Vibrational Stark Fields in Carboxylic Acid Dimers

Carboxylic acids form exceptionally stable dimers and have been used to model proton and double proton transfer processes. The stabilization energies of the carboxylic acid dimers are very weakly dependent on the nature of the substitution. However, the electric field experienced by the OH group of a particular carboxylic acid is dependent more on the nature of the substitution on the dimer partner. In general, the electric field was higher when the partner was substituted with electron-donating group and lower with electron-withdrawing substituent on the partner. The Stark tuning rate (∆μ) of the O–H stretching vibrations calculated at the MP2/aug-cc-pVDZ level was found to be weakly dependent on the nature of substitution on the carboxylic acid. The average Stark tuning rate of O–H stretching vibrations of a particular carboxylic acid when paired with other acids was 5.7 cm–1 (MV cm–1)–1, while the corresponding average Stark tuning rate of the partner acids due to a particular carboxylic acid was 21.9 cm–1 (MV cm–1)–1. The difference in the Stark tuning rate is attributed to the primary and secondary effects of substitution on the carboxylic acid. The average Stark tuning rate for the anharmonic O–D frequency shifts is about 40-50% higher than the corresponding harmonic O–D frequency shifts calculated at B3LYP/aug-cc-pVDZ level, much greater than the typical scaling factors used, indicating the strong anharmonicity of O–H/O–D oscillators in carboxylic acid dimers. Finally, the linear correlation observed between pKa and the electric field was used to estimate the pKa of fluoroformic acid to be around 0.9.

Pocket Mercury-Vapour Detection System Employing a Preconcentrator Based on Au-TiO2 Nanomaterials

In environments polluted by mercury vapors that are potentially harmful to human health, there is a need to perform rapid surveys in order to promptly identify the sources of emission. With this aim, in this work, a low cost, pocket-sized portable mercury measurement system, with a fast response signal is presented. It consists of a preconcentrator, able to adsorb and subsequently release the mercury vapour detected by a quartz crystal microbalance (QCM) sensor. The preconcentrator is based on an adsorbing layer of titania/gold nanoparticles (TiO2NP/AuNPs), deposited on a micro-heater that acts as mercury thermal desorption. For the detection of the released mercury vapour, gold electrodes QCM (20 MHz) have been used. The experimental results, performed in simulated polluted mercury-vapour environments, showed a detection capability with a prompt response. In particular, frequency shifts (−118 Hz ± 2 Hz and −30 Hz ± 2 Hz) were detected at concentrations of 65 µg/m3 Hg0 and 30 µg/m3 Hg0, with sampling times of 60 min and 30 min, respectively. A system limit of detection (LOD) of 5 µg/m3 was evaluated for the 30 min sampling time.

A Resonant Coupler for Subcutaneous Implant

A resonator coupler for subcutaneous implants has been developed with a new impedance matching pattern added to the conventional loop antenna. The tuning element of a concentric metal pad contributes distributed capacitance and inductance to the planar inductive loop and improves resonance significantly. It provides a better qualify factor for resonant coupling and a much lower reflection coefficient for the implant electronics. Practical constraints are taken into account for designs including the requirement of operation within a regulated frequency band and the limited thickness for a monolithic implant. In this work, two designs targeting to operate in the two industrial, scientific, and medical (ISM) bands at 903 MHz and 2.45 GHz are considered. The tuning metal pad improves their resonances significantly, compared to the conventional loop designs. Since it is difficult to tune the implant antenna after implantation, the effects of tissue depth variations due to the individual’s surgery and the appropriate implant depths are investigated. Simulations conducted with the dielectric properties of human skin documented in the literature are compared to measurements done with hydrated ground pork as phantoms. Experiments and simulations are conducted to explain the discrepancies in frequency shifts due to the uses of pork phantoms. The design method is thus validated for uses on human skin. A noninvasive localization method to identify the implant under the skin has been examined and demonstrated by both simulations and measurements. It can efficiently locate the subcutaneous implant based on the high quality-factor resonance owing to the tuning elements in both implant and transmitter couplers. The planar resonant coupler for wireless power transfer shows good performance and promise in subcutaneous applications for implants.

