Polymer pixel enhancement by laser-induced forward transfer for sensor applications

This paper presents polymer pixel printing for applications in chemoselective sensors where nanosecond laser direct transfer methods, with a triazene polymer (TP) acting as a Dynamic Release Layer (DRL), are used. A systematic study of laser fluence, donor film morphology and both single- and multiple-pixel deposition were optimized with the final goal to obtain continuous pixels of sensitive polymers, polyethylenimine (PEI) and polyisobutylene (PIB), on SAW surfaces. Morphology characterization after the laser transfer has been performed by Optical Microscopy and Scanning Electron Microscopy (SEM). The responses of the coated transducers were measured after deposition with different laser fluences and it was found that a fluence under 625 mJ/cm² was required in order to prevent damage of the interdigital transducers (IDT) of the sensor devices. The sensitivity of the polymer coated devices to acetone concentrations gives an indication that LIFT can be used for printing sensitive polymer pixels onto transducer devices.     

Dual‐Polymer‐Functionalized Nanoscale Graphene Oxide as a Highly Effective Gene Transfection Agent for Insect Cells with Cell‐Type‐Dependent Cellular Uptake Mechanisms

Efficient and safe gene transfection carriers, especially for hard‐to‐transfect cells, are urgently demanded in basic biological research and gene therapy applications. Many insect cell lines widely used in molecular cell biology exhibit relatively low transfection efficiencies when treated by conventional non‐viral agents. Herein, we develop a novel gene delivery vector by coating graphene oxide (GO) with both polyethylene glycol (PEG) and polyethylenimine (PEI), obtaining a dual‐polymer‐functionalized nanoscale GO (nGO‐PEG‐PEI) to transfect insect cells. While exhibiting remarkably reduced cytotoxicity compared with PEI, nGO‐PEG‐PEI, when used as the plasmid DNA transfection agent to treat Drosophila S2 cells, offers ≈7‐fold and ≈2.5‐fold higher efficiency compared with those achieved by using bare PEI and Lipofectamine 2000, a widely used commercial transfection agent, respectively. Interestingly, the advantages of nGO‐PEG‐PEI are even more dramatic when transfecting cells with lower‐quality linearized DNA. It is revealed that nGO‐PEG‐PEI/pDNA complexes enter insect cells via a unique pathway working even at a low temperature, rather different from their entry into mammalian adherent cells. Our results encourage the development of nano‐GO‐based gene carriers to treat special types of hard‐to‐transfect cells (e.g., insect cells), and indicate that nanomaterials would enter cells by cell‐type‐dependent mechanisms, which merit significantly more future attentions.     

Characterize the interaction between polyethylenimine and serum albumin using surface plasmon resonance and fluorescence method

Polyethylenimine (PEI) is a type of cationic polymer which is efficient in DNA transfer. The characters of PEI binding to bovine serum albumin and human serum albumin (HSA) were described by fluorescence quenching, surface plasmon resonance (SPR) and circular dichroism (CD) spectroscopy. The fluorescence quenching results showed that the binding processes occurred on the surface of the protein molecules. The accurate binding constants between PEI and the two proteins were obtained by SPR spectroscopy. The CD spectra results showed that the confirmations of the two proteins were affected with the addition of PEI.     

Fabrication of piezoelectric components for a tunable and efficient device for DNA delivery into mammalian cells

We fabricated three piezoelectric components (PZT) that can produce ultrasonic waves with various generated power in order to improve the delivery of DNA molecule and polymer/DNA complexes into cells. Two cationic polymers (PEI and PDMAEMA) were interacted with DNA to form nano-scaled DNA/polymer complexes with/without the help of PZT devices. The application of PZT devices under optimal conditions helped to avoid cytotoxicity and greatly increased the transfection (DNA delivery) efficiency of these complexes in mammalian cells. The cytotoxicity and transfection efficiency were found to be correlated with the PZT-generated power, waveforms and duration of ultrasonic treatment. There was no observable cytotoxicity in our experimental models and, a maximum transfection efficiency 700% greater than that of polymer/DNA complexes without applying ultrasound was achieved. The transfection efficiency of plain polymer/DNA complexes (without PZT treatment) corresponded to a 630-fold increase in comparison to the naked DNA. The waveforms of generated ultrasound greatly influenced the transfection efficiency, while cytotoxicity was not significantly affected. This means that, for optimal DNA delivery, duration of the peak voltage (V_max/Div) also plays a role. In addition, the generated waves from PZT do not cause dissociation of polymer/DNA complexes or a change in the particle sizes of these complexes. In conclusion, these results suggest that the operation of PZT devices can be a tunable/safe way to greatly improve DNA delivery for gene therapy.     

