scholarly journals Substituent Effects Impact Surface Charge and Aggregation of Thiophenol-Labeled Gold Nanoparticles for SERS Biosensors

Biosensors ◽  
2022 ◽  
Vol 12 (1) ◽  
pp. 25
Author(s):  
Nolan File ◽  
Joseph Carmicheal ◽  
Alexey V. Krasnoslobodtsev ◽  
Nicole C. Japp ◽  
Joshua J. Souchek ◽  
...  

SERS immunoassay biosensors hold immense potential for clinical diagnostics due to their high sensitivity and growing interest in multi-marker panels. However, their development has been hindered by difficulties in designing compatible extrinsic Raman labels. Prior studies have largely focused on spectroscopic characteristics in selecting Raman reporter molecules (RRMs) for multiplexing since the presence of well-differentiated spectra is essential for simultaneous detection. However, these candidates often induce aggregation of the gold nanoparticles used as SERS nanotags despite their similarity to other effective RRMs. Thus, an improved understanding of factors affecting the aggregation of RRM-coated gold nanoparticles is needed. Substituent electronic effects on particle stability were investigated using various para-substituted thiophenols. The inductive and resonant effects of functional group modifications were strongly correlated with nanoparticle surface charge and hence their stability. Treatment with thiophenols diminished the negative surface charge of citrate-stabilized gold nanoparticles, but electron-withdrawing substituents limited the magnitude of this diminishment. It is proposed that this phenomenon arises by affecting the interplay of competing sulfur binding modes. This has wide-reaching implications for the design of biosensors using thiol-modified gold surfaces. A proof-of-concept multiplexed SERS biosensor was designed according to these findings using the two thiophenol compounds with the most electron-withdrawing substitutions: NO2 and CN.

1975 ◽  
Vol 53 (6) ◽  
pp. 898-906 ◽  
Author(s):  
J. Peter Guthrie

Equilibrium constants for hydrate–hemiacetal interconversion in aqueous solution at 25° have been measured for four fluorinated carbonyl compounds: compound, alcohol, K4 (M−1): CF3CHO, C2H5OH, 2.3; CF3COCH3, CH3OH, 1.0; CF3COPh, CH3OH, 3.5; CF3COCF3, CH3OH, 0.14. These values, combined with values from the literature, permit an examination of substituent effects upon the equilibrium constant for[Formula: see text]The free energy change for this process, corrected for symmetry and steric effects, follows the equation[Formula: see text]Thus electronic effects upon this equilibrium are generally small and in fact are often smaller than steric effects.This analysis permits and justifies the calculation of free energies of formation of [Formula: see text] compounds from the (more generally measurable) free energies of formation of the analogous [Formula: see text] compounds.


Sensors ◽  
2021 ◽  
Vol 22 (1) ◽  
pp. 161
Author(s):  
Iwona Grabowska ◽  
Maria Hepel ◽  
Katarzyna Kurzątkowska-Adaszyńska

In recent years, the need for simple, fast, and economical detection of food and environmental contaminants, and the necessity to monitor biomarkers of different diseases have considerably accelerated the development of biosensor technology. However, designing biosensors capable of simultaneous determination of two or more analytes in a single measurement, for example on a single working electrode in single solution, is still a great challenge. On the other hand, such analysis offers many advantages compared to single analyte tests, such as cost per test, labor, throughput, and convenience. Because of the high sensitivity and scalability of the electrochemical detection systems on the one hand and the specificity of aptamers on the other, the electrochemical aptasensors are considered to be highly effective devices for simultaneous detection of multiple-target analytes. In this review, we describe and evaluate multi-label approaches based on (1) metal quantum dots and metal ions, (2) redox labels, and (3) enzyme labels. We focus on recently developed strategies for multiplex sensing using electrochemical aptasensors. Furthermore, we emphasize the use of different nanomaterials in the construction of these aptasensors. Based on examples from the existing literature, we highlight recent applications of multiplexed detection platforms in clinical diagnostics, food control, and environmental monitoring. Finally, we discuss the advantages and disadvantages of the aptasensors developed so far, and debate possible challenges and prospects.


Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3282
Author(s):  
Alina Secrieru ◽  
Rabah Oumeddour ◽  
Maria L. S. Cristiano

1,4- and 1,5-disubstituted tetrazoles possess enriched structures and versatile chemistry, representing a challenge for chemists. In the present work, we unravel the fragmentation patterns of a chemically diverse range of 5-allyloxy-1-aryl-tetrazoles and 4-allyl-1-aryl-tetrazolole-5-ones when subjected to electron impact mass spectrometry (EI-MS) and investigate the correlation with the UV-induced fragmentation channels of the matrix-isolated tetrazole derivatives. Our results indicate that the fragmentation pathways of the selected tetrazoles in EI-MS are highly influenced by the electronic effects induced by substitution. Multiple pathways can be envisaged to explain the mechanisms of fragmentation, frequently awarding common final species, namely arylisocyanate, arylazide, arylnitrene, isocyanic acid and hydrogen azide radical cations, as well as allyl/aryl cations. The identified fragments are consistent with those found in previous investigations concerning the photochemical stability of the same class of molecules. This parallelism showcases a similarity in the behaviour of tetrazoles under EI-MS and UV-irradiation in the inert environment of cryogenic matrices of noble gases, providing efficient tools for reactivity predictions, whether for analytical ends or more in-depth studies. Theoretical calculations provide complementary information to articulate predictions of resulting products.


2021 ◽  
Vol 22 (7) ◽  
pp. 3691
Author(s):  
Oliver Schmutzler ◽  
Sebastian Graf ◽  
Nils Behm ◽  
Wael Y. Mansour ◽  
Florian Blumendorf ◽  
...  

Quantitative cellular in vitro nanoparticle uptake measurements are possible with a large number of different techniques, however, all have their respective restrictions. Here, we demonstrate the application of synchrotron-based X-ray fluorescence imaging (XFI) on prostate tumor cells, which have internalized differently functionalized gold nanoparticles. Total nanoparticle uptake on the order of a few hundred picograms could be conveniently observed with microsamples consisting of only a few hundreds of cells. A comparison with mass spectroscopy quantification is provided, experimental results are both supported and sensitivity limits of this XFI approach extrapolated by Monte-Carlo simulations, yielding a minimum detectable nanoparticle mass of just 5 pg. This study demonstrates the high sensitivity level of XFI, allowing non-destructive uptake measurements with very small microsamples within just seconds of irradiation time.


Author(s):  
Peter A. Kavsak ◽  
Tara Edge ◽  
Chantele Roy ◽  
Paul Malinowski ◽  
Karen Bamford ◽  
...  

AbstractObjectivesTo analytically evaluate Ortho Clinical Diagnostics VITROS high-sensitivity cardiac troponin I (hs-cTnI) assay in specific matrices with comparison to other hs-cTn assays.MethodsThe limit of detection (LoD), imprecision, interference and stability testing for both serum and lithium heparin (Li-Hep) plasma for the VITROS hs-cTnI assay was determined. We performed Passing-Bablok regression analyses between sample types for the VITROS hs-cTnI assay and compared them to the Abbott ARCHITECT, Beckman Access and the Siemens ADVIA Centaur hs-cTnI assays. We also performed Receiver-operating characteristic curve analyses with the area under the curve (AUC) determined in an emergency department (ED)-study population (n=131) for myocardial infarction (MI).ResultsThe VITROS hs-cTnI LoD was 0.73 ng/L (serum) and 1.4 ng/L (Li-Hep). Stability up to five freeze-thaws was observed for the Ortho hs-cTnI assay, with the analyte stability at room temperature in serum superior to Li-Hep with gross hemolysis also affecting Li-Hep plasma hs-cTnI results. Comparison of Li-Hep to serum concentrations (n=202), yielded proportionally lower concentrations in plasma with the VITROS hs-cTnI assay (slope=0.85; 95% confidence interval [CI]:0.83–0.88). In serum, the VITROS hs-cTnI concentrations were proportionally lower compared to other hs-cTnI assays, with similar slopes observed between assays in samples frozen <−70 °C for 17 years (ED-study) or in 2020. In the ED-study, the VITROS hs-cTnI assay had an AUC of 0.974 (95%CI:0.929–0.994) for MI, similar to the AUCs of other hs-cTn assays.ConclusionsLack of standardization of hs-cTnI assays across manufacturers is evident. The VITROS hs-cTnI assay yields lower concentrations compared to other hs-cTnI assays. Important differences exist between Li-Hep plasma and serum, with evidence of stability and excellent clinical performance comparable to other hs-cTn assays.


