Continuous Flow Reactor for the Controlled Synthesis and Inline Photocatalysis of Antibacterial Ag2S Nanoparticles

The present study is focused on the integration of microreactors to synthesize visible light active nanophotocatalysts for inline photocatalytic degradation of organic dye and antibacterial activity. A wire-assisted and a rapid laser micromachining technique has been employed for the fabrication of polydimethylsiloxane (PDMS) and poly(methyl methacrylate) (PMMA)-based microreactors, respectively. By varying the design and chemical reagents involved, different sizes of visible light active Ag₂S nanoparticles were prepared via a continuous microfluidics approach using fabricated microreactors. When polyvinylpyrrolidone (PVP) was utilized as the capping agent during the reaction, smaller particles of the size of ~ 15 nm were observed. The photocatalytic performance of these nanoparticles has been evaluated inline by employing the single-inlet planar microreactor as a function of flow rate and channel length. The photocatalyst durability test and a comparative photocatalytic efficiency study between the microreactor and the conventional beaker reactor have also been carried out. Under visible light, these nanoparticles exhibit a remarkable enhancement of ~ 94.5% in the inline microreactor-based photocatalytic degradation of methylene blue dye. The slower the flow rate and longer the channel length, gradual enhancement in the performance has been observed. Also, these nanoparticles express an antibacterial effect with very high efficacy even at very low (2 mg mL⁻¹) concentration toward the inhibition of Escherichia Coli.     

一种可逆键合电泳微芯片的制作及在蛋白质分离中的应用

阐述了一种可逆键合电泳微芯片的制作方法, 以及电泳微芯片在蛋白质分离、临床尿蛋白检测方面的应用. 用标准光刻腐蚀技术在石英基片上腐蚀泳道, 清洗腐蚀好的基片和盖片后, 在真空条件下实现键合. 此种方法键合制作的电泳微芯片可重复键合使用, 制得的电泳微芯片成功地用于标准蛋白质分离以及临床尿蛋白分析.     

Glucose microfluidic biosensors based on immobilizing glucose oxidase in poly(dimethylsiloxane) electrophoretic microchips

Here we reported a novel microfluidic biosensor with an on-column immobilized enzyme microreactor. The fabrication approach of this biosensor is simple and the enzyme microreactors with controlled sizes can be placed at any desired position on the microchip. Taking glucose oxidase (GOx) as an example, electroosmotic flow (EOF) as a driving force and amperometry as a detection method, the performance of biosensors were modulated by changing the length of enzyme reactor from 0.5 cm to 3 cm, and the linear ranges were changed from 0-8.0 mM to 0-30.0 mM with the detection limits from 42 microM to 6.5 microM. The enzyme reactor remained its 65% activity after 23 days storage. It also showed good anti-interference ability and was used to quantify glucose in human serum samples.     

Microarrays by structured substrate swelling

A technique is presented for manufacturing surface microstructures on polymer substrates. It is based on the uptake of solvent vapors by a prestructured polymer, selective swelling, and the flow of the softened polymer. Prestructuring is done by evaporating material, UV illumination, or ion bombardment through a mask. As an application we describe the fabrication of two-dimensional ordered arrays of microvessels which can be of different shape, size, and material. The bottom of the microvessels can be functionalized by several means and it can be transparent to allow for optical analysis. Applications of the microvessel array are seen in combinatorial chemistry, as microreactors, and as confined spaces for controlling crystal growth.     

A low-cost, disposable card for rapid polymerase chain reaction

A low-cost, disposable card for rapid polymerase chain reaction (PCR) was developed in this work. Commercially available, adhesive-coated aluminum foils and polypropylene films were laminated with structured polycarbonate films to form microreactors in a card format. Ice valves [1] were employed to seal the reaction chambers during thermal cycling and a Peltier-based thermal cycler was configured for rapid thermal cycling and ice valve actuation. Numerical modeling was conducted to optimize the design of the PCR reactor and investigate the thermal gradient in the reaction chamber in the direction of sample thickness. The PCR reactor was experimentally characterized by using thin foil thermocouples and validated by a successful amplification of 10 copy of E. coli tuf gene in 27 min.     

