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Bitumen is a complex mixture of hydrocarbons for which microstructural knowledge is incomplete. In an effort to detail this microstructure, 13 bitumens were analysed by phase-detection atomic force microscopy. Based on morphology, the bitumens could be classified into three distinct groups. One group showed fine domains down to 0.1 µm, another showed domains of about 1 µm, and a third group showed up to four different domains or phases of different sizes and shapes. No correlation was found between the atomic force microscopy morphology and the composition based on asphaltenes, polar aromatics, naphthene aromatics and saturates. A high correlation was found between the area of the ‘bee-like’ structures and the vanadium and nickel content in bitumen, and between the atomic force microscopy groups and the average size of molecular planes made of fused aromatics. The morphology and the molecular arrangements in bitumen thus appear to be partly governed by the molecular planes and the polarity defined by metallic cations. [ABSTRACT FROM AUTHOR]

Abstract: Single-crystal sapphire-fiber optic sensors based on surface plasmon resonance (SPR) for refractive index (RI) measurements of aqueous and hydrothermal water solutions are described. Accurate measurement of RIs is essential to efficient operation and control of broad range of engineering processes. Some of these processes are carried out with harsh environments, such as high-temperature, high pressure, and chemical corrosion. These extreme physical conditions are proving a limiting factor in application of the conventional silica-based optical sensors. Single-crystal sapphire is an ideal material for sensor applications, where reliable performance is required in the extreme environment conditions. With regard to the liquid species detection, most applications of SPR sensors are designed to function near the refractive index of water (1.3330RI). The RI changes of aqueous solution can be easily monitored by silica-fiber (RI, 1.4601 at 550nm) based SPR sensor. However, the sapphire waveguide has a prohibitively high RI (1.7708 at 546nm) for unmodified monitoring of the RI changes of aqueous solutions. For that purpose, a practical SPR probe geometry has been applied to the ability to tune the SPR coupling wavelength/angle pair with sapphire-fiber based SPR probe. [Copyright &y& Elsevier]

Abstract: The elimination or minimization of non-specific protein adsorption from serum is critical for the use of surface plasmon resonance (SPR) sensors for in vitro and in vivo analysis of complex biological solutions. The ultimate goals in this application are to minimize non-specific adsorption of protein and to maximize analyte signal. A reduction of the non-specific protein adsorption from serum of up to 73% compared to carboxymethylated-dextran 500kDa (CM-dextran) was achieved following a survey of eight biocompatible polymers and 10 molecular weights of CM-dextran. These coatings minimize non-specific adsorption on the sensor while also serving as immobilization matrices for antibody fixation to the probes. Polymers including polysaccharides: CM-dextrans, CM-hyaluronic acid, hyaluronic acid, and alginic acid were investigated. Humic acid, polylactic acid, polyacrylic acid, orthopyridyldisuldfide–polyethyleneglycol–N-hydroxysuccinimide (OPSS–PEG–NHS), and a synthesized polymer; polymethacrylic-acid-co-vinyl-acetate (PMAVA) were also used. The non-specific protein adsorption reduction was measured over a 14 day period at 0°C for each polymer. Calibration curves using some of these polymers were constructed to show the performance and low detection limit possibilities of these new antibody supports. For many of the polymers, this is the first demonstration of employment as an antibody support for an optical or surface active sensor. CM-dextran is the polymer offering the largest signal for the antigen detection. However, the biocompatible polymers demonstrate a greater stability to non-specific binding in serum. These biocompatible polymers offer different alternatives for CM-dextran. [Copyright &y& Elsevier]