Micromachines ◽  
2021 ◽  
Vol 12 (7) ◽  
pp. 826
Author(s):  
Yanting Liu ◽  
Xuming Zhang

This review aims to summarize the recent advances and progress of plasmonic biosensors based on patterned plasmonic nanostructure arrays that are integrated with microfluidic chips for various biomedical detection applications. The plasmonic biosensors have made rapid progress in miniaturization sensors with greatly enhanced performance through the continuous advances in plasmon resonance techniques such as surface plasmon resonance (SPR) and localized SPR (LSPR)-based refractive index sensing, SPR imaging (SPRi), and surface-enhanced Raman scattering (SERS). Meanwhile, microfluidic integration promotes multiplexing opportunities for the plasmonic biosensors in the simultaneous detection of multiple analytes. Particularly, different types of microfluidic-integrated plasmonic biosensor systems based on versatile patterned plasmonic nanostructured arrays were reviewed comprehensively, including their methods and relevant typical works. The microfluidics-based plasmonic biosensors provide a high-throughput platform for the biochemical molecular analysis with the advantages such as ultra-high sensitivity, label-free, and real time performance; thus, they continue to benefit the existing and emerging applications of biomedical studies, chemical analyses, and point-of-care diagnostics.


Author(s):  
Constantin A. Marschner ◽  
Vincent Schwarze ◽  
Regina Stredele ◽  
Matthias F. Froelich ◽  
Johannes Rübenthaler ◽  
...  

BACKGROUND: Vesicoureteral reflux (VUR) represents a common pediatric anomaly in children with an upper urinary tract infection (UTI) and is defined as a retrograde flow of urine from the bladder into the upper urinary tract. There are many diagnostic options available, including voiding cystourethrography (VCUG) and contrasted-enhanced urosonography (ceVUS). ceVUS combines a diagnostic tool with a high sensitivity and specificity which, according to previous study results, was even shown to be superior to VCUG. Nevertheless, despite the recommendation of the EFSUMB, the ceVUS has not found a widespread use in clinical diagnostics in Europe yet. MATERIALS AND METHODS: Between 2016 and 2020, 49 patients with a marked female dominance (n = 37) were included. The youngest patient had an age of 5 months, the oldest patient 60 years. The contrast agent used in ceVUS was SonoVue®, a second-generation blood-pool agent. All examinations were performed and interpreted by a single experienced radiologist (EFSUMB Level 3). RESULTS: The 49 patients included in the study showed no adverse effects. 51%of patients (n = 26) were referred with the initial diagnosis of suspected VUR, while 49%of patients (n = 23) came for follow-up examination or to rule out recurrence of VUR. The vast majority had at least one febrile urinary tract infection in their recent medical history (n = 45; 91,8%). CONCLUSION: ceVUS is an examination method with a low risk profile which represents with its high sensitivity and specificity an excellent diagnostic tool in the evaluation of vesicoureteral reflux, especially in consideration of a generally very young patient cohort.


2017 ◽  
Vol 95 (12) ◽  
pp. 1267-1272 ◽  
Author(s):  
Zhiyou Xiao ◽  
Anjiang Tang ◽  
Hongsheng Huang ◽  
Ze Wang

A simple and sensitive assay for Ag+ was developed with unmodified gold nanoparticles (AuNPs) by using dynamic light scattering techniques. Ag+ could induce the oligonucleotide (5′-ATC ACT ATA TCA TAT ACT CAT-3′) to change from a single-stranded structure to a double-stranded structure and desorb from the surface of AuNPs, which triggered the aggregation of AuNPs in the salt solution. The average hydrodynamic diameter of aggregated AuNPs could be detected by using dynamic light scattering techniques. Under the optimum conditions, the average hydrodynamic diameter of AuNPs is proportional to the concentration of Ag+ within the range of 13.3–100.0 nmol/L, with a detection limit of 3.2 nmol/L. The method is easy to operate and has low sample consumption, high sensitivity and selectivity.


Sign in / Sign up

Export Citation Format

Share Document