Conformally anchoring nanocatalyst onto quartz fibers enables versatile microreactor platforms for continuous-flow catalysis

Continuous-flow microreactors offer increased reactivity and reusability via unique reaction pathways to address a wide range of practical nanocatalysis problems. However, only limited platforms exist to employ these microreactors for versatile nanocatalytic reactions. In this work, we conformally anchored nickel oxide(Ni O) nanosheets onto quartz fibers(QFs), which exhibited a high catalytic activity using the hydrogenation of 4-nitrophenol(4-NP) as a model reaction in a batch reaction study. More importantly, we demonstrated that fiber-based QF@Ni O composites(e.g., cotton, fabric, belt, felt) can be integrated as versatile platforms to develop microreactors for continuous-flow catalytic applications including hydrogenation reactions and dyecatalyzed degradation. This fiber-based three-dimensional(3 D) nanocatalyst architecture effectively drives continuous-flow catalytic reactions with unprecedented efficiency due to the easy diffusion of reactant molecules into the fibrous structure,allowing contact with catalytic active sites. Our approach to continuous-flow microreactor design uses surface hybridization as a guideline to immobilize nanocatalysts onto the QFs. These QF-based platforms, coupled with rational design, are expected to be applied to a wide range of nanocatalytic reactions.     

Organic vapor sensing properties and characterization of α-naphthylmethacrylate LB thin films

Determination of organic vapor sensing properties of α-Naphthylmethacrylate (α-NMA) monomer based Langmuir-Blodgett (LB) thin films was aimed in this study. LB thin film fabrication was performed on quartz glass and quartz crystal substrates in order to investigate the characterization and organic vapor properties of α-NMA materials by using UV-Visible, Atomic Force Microscopy (AFM) and Quartz Crystal Microbalance (QCM) techniques. π-A isotherm graph was taken and a suitable surface pressure value were primarily determined as 13?mN m^?1 for successful α-NMA LB thin film fabrication. Transfer ratio value was found to be ≥ 0.93 for quartz glass and quartz crystal substrates. The typical frequency shift per layer was obtained as 16.93?Hz/layer and the deposited mass onto a quartz crystal was calculated as 271.30?ng/layer (1.02?ng mm^?2). The sensing responses of α-NMA LB films against dichloromethane, chloroform, toluene and m-xylene were measured by QCM system. Dichloromethane created the maximum shift in the resonance frequency than other organic vapors used in this study. Results exhibited that α-NMA LB thin films were potential candidates for organic vapor sensing applications, especially high sensitive detection of dichloromethane at room temperature.     

Highly sensitive biomolecular fluorescence detection using nanoscale ZnO platforms

Fluorescence detection is currently one of the most widely used methods in the areas of basic biological research, biotechnology, cellular imaging, medical testing, and drug discovery. Using model protein and nucleic acid systems, we demonstrate that engineered nanoscale zinc oxide structures can significantly enhance the detection capability of biomolecular fluorescence. Without any chemical or biological amplification processes, nanoscale zinc oxide platforms enabled increased fluorescence detection of these biomolecules when compared to other commonly used substrates such as glass, quartz, polymer, and silicon. The use of zinc oxide nanorods as fluorescence enhancing substrates in our biomolecular detection permitted sub-picomolar and attomolar detection sensitivity of proteins and DNA, respectively, when using a conventional fluorescence microscope. This ultrasensitive detection was due to the presence of ZnO nanomaterials which contributed greatly to the increased signal-to-noise ratio of biomolecular fluorescence. We also demonstrate the easy integration potential of zinc oxide nanorods into periodically patterned nanoplatforms which, in turn, will promote the assembly and fabrication of these materials into multiplexed, high-throughput, optical sensor arrays. These zinc oxide nanoplatforms will be extremely beneficial in accomplishing highly sensitive and specific detection of biological samples involving nucleic acids, proteins and cells, particularly under detection environments involving extremely small sample volumes of ultratrace-level concentrations.     