In clinical chemistry, frequent monitoring of drug levels in patients has gained considerable importance because of the benefits of drug monitoring on human health, such as the avoidance of high risk of over dosage or increased therapeutic efficacy. In this work, we demonstrate that the drug doxycycline can act as an Au nanoparticle (doxy-AuNP) growth and capping agent to enhance the response of a surface plasmon resonance (SPR) biosensor for this drug. SPR analysis revealed the high sensitivity of doxy-AuNPs towards the detection of free doxycycline. More specifically, doxy-AuNPs bound with protease-activated receptor-1 (PAR-1) immobilized on the SPR sensing surface yield the response in SPR, which was enhanced following the addition of free doxy (analyte) to the solution of doxy-AuNPs. This biosensor allowed for doxycycline detection at concentrations as low as 7 pM. The study also examined the role of colloidal stability and growth of doxy-AuNPs in relation to the response-enhancement strategy based on doxy-AuNPs. Thus, the doxy-AuNPs-based SPR biosensor is an excellent platform for the detection of doxycycline and demonstrates a new biosensing scheme where the analyte can provide enhancement. [ABSTRACT FROM AUTHOR]

A series of thermally shrinkable polymer surface-enhanced Raman scattering (SERS) substrates were prepared with bimetallic Au and Ag (oxidized or not) films and with Au nanoparticles (AuNPs) located at different places in the layered structure to evaluate the synergistic effect of different known SERS amplification methods to enhance the Raman signal for low concentration dopamine detection. A bimetallic Au and Ag layered structure improved the Raman signal by 5 and 2 times compared to the single-layered Au and Ag films. Oxidizing the Ag layer prior to deposition of Au further improved the signal by a factor of 2, while adding AuNP on wrinkled films increased another 10 times the intensity of the Raman signal. It was found that the enhancement was another 10 times stronger when using AuNPs in combination with other means of enhancement such as with a silver underlayer or surface wrinkling. Wrinkling alone only gave a few-fold increase compared to a flat film, but the combination of wrinkling with AuNPs and a silver underlayer improved the SERS intensity by more than 3 orders of magnitude, showing the synergistic effect of these enhancement methods. The optimized sensors were then tested in dynamic SERS with low concentration dopamine solutions, where the signal showed characteristics of a digital SERS response. Raman spectra preprocessing and sorting software was developed to triage the SERS-active spectra from the null spectra, to count the detection events such as the ones observed in single molecule experiments. [ABSTRACT FROM AUTHOR]

Mapping the transition of Ag nanotriangle to nanohole arrays revealed that the optimal SERS response was obtained near the transition. Correlated AFM and Raman imaging provided novel experimental proof that hot spots are located on Ag islands for nanotriangle arrays and in the core area of the hole for nanohole arrays, which is in agreement with previous theoretical predictions. [ABSTRACT FROM AUTHOR]

Bovine serum albumin (BSA) containing buffers are the standard blocking buffer in biosensing, yet human serum is the intended application for most clinical sensors. However, the effect of human serum albumin (HSA) on binding assays remains underexplored. A simple and well-studied assay (human IgG/goat anti-human IgG) was investigated with a surface plasmon resonance (SPR) sensor to address this fundamental question in sensing. Calibrations were performed with buffers containing various concentrations of bovine or human serum albumin, as well as full and diluted bovine or IgG-depleted human serum. It was found that HSA or human serum, but not BSA or bovine serum, significantly affected the SPR shift and binding constants of the assay. Interestingly, large differences were also observed depending on whether the animal or human antibody was immobilized on the SPR chip for detection, highlighting that matrix protein/analyte/receptor interactions play a significant role in the response. We find that the interaction of soluble HSA with human IgG interferes with the recognition region, affecting the binding constant, and thus results obtained in BSA are not necessarily applicable to clinical samples or in vivo conditions. We also clearly demonstrate why a minimum dilution of 1 : 10 is often required in SPR assays to remove most background effects. Taken together, these results show that: (1) BSA does not affect the binding constant between antibodies and thus serves its purpose well when only surface blocking is intended, (2) HSA is an adequate surrogate for human serum in assay optimization, and (3) blocking buffers should be prepared with HSA in the optimization steps of assays to be translated to human blood or serum. [ABSTRACT FROM AUTHOR]