Effect of Cationic Polyelectrolyte on the Flow Behavior of Hydroxypropyl Methyl Cellulose/Polyacrylic Acid Interpolymer Complexes

Association of polyacrylic acids and nonionic polymers in solutions via hydrogen bonding results in formation of novel polymeric materials. These complexes are novel individual compounds and their properties are entirely different from the properties of their component polymers. In this study, the effects of a cationic polyelectrolyte (polyethylenimine, PEI) on the interpolymer complexation of hydroxypropyl methyl cellulose (HPMC) with polyarcylic acid (PAA) in aqueous media were studied. Results showed that at low pH, interpolymer complex (IPC) formation was observed between HPMC and PAA at a 3:0.5 polymer ratio. Under basic conditions, the viscosity of the IPC increased accompanied with the transition from coiled structure to an extended conformation of associates. Addition of PEI to the same system caused some structural changes in the polymer solution mixtures depending on the pH of the system. PEI worked as a destructive agent for the HPMC/PAA interpolymer complexes and associates. This behavior was attributed to the complex formation between PEI and HPMC via hydrogen bonding.     

Laser Molding in Polymeric Materials Using Femto-Second Laser Pulse and Replication via Electroforming

The upheaval structure on the surface of polymer induced by the irradiation of a near-infrared (NIR) femto-second laser pulse in polymer bulk was investigated. Copolymers, such as poly(acrylonitrile-styrene) (AS) and poly(acrylonitrilebutadiene-styrene-methyl methacrylate) (ABSM) produced upheaval structures with a flattop just like the crater of a volcano, whereas homopolymers with relatively high glass transition temperature (T_g), such as polycarbonate (PC) and polyether imide (PEI) were more often formed a bell-shaped upheaval structure. A micro-lens effect was observed for the bell-shaped upheaval structure, but that effect was not observed in the case of copolymers with a flattop structure. Replication of the bell-shaped upheaval structure in PC was carried out by electroforming (non-electrolytic plating of Ni and the following electrolytic plating of Ni) and potting approximately 30 wt% THF solution of AS copolymer. A micro-scale bell-shaped upheaval structure in PC induced by a laser pulse was replicated using a Ni mother mold with suitable precision, and the replicated bell-shaped structure also showed a micro-lens effect.     

Vitamin C functionalized multi-walled carbon nanotubes and its reinforcement on poly(ester-imide) nanocomposites containing L-isoleucine amino acid moiety

The aim of this research was to prepare poly(ester–imide) (PEI)-based nanocomposites (NCs) through the functionalization of carboxylated-multiwalled carbon nanotubes (MWCNT)s with ascorbic acid, in order to ensure better filler dispersion and good interfacial adhesion between filler and matrix. Chiral and biodegradable PEI was synthesized from amino acid-based diacid with 4,4′-thiobis(2-tert-butyl-5-methylphenol) by a direct polycondensation method. Using the solution mixing technique, the NCs containing modified MWCNTs with different loading levels of 5,10, 15 wt% were produced and examined in terms of chemical structure, morphology, and thermal stability by FT-IR spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction, transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM). TEM and FE-SEM photographs of the obtained NCs indicated well-dispersed morphologies and strong interaction between the functionalized MWCNTs and the polymer matrix. TGA results revealed that the addition of MWCNT resulted in a significant increase of the thermal stability and char yields of the NCs compared to those of the neat PEI.     