Novel quartz flow-cell as a post-column photochemical reactor for high-performance liquid chromatography

The construction of a new post-column photochemical reactor with quartz flow cells in series for high-performance liquid chromatography (HPLC) is described. The performance of the new reactor was compared with a conventional open tubular PTFE coil reactor. The sensitivity, accuracy and precision obtained with both reactors are comparable. The new reactor has the obvious advantages of smaller cell volume as well as inertness and resistance to not only light and heat produced by the UV lamp, but also to organic solvents in the mobile phases, which results in greatly improved durability, reduced peak broadening and shorter chromatographic run times. Application of the new reactor to the fluorescence detection of DU-6859a, a new fluoroquinolone antimicrobial agent, in human serum is reported.     

Fabrication of quartz microchips with optical slit and development of a linear imaging UV detector for microchip electrophoresis systems

We have developed quartz microchips for electrophoresis and a linear imaging UV detector along with the microchip. The microchips have an optical slit, which cut off the stray light in order to improve the sensitivity of UV absorption detection on the chip, at the bonding interface. They have been successfully fabricated on synthesized quartz glass substrates using the hydrofluoric acid (HF) solution bonding method. The signal level of UV absorption detection was effectively improved by applying microchips with the "on-chip" optical slit. It is also possible to improve the signal-to-noise ratio by repetitive scanning of linear photodiode array located along the separation channel, and signal averaging during elimination of the potential. Furthermore, the analysis may be performed until the separation of the target component is complete, because the real-time migration pattern of each component in the sample can be seen just as in a slab-gel electrophoresis, thus enabling a shorter analysis time.     

A new soft lithographic route for the facile fabrication of hydrophilic sandwich microchips

Manufacturing materials are an essential element for the fabrication of microfluidic chips. PDMS, the most widely used polymeric material, is associated with apparent disadvantages such as hydrophobic nature, while other materials also suffer from some limitations. In this paper, a new soft lithographic route was proposed for the facile manufacturing of hydrophilic sandwich microchips, using bisphenol A based epoxy acrylate (BABEA) as a new patterning material. The BABEA copolymers are hydrophilic, highly transparent in visible range while highly untransparent when the wavelength is less than 290 nm, and of high replication fidelity. By combining with appropriate monomers, including glycidyl methacrylate, methylmethacrylate, and acrylic acid, the copolymers contain active functional groups, which allows for easy postmodification for desirable functional units. A fabrication procedure was proposed for manufacturing hybrid quartz/BABEA copolymer/quartz microchips. In the procedure, no micromachining equipments, wet etching, or imprinting techniques were involved, making the fabrication approach applicable in ordinary chemistry laboratories. The performance of the prepared microchips was demonstrated in terms of CIEF with UV-whole channel imaging detection. The hydrophilic microchannel ensures stable focusing while the polymeric middle layer acts as a perfectly aligned optical slit for whole channel UV absorbance detection.     

Integrated microfluidic UV absorbance detector with attomol-level sensitivity for BSA

An integrated UV absorbance detection system employing a novel silicon-in-plastic technology to seamlessly integrate bare UV photodiode chips into polymer microfluidic systems has been developed. Detection platforms fabricated using this approach exhibit exceptionally low concentration and mass detection limits down to 15 nM and 9.8 amol, respectively, for bovine serum albumin (BSA) as a model protein. In addition to providing high sensitivity, sub-nanoliter detection volumes are enabled by the use of direct photodiode integration. The fabrication methodology is detailed, and system performance metrics including detection limits, detection volume, dynamic range, and linearity are reported.     