ATP mediates chemoexcitation via binding to P2X2-P2X3 receptors. We developed amperometric ATP microbiosensors to determine the role of ATP in mediating maturation of chemosensitivity of peripheral arterial chemoreceptors at the carotid body (CB) to physiological stimuli. ATP is detected by immobilizing glucose oxidase and hexokinase within a polymer matrix at the surface of a 25 µm-diameter Pt disk electrode. The age-dependent ATP release from CBs was measured in real-time in response to hypoxia ([O2] < 1 ppm), and to normoxic hypercapnia (10-12% CO2). During hypoxia, ATP released at the CB was 4.3 ± 0.3 µM (median = 4.2 µM, n = 9) in rats between 3-6 postnatal days (PNDs), which increased to 91 ± 28 µM ATP (median = 19 µM, n = 6) at CBs of rats between 16-20 PNDs. The significant difference in ATP release from CBs of older animals suggests that hypoxic ATP release mechanisms are maturating during the 3rd week of postnatal development. However, in response to hypercapnia ATP release was only 6.1 ± 0.9 µM (median = 4.9 µM, n = 7) during the 3rd week, indicating that the development of hypercapnic ATP release mechanisms is different from hypoxia in rats. The 5-fold increase in ATP release in response to hypoxia during the first 3 weeks of postnatal development may contribute to the increase in hypoxic chemosensitivity, which occurs during early postnatal development. [ABSTRACT FROM AUTHOR]

Metallic thin films patterned with micrometer size triangle or hole arrays present plasmonic properties when excited in the Kretschmann configuration, that are improved in comparison to conventional thin film surface plasmon resonance (SPR). These optical properties can be tuned by varying the physical aspects of the microplasmonic structures. Triangles and microhole arrays were prepared with modified nanosphere lithography (NSL) using latex spheres of 0.65, 0.82, 1.0, 1.5, or 3.2 pm in diameter. This allowed the preparation of triangles with edge lengths between 275 to 2000 nm and microhole arrays of various periodicities, diameters, and hole depths. These microstructures were studied to understand the relationship between the physical aspects and the optical properties, such as the sensitivity, working refractive index range, spectral width of the plasmonic peaks, spectral noise, and refractive index resolution. Microhole arrays with a hole diameter equal to half the periodicity were found to combine the advantages of both localized surface plasmon resonance (LSPR) on nanoparticles and SPR on a thin film. These microhole arrays exhibited high sensitivity to refractive index (>3000 nm/RIU), sensitivity to monolayer formation (2-fold improvement compared to thin films), and excellent refractive index resolution (10-6 RIU). Finally, a biosensor for the detection of 10 nM of immunoglobulin G (lgG) exhibited a greater response with microplasmonic materials compared to conventional thin Au films. Hence, these novel plasmonic materials exhibit a strong potential as an SPR sensing platform. They can be implemented on existing insinimentation and use detection protocols developed for current SPR sensors. [ABSTRACT FROM AUTHOR]

Near-zero fouling monolayers based on binaiy patterned peptides allow low nanomolar detection of the matrix metalloproteinase-3 (MMP-3) directly in crude bovine serum, without sample pretreatment, secondary antibody detection or signal amplification. The peptide 3-MPA-HHHDD-OH (3-MPA, 3-mercaptopropionic acid) was found optimal compared to other binary patterned peptides based on 3-MPA-Ax-By-OH, where 0 ⩽ x, y ⩽ 5, and x + y = 5, and compared to PEG. In this study, amino acid A was His, Asp, Ser, or Leu, and amino acid B was His, Asp, or Ser. Zwitterionic peptides and other peptides exhibited excellent resistance to non-specific adsorption. Binary patterned peptides were capped with 3-MPA on the N-terminus providing a monolayer with the C-terminus carboxylic acid available to subsequently immobilize antibodies. Thereby, an IgG biosensor demonstrated the efficiency of binary patterned peptides in SPR biosensingwith a detection limit of 1-10 μM In PBS, similar to other optical or electrochemical techniques. This protocol was applied to establish a calibration curve for MMP-3, an analyte of clinical interest for many pathologies and a potential indicator of cancer. The LOD for MMP-3 was 0.14 nM in PBS, with a linearity of up to 50 nM. With the use of PBS calibration, MMP-3 was quantified at low nanomolar in undiluted bovine serum. The SPR response in serum was statistically the same as in PBS. A sensor exposed to blank serum exhibited negligible nonspecific adsorption. Hence, binary patterned peptides are suitable for bio-sensing directly in complex biological matrixes. [ABSTRACT FROM AUTHOR]

