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The conjugation of ionic gold with bacterial antibodies makes it possible to induce a specific interaction between targeted bacteria and the surface of a GaAs/AlGaAs biochip. The process of immobilization is based on a galvanic displacement reaction (GDR) involving electron transfer between GaAs and Au 3+ ions that leads to the formation of a Au-Ga alloy anchoring bacteria to the biochip surface. The GDR-based immobilization of Escherichia coli on biochips comprising a stack of GaAs/AlGaAs nanolayers ( d GaAs = 12 nm, d AlGaAs = 10 nm) was confirmed by X-ray photoelectron spectroscopy and atomic force microscopy-based infrared experiments. We report the successful application of this approach for highly sensitive detection of E. coli with a digital photocorrosion (DIP) biosensor. The photoluminescence (PL) monitored DIP of GaAs/AlGaAs nanolayers results in the formation of a PL intensity maximum whose temporal appearance depends on the electric charge transfer between bacteria and the biochip. The formation of a robust bacteria-biochip interface achieved with the GDR process allowed us to observe the role of bacteria on the temporal position of a PL intensity maximum related to the etching of two pairs of GaAs/AlGaAs nanolayers extending up to 24 nm below the biochip surface. We demonstrate the attractive detection of E. coli at 250 CFU/mL, and we discuss the potential of this approach for designing a family of biosensors addressing the quasi-continuous monitoring of a water environment for the presence of pathogenic bacteria., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Monitoring the presence of pathogenic Bacillus spores is important for industrial applications, as well as necessary for ensuring human health. Bacillus thuringiensis is used as a biopesticide against several insect pests. Bacillus cereus spores are a significant cause of food poisoning, and Bacillus anthracis is a recognized biosecurity threat. Laboratory-based methods, such as polymerase chain reaction, enzyme-linked immunosorbent assay, or matrix-assisted laser desorption ionization spectroscopy provide sensitive detection of bacteria and spores, but the application of those methods for quasi-continuous environmental monitoring presents a significant challenge requiring frequent human intervention. To address this challenge, we developed a workstation for quasi-autonomous monitoring of water reservoirs for the presence of bacteria and spores, and designed and validated the functionality of a microprocessor-controlled module capable of repetitive collection and pre-concentration of spores in liquid samples tested with fiberglass (FG), polyether sulfone and polyvinylidene fluoride filters. The best results were obtained with FG filters delivering a 20× concentration of B. thuringiensis and B. cereus spores from saline suspensions. The successful 20× pre-concentration of Bacillus spores demonstrated with FG filters could be repeated up to 3 times when bleach decontamination is applied between filtrations. Taken together, our results demonstrate an attractive instrument suitable for semi-automated, quasi-continuous sampling and pre-processing of water samples for biosensing of bacterial spores originating from a complex environment., (© 2023. Crown.)

This work reports on the potential of polymer brushes (PBs) grown on GaAs substrates (PB-GaAs) as a promising platform for the detection of Legionella pneumophila (Lp) . Three functionalization approaches of the GaAs surface were used, and their compatibility with antibodies against Lp was evaluated using Fourier transform infrared spectroscopy and fluorescence microscopy. The incorporation of PBs on GaAs has allowed a significant improvement of the antibody immobilization by increased surface coverage. Bacterial capture experiments demonstrated the promising potential for enhanced immobilization of Lp in comparison with the conventional alkanethiol self-assembled monolayer-based biosensing architectures. Consistent with an eightfold improved capture of bacteria on the surface of a PB-functionalized GaAs/AlGaAs digital photocorrosion biosensor, we report the attractive detection of Lp at 500 CFU/mL., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Bacillus cereus is a spore-forming ubiquitous bacterium notable as a food poisoning agent. Detection of B. cereus spores using selective media is laborious and non-specific. Herein, the quantitative detection of B. cereus spores was investigated with commercial antibodies and published aptamer sequences. Several detection reagents were screened for affinity to Bacillus collagen-like protein A (BclA), an abundant exosporium glycoprotein. Sensitivity and selectivity toward B. cereus spores were tested using immunoassays and multi-analyte profiling (xMAP). A recombinant antibody developed in llama against BclA protein showed B. cereus spore selectivity and sensitivity between 10 2 and 10 5 spores/mL using xMAP. DNA aptamer sequences demonstrated sensitivity from 10 3 to 10 7 spores/mL and no cross-reaction to B. megaterium and B. subtilis . Selectivity for B. cereus spores was also demonstrated in a mixture of several diverse microorganisms and within a food sample with no compromise of sensitivity. As proof of concept for multiplexed measurement of human pathogens, B. cereus and three other microorganisms, E. coli, P. aeruginosa , and S. cerevisiae , were simultaneously detected using xMAP. These data support the development of a rapid, sensitive, and selective system for quantitation of B. cereus spores and multiplexed monitoring of human pathogens in complex matrices.

