Laser-induced forward transfer of focussed ion beam pre-machined donors

In this paper we report femtosecond laser-induced forward transfer (LIFT) of pre-machined donor films. 1 μm thick zinc oxide (ZnO) films were first machined using the focussed ion beam (FIB) technique up to a depth of 0.8 μm. Debris-free micro-pellets of ZnO with extremely smooth edges and surface uniformity were subsequently printed from these pre-machined donors using LIFT. Printing results of non-machined ZnO donor films and films deposited on top of a polymer dynamic release layer (DRL) are also presented for comparison, indicating the superior quality of transfer achievable and utility of this pre-machining technique.     

Facile and Low-Cost SPE Modification Towards Ultra-Sensitive Organophosphorus and Carbamate Pesticide Detection in Olive Oil

Despite the fact that a considerable amount of effort has been invested in the development of biosensors for the detection of pesticides, there is still a lack of a simple and low-cost platform that can reliably and sensitively detect their presence in real samples. Herein, an enzyme-based biosensor for the determination of both carbamate and organophosphorus pesticides is presented that is based on acetylcholinesterase (AChE) immobilized on commercially available screen-printed carbon electrodes (SPEs) modified with carbon black (CB), as a means to enhance their conductivity. Most interestingly, two different methodologies to deposit the enzyme onto the sensor surfaces were followed; strikingly different results were obtained depending on the family of pesticides under investigation. Furthermore, and towards the uniform application of the functionalization layer onto the SPEs’ surfaces, the laser induced forward transfer (LIFT) technique was employed in conjunction with CB functionalization, which allowed a considerable improvement of the sensor’s performance. Under the optimized conditions, the fabricated sensors can effectively detect carbofuran in a linear range from 1.1 × 10^?9 to 2.3 × 10^?8 mol/L, with a limit of detection equal to 0.6 × 10^?9 mol/L and chlorpyrifos in a linear range from 0.7 × 10^?9 up to 1.4 × 10^?8 mol/L and a limit of detection 0.4 × 10^?9 mol/L in buffer. The developed biosensor was also interrogated with olive oil samples, and was able to detect both pesticides at concentrations below 10 ppb, which is the maximum residue limit permitted by the European Food Safety Authority.     

Fusaricidins from Paenibacillus polymyxa M‐1, a family of lipohexapeptides of unusual complexity—a mass spectrometric study

Paenibacillus polymyxa are rhizobacteria with a high potential to produce natural compounds of biotechnological and medical interest. Main products of P . polymyxa are fusaricidins, a large family of antifungal lipopeptides with a 15‐guanidino‐3‐hydroxypentadecanoic acid (GHPD) as fatty acid side chain. We use the P . polymyxa strain M‐1 as a model organism for the exploration of the biosynthetic potential of these rhizobacteria. Using matrix‐assisted laser‐desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) about 40 new fusaricidins were detected which were fractionated by reversed‐phase (rp) HPLC. Their structure was determined by MALDI‐LIFT‐TOF/TOF fragment analysis. The dominant fragment in the product ion spectra of fusaricidins appeared at m /z 256.3, 284.3 and 312.4, respectively, indicating variations in their fatty acid part. Two new subfamilies of fusaricidins were introduced which contain guanidino‐3‐hydroxyhepta‐ and nonadecanoic acid as fatty acid constituents. Apparently, the end‐standing guanidine group is not modified as shown by direct infusion nano‐electrospray ionization mass spectrometry (nano‐ESI MS). The results of this study suggest that advanced mass spectrometry is the method of choice for investigating natural compounds of unusual diversity, like fusaricidins. Copyright © 2016 John Wiley & Sons, Ltd.     

Liquids microprinting through laser-induced forward transfer

Laser-induced forward transfer (LIFT) is a direct-writing technique which allows the deposition of tiny amounts of material from a donor thin film onto a receptor substrate. When LIFT is applied to liquid donor films, the laser radiation affects only a localized fraction of the liquid, thereby impelling the unaffected portion towards the receptor substrate. Thus, transfer takes place with no melting or vaporization of the deposited fraction and, in this way, LIFT can be used to successfully print complex materials like inorganic inks and pastes, biomolecules in solution, and even living cells and microorganisms. In addition, and for a wide range of liquid rheologies, the material can be deposited in the form of circular microdroplets; this provides LIFT with a high degree of spatial resolution leading to feature sizes below 10 μm, and making it competitive in front of conventional printing techniques. In this work, a revision of the main achievements of the LIFT of liquids is carried out, correlating the morphological characteristics of the generated features with the results of the study of the transfer process. Special emphasis is put on the characterization of the dynamics of liquid ejection, which has provided valuable information for the understanding of microdroplets deposition. Thus, new time-resolved imaging analyses have shown a material release behavior which contrasts with most of the previously made assumptions, and that allows clarifying some of the questions open during the study of the LIFT technique.     