SARS-CoV-2 variants of concern (VOCs) have emerged worldwide, with implications on the spread of the pandemic. Characterizing the cross-reactivity of antibodies against these VOCs is necessary to understand the humoral response of non-hospitalized individuals previously infected with SARS-CoV-2, a population that remains understudied. Thirty-two SARS-CoV-2-positive (PCR-confirmed) and non-hospitalized Canadian adults were enrolled 14–21 days post-diagnosis in 2020, before the emergence of the B.1.351 (also known as Beta), B.1.617.2 (Delta) and P.1 (Gamma) VOCs. Sera were collected 4 and 16 weeks post-diagnosis. Antibody levels and pseudo-neutralization of the ectodomain of SARS-CoV-2 spike protein/human ACE-2 receptor interaction were analyzed with native, B.1.351, B.1.617.2 and P.1 variant spike proteins. Despite a lower response observed for the variant spike proteins, we report evidence of a sustained humoral response against native, B.1.351, B.1.617.2 and P.1 variant spike proteins among non-hospitalized Canadian adults. Furthermore, this response inhibited the interaction between the spike proteins from the different VOCs and ACE-2 receptor for ≥ 16 weeks post-diagnosis, except for individuals aged 18–49 years who showed no inhibition of the interaction between B.1.617.1 or B.1.617.2 spike and ACE-2. Interestingly, the affinity (KD) measured between the spike proteins (native, B.1.351, B.1.617.2 and P.1) and antibodies elicited in sera of infected and vaccinated (BNT162b2 and ChAdOx1 nCoV-19) individuals was invariant. Relative to sera from vaccine-naïve (and previously infected) individuals, sera from vaccinated individuals had higher antibody levels (as measured with label-free SPR) and more efficiently inhibited the spike–ACE-2 interactions, even among individuals aged 18–49 years, showing the effectiveness of vaccination. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • FeOx overcome single crystal phases generally suffering from serious agglomeration and poor electrical conductivity. • The synergistic effect between the electrocatalytic property and the polycrystalline structure of FeOx was verified. • Hybrid FeOx with variable oxidation states remarkably facilitate the efficient redox charge transfer. Abstract Investigations on interplay between sensing platform performance and crystal phase of material are the new beginning of designing advanced bioanalytical systems. Herein, FeO x nanoparticles (NPs, ∼100 nm), including superfine magnetic (Fe 3 O 4) and hematite (α-Fe 2 O 3) nanocrystals in single particles, have been employed to verify the synergistic effect between the electrocatalytic property and the polycrystalline structure of the materials. Moreover, this strategy overcomes that single crystal phases generally suffer from serious agglomeration and poor electrical conductivity. More importantly, hybrid metal oxides (e.g., α-Fe 2 O 3 /Fe 3 O 4) with variable oxidation states remarkably facilitate the efficient redox charge transfer. Taking the detection of Flutamide (FLT) in prostate cancer cells (VCaP cells) as example, the dynamic ranges of the oxidation states from the different crystal phases were integrated into a single electrochemical sensor interface. Furthermore, good selectivity, accuracy, satisfactory sensitivity (769.1 μA mM−1 cm-2) and low detection limits (46.6 nM) were achieved. Going beyond the conventional single-crystal phase-driven electrochemical sensing, the elaborate of polycrystalline structure in a single particle may open a new approach for the design of outstanding electrode materials, which not only can significantly improve the performance of sensing platforms, but also can be used to rationally design the material properties according to the applications. [ABSTRACT FROM AUTHOR]