Immobilization of silver nanoparticles into POEGMA polymer brushes as SERS‐active substrates

Surface‐enhanced Raman scattering (SERS) has attracted a great deal of interest during the past four decades and emerged as an ultrasensitive optical technique for chemical and biomedical analysis. It is widely accepted that the facile fabrication of SERS substrates with high activity and good reproducibility is of crucial importance for their applications. Herein, we report on a fast and robust method for the synthesis and immobilization of silver nanoparticles (AgNPs) into poly(oligo(ethylene glycol) methacrylate) (POEGMA) brushes under mild conditions without using any reducing agents. POEGMA brushes of different chain lengths were synthesized directly on silicon wafers by surface‐initiated atom transfer radical polymerization with various reaction time. X‐ray photoelectron spectroscopy and field emission scanning electron microscope measurements indicated that the AgNPs were firmly and homogeneously embedded into POEGMA brushes. The resulting POEGMA–AgNP hybrid films were employed as SERS substrates for the detection of 4‐aminothiophenol, giving rise to an enhancement factor of up to 1.9 × 10⁶. The influence of the POEGMA's chain length on SERS performance was also investigated. Copyright © 2016 John Wiley & Sons, Ltd.     

Hybrid electro-optical nanosystem for neurons investigation

The scope of this paper is development of a new laboratory-on-a-chip (LOC) device for biomedical studies consisting of a microfluidic system coupled to microelectronic/optical transducers with nanometric features, commonly called biosensors. The proposed device is a hybrid system with sensing element on silicon (Si) chip and microfluidic system on polydimethylsiloxane (PDMS) substrates, taking into accounts their particular advantages. Different types of nanoelectrode arrays, positioned in the reactor, have been investigated as sensitive elements for electrical detection and the recording of neuron extracellular electric activity has been monitorized in parallel with whole-cell patch-clamp membrane current. Moreover, using an additional porosification process the sensing element became efficient for optical detection also. The preliminary test results demonstrate the functionality of the proposed design and also the fabrication technology, the devices bringing advantages in terms enhancement of sensitivity in both optoelectronic detection schemes.     

Ceramic microreactors for on-site hydrogen production from high temperature steam reforming of propane

The steam reforming of hydrocarbon fuels is a promising method for the production of hydrogen for portable electrical power sources. A suitable reactor for this application, however, must be compatible with temperatures above 800 degrees C to avoid coking of the catalytic structures during the reforming process. Here, ceramic microreactors comprising high surface area, tailored macroporous SiC porous monoliths coated with ruthenium (Ru) catalyst and integrated within high-density alumina reactor housings were used for the steam reforming of propane into hydrogen at temperatures between 800 and 1000 degrees C. We characterized these microreactors by studying C3H8 conversion, H2 selectivity, and product stream composition as a function of the total inlet flow rate, steam-to-carbon ratio (S/C), and temperature. As much as 18.2 sccm H2, or 3.3 x 104 sccm H2 per cm3 of monolith volume, was obtained from a 3.5 sccm entering stream of C3H8 at a S/C of 1.095 and temperatures greater than 900 degrees C. Operating at a S/C close to 1 reduces the energy required to heat excess steam to the reaction temperature and improves the overall thermal efficiency of the fuel processor. Kinetic analysis using a power law model showed reaction orders of 0.50 and -0.23 with respect to propane and steam, respectively, indicating that the rate limiting step in the steam reforming reaction is the dissociative adsorption of propane on the Ru catalyst. The performance of the microreactor was not affected after exposure to more than 15 thermal cycles at temperatures as high as 1000 degrees C, and no catalyst deactivation was observed after more than 120 h of continuous operation at 800 degrees C, making these ceramic microreactors promising for efficient on-site hydrogen production from hydrocarbons for use in polymer electrolyte membrane (PEM) fuel cells.     

