The control of low-energy electrons by carrier-envelope-phase-stable near-single-cycle THz pulses is demonstrated. A femtosecond laser pulse is used to create a temporally localized wave packet through multiphoton absorption at a well defined phase of a synchronized THz field. By recording the photoelectron momentum distributions as a function of the time delay, we observe signatures of various regimes of dynamics, ranging from recollision-free acceleration to coherent electron-ion scattering induced by the THz field. The measurements are confirmed by three-dimensional time-dependent Schrödinger equation simulations. A classical trajectory model allows us to identify scattering phenomena analogous to strong-field photoelectron holography and high-order above-threshold ionization.
Glutathione and malondialdehyde are two compounds commonly used to evaluate the oxidative stress status of an organism. Although their determination is usually performed in blood serum, saliva is gaining ground as the biological fluid of choice for oxidative stress determination at the point of need. For this purpose, surface-enhanced Raman spectroscopy (SERS), which is a highly sensitive method for the detection of biomolecules, could offer additional advantages regarding the analysis of biological fluids at the point of need. In this work, silicon nanowires decorated with silver nanoparticles made by metal-assisted chemical etching were evaluated as substrates for the SERS determination of glutathione and malondialdehyde in water and saliva. In particular, glutathione was determined by monitoring the reduction in the Raman signal obtained from substrates modified with crystal violet upon incubation with aqueous glutathione solutions. On the other hand, malondialdehyde was detected after a reaction with thiobarbituric acid to produce a derivative with a strong Raman signal. The detection limits achieved after optimization of several assay parameters were 50 and 3.2 nM for aqueous solutions of glutathione and malondialdehyde, respectively. In artificial saliva, however, the detection limits were 2.0 and 0.32 μM for glutathione and malondialdehyde, respectively, which are, nonetheless, adequate for the determination of these two markers in saliva.
In this study, we developed active substrates consisting of Ag-decorated silicon nanowires on a Si substrate using a single-step Metal Assisted Chemical Etching (MACE) process, and evaluated their performance in the identification of low concentrations of Rhodamine 6G using surface-enhanced photoluminescence spectroscopy. Different structures with Ag-aggregates as well as Ag-dendrites were fabricated and studied depending on the etching parameters. Moreover, the addition of Au nanoparticles by simple drop-casting on the MACE-treated surfaces can enhance the photoluminescence significantly, and the structures have shown a Limit of Detection of Rhodamine 6G down to M for the case of the Ag-dendrites enriched with Au nanoparticles.
Nanostructured noble metal surfaces enhance the photoluminescence emitted by fluorescent molecules, permitting the development of highly sensitive fluorescence immunoassays. To this end, surfaces with silicon nanowires decorated with silver nanoparticles in the form of dendrites or aggregates were evaluated as substrates for the immunochemical detection of two ovarian cancer indicators, carbohydrate antigen 125 (CA125) and human epididymis protein 4 (HE4). The substrates were prepared by metal-enhanced chemical etching of silicon wafers to create, in one step, silicon nanowires and silver nanoparticles on top of them. For both analytes, non-competitive immunoassays were developed using pairs of highly specific monoclonal antibodies, one for analyte capture on the substrate and the other for detection. In order to facilitate the identification of the immunocomplexes through a reaction with streptavidin labeled with Rhodamine Red-X, the detection antibodies were biotinylated. An in-house-developed optical set-up was used for photoluminescence signal measurements after assay completion. The detection limits achieved were 2.5 U/mL and 3.12 pM for CA125 and HE4, respectively, with linear dynamic ranges extending up to 500 U/mL for CA125 and up to 500 pM for HE4, covering the concentration ranges of both healthy and ovarian cancer patients. Thus, the proposed method could be implemented for the early diagnosis and/or prognosis and monitoring of ovarian cancer.
The nonlinear single and double ionization of Sr atoms as a result of their interaction with 800-nm Ti-sapphire laser pulses of 25-fs duration is experimentally investigated within the laser intensity range . The latter range includes the over-the-barrier intensities for both Sr and , while the corresponding Keldysh adiabaticity parameters are larger than unity. Nevertheless, for the recorded photoelectron-energy spectra show evidence of the (partial) applicability of tunneling or over-the-barrier ionization concepts, whereas below this value they can be discussed in terms of multiphoton ionization processes. More importantly, the data additionally point towards a further division of the multiphoton regime into two subranges separated roughly at . Above this value above-threshold-ionization structures and the single-active-electron picture dominate. On the contrary, at the lowest laser intensities the photoelectron spectra and angular distributions reveal single ionization pathways where the remaining ion is left into excited states. These pathways also require photon absorption in the continuum, which in the case of strontium and other alkaline-earth-metal atoms is structured by the presence of doubly excited states which are embedded in it. Hence, in this case ionization proceeds via quasiresonant ionization ladders formed by these doubly excited states which are dominated by the interaction between the two valence electrons of Sr. We discuss in detail the above rich phenomenology and relevant ionization mechanisms and propose possible directions of further work towards the elucidation of the role of configuration interaction in ionization processes.
Oxidative stress refers to the overproduction of reactive oxygen species and is often associated with numerous pathological conditions. Superoxide dismutase (SOD) is a widely used enzyme for evaluating oxidative stress, with numerous methods being developed for its detection in biological specimens like blood, urine, and saliva. In this study, a simple metal-assisted chemical etching method was employed for the fabrication of nanostructured silicon surfaces decorated with either silver dendrites or silver aggregates. Those surfaces were used as substrates for the immunochemical determination of SOD in synthetic saliva through surface-enhanced Raman spectroscopy (SERS) and surface-enhanced fluorescence (SEF). The immunoassay was based on a 3-step competitive assay format, which included, after the immunoreaction with the specific anti-SOD antibody, a reaction with a biotinylated secondary antibody and streptavidin. Streptavidin labeled with peroxidase was used in combination with a precipitating tetramethylbenzidine substrate for detection through SERS, whereas for SEF measurements, streptavidin labeled with the fluorescent dye Rhodamine Red-X was utilized. Both immunoassays were sensitive, with a detection limit of 0.01 μg/mL and a linear dynamic range from 0.03 to 3.3 μg/mL, enabling the evaluation of the oxidative stress status of an organism.