Applicability of MALDI‐TOF MS for determination of quinolone residues in fish

MALDI‐TOF MS approach for determination of six quinolones residues in fillets of pangasius (Pangasionodon hypophthalmus) was studied, considering that is a very sensitive analytical technique with simple and high‐throughput operation, contributing to knowledge regarding application of this technique to the determination of small‐molecular‐weight organic compound residues in foods. LIFT‐MS/MS showed to be a successful approach to identify the presence of all quinolone residues in the fish fillet, at their respective MRL level. This study opens an important field of research for the development of simple and high‐throughput bioanalytical screening methods for the determination of veterinary drug residues in foods.     

Study of the laser-induced forward transfer of liquids for laser bioprinting

Laser-induced forward transfer (LIFT) is a direct-writing technique that allows printing patterns of diverse materials with a high degree of spatial resolution. In conventional LIFT a small fraction of a solid thin film is vaporized by means of a laser pulse focused on the film through its transparent holder, and the resulting material recondenses on the receptor substrate. It has been recently shown that LIFT can also be used to transfer materials from liquid films. This widened its field of application to biosensors manufacturing, where small amounts of biomolecules-containing solutions have to be deposited with high precision on the sensing elements. However, there is still little knowledge on the physical processes and parameters determining the characteristics of the transfers.In this work, different parameters and their effects upon the transferred material were studied. It was found that the deposited material corresponds to liquid droplets which volume depends linearly on the laser pulse energy, and that a minimum threshold energy has to be overcome for transfer to occur. The liquid film thickness was varied and droplets as small as 10 μm in diameter were obtained. Finally, the effects of the variation of the film to substrate distance were also studied and it was found that there exists a wide range of distances where the morphology of the transferred droplets is independent of this parameter, what provides LIFT with a high degree of flexibility.     

Study of liquid deposition during laser printing of liquids

Laser-induced forward transfer (LIFT) is a direct-writing technique which can be used to successfully print various complex and sensitive materials with a high degree of spatial resolution. However, the optimization of its performances requires a deep understanding of the LIFT dynamics. Such understanding should allow correlating the phenomena underlying the liquid transfer process with the morphology of the obtained deposits. To this end, in this work it is presented a study related to two aspects: first, the correlation of the morphological characteristics of the transferred droplets with the variation of the film thickness combined with laser fluence; and second, a correlation of the dependences observed with the dynamics of the transfer process. The work is focused on the understanding of the observed dependences for which the information provided by time-resolved analysis on liquid transfer dynamics has proved to be crucial.     

Experimental investigations of laser-induced forward transfer process of organic thin films

This paper deals with transfer induced by laser of thin layers of a conducting polymer, the poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate), for applications in plastic electronics. This relatively simple technique of direct writing offers the ability to make surface micro-patterning by localized deposits of material. The study of the various mechanisms (ablation, transfer and deposit) has been carried out according to different conditions of irradiation: wavelength (from ultraviolet to infrared radiation), pulse duration (nanosecond and sub-nanosecond) and fluence. The morphology of the transferred patterns has been analyzed by optical microscopy and scanning electronic microscopy. Our objective is to understand the different mechanisms involved in the process in order to optimize it in terms of geometrical resolution while preserving the properties of the transferred material.     

Parameters optimization for biological molecules patterning using 248-nm ultrafast lasers

Laser-induced forward transfer has been used for the deposition of photoactive biotin in micron-scale patterns. The process uses a 500 fs pulsed KrF laser beam to transfer small amounts of a liquid solution target as micron-size droplets to a substrate placed parallel and in close proximity to it. The biomolecules remain active after the transfer; this is demonstrated through fluorescence assays. In addition to the laser parameters, those regarding the target composition and the receiving surface for the miniaturization of the transferred patterns have been studied and optimized. Droplets as small as 5 μm have been obtained by reducing the target thickness and transfer energy; by increasing the percentage of glycerol added in the biomolecules solution and by using hydrophobic surfaces as receiving substrates. The influence of the glycerol addition and the hydrophobicity of the receiving surfaces on the activity of the transferred biomolecules have also been studied.