Infrared Spectroscopy of Jet-cooled “GrandPAHs” in the 3–100 μm Region

Although large polycyclic aromatic hydrocarbons (PAHs) are likely to be responsible for IR emission of gaseous and dusty regions, their neutral experimental high-resolution gas-phase IR spectra—needed to construct accurate astronomical models—have so far remained out of reach because of their nonvolatility. Applying laser desorption to overcome this problem, we report here the first IR spectra of the jet-cooled large PAHs coronene (C24H12), peropyrene (C26H14), ovalene (C32H14), and hexa(peri)benzocoronene (C42H18) in the 3–100 μm region. Apart from providing experimental spectra that can be compared directly to astronomical data, such IR spectra are crucial for assessing the accuracy of theoretically predicted spectra used to interpret interstellar IR emission. Here we use the experimental spectra to evaluate the performance of conventional calculations using the harmonic approximation, as well as calculations with an anharmonic (GVPT2) treatment. The harmonic prediction agrees well with the experiment between 100 and 1000 cm−1 (100 and 10 μm) but shows significant shortcomings in the combination band (1600–2000 cm−1, 6.25–5 μm) and CH-stretch (2950–3150 cm−1, 3.4–3.17 μm) regions. Especially the CH-stretch region is known to be dominated by the effects of anharmonicity, and we find that large PAHs are no exception. However, for the CH out-of-plane region (667–1000 cm−1, 15–10 μm) the anharmonic treatment that significantly improves the predicted spectra for small PAHs leads to large and unrealistic frequency shifts, and intensity changes for large PAHs, thereby rendering the default results unreliable. A detailed analysis of the results of the anharmonic treatment suggests a possible route for improvement, although the underlying cause for the large deviations remains a challenge for theory.

Reconfigurable bandstop filter using active frequency selective surface, design and fabrication

In this paper a novel FSS array is proposed, that provides dynamic band-gap in C-band. Inside the band-gap, the FSS acts as a bandstop filter. Outside the band-gap the amplitude of the reflected wave from the FSS array decreases. Therefore, the outside band is very useful in radar cross section (RCS) reduction. In this paper, at first a new FSS unit cell is designed, then in order to achieve the maximum bandwidth (1.2 GHz), dimensions of the cell are optimized. In the next step, the FSS cell is equipped with PIN diodes. Turning the diodes ON or OFF, shifts the resonant frequency of the band-gap electronically. When diodes are OFF, the resonant frequency and −10 dB bandwidth of the FSS are 5.23 and 0.9 GHz respectively. When the diodes turn ON, the resonant frequency shifts to 4.75 GHz over a bandwidth of about 1 GHz. While the band-gap is shifted dynamically, the bandwidth is kept wide, which is the novelty of this paper. In order to validate the design process, an array of active cells consisting of 128 pin diodes was designed, fabricated and then tested. Finally, the simulation and measurement results are compared with each other and a good agreement is observed between them.

Introducing Berry phase gradients along the optical path via propagation-dependent polarization transformations

As a classical or quantum system undergoes a cyclic evolution governed by slow change in its parameter space, it acquires a topological phase factor known as the geometric or Berry phase. One popular manifestation of this phenomenon is the Gouy phase which arises when the radius of curvature of the wavefront changes adiabatically in a cyclic manner, for e.g., when focused by a lens. Here, we report on a new manifestation of the Berry phase in 3D structured light which arises when its polarization state adiabatically evolves along the optical path. We show that such a peculiar evolution of angular momentum, which occurs under free space propagation, is accompanied by an accumulated phase shift that elegantly coincides with Berry’s prediction. Unlike the conventional dynamic phase, which accumulates monotonically with propagation, the Berry phase observed here can be engineered on demand, thereby enabling new possibilities; such as spin-dependent spatial frequency shifts, and modified phase matching in resonators and nonlinear interactions. Our findings expand the laws of wave propagation and can be applied in optics and beyond.

Mapping Tumor Spheroid Mechanics in Dependence of 3D Microenvironment Stiffness and Degradability by Brillouin Microscopy

Altered biophysical properties of cancer cells and of their microenvironment contribute to cancer progression. While the relationship between microenvironmental stiffness and cancer cell mechanical properties and responses has been previously studied using two-dimensional (2D) systems, much less is known about it in a physiologically more relevant 3D context and in particular for multicellular systems. To investigate the influence of microenvironment stiffness on tumor spheroid mechanics, we first generated MCF-7 tumor spheroids within matrix metalloproteinase (MMP)-degradable 3D polyethylene glycol (PEG)-heparin hydrogels, where spheroids showed reduced growth in stiffer hydrogels. We then quantitatively mapped the mechanical properties of tumor spheroids in situ using Brillouin microscopy. Maps acquired for tumor spheroids grown within stiff hydrogels showed elevated Brillouin frequency shifts (hence increased longitudinal elastic moduli) with increasing hydrogel stiffness. Maps furthermore revealed spatial variations of the mechanical properties across the spheroids’ cross-