Since Legionella pneumophila has caused punctual epidemics through various water systems, the need for a biosensor for fast and accurate detection of pathogenic bacteria in industrial and environmental water has increased. In this report, we evaluated conditions for the capture of live L. pneumophila on a surface by polyclonal antibodies (pAb) and recombinant antibodies (recAb) targeting the bacterial lipopolysaccharide. Using immunoassay and PCR quantification, we demonstrated that, when exposed to live L. pneumophila in PBS or in a mixture containing other non-target bacteria, recAb captured one third fewer L. pneumophila than pAb, but with a 40% lower standard deviation, even when using the same batch of pAb. The presence of other bacteria did not interfere with capture nor increase background by either Ab. Increased reproducibility, as manifested by low standard deviation, is a characteristic that is coveted for biosensing. Hence, the recAb provided a better choice for immune adhesion in biosensors even though it was slightly less sensitive than pAb. Polyclonal or recombinant antibodies can specifically capture large targets such as whole bacteria, and this opens the door to multiple biosensor approaches where any of the components of the bacteria can then be measured for detection or characterisation.

Rapid detection of Legionella pneumophila ( L. pneumophila ) is important for monitoring the presence of these bacteria in water sources and preventing the transmission of the Legionnaires' disease. We report improved biosensing of L. pneumophila with a digital photocorrosion (DIP) biosensor functionalized with an innovative structure of cysteine-modified warnericin antimicrobial peptides for capturing bacteria that are subsequently decorated with anti- L. pneumophila polyclonal antibodies (pAbs). The application of peptides for the operation of a biosensing device was enabled by the higher bacterial-capture efficiency of peptides compared to other traditional ligands, such as those based on antibodies or aptamers. At the same time, the significantly stronger affinity of pAbs decorating the L. pneumophila serogroup-1 (SG-1) compared to serogroup-5 (SG-5) allowed for the selective detection of L. pneumophila SG-1 at 50 CFU/mL. The results suggest that the attractive sensitivity of the investigated sandwich method is related to the flow of an extra electric charge between the pAb and a charge-sensing DIP biosensor. The method has the potential to offer highly specific and sensitive detection of L. pneumophila as well as other pathogenic bacteria and viruses.

Bacillus thuringiensis (Bt) is used as a bioinsecticide since it effectively kills insect larvae. Bt is also genetically similar to Bacillus cereus (Bc), a well recognized foodborne human pathogen; they are both members of the Bacillus cereus group (BC group). Although approved Bt bioinsecticide products have been confirmed to be non-pathogenic to humans, close monitoring of Bt during dissemination is important for cost considerations and to limit impact on biodiversity towards nontarget organisms. As such, developing rapid, sensitive, and specific tools for quantitative detection of Bt spores during and following spray operations is highly desirable. The goals of this study were to investigate commercially available detection reagents for sensitivity and selectivity in detecting Bt spores, and then functionalize a surface of (001) GaAs used in photonic biosensing. To achieve these goals, we (1) screened commercial antibodies for their capacity to bind recombinant proteins from Bt spores, (2) screened antibodies and aptamers for their sensitivity and selectivity against Bt spores, and (3) tested the efficiency of selected antibodies and aptamers in capturing Bt spores on the surface of functionalized GaAs biochips. Seven genes encoding Bt spore proteins were cloned and expressed in Escherichia coli. The binding of each purified spore antigen was tested by commercially available polyclonal and monoclonal antibodies claimed to exclusively target spores. Of the seven targets, Bacillus collagen-like protein A, was the most abundant protein on Bt spores and demonstrated the strongest binding affinity to all test antibodies. The commercial antibodies (Abs) were also tested for specificity to BC Group versus non-BC Group spores. Three of six commercial antibodies showed selectivity to Bt spores, with recombinant Abs providing the most robust lower range of detection (10 2 to 6 × 10 3 spores/mL). The sensitivity and selectivity of three published DNA aptamer sequences demonstrated a wide range of detection sensitivity for Bt spores. Two of the three test aptamers also showed reasonable selectivity towards Bt spores while the third demonstrated reactivity to non-BC Group B. megaterium and B. subtilis. Of the reagents tested, a thiolated aptamer and llama recombinant Ab showed highest Bt spore capture efficiency as measured by spore coverage of the GaAs surface. These results confirm that the selected aptamer and llama rAb can be considered strong candidates for the development of GaAs-based biosensing devices., (Crown Copyright © 2021. Published by Elsevier B.V. All rights reserved.)

A regenerable bulk acoustic wave (BAW) biosensor is developed for the rapid, label-free and selective detection of Escherichia coli in liquid media. The geometry of the biosensor consists of a GaAs membrane coated with a thin film of piezoelectric ZnO on its top surface. A pair of electrodes deposited on the ZnO film allows the generation of BAWs by lateral field excitation. The back surface of the membrane is functionalized with alkanethiol self-assembled monolayers and antibodies against E. coli . The antibody immobilization was investigated as a function of the concentration of antibody suspensions, their pH and incubation time, designed to optimize the immunocapture of bacteria. The performance of the biosensor was evaluated by detection tests in different environments for bacterial suspensions ranging between 10 3 and 10 8 CFU/mL. A linear dependence between the frequency response and the logarithm of E. coli concentration was observed for suspensions ranging between 10 3 and 10 7 CFU/mL, with the limit of detection of the biosensor estimated at 10 3 CFU/mL. The 5-fold regeneration and excellent selectivity towards E. coli detected at 10 4 CFU/mL in a suspension tinted with Bacillus subtilis at 10 6 CFU/mL illustrate the biosensor potential for the attractive operation in complex biological media.