低分子量聚乙烯亚胺/金纳米棒纳米载体的制备及毒性研究

以表面修饰巯基十一烷酸的金纳米棒 (GNRs/MUA)为骨架, 将低分子量的聚乙烯亚胺(PEI)连接到GNRs/MUA表面, 构建GNRs/MUA/PEI纳米载体.首先采用MUA对GNRs进行表面修饰, 减少由于GNRs表面的十六烷基三甲基溴化铵(CTAB)所造成的生物毒性.然后采用低分子量 PEI 进一步修饰, 同时利用GNRs巨大的比表面积进一步放大 PEI 的携带基因能力, 这样既能够降低阳离子聚合物的毒性, 又能够提高整个体系的转染效率.利用透射电子显微镜(TEM)、紫外可见吸收光谱(UV-Vis)、Zeta电位等对纳米载体进行了表征.结果显示, MUA与PEI已成功修饰到GNRs表面, 并很好地保留了GNRs的光学性质, 其表面电位发生正负交替变化.采用噻唑蓝(MTT)比色法对纳米载体进行细胞毒性研究, 结果显示GNRs/MUA/PEI(1.8 kDa)非病毒纳米载体, 细胞存活率在控制聚合物浓度为300 μg/mL时仍然稳定在75%以上, 明显高于商品化的PEI(25 kDa).     

PEGylated polyethylenimine-stabilized polypyrrole nanoparticles loaded with DOX for chemo-photothermal therapy of cancer cells

Combination of kinds of therapy modalities is promising for effective cancer treatment. Herein, a kind of multifunctional nanoparticles (NPs) was developed for cancer chemo-photothermal therapy applications. Polypyrrole (PPy) NPs were formed using a facile polymerization method using poly(ethyleneimine) (PEI) as stabilizer, followed by polyethylene glycol (PEG) modification and anticancer drug doxorubicin (DOX) loading. Showing obvious absorbance in the NIR range, the obtained PPy-PEI-PEG NPs displayed well photothermal ability with desirable photothermal stability. The release of the loaded DOX can be promoted by pH and laser stimulation. Compared with single therapy modality, the combination of chemotherapy and photothermal therapy showed higher cancer cell killing effect. The cellular internalization of the obtained NPs was proved to be effective. The developed multifunctional NPs are promising candidates for combined therapy of cancer cells.     

Theoretical and experimental approach to the texturization process of bioreactive surfaces by high-power laser

The properties of orthopaedic/dental implants can be tuned through the laser surface modifications that take place during a laser ablation process. Processing assisted by a laser is adequate to produce macro- and micro-structures on metallic alloys and polymer surfaces in order to improve their biological response.     

Studies on the surface modification of diatomite with polyethyleneimine and trapping effect of the modified diatomite for phenol

The adsorption isotherm of polyethyleneimine (PEI) on diatomite was studied using UV spectrophotometry, the surface of diatomite was modified with polyethyleneimine by using impregnation method, and the trapping behavior of the modified diatomite for phenol was investigated by using 4-aminoantipyrine (4-AAP) spectrophotometric method. The experiment results show that negatively charged diatomite particles have very strong absorption effect for cationic macromolecule PEI, the adsorption isotherm fits in Freundlich equation. The character that there is a maximum value after intitial sharp increase of adsorption capacity on the adsorption curve indicates that there is strong affinity between diatomite particles and polyethyleneimine macromolecules, and it attributes to the strong electrostatic interaction. After modification with PEI, the electric property of diatomite particle surface changes essentially, and the isoelectric point of diatomite particles moves from pH 2.0 to 10.5. In acidic solution, phenol exists as molecular state, and the modified diatomite particles adsorb phenol through hydrogen bond interaction. However, the hydrogen bond interaction between nitrogen atoms on PEI chains and phenol is weaker because of high degree of protonation of polyethyleneimine macromolecules, so the adsorption quantity is lower. In basic solution, phenol exists as negative benzene–oxygen ion, and the modified diatomite particles adsorb phenol through electrostatic interaction. However, the electrostatic interaction between PEI and negative benzene–oxygen ion is very weak because of low degree of protonation of polyethyleneimine macromolecules, so the adsorption quantity is much lower. The modified diatomite particles produce very strong trapping effect for phenol in neutral aqueous solution via the cooperating of strong electrostatic interaction and hydrogen bond interaction, and the saturated adsorption capacity can attain to 92 mg g⁻¹.     