Site-selective direct photochemical deposition of copper on glass substrates using TiO2 nanocrystals

Deposition of copper thin films was achieved by a photocatalytic reaction of site-selectively adsorbed TiO(2) nanocrystals for direct fabrication of copper circuit patterns on glass substrates. The nanocrystal monolayers absorbed on hydrophobic surface templates serve as an effective photocatalyst, producing metallic copper and formic acid via oxidation of methanol in solution. The formic acid generated has also been suggested to serve as an electron donor that accelerates copper deposition through a UV-mediated autocatalytic reaction, even after nanocrystals are embedded into the grown copper films. The thickness of the deposited copper films was easily controlled by varying the UV irradiation time, irradiation power, and initial concentration of methanol as a hole scavenger. The process presented herein provides an effective methodology for resist-free, direct metallization of insulating substrates.     

Pile-up glass microreactor

We made a 'pile-up' microreactor in which ten levels of microchannel circuits were integrated to form a single glass entity. Solutions were distributed to each layer via cylindrical holes with a diameter much larger than that of the microchannel. Fabrication of the pile-up reactor was completed using only conventional photolithography, wet etching and thermal bonding techniques, and no special facilities or instruments were required. An amide formation reaction between amine in aqueous solution and acid chloride in organic solution was carried out using the pile-up reactor. The yield of the amide formation reaction is dependent on the size of the specific surface area between the two solutions, and the small space inside the microchannels is good for acquiring a large specific surface area without any stirring processes. The maximum throughput for the ten-layered pile-up reactor was ten times larger than that of a single-layered one, yet the reaction yield was still high. Productivity of the pile-up reactor for the reaction was as high as on a gram per hour scale. This value suggests that many conventional plants producing fine chemicals can be replaced by microreactors through the numbering-up technology.     

纳米沸石修饰微通道反应器内固定化酶催化的水解反应动力学

通过在毛细管内层叠层组装纳米沸石并固定脂肪酶来构建纳米沸石修饰的固定化酶微反应器通道,将纳米沸石良好的生物相容性和高的酶固定能力与微反应器反应效率高、扩散传质快等优点相结合. 以对硝基苯棕榈酸酯的水解作为探针反应对该微反应器内固定化酶催化水解反应动力学进行了研究和计算,并与普通反应器内同样的反应进行比较. 通过对比米氏方程参数,证实在微反应器内酶催化水解反应效率可比普通反应器内提高3倍以上并可提高酶和反应底物的亲和能力.     

Development of a multireactor microfluidic system for the determination of DNA using real-time polymerase chain reaction

A microfluidic system that allowed us to perform the real-time polymerase chain reaction (PCR) in a glass-silicon microchip containing nine 250-nL microreactors was developed and studied. The resulting high heating/cooling rates of a PCR mixture in a microreactor allowed us to optimize the amplification mode (1 min/cycle). The silicon surface of microreactors was successfully passivated. The resulting analytical system allowed us to measure the PCR kinetic curves in chip microreactors at a DNA concentration of ～5 × 10⁴ copies per microreactor. It was found that, if the PCR is performed in a microchip with real-time detection using the optimized amplification mode, the result can be obtained 13–14 min after the onset of reaction.     

Surface modification of polymers by photoinitiated graft polymerization

Two methods for modification of polymer surfaces by photoinitiated grafting have been developed and applied to films and fibers of synthetic polymers, e.g. polyethylene and polypropylene with acrylic monomers. In the batch process the substrate is enclosed in a cell containing initiator and monomer vapor. UV light through a quartz window initiates the grafting reaction by exciting the initiator (e.g. benzophenone). The grafting reaction is slow (1 to 3 min) due to the inefficient transfer of initiator and monomer through vapor phase. In the continuous process the substrate is presoaked in a solution of initiator and monomer and then drawn into a reactor “on line” where the substrate is irradiated by UV light through a quartz window. The grafting takes place in the very thin surface layer of solution on the substrate. The grafting efficiency is high (70–80% of the polymer formed is grafted) and the process is rapid (5–15 s due to the efficient transfer of initiator and monomer through the liquid phase. The continuous surface grafting process is promising for industrial applications.