Despite evidence showing that polymer brushes (PBs) are a powerful tool used in biosensing for minimizing nonspecific interactions, allowing for optimization of biosensing performance, and the fact that GaAs semiconductors have proven to have a remarkable potential for sensitive biomolecule detection, the combination of these two robust components has never been considered nor evaluated as a platform for biosensing applications. This work reports different methodologies to prepare and tune PBs on the GaAs interface (PB-GaAs) and their potential as useful platforms for antibody grafting, with the ultimate goal of demonstrating the innovative and attractive character of the PB-GaAs interfaces in the enhanced capture of antibodies and control of nonspecific interactions. Three different functionalization approaches were explored, one "grafting-to" and two "grafting-from," in which atom transfer radical polymerization (ATRP) was performed, followed by their corresponding characterizations. Demonstration of the compatibility of Escherichia coli ( E. coli ) and Legionella pneumophila ( Lp ) antibodies with the PB-GaAs platform compared to the results obtained with conventional biosensing architectures developed for GaAs indicates the attractive potential for operation of a sensitive biosensor. Furthermore, these results showed that by carefully choosing the nature and preparation methodology of a PB-GaAs interface, it is possible to effectively tune the affinity of PB-GaAs-based sensors toward E. coli and Lp antibodies ultimately demonstrating the superior specificity of the developed biosensing platform., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The detection of water contamination with Legionella pneumophila is of critical importance to manufacturers of water processing equipment and public health entities dealing with water networks and distribution systems. Detection methods based on polymerase chain reaction or biosensor technologies require preconcentration steps to achieve attractive sensitivity levels. Preconcentration must also be included in protocols of automated collection of water samples by systems designed for quasi-continuous monitoring of remotely located water reservoirs for the presence of L. pneumophila . We designed and characterized a water sampling module for filtration and backwashing intended for analysis of low-to-medium contaminated water, typically with L. pneumophila bacteria not exceeding 50 colony-forming units per milliliter. The concentration factors of 10× and 21× were achieved with 0.22 and 0.45 µm filters, respectively, for samples of bacteria prepared in clean saline solutions. However, a 5× concentration factor was achieved with 0.45 µm filters for a heavily contaminated or turbid water typical of some industrial water samples.

Culture-based methods for the detection of Legionella pneumophila are prohibitively slow and frequently inadequate. The problem has been addressed with biosensing technology that employs a variety of ligands for the specific capture of bacteria. However, the limited success of the application of mammalian antibodies, aptamers, and nucleic acid-based probes for sensitive biosensing has generated growing interest in exploring alternative biosensing architectures, such as those based on antimicrobial peptides (AMP) that are known for their attractive therapeutic applications. We report on the successful employment of cysteine-modified warnericin RK AMP for the operation of a highly sensitive biosensor of L. pneumophila based on digital photocorrosion of GaAs/AlGaAs nanoheterostructures. The replacement of the relatively cumbersome procedure commonly applied for the attachment of antibodies to COOH-terminated mercaptohexadecanoic acid self-assembled monolayers has allowed for a significant reduction in the distance at which bacteria are immobilized above the biosensor surface. An important consequence of this approach is the attractive limit of detection of L. pneumophila estimated at 2 × 10 2 CFU/mL. The target bacteria were captured four times more efficiently than P. fluorescens , B. subtilis , and E. coli , which is highly promising for environmental monitoring., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

An understanding of the inter-species relationships, especially their metabolic network in a mixed-culture system, is crucial to design an effective inoculum for enhancing the power generation of wastewater fed microbial fuel cell (MFC). In the present study, the influence of microbial mutualistic interactions on the power generation of palm oil mill effluent fed MFCs has been widely investigated by designing several co-culture and mixed culture inoculums. Among the different inoculum compositions, the highest power density of 14.8 W/m 3 was achieved by Pseudomonas aeruginosa and Klebsiella variicola co-culture inoculum due to their synergistic relationships which were inter-linked via fermentation-based metabolites. Besides, the interaction of K. variicola and Bacillus cereus positively influenced the power generation resulting in a maximum power density of 11.8 W/m 3 whereas the antagonistic relationship between B. cereus and P. aeruginosa resulted in a lower power generation of 1.9 W/m 3 . The microbial mutualistic interactions were investigated with polarization, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), as well as by using metabolite and biofilm analysis. It was observed that the synergism between bacteria enhanced power generation through the production of higher electron shuttling mediators and efficient biofilm formation as evidenced by polarization, CV and EIS analysis. In contrast, the antagonistic relationship resulted in production of cell inhibiting metabolites leading to the formation of ineffective biofilm. These findings demonstrate that the synergistic interaction between or within microorganisms is emergent in designing co-culture or mixed-culture inoculum for achieving maximum power generation in MFCs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The spontaneous electron transfer between GaAs and ionic gold through the galvanic displacement reaction results in the formation of gold nanoparticles and a Au 9 Ga 4 alloy. We investigated this process for decorating Legionella pneumophila and Escherichia coli , aiming at enhanced imaging of these bacteria. The surface of bacteria was modified with gold ions through the electrostatic linkage of ionic liquids with phosphate units of the bacterial cell wall. The modified bacteria were further incubated with an antibody-functionalized GaAs substrate. Due to a large gap in the reduction potential of gold and gallium ions, the induced reaction involving bacteria resulted in a reduction of the gold ions to gold nanoparticles and oxidation of GaAs to Ga 2 O 3 and a Au 9 Ga 4 alloy. The bacteria covered with a Au/AuGa nanoshell, if excited at 377 nm, show a bright emission at 447 nm originating from Au/Au 9 Ga 4 . This approach offers a simple and potentially less expensive method for high-contrast imaging of bacteria in comparison to the conventional methods of staining with different dyes or by conjugating green fluorescent proteins.

