Ciprofloxacin: pH-dependent SERS signal and its detection in spiked river water using LoC-SERS.

Monitoring the successful removal of antibiotics in waste and surface waters is of high interest to overcome the occurrence of antibacterial resistance in the ecosystem. Among the newly developed analytical methods, the lab-on-a-chip surface-enhanced Raman spectroscopic (LoC-SERS) technique has gained the interest of the scientific community in the last few years. Ciprofloxacin, a second-generation fluoroquinolone, is widely used and administered to patients in dosages up to 1000 mg. In addition, more than 50 % of the antibiotic is excreted in urine as the parental drug. Thus, ciprofloxacin in environmental samples may exceed the minimum inhibitory concentration (MIC) values. The present study aims to assess the potential of the LoC-SERS technique to detect the target analyte in spiked river water samples at MIC concentrations. As sample clean-up procedure, a simple filtration is proposed, while as SERS, active substrates silver nanoparticles prepared at room temperature are employed. Ciprofloxacin was successfully quantified in the 0.7-10 µM concentration range with data that were measured on two different days. Furthermore, because of the low solubility of the antibiotic at the neutral pH range, insights into the effect of pH on the SERS signal of the target molecule are also presented. Graphical Abstract Ciprofloxacin detected at MIC values by LOC-SERS.

Lab-on-a-Chip-Surface Enhanced Raman Scattering Combined with the Standard Addition Method: Toward the Quantification of Nitroxoline in Spiked Human Urine Samples.

The emergence of antibacterial resistance and the development of new drugs lead to a continuous change of guidelines for medical treatments. Hence, new analytical tools are required for the detection of drugs in biological fluids. In this study, the first surface enhanced Raman scattering (SERS) detection of nitroxoline (NTX) in purified water and in spiked human urine samples is reported. Insights concerning the nature of the molecule-metal interaction and its influence on the overall SERS signal are provided. Furthermore, three randomly collected urine samples originating from a healthy volunteer were spiked to assess the limit of detection (LOD), the limit of quantification (LOQ), and the linear dynamic range of the lab-on-a-chip SERS (LoC-SERS) method for NTX detection in human urine. The LOD is ∼3 µM (0.57 mg/L), LOQ ∼ 6.5 µM (1.23 mg/L) while the linear range is between 4.28 and 42.8 µM (0.81-8.13 mg/L). This covers the minimum inhibitory concentration (MIC) values of the most commonly encountered uropathogens. Finally, seven clinical samples having an "unknown" NTX concentration were simulated. The LoC-SERS technique combined with the standard addition method and statistical data analysis provided a good prediction of the unknown concentrations. Additionally, it is also demonstrated that the predictions carried out by multicurve resolution alternating least-squares (MCR-ALS) algorithm provides reliable results, and it is preferred to a univariate statistical approach.

Plasmonic nanostructures for surface enhanced spectroscopic methods.

A comprehensive review of theoretical approaches to simulate plasmonic-active metallic nano-arrangements is given. Further, various fabrication methods based on bottom-up, self-organization and top-down techniques are introduced. Here, analytical approaches are discussed to investigate the optical properties of isotropic and non-magnetic spherical or spheroidal particles. Furthermore, numerical methods are introduced to research complex shaped structures. A huge variety of fabrication methods are reviewed, e.g. bottom-up preparation strategies for plasmonic nanostructures to generate metal colloids and core-shell particles as well as complex-shaped structures, self-organization as well as template-based methods and finally, top-down processes, e.g. electron beam lithography and its variants as well as nanoimprinting. The review article is aimed at beginners in the field of surface enhanced spectroscopy (SES) techniques and readers who have a general interest in theoretical modelling of plasmonic substrates for SES applications as well as in the fabrication of the desired structures based on methods of the current state of the art.