A highly sensitive surface plasmon resonance (SPR) sensor is reported for glucose detection using self-assembled p-mercaptophenylboronic acid (PMBA) monolayer on Au coated optical fibers. The cis-diol group of saccharides, such as for glucose, interacted with the self-assembled PMBA monolayers on the optical fibers, but the low molecular mass of glucose is insufficient for measuring a significant shift in SPR wavelength. The response for glucose was thus enhanced with Au nanoparticles (Au NPs) modified with 2-aminoethanethiol (AET) and PMBA. Selectivity was assured since glucose has the ability to capture the signal amplification tags (Au NPs/AET- PMBA) through secondary binding with another set of syn-periplanar diol groups and the PMBA on the gold surface. Accordingly, a glucose concentration-dependent sandwich structure was formed and the coupling between Au NPs and Au film results in the red shift of SPR resonance wavelength. The experimental results demonstrated that this SPR sensor responded to glucose within a range of 0.01–30 mM better than to fructose and galactose. The minimum concentration for quantify glucose is as low as 80 nM, which is lower than the physiological blood glucose level. Glucose was then accurately detected in urine sample, which indicated the potential application of the sensor for the analysis of glucose in urine. We believe that our proposed PMBA-modified single amplification tag and sensing principle can also be used for biomolecules consisting of carbohydrate structures, particularly for DNA-associated bioanalysis. [ABSTRACT FROM AUTHOR]

MicroRNA (miRNA) sensing, especially the miRNA-200 family, is increasingly targeted for cancer diagnostics. As the sensing schemes often rely on nanoparticles functionalized with a specific oligonucleotide, we investigate the hydribization conditions using the common case of surface plasmon resonance (SPR) sensing of miRNA and a gold nanoparticle (Au NP) competitor. In this type of assays, the Au NPs compete with the microRNA to bind the capture probe immobilized on the gold surface. In our study, we simplify and improve the detection procedure by adopting 11-mercaptoundecanoic acid (11-MUA) as linker to the gold surface, not only omitting the blocking step of 6-mercapto-1-hexanol (MCH), but also increasing the probe density. We report that the response in our SPR sensing studies increased with the size of Au NPs according to the plasmon ruler equation, but the larger AuNPs of 32 nm lacked colloidal stability. In addition, decreasing the ratio of oligonucleotide to Au NPs and the addition of polyethylene glycol (PEG) to hybridization buffer also favored a better response in SPR sensing of miRNA. The optimization led to an improved detection sensitivity in our competition method and a detection limit as low as 500 pM for miRNA-200b without amplification of miRNA and use of other amplification schemes. [ABSTRACT FROM AUTHOR]

In this paper, we report a novel wavelength interrogation-based surface plasmon resonance (SPR) system, in which a film of three Ag layers and three Au layers are alternately deposited on a Kretschmann configuration as sensing element. This multilayer film shows higher sensitivity for refractive index (RI) measurement by comparing with single Au layer structure, which is consistent with its theoretical calculation. A sensitivity range of 2056-5893 nm/RIU can be achieved, which is comparable to RI sensitivities of other wavelength-modulated SPR sensors. Compared with Ag film, this Ag/Au multilayer arrangement offers anti-oxidant protection. This SPR biosensor based on a cost-effective Ag/Au multilayer structure is applicable to the real-time detection of specific interactions and dissociation of low protein concentrations. To extend the application of this highly-sensitive metal film device, we integrated this concept on an optical fiber. The range of RI sensitivities with Ag/Au multilayer was 1847-3309 nm/RIU. This miniaturized Ag/Au multilayer-based fiber optic sensor has a broad application in chemical and biological sensing. [ABSTRACT FROM AUTHOR]

In this paper, the coupling interaction is investigated between a metallic nanowire array and a metal film under the Kretschmann condition. The plasmonic multilayer is composed of a metallic nanowire array embedded in a polymer layer positioned above a metal film, exploiting the classical surface plasmon resonance (SPR) configuration. We analyze the influence of various structural parameters of the metallic nanowire array on the SPR spectrum of thin metal film. The results show that the coupling interactions of nanowires with the metal film can greatly affect SPR resonance wavelength and increase SPR sensitivity. The coupling strength of metallic nanowire array and metal film also impacts resonance wavelength, which can be used to adjust SPR range but have little effect on its sensitivity. The results are confirmed using a dipole coupling resonance model of metallic nanowire. We demonstrated that this nanostructured hybrid structure can be used for high sensitivity SPR monitoring in a large spectral range, which is important for advanced SPR measurement including fiber-optic SPR sensing technology. [ABSTRACT FROM AUTHOR]