In recent years, transition metal complexes have been developed for catalytical degradation of a phosphate ester bond, particularly in RNA and DNA; however, less consideration has been given for development of complexes for the degradation of a phosphorothioate bond, as they are the foremost used pesticides in the environment and are toxic to human beings. In this context, we have developed copper complexes of benzimidazolium based ligands for catalytical degradation of a series of organophosphates (parathion, paraoxon, methyl-parathion) at ambient conditions. The copper complexes (assigned as N1 - N3 ) were characterized using single X-ray crystallography which revealed that all three complexes are mononuclear and distorted square planner in geometry. Further, the solution state studies of the prepared complexes were carried out using UV-visible absorption, fluorescence spectroscopy, and cyclic voltametry. The complexes N1 and N2 have benzimidazolium ionic liquid as base attached with two 2-mercapto-benzimidazole pods, whereas complex N3 contains a nonionic ligand. The synthesized copper complexes were evaluated for their catalytic activity for degradation of organophosphates. It is interesting that the complex containing the ionic ligand efficiently degrades phosphorothioate pesticides, whereas complex N3 was not found to be appropriate for degradation due to a weaker conversion rate. The organophosphate degradation studies were monitored by recording absorbance spectra of parathion in the presence of catalyst, i.e., copper complexes with respect to time. The parathion was hydrolyzed into para -nitrophenol and diethyl thiophosphate. Moreover, to analyze the inhibition activity of the pesticides toward acetylcholine esterase enzyme in the presence of prepared metal complexes, Ellman's assay was performed and revealed that, within 20 min, the inhibition of acetylcholine esterase enzyme decreases by up to 13%.

Photo-atomic layer etching (photo-ALE) of GaAs and AlGaAs semiconductors was investigated in deionized H 2 O and aqueous solution of NH 4 OH under weak excitation conditions ( P ≈ 20 mW/cm 2 ). The process is based on digital photocorrosion in a processed solution and a negligible corrosion during the light-off phase employed for dissolution of the photocorrosion products. An inductively coupled plasma mass spectroscopy (ICP-MS) analysis revealed that photo-ALE of GaAs in an aqueous solution of NH 4 OH proceeds linearly with the number of reaction cycles, typically at ∼0.1 nm/cycle, and with the light-off phase as short as 22 s sufficient to entirely dissolve the photocorrosion products generated during a 3 s irradiation. In agreement with the ICP-MS data, the constant photo-ALE rates in NH 4 OH were also demonstrated in situ with the photoluminescence measurements. Our results suggest that the congruent decomposition of III-V materials and the etching of deep structures with atomic layer resolution could be facilitated by switching in situ between different etching environments.

We report on the formation kinetics of mixed self-assembled monolayers (SAMs) comprising 16-mercaptohexadecanoic acid (MHDA) and 11-mercapto-1-undecanol (MUDO) thiols on GaAs(100) substrates. These compounds were selected for their potential in constructing highly selective and efficient architectures for biosensing applications. The molecular composition and quality of one-compound and mixed SAMs were determined by the Fourier transform infrared absorption spectroscopy measurements. The formation of enhanced-quality mixed SAMs was investigated as a function of the molecular composition of the thiol mixture and the proportion of ethanol/water solvent used during their arrangement. Furthermore, the formation of mixed SAMs has been carried out by successive immersion of MHDA SAMs in MUDO thiol solutions and MUDO SAMs in MHDA thiol solution through the process involving thiol-thiol substitution. Our results, in addition to confirming that water-ethanol-based solvents improve the packing density of single thiol monolayers, demonstrate the attractive role of water-ethanol solvents in forming superior quality mixed SAMs.

