Sensitivity Analysis of Single- and Bimetallic Surface Plasmon Resonance Biosensors.

Comparative analysis of the sensitivity of two surface plasmon resonance (SPR) biosensors was conducted on a single-metallic Au sensor and bimetallic Ag-Au sensor, using a cathepsin S sensor as an example. Numerically modeled resonance curves of Au and Ag-Au layers, with parameters verified by the results of experimental reflectance measurement of real-life systems, were used for the analysis of these sensors. Mutual relationships were determined between ∂Y/∂n components of sensitivity of the Y signal in the SPR measurement to change the refractive index n of the near-surface sensing layer and ∂n/∂c sensitivity of refractive index n to change the analyte's concentration, c, for both types of sensors. Obtained results were related to experimentally determined calibration curves of both sensors. A characteristic feature arising from the comparison of calibration curves is the similar level of Au and Ag-Au biosensors' sensitivity in the linear range, where the signal of the AgAu sensor is at a level several times greater. It was shown that the influence of sensing surface morphology on the ∂n/∂c sensitivity component had to be incorporated to explain the features of calibration curves of sensors. The shape of the sensory surface relief was proposed to increase the sensor sensitivity at low analyte concentrations.

Rheological and Technological Aspects in Designing the Properties of Shear Thickening Fluids.

This work focuses on shear thickening fluids (STFs) as ceramic-polymer composites with outstanding protective properties. The investigation aims to determine the influence of raw material parameters on the functional properties of STFs. The following analyses were used to characterize both the raw materials and the STFs: scanning electron microscopy, dynamic light scattering, matrix-assisted laser desorption/ionization time-of-flight, chemical sorption analysis, rheological analysis, and kinetic energy dissipation tests. It was confirmed that the morphology of the solid particles plays a key role in designing the rheological and protective properties of STFs. In the case of irregular silica, shear thickening properties can be obtained from a solid content of 12.5 vol.%. For spherical silica, the limit for achieving shear thickening behavior is 40 vol.%. The viscosity curve analysis allowed for the introduction of a new parameter defining the functional properties of STFs: the technological critical shear rate. The ability of STFs to dissipate kinetic energy was determined using a unique device that allows pure fluids to be tested without prior encapsulation. Because of this, it was possible to observe even slight differences in the protective properties between different STFs, which has not been possible so far. During tests with an energy of 50 J, the dissipation factor was over 96%.

Potential of surface plasmon resonance biosensors in cancer detection.

A review is made of 71 papers on surface plasmon resonance biosensors, published between 2005 and 2020, mostly in the last decade. The reviewed papers are divided into two groups, depending on the validation of the developed biosensor. Validated biosensors are briefly characterized, while those that are not validated are listed in a table. Focus is placed on applications of SPR biosensors in testing the effectiveness of cancer markers and in the discovery of new cancer markers. Seven new markers are proposed, two of them having high sensitivity and diagnostic selectivity as determined by ROC curves. Papers concerning the determination of micro RNA and large particles such as vesicles, exosomes and cancer cells are also reviewed.

An Immunosensor for the Determination of Cathepsin S in Blood Plasma by Array SPRi-A Comparison of Analytical Properties of Silver-Gold and Pure Gold Chips.