Dynamic generation of Debye diffraction-limited multifocal arrays for direct laser printing nanofabrication

We propose a Debye-theory-based iterative method to produce accurate phase patterns for generating highly uniform diffraction-limited multifocal arrays with a high-NA objective. It is shown that by using the Debye method, the uniformity of the diffraction-limited focal arrays can reach 99%, owing to the critical consideration of the depolarization effect associated with high-NA objectives. The generated phase patterns are implemented in fast dynamic laser printing nanofabrication for the generation of individually controlled high-quality microvoid arrays in a solid polymer material by a single exposure of a femtosecond laser beam. As a result of the high-quality multifocal arrays, functional three-dimensional photonic crystals possessing multiple stopgaps with suppression up to 80% in transmission spectra are demonstrated.     

Thermal and electrical conductivity of poly(l-lactide)/multiwalled carbon nanotube nanocomposites

Multiwalled carbon nanotubes (MWCNTs) are considered to be the ideal reinforcing agent for high-strength polymer composites, because of their fantastic mechanical strength, high electrical and thermal conductivity and high aspect ratio. Polymer/MWCNTs composites are easily molded, and the resulting shaped plastic articles have a perfect surface appearance compared with polymer composites made using usual carbon or glass fibers. Good interfacial adhesion between the MWCNTs and the polymer matrix is essential for efficient load transfer in the composite. The ultrahigh strength polymer composites demand the uniform dispersion of the MWCNTs in the polymer matrix without their aggregation and the good miscibility between MWCNT and polymer matrix. This approach can also be applied to biodegradable synthetic aliphatic polyesters such as poly(l-lactide) (PLLA), which has received a great deal of attention due to environmental concerns. In this study, PLLA was melt-compounded with MWCNTs. A high degree of dispersion of the MWCNTs in the composites was obtained by grafting PLLA onto the MWCNTs (PLLA-g-MWCNTs). After oxidizing the MWCNTs by treating them with strong acids, they were reacted with l-lactide to produce the PLLA-g-MWCNTs. The mechanical properties of the PLLA/PLLA-g-MWCNT composite were higher than those of the PLLA/MWCNT composite. The electrical conductivity of the composites was determined by measuring the volume resistivity, which is a value of the resistance expressed in a unit volume by two-probe method. The thermal diffusivity and heat capacity of composites was measured by laser flash method, and the effects of modification of the MWCNT in PLLA matrix are discussed.     

Fabrication of polymer dot pattern containing fluorescent molecules by laser photopolymerization

A simple and easy method for micro-patterning of organic molecules was developed. Fluorescent molecules were added to an ultraviolet (UV) photopolymerization polymer solution, and dot patterns were formed by a photopolymerization process with a conventional nanosecond pulsed UV laser. Since the molecules fixed in the dot pattern showed fluorescence corresponding to the added molecules in all cases, it is suggested that this method is applicable to micro-patterning of various kinds of organic molecules without serious damage to the molecules. Micro-patterning was also achieved using a visible pulsed laser by adding coumarin 6 to the polymer solution.PACS 82.50.Hp; 81.65.Cf; 81.05.Lg     

超短脉冲激光微束对细胞作用的研究

本文详细地介绍了我们自己设计和安装的一个Nd:YAG超短脉冲激光微束系统,该系统分成二个部分:激光源和显微镜。由电光调Q非稳腔Nd:YAG激光倍频后得到355nm紫外光进入显微镜并由物镜聚焦。同时,这超短脉冲激光微束照射在细胞上并且在细胞上产生一个可以自恢复的小孔。在文中我们还讨论了超短脉冲激光微束与细胞之间作用效应及机理。     

DNA Vector Polyethyleneimine Affects Cell pH and Membrane Potential: A Time-Resolved Fluorescence Microscopy Study