The development of organic molecules to target nucleic acid is an active area of research at the interface of chemistry and biochemistry, which involves DNA binding, nuclear imaging, and antitumor studies. These molecules bind with DNA through covalent interactions, electrostatic interactions, or intercalation. However, they are less permeable to membrane, and they have a significant cytotoxicity, which limits their application under in vivo conditions. In the present work, various mono- and disubstituted 1,8-naphthalimides-based derivatives ( S-12 , S-13 , S-15 , and S-21 ) have been synthesized and characterized through various spectroscopic techniques. Among these, 3-amino-4-bromo-1,8-naphthalimide ( S-15 ) was found to have an attractive water solubility and act as a nuclear imaging agent. The spectroscopic absorption and emission data showed that S-15 has a strong affinity for salmon sperm DNA with a binding constant of 6.61 × 10 4 M -1 , and the ratiometric fluorescence intensity ( I 489 / I 552 ) of S-15 has a linear relationship in the 0-50 μM range of DNA concentrations. It intercalates with DNA through the hydrophobic planar naphthalimide core as confirmed through cyclic voltammetry, circular dichroism, 1 H NMR titration, and thermal denaturation studies. Positively charged amine groups also participate in H-bonding with the bases and backbone of DNA. The S-15 intercalator showed a large Stokes shift and photostability, which made it attractive for direct imaging of Legionella pneumophila , without the need for a prior membrane permeabilization., Competing Interests: The authors declare no competing financial interest.

Antibiotic resistant bacteria have become a threat to world health. An advanced method of detection, based on matrix assisted laser desorption ionization time-of-flight mass spectroscopy can identify bacteria relatively rapidly, but it is not suitable to measure bacterial antibiotic resistance. Biosensors may be able to detect resistance by monitoring growth after capture on sensor surfaces but this option has not been addressed adequately. We have evaluated the growth of Escherichia coli after capture in 96 well microplates and observed that growth/capture efficiency was relatively similar for antibody-based techniques, but non-specific capture varied considerably. We confirm that neutravidin binds E. coli non-specifically, which limited its use with biotinylated antibodies or aptamers. Centrifugation enhanced bacterial growth/capture considerably, indicating that procedures enhancing the interaction between bacteria and surface-bound antibody have the potential to improve growth efficiency. Capture and growth required larger numbers of bacteria than capture and detection on biosensor surfaces. Previously, we reported that the minimum concentration of live E. coli required for initiating growth on a GaAs/AlGaAs biosensor was ~ 10 5 CFU/mL (Nazemi et al., 2018), and we speculated that this could be related to the poisonous effect of Ga- and As-ions released during dark corrosion of the biosensor, however in the present report we observed that the same minimum concentration of E. coli was required for growth in an ELISA plate. Thus, we argue that this limitation was related rather to bacterial inhibition by the capture antibodies. Indeed, antibodies at titres designed to capture bacteria inhibited bacterial growth when the bacteria were added to growth medium at titres less than 10 5 CFU/mL, indicating that antibodies may be responsible for the higher limits of sensitivity due to their potential to restrict bacterial growth. However, we did not observe E. coli release after 6 h following the capture indicating that these bacteria did not degrade antibodies., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Detection of pathogenic bacteria and monitoring their susceptibility to antibiotics are of great importance in the fields of medicine, pharmaceutical research, as well as water and food industries. In order to develop a photonic biosensor for detection of bacteria by taking advantage of photoluminescence (PL) of GaAs-based devices, we have investigated the capture and growth of Escherichia coli K12 on bare and biofunctionalized surfaces of GaAs (001) - a material of interest for capping different semiconductor microstructures. The results were compared with the capture and growth of Escherichia coli K12 on Au surfaces that have commonly been applied for studying a variety of biological and biochemical reactions. We found that neither GaAs nor Au-coated glass wafers placed in Petri dishes inoculated with bacteria inhibited bacterial growth in nutrient agar, regardless of the wafers being bare or biofunctionalized. However, the capture and growth of bacteria on biofunctionalized surfaces of GaAs and Au wafers kept in a flow cell and exposed to different concentrations of bacteria and growth medium revealed that the initial surface coverage and the subsequent bacterial growth were dependent on the biofunctionalization architecture, with antibody-coated surfaces clearly being most efficient in capturing bacteria and offering better conditions for growth of bacteria. We have observed that, as long as the GaAs wafers were exposed to bacterial suspensions at concentrations of at least 10 5 CFU/mL, bacteria could grow on the surface of wafers, regardless of the type of biofunctionalization architecture used to capture the bacteria. These results provide important insight towards the successful development of GaAs-based devices designed for photonic monitoring of bacterial reactions to different biochemical environments., (Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.)

