Subwavelength Diffractive Optical Elements for Generation of Terahertz Coherent Beams with Pre-Given Polarization State.

Coherent terahertz beams with radial polarization of the 1st, 2nd, and 3rd orders have been generated with the use of silicon subwavelength diffractive optical elements (DOEs). Silicon elements were fabricated by a technology similar to the technology used before for the fabrication of DOEs forming laser terahertz beams with pre-given mode content. The beam of the terahertz Novosibirsk Free Electron Laser was used as the illuminating beam. The experimental results are in good agreement with the results of the computer simulation.

Numerical Optimization of Refractive Index Sensors Based on Diffraction Gratings with High Aspect Ratio in Terahertz Range.

Terahertz surface plasmon resonance (SPR) sensors have been regarded as a promising technology in biomedicine due to their real-time, label-free, and ultrasensitive monitoring features. Different authors have suggested a lot of SPR sensors, including those based on 2D and 3D metamaterials, subwavelength gratings, graphene, and graphene nanotube, as well as others. However, one of the traditional approaches to realize high sensitivity SPR sensors based on metal diffraction gratings has been studied poorly in the terahertz frequency range. In this article, a linear metal rectangular diffraction grating with high aspect ratio is studied. The influence of the grating structure parameters on the sensor sensitivity is simulated. Effects arising from different ratios of depth and width were discovered and explained. The results show that the sensitivity can be increased to 2.26 THz/RIU when the refractive index range of the gas to measure is between 1 and 1.002 with the resolution 5×10-5 RIU.

Thiourea Modified Doxorubicin: A Perspective pH-Sensitive Prodrug.

A novel approach to the synthesis of pH-sensitive prodrugs has been proposed: thiourea drug modification. Resulting prodrugs can release the cytotoxic agent and the biologically active 2-thiohydantoin in the acidic environment of tumor cells. The concept of acid-catalyzed cyclization of thioureas to 2-thiohydantoins has been proven using a FRET model. Dual prodrugs of model azidothymidine, cytotoxic doxorubicin, and 2-thiohydantoin albutoin were obtained, which release the corresponding drugs in the acidic environment. The resulting doxorubicin prodrug was tested on prostate cancer cells and showed that the thiourea-modified prodrug is less cytotoxic (average IC50 ranging from 0.5584 to 0.9885 µM) than doxorubicin (IC50 ranging from 0.01258 to 0.02559 µM) in neutral pH 7.6 and has similar toxicity (average IC50 ranging from 0.4970 to 0.7994 µM) to doxorubicin (IC50 ranging from 0.2303 to 0.8110 µM) under mildly acidic conditions of cancer cells. Cellular and nuclear accumulation in PC3 tumor cells of Dox prodrug is much higher than accumulation of free doxorubicin.

Comparative Study of Single Crystal and Polymeric Pyroelectric Detectors in the 0.9-2.0 THz Range Using Monochromatic Laser Radiation of the NovoFEL.

The development of efficient and reliable sensors operating at room temperature is essential to advance the application of terahertz (THz) science and technology. Pyroelectric THz detectors are among the best candidates, taking into account their variety, outstanding performance, ease of fabrication, and robustness. In this work, we compare the performance of six different detectors, based on either LaTiO3 crystal or different polymeric films, using monochromatic radiation of the Novosibirsk Free Electron Laser facility (NovoFEL) in the frequency range of 0.9-2.0 THz. The main characteristics, including noise equivalent power and frequency response, were determined for all of them. Possible reasons for the differences in the obtained characteristics are discussed on the basis of the main physicochemical characteristics and optical properties of the sensitive area. At least three detectors showed sufficient sensitivity to monitor the shape and duration of the THz macropulses utilizing only a small fraction of the THz radiation from the primary beam. This capability is crucial for accurate characterization of THz radiation during the main experiment at various specialized endstations at synchrotrons and free electron lasers. As an example of such characterization, the typical stability of the average NovoFEL radiation power at the beamline of the electron paramagnetic resonance endstation was investigated.

Optimal Design of an Ultrasound Transducer for Efficient Acousto-Optic Modulation of Terahertz Radiation.

Acousto-optic (AO) interaction in the terahertz range was investigated with the use of monolithic ultrasound transducers of various widths. Sulfur hexafluoride (SF6) liquefied at a temperature of about 23 °C and a pressure of 25 bar was used as a medium for AO interaction. The angular and frequency bandwidths of effective AO interaction, as well as the diffraction efficiency per 1 W of the driving electric power, were determined. For the first time, a correct comparison of the AO diffraction efficiency in SF6 with the use of ultrasound transducers with different widths was carried out. In the experiments performed, the highest energy efficiency of the AO modulator was achieved with a transducer with a width of 12 mm.