The array SPR imaging (SPRi) technique is well suited to the determination of biomarkers in body fluids, called liquid biopsy. No signal enhancement or analyte preconcentration is required. With the aim of achieving signal enhancement and lowering the cost of a single determination, the replacement of gold-covered chips by silver-gold chips was investigated. The aim of this work was to investigate the analytical characteristics of a biosensor formed on a Ag/Au chip and to compare them with those of a biosensor formed on a gold chip. A biosensor for the determination of cathepsin S (Cath S) was chosen as an example. The biosensor consisted of the linker cysteamine and an immobilized rat monoclonal antibody specific for cathepsin S. Both biosensors exhibited a Langmuirian response to Cath S concentration, with linear response ranging from LOQ to 1.5 ng mL-1. The LOQ is 0.1 ng mL-1 for the biosensor formed on the Ag/Au chip, and 0.22 ng mL-1 for that formed on the gold chip. Recoveries and precision for medium and high Cath S concentrations were acceptable for both biosensors, i.e., precision better than 10% and recoveries within the range 102-105%. However, the results for the lowest Cath S concentration were better for the biosensor formed on the Ag/Au chip (9.4 and 106% for precision and recovery, respectively). Generally, no significant differences in analytical characteristics were observed between the Ag/Au and Au chips. The two biosensors were also compared in the determination of Cath S in real samples. Nine plasma samples from healthy donors and nine from patients with ovarian cancer were analyzed for Cath S concentration with the biosensors formed on Ag/Au and Au chips. The results obtained with the two biosensors were very similar and show no significant differences on the Bland-Altman plot. The Cath S concentration in the blood plasma of ovarian cancer patients was elevated by one order of magnitude as compared with the control (12.6 ± 3.6 vs. 1.6 ± 1.2 ng mL-1).

A Comparison of Various Chips Used for the Manufacture of Biosensors Applied in Non-Fluidic Array SPRi, Based on the Example of Determination of Cathepsin D.

Non-fluidic array SPR imaging (SPRi) with appropriate biosensors is a new tool for the determination of various biomarkers in body fluids. Numerous biomarkers can be determined without signal enhancement or preliminarily preconcentration. The introduction of a new material solution of the chip may increase the scope of the application of this technique. Solutions with adhesive separating foil and an Ag/Au chip were compared with the previously used two-paint separating polymer and pure gold chip. These solutions were tested using the example of a biosensor for cathepsin D (Cath D), which consisted of pepstatin A (a Cath D inhibitor) immobilized via a cysteamine linker using the NHS/EDC protocol. Four material versions of the Cath D biosensor proved adequate in terms of range of linearity, LOQ, precision and recovery. All four versions of the biosensor were used for the determination of Cath D in the blood serum patients with glioblastoma and control samples, producing very similar results and showing an elevated biomarker concentration in the case of cancer. Therefore, the problem of determining the correct level of Cath D in the serum of healthy individuals has been resolved, correcting literature data which ranged over three orders of magnitude.

Thermally induced structural transformations of linear coordination polymers based on aluminum tris(diorganophosphates).

The thermal transitions of inorganic-organic hybrid polymers composed of linear aluminum tris(diorganophosphate) chains with a general formula of catena-Al[O2P(OR)2]3 (where R = C1-C8 alkyl group or phenyl moiety) have been studied by means of DSC, powder XRD, TGA and TG-QMS, as well as optical spectroscopy. DSC and XRD reveal that most of them undergo reversible structural transformations in the solid state between -100 and 200 °C caused by the changes in conformation of their organic substituents; however, a translational displacement of the rigid polymeric chains occurs only in the case of the derivative bearing long 2-ethylhexyl groups, which becomes liquid at about 140 °C. The thermal decomposition of the studied polymers begins between 200 and 265 °C depending on the type of organic substituent R decorating their aluminophospate core. TGA combined with mass spectrometry of the evolved gaseous products shows that the pyrolytic decomposition of Al[O2P(OR)2]3 proceeds either through ß-elimination of olefin (for compounds with C2-C8 aliphatic ligands), or a homolytic cleavage of the P-OR bond (for methyl and phenyl derivatives); both processes are accompanied by condensation of the newly formed POH groups and liberation of water. Powder XRD, FTIR and SEM analyses of the solid residues indicate that thermolysis of Al[O2P(OR)2]3 accompanied by olefin elimination leads to the formation of condensed aluminum phosphates, mainly aluminum cyclohexaphosphate, exhibiting porous morphology. On the other hand, thermal degradation of methyl or phenyl derivatives results in amorphous aluminophosphate residues, and the latter contains conducting carbonaceous phases.