Development of quick and reliable methods to investigate antibiotic susceptibility of bacteria is vital to prevent inappropriate and untargeted use of antibiotics and control the antibiotic resistance crisis. The authors have developed an innovative, low-cost and rapid approach to evaluate antibiotic susceptibility of bacteria by employing photoluminescence (PL) emission of photocorroding GaAs/AlGaAs quantum well (QW) biochips. The biochips were functionalized with self-assembled monolayers of biotinylated polyethylene glycol thiols, neutravidin and biotinylated antibodies to immobilize bacteria. The illumination of a QW biochip with the above bandgap radiation leads to formation of surface oxides and dissolution of a limited thickness GaAs cap material (≤10nm) that results in the appearance of a characteristic maximum in the PL plot collected over time. The position of the PL maximum depends on the photocorrosion rate which, in turn, depends on the electric charge immobilized on the surface of the GaAs/AlGaAs biochips. Bacteria captured on the surface of biochips retard the PL maximum, while growth of these bacteria further delays the PL maximum. For the bacteria affected by antibiotics a faster occurring PL maximum, compared with growing bacteria, is observed. By exposing bacteria to nutrient broth and penicillin or ciprofloxacin, the authors were able to distinguish in situ antibiotic-sensitive and resistant Escherichia coli bacteria within less than 3h, considerable more rapid than with culture-based methods. The PL emission of the heterostructures was monitored with an inexpensive reader. This rapid determination of bacterial sensitivity to different antibiotics could have clinical and research applications., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The authors have investigated the effect of chemotaxis on immobilization of bacteria on the surface of biofunctionalized GaAs (001) samples. Escherichia coli K12 bacteria were employed to provide a proof-of-concept of chemotaxis-enhanced bacterial immobilization, and then, these results were confirmed using Legionella pneumophila. The recognition layer was based on a self-assembled monolayer of thiol functionalized with specific antibodies directed toward E. coli or L. pneumophila, together with the enzyme beta-galactosidase (β-gal). The authors hypothesized that this enzyme together with its substrate lactose would produce a gradient of glucose which would attract bacteria toward the biochip surface. The chemotaxis effect was monitored by comparing the number of bacteria bound to the biochip surface with and without attractant. The authors have observed that β-gal plus lactose enhanced the immobilization of bacteria on our biochips with a higher effect at low bacterial concentrations. At 100 and 10 bacteria/ml, respectively, for E. coli and L. pneumophila, the authors observed up to 11 and 8 times more bacteria bound to biochip surfaces assisted with the chemotaxis effect in comparison to biochips without chemotaxis. At 10(4) bacteria/ml, the immobilization enhancement rate did not exceed two times.

Photocorrosion of semiconductors is strongly sensitive to the presence of surface states, and it could be influenced by electrically charged molecules immobilized near the semiconductor/electrolyte interface. The underlying mechanism is related to band bending of the semiconductor structure near the surface and the associated distribution of excited electrons and holes. The authors have employed photoluminescence of GaAs/AlGaAs quantum heterostructures for monitoring in situ the photocorrosion effect, and demonstrating detection of nongrowing Legionella pneumophila suspended in phosphate buffered saline solution. Antibody functionalized samples allowed direct detection of these bacteria at 10(4) bacteria/ml. The authors discuss the sensitivity of the process related to the ability of creating conditions suitable for photocorrosion proceeding at extremely slow rates and the interaction of an electric charge of bacteria with the surface of a biofunctionalized semiconductor.

Wet chemical processes were investigated to remove alkanethiol self-assembled monolayers (SAMs) and regenerate GaAs (001) samples studied in the context of the development of reusable devices for biosensing applications. The authors focused on 16-mercaptohexadecanoic acid (MHDA) SAMs that are commonly used to produce an interface between antibodies or others proteins and metallic or semiconductor substrates. As determined by Fourier transform infrared absorption spectroscopy, among the investigated solutions of HCl, H2O2, and NH4OH, the highest efficiency in removing alkanethiol SAM from GaAs was shown by NH4OH:H2O2 (3:1 volume ratio) diluted in H2O. The authors observed that this result was related to chemical etching of GaAs that even in a weak solution of NH4OH:H2O2:H2O (3:1:100) proceeded at a rate of 130 nm/min. The surface revealed by a 2-min etching under these conditions allowed depositing successfully a new MHDA SAM with comparable quality and density to the initial coating. This work provides an important view on the perspective of the development of a family of cost-effective GaAs-based biosensors designed for repetitive detection of a variety of biomolecules immobilized with dedicated antibody architectures.

The wettability of silicon (Si) is one of the important parameters in the technology of surface functionalization of this material and fabrication of biosensing devices. We report on a protocol of using KrF and ArF lasers irradiating Si (001) samples immersed in a liquid environment with low number of pulses and operating at moderately low pulse fluences to induce Si wettability modification. Wafers immersed for up to 4 hr in a 0.01% H2O2/H2O solution did not show measurable change in their initial contact angle (CA) ~75°. However, the 500-pulse KrF and ArF lasers irradiation of such wafers in a microchamber filled with 0.01% H2O2/H2O solution at 250 and 65 mJ/cm(2), respectively, has decreased the CA to near 15°, indicating the formation of a superhydrophilic surface. The formation of OH-terminated Si (001), with no measurable change of the wafer's surface morphology, has been confirmed by X-ray photoelectron spectroscopy and atomic force microscopy measurements. The selective area irradiated samples were then immersed in a biotin-conjugated fluorescein-stained nanospheres solution for 2 hr, resulting in a successful immobilization of the nanospheres in the non-irradiated area. This illustrates the potential of the method for selective area biofunctionalization and fabrication of advanced Si-based biosensing architectures. We also describe a similar protocol of irradiation of wafers immersed in methanol (CH3OH) using ArF laser operating at pulse fluence of 65 mJ/cm(2) and in situ formation of a strongly hydrophobic surface of Si (001) with the CA of 103°. The XPS results indicate ArF laser induced formation of Si-(OCH3)x compounds responsible for the observed hydrophobicity. However, no such compounds were found by XPS on the Si surface irradiated by KrF laser in methanol, demonstrating the inability of the KrF laser to photodissociate methanol and create -OCH3 radicals.