Acousto-Optic Modulation and Deflection of Terahertz Radiation.

It is known that one of the ways to increase the energy efficiency of acousto-optic devices is to use ultrasound beams with a higher power density. It has been established experimentally that the use of a partially electroded ultrasonic transducer significantlyincreases the energy efficiency of the acousto-optic modulator of terahertz radiation. In addition, the operation of an acousto-optic deflector of terahertz radiation with the use of a sectioned ultrasound transducer was theoretically investigated. It showed that a deflector of this kind enables one to achieve higher angular resolution.

Temperature Effects in an Acousto-Optic Modulator of Terahertz Radiation Based on Liquefied SF6 Gas.

The acousto-optic (AO) diffraction of terahertz (THz) radiation in liquefied sulfur hexafluoride (SF6) was investigated in various temperature regimes. It was found that with the increase in the temperature from +10 to +23 °C, the efficiency of the AO diffraction became one order higher at the same amplitude of the driving electrical signal. At the same time, the efficiency of the AO diffraction per 1 W of the sound power as well as the angular bandwidth of the efficient AO interaction were temperature independent within the measurement error. Increase of the resonant sound frequency with decreasing temperature and strong narrowing of the sound frequency bandwidth of the efficient AO interaction were detected.

Novel Copper-Containing Cytotoxic Agents Based on 2-Thioxoimidazolones.

A series of 73 ligands and 73 of their Cu+2 and Cu+1 copper complexes with different geometries, oxidation states of the metal, and redox activities were synthesized and characterized. The aim of the study was to establish the structure-activity relationship within a series of analogues with different substituents at the N(3) position, which govern the redox potentials of the Cu+2/Cu+1 redox couples, ROS generation ability, and intracellular accumulation. Possible cytotoxicity mechanisms, such as DNA damage, DNA intercalation, telomerase inhibition, and apoptosis induction, have been investigated. ROS formation in MCF-7 cells and three-dimensional (3D) spheroids was proven using the Pt-nanoelectrode. Drug accumulation and ROS formation at 40-60 µm spheroid depths were found to be the key factors for the drug efficacy in the 3D tumor model, governed by the Cu+2/Cu+1 redox potential. A nontoxic in vivo single-dose evaluation for two binuclear mixed-valence Cu+1/Cu+2 redox-active coordination compounds, 72k and 61k, was conducted.

Mixed valence copper(I,II) binuclear complexes with unexpected structure: synthesis, biological properties and anticancer activity.

We have synthesized and characterized a panel of new binuclear mixed valence Cu(I,II) complexes containing substituted 2-alkylthio-5-arylmethylene-4H-imidazolin-4-ones with unusual structure. These complexes are shown to be cytotoxic for various cell lines. We have found that these compounds did not intercalate DNA, inhibited number of polymerases (telomerase predominantly), accumulated in the cell nucleus, and caused DNA degradation. Preliminary studies revealed that lead compound inhibited human breast adenocarcinoma growth in mice model.

Two-phase channel structures based on alpha-cyclodextrin-polyethylene glycol inclusion complexes.

Wide-angle X-ray scattering observations of alpha-cyclodextrin (CD)-poly(ethylene glycol) (PEG) inclusion complexes (ICs) have shown for the first time that two crystalline columnar modifications (forms I and II) are produced in the process of their formation. This was made possible by precise azimuthal X-ray diffraction scanning of oriented IC samples. Form I is characterized by CDs threaded onto PEG chains and arranged along channels in the order head-to-head/tail-to-tail, while form II is formed by unbound CDs also arranged into columns in a head-to-tail and also possibly a head-to-head/tail-to-tail manner, probably as a result of template crystallization on the form I IC crystals. It was shown that similar structural peculiarities are inherent for channel structures based on ICs obtained with PEG with a wide range of molecular weights (MWs). The characteristic feature of ICs based on PEG, especially with MW > 8000, is the presence of unbound polymer in the composition of the complex. The amount of unbound PEG was shown to rise with increasing MW of PEG, resulting in greater imperfections in the IC crystalline structure. The polyblock structure of ICs based on alpha-CD and PEG was therefore proposed.