 4.908

Hyperbranched poly(amido amine) demulsifiers with ethylenediamine/1,3-propanediamine as an initiator for oil-in-water emulsions with microdroplets

Lifeng Zhang,Hao Ying,Shu Yan,Ningning Zhan,Yongsheng Guo,Wenjun Fang

Two kinds of hyperbranched poly(amido amine) (h-PAMAM) with abundant terminal amine groups are synthesized to break the oil-in-water (O/W) emulsions consisting of microdroplets. The demulsification performance of h-PAMAM is systematically evaluated with assistance of UV–vis spectra, micrograph, DLS and SAXS analyses. The demulsifier with 1,3-propanediamine as initiator shows a striking demulsification ability with small dosage (<40 mg/L). The demulsification equilibrium can be obtained within 30 min, and oil removal ratio reaches to 92%, which is ascribed to the highly hyperbranched structure and the adequate molecular weight. The demulsifier molecules with hyperbranched structure easily diffuse to the oil-water interface and reveal a high interfacial activity, which causes film break and coalescence of oil droplets, and consequently leads to high oil removal ratio. The combination of UV–vis spectra, micrograph, DLS and SAXS analyses provides a new approach to monitor demulsification process and comprehend demulsification mechanism. The excellent demulsification performance of h-PAMAM shows a considerable potential applications of this hyperbranched polymer for wastewater treatment and petroleum industry.

研究领域: 化学工程 · 环境科学 · 石油工业
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