These authors contributed equally: Maryam Hojjat Jodaylami, Abdelhadi Djaïleb and Pierre Ricard. Correction to: I Scientific Reports i https://doi.org/10.1038/s41598-021-00844-z, published online 08 November 2021 The original version of this Article contained an error in the spelling of the author Stella Cellier-Goetghebeur which was incorrectly given as Stella Cellier-Goethebeur. [Extracted from the article]

Abstract: We validate, by comparison with experimental data, a theoretical description of the amperometric response of microbiosensors formed via enzyme entrapment. The utility of the theory is further illustrated with two relevant examples supported by experiments: (1) quantitative detection of glucose and (2) quantitative detection of adenosine triphosphate (ATP). [Copyright &y& Elsevier]

Abstract: We have developed a theoretical description of the amperometric response of ultramicroelectrode (UME) biosensors formed via enzyme entrapment. Our model allows for multiple enzymes and co-substrates, and results in a closed-form analytical expression for the steady-state current response of the disk ultramicroelectrode. It captures the effects of enzyme-entrapment domain size, species transport properties (which can be different in the polymer and surrounding electrolyte), enzyme kinetics, and axisymmetric diffusion. Assumptions inherent in the derivation are carefully explained, as are the resulting limits on the applicability of the results. The ability to theoretically predict the response of enzyme entrapped UMEs should enable improved design, operation, and data interpretation for this important class of biosensors. [Copyright &y& Elsevier]

• An optical fiber LSPR biosensor via diblock copolymer-templated AuNRs monolayer was reported. • PS- b -PV4P-templated citrate-AuNR film led to higher RI sensitivity than that of PS- b -PAA-templated CTAB-AuNR film. • PS- b -PV4P-templated biosensor exhibited better spectral characteristics than polyelectrolyte and APTES-based biosensors. • PS- b -PV4P-templated biosensor exhibited an excellent response to human IgG with LOD of 0.6 nM. Block copolymer (BCP) brush-like layer absorbed on optical fibers are shown to address the longstanding challenge of forming dense and well-dispersed gold nanorods (AuNRs) films on highly curved surface, allowing the development of real-time localized surface plasmon resonance (LSPR) biosensors for antigen-antibody interaction. This method requires only solution-based manufacturing processes and a plasma cleaning step to self-assemble AuNRs with various aspect ratios on the optical fibers. Because AuNRs capped with cetyltrimethylammonium bromide (CTAB) have been problematic for biosensing applications due to their cytotoxicity and displacement difficulty in the construction of biosensors, citrate-stabilized AuNRs were prepared from CTAB-stabilized AuNRs via surfactant exchange. For comparison, both a poly(styrene)- b -poly(acrylic acid) (PS- b -PAA) BCP template with CTAB-stabilized AuNRs and a poly(styrene)- b -poly(4-vinyl pyridine) (PS- b -P4VP) BCP template with citrate-stabilized AuNRs were employed for the fabrication of the optical fiber biosensor. The LSPR spectral analysis results demonstrate that the sensitivity of the sensor produced by the PS- b -P4VP templating method was 1.5 times better than that of the sensor produced by the PS- b -PAA templating method, which was due to the improved surface coverage and reduced aggregation of nanoparticles. The detection limit of the PS- b -P4VP-templated sensor for human IgG was 0.6 nM. Furthermore, for citrate-stabilized AuNRs, the PS- b -P4VP templating method also led to a better surface morphology and higher sensitivity as compared to the standard particle absorption methods using alkoxysilanes or polyelectrolytes on identical fibers. The simplicity of the fabrication process and the far superior optical performance of the PS- b -P4VP-templated LSPR optical fiber sensor illustrate the ability to regulate the detection range by tuning the aspect ratios of the AuNRs, and demonstrate its application prospects as a real-time biosensor without cytotoxicity. [ABSTRACT FROM AUTHOR]