Polyethyleneimine (PEI) is one of the very efficient nonviral vectors being developed and tested for artificial gene transfer into target cells. One of its serious limitations is the significant cytotoxicity of the large amounts of free PEI in the mixtures of DNA and PEI used for transfection. To further investigate the cellular effects of free PEI, we have analyzed the PEI-induced alterations of various cell parameters such as membrane heterogeneity and fluidity, cytoplasmic pH, and plasma membrane potential in a variety of cells such as Swiss 3T3 fibroblast, Chinese hamster ovary, insect cells SF9, plant cell line BY2, and Saccharomyces cerevisae. Fluorescence probes such as Nile red, SNARF-1, and cyanine dye DiSC₂(3), coupled with the technique of picosecond time-resolved fluorescence microscopy, were used in estimating the above-mentioned cell parameters. It was found that the cell membranes were largely unperturbed by PEI. However, the cytoplasmic pH showed an increase of 0.1–0.4 units when the cells were treated with PEI. The plasma membrane potential was found to be depolarized in S. cerevisae and Swiss 3T3 cells. These results suggest that the cytotoxic effects of PEI may partly originate from inhibition of regulation of cytoplasmic pH and plasma membrane potential. Further, it is proposed that the resultant cell alterations favors the transfection process.     

激光烧蚀制备分布反馈式有机激光器件

采用激光烧蚀的方法结合激光全息技术,直接在高分子聚合物MEH-PPV薄膜表面烧蚀光栅结构,制备了分布反馈式有机激光器。这一方法具有工艺简单、光栅参数的可控性和重复性好等优点。器件MEH-PPV的膜厚是400 nm。利用波长为355 nm的Nd-YAG纳秒激光器进行单脉冲烧蚀,获得的光栅周期和光栅高度分别为370 nm和 100 nm。利用飞秒激光放大器作为泵浦源激射DFB激光器件,得到激射阈值约为182 μJ·cm^-2·pulse^-1,光谱的波峰约在609 nm处,半高宽为4.2 nm。通过改变两光束的夹角获得了周期为360, 370, 380, 390 nm的光栅,它们对应的激光波峰分别为602.91, 609.24, 613.26, 619.01 nm。     

Surface modification of the polyethyleneimine layer on silicone oxide film via UV radiation

We herein report a novel method of employing 254 nm of UV radiation (UV) for the modification of a polyethyleneimine (PEI) layer on silicone oxide film. In this study, a PEI layer composed of a 50 mM sodium carbonate solution (pH 8.2) was formed on the surface of a silicone oxide film with spontaneous adsorption. Then, thin film of PEI was patterned by UV radiation. To determine the effect of the UV radiation, fluorescence microscopy, X-ray electron spectroscopy (XPS), and Fourier Transform Infrared spectroscopy (FT-IR) analyses were performed. These results indicated that UV radiation could cause changes in the surface characteristics of the PEI layer. Subsequently, FT-IR analysis showed changes in the chemical composition of the PEI exposed to UV radiation, such as the disappearance of the amine. Based on these results, we can conclude that UV radiation could be used to eliminate the amine group selectively and that this technique could be applied to create a pattern on the surface of a PEI layer.     

Superhydrophobic surface structures in thermoplastic polymers by interference lithography and thermal imprinting

We present a method to produce superhydrophobic surfaces in thermoplastic polymer substrates. The method involves the creation of a nickel stamp using a customized laser interference lithography technique and electroplating processes. This stamp is used to emboss sub-micrometer periodic structures into the thermoplastic. The modified surface is coated with a hydrophobic plasma-polymerized hexafluoropropene layer. Surfaces with different periodicity and relief depth were created. On the surface with the highest aspect ratio, advancing water contact angles of 167° were measured with a water contact angle hysteresis of below 5°.     

Low-Threshold Conjugated Polymer Distributed Feedback Lasers on InP Substrate

We demonstrate a low threshold polymer solid state thin-film distributed feedback （DFB） laser on an InP substrate with the DFB structure. The used gain medium is conjugated polymer poly[2-methoxy-5-（2-ethylhexyloxy）-l, 4- phenylenevinylene] （MEH-PPV） doped polystyrene （PS） and formed by drop-coating method. The second order Bragg scattering region on the InP substrate gave rise to strong feedback, thus a lasing emission at 638.9nm with a line width of 1.2nm is realized when pumped by a 532nm frequency-doubled Nd：YAG pulsed laser. The devices show a laser threshold as low as 7n J/pulse.