We report on the fast wavelength switching in V-cavity laser (VCL) with quantum well intermixed tuning section. The laser wavelength can be switched between 32 channels at 100 GHz spacing using a single electrode control. The fabrication process involves a quantum well intermixing (QWI) process using KrF laser irradiation and rapid thermal annealing (RTA). The tuning current is less than 40 mA, much lower than previously demonstrated tunable VCL based on electro-thermal-optic effect. The wavelength switching is also faster by three orders of magnitude. The dynamic switching characteristics between two channels with different numbers of intermediate channels are investigated. It shows that the switching time is about 1 ns between adjacent channels and increases up to 12 ns with increasing number of intermediate channels.

Compact and portable surface plasmon resonance (SPR) biosensors of high sensitivities can be made through integration of discrete components in a single device. We report on a device comprising a vertical cavity light emitting diode (VLED) integrated with gold-based biosensing nanostructures fabricated atop its surface. Coupling of surface plasmon waves was achieved by the introduction of a spacer SiO2 layer located between the light source and the functionalized Au thin film. The SPR signal was extracted in far field with a Au-based nanograting and detected using a custom designed hyperspectral imager. We discuss the performance of a VLED-based SPR device employed for detection of different concentration saltwater solutions.

Excimer (ultraviolet) laser-induced quantum well intermixing (UV-Laser-QWI) is an attractive technique for wafer level post-growth processing and fabrication of a variety of monolithically integrated photonic devices. The results of UV-Laser-QWI employed for the fabrication of multibandgap III-V semiconductor wafers have demonstrated the attractive character of this approach although the process accuracy and reproducibility have remained relatively weakly covered in related literature. We report on a systematic investigation of the reproducibility of this process induced with a KrF excimer laser. The influence of both the irradiation with different laser doses and the annealing temperatures on the amplitude of intermixing in InGaAs/InGaAsP/InP quantum well heterostructures has been evaluated based on the photoluminescence measurements. Under optimized conditions, the process allows to blue shift the bandgap of a heterostructure by more than 100 nm with a remarkable 5.3% relative standard deviation.

The concept of a portable, inexpensive and semi-automated biosensing platform, or lab-on-a-chip, is a vision shared by many researchers and venture industries. Under this scope, we have investigated the application of optical emission from quantum well (QW) microstructures for monitoring surface phenomena on gold layers remaining in proximity (<300 nm) with QW microstructures. The uncollimated QW radiation excites surface plasmons (SP) and through the surface plasmon resonance (SPR) effect allows for detection of small perturbation in the density surface adsorbates. The SPR technology is already commonly used for biochemical characterization in pharmaceutical industries, but the reduction of the distance between the SP exciting source and the biosensing platform to a few hundreds of nanometers is an innovative approach enabling us to achieve an ultimate miniaturization of the device. We evaluate the signal quality of this nanophotonic QW-SPR device using hyperspectral-imaging technology, and we compare its performance with that of a standard prism-based commercial system. Two standard biochemical agents are employed for this characterization study: bovine serum albumin and inactivated influenza A virus. With an innovative conical method of SPR data collection, we demonstrate that individually collected SPR scan, each in less than 2.2 s, yield a resolution of the detection at 1.5 × 10-6 RIU.

The electro-optic characteristics of the semi-insulating and n(+)-type GaAs(001) surfaces passivated with n-alkanethiol self-assembled monolayers were investigated using Kelvin probe surface photovoltage (SPV) and photoluminescence (PL) techniques. Referencing the equilibrium surface barrier height established in an earlier report, SPV measurements demonstrated a significant (>100 mV) increase in the non-equilibrium band-bending potential observed under low-level photo-injection. Modeling of the SPV accounts for these observations in terms of a large (>10(4)) decrease in the hole/electron ratio of surface carrier capture cross-sections, which is suggested to result from the electrostatic potential of the interfacial dipole layer formed upon thiol chemisorption. The cross-section effects are verified in the high-injection regime based on carrier transport modeling of the PL enhancement manifested as a reduction of the surface recombination velocity.

A surface plasmon resonance (SPR) scheme is proposed in which the local phase modulations of the coupled plasmons can interfere and yield phase-sensitive intensity modulations in the measured signal. The result is an increased traceability of the SPR shifts for biosensing applications. The main system limitation is the propagation distance of the coupled plasmon modes. This aspect is therefore studied for thin film microstructures operating in the visible and near-infrared spectral regions. The surface roughness of the substrate layer is examined for different dielectrics and deposition methods. The Au layer, on which the plasmonic modes are propagating and the biosensing occurs, is also examined. The surface roughness and dielectric values for various deposition rates of very thin Au films are measured. We also investigate an interferometric SPR setup where, due to the power flux transfer between plasmon modes, the specific choice of grating coupler can either decrease or increase the plasmon propagation length.

We present the results of far field measurements of the complete 3D dispersion relation of a surface plasmon resonance (SPR) effect induced by an integrated quantum well nanodevice. The light modulations in the far field, where the surface plasmons are extracted by a grating, has been calculated for a continuum of energies and wavevectors injected by the luminescent substrate. We introduce a novel experimental method for direct mapping of the EM wave dispersion that enables the monitoring of massive amounts of light-scattering related information. The quasi-real time method is applied for tracking, in the E(k) space, the SPR peak surfaces generated by the investigated nanodevice. Those additional dimensions, measured with scalable tracking precision, reveal anisotropic surficial interactions and provide spectroscopic response for SPR.

The work function of n-alkanethiol self-assembled monolayers (SAMs) prepared on the GaAs(001) surface was measured using the Kelvin probe technique yielding the SAM 2D dipole layer potential (DLP). Direct n-dependent proportionality between the DLP values and the C-H stretching mode infrared (IR) absorption intensities was observed, which supports a correspondence of reported IR enhancements with the electrostatic properties of the interface. X-ray photoelectron spectroscopy is also used to verify the work function measurements. In addition, the principal components of the refractive index tensor are shown to be n-invariant in the ordered SAM phase. Our results suggest that a local field correction to the transition dipole moment accounts for the observed increase in IR activity through an increase to the electronic polarizability.

We report on the application of a laser rapid thermal annealing technique for iterative bandgap engineering at selected areas of quantum semiconductor wafers. The approach takes advantage of the quantum well intermixing (QWI) effect for achieving targeted values of the bandgap in a series of small annealing steps. Each QWI step is monitored by collecting a photoluminescence map and, consequently, choosing the annealing strategy of the next step. An array of eight sites, 280 mum in diameter, each emitting at 1480 nm, has been fabricated with a spectral accuracy of better than 2 nm in a standard InGaAs/InGaAsP QW heterostructure that originally emitted at 1550 nm.

On the basis of high resolution STM images and DFT modeling, we have resolved low- and high-coverage structures of methylthiolate (CH(3)S) self-assembled on the Au(111) surface. The key new finding is that the building block of all these structures has the same stoichiometry of two thiolate species joined by a gold adatom. The self-arrangement of the methylthiolate-adatom complexes on the surface depends critically on their stereochemical properties. Variations of the latter can produce local ordering of adatom complexes with either (3 x 4) or (3 x 4 square root(3)) periodicity. A possible structural connection between the (3 x 4 square root(3)) structure and commonly observed (square root(3) x square root(3))R30 degrees phase in methylthiolate self-assembled monolayers is developed by taking into account the reduction in the long-range order and stereochemical isomerization at high coverage. We also suggest how the observed self-arrangements of methylthiolate may be related to the c(4 x 2) phase of its longer homologues.

In the quest for the development of an all-optical biosensor for rapid detection and typing of viral pathogens, we investigate biosensing architectures that take advantage of strong photoluminescence emission from III-V quantum semiconductors (QS). One of the key elements in the development of such a biosensor is the ability to attach various analytes to GaAs--a material of choice for capping III-V QS of our interest. We report on the study of biofunctionalization of GaAs (001) with polyethylene-glycol (PEG) thiols and the successful immobilization of influenza A virus. A diluted solution of biotinylated PEG thiols in OH-terminated PEG thiols is used to form a network of sites for the attachment of neutravidin. Biotinylated polyclonal influenza A antibodies are applied to investigate the process of the immobilization of inactivated influenza A virus. The successful immobilization is demonstrated using atomic force microscopy and fluorescence microscopy measurements.

Using alkanethiol dense packing as a starting point, we have found six prototypical packing structures commensurate with the (3x2 radical3) supercell of the Au (111) surface. Five of the six structures are not compatible with the flat surface conditions but can be fitted to a reconstructed surface. Combined with density functional theory calculations and simulations of grazing incidence X-ray diffraction maps and of scanning tunneling microscopy images, this allowed us to refine and assess the recently proposed models of the c(4x2) self-assembled monolayers involving thiolate-adatom and thiolate-adatom-thiolate species and to propose a new model with four gold adatoms per unit cell.

We have recently proposed an innovative microstructure for a monolithically integrated surface plasmon resonance (SPR) device comprising a metal coated SiO(2) layer deposited atop a photoluminescence emitting quantum well (QW) wafer. The functioning of such a device is based on the uncollimated and incoherent emission of semiconductors. We discuss the results of our calculations aimed at the description of SPs coupling in QW semiconductor-based SPR architectures designed for biosensing applications. Two SPs modes could be coupled in the 0(th) diffraction order where the injected in-plane wavevectors from the QW structures can always meet SPR conditions. This results in increasing the SPs coupling efficiency up to 100 times higher than in case of indirect SPs injection.

Observed properties of thiol self-assembled monolayers (SAMs) on GaAs (001) surfaces can be explained by the presence of surface reconstructions, but their exact form is generally unknown. We propose a new approach to modeling the SAM-surface interface based on using alkanethiol dense packing structures as a starting point and adjusting the surface reconstruction to accommodate them. Obtained in such a way, model SAMs adsorb along the trenches in the [110] direction and exhibit a 19 degrees tilt and +/- 45 degrees twist angles, in agreement with available experimental data. The molecules of the SAM bind to both Ga and As, and cover only 50% of the available surface sites. The requirements for the SAM formation process to achieve the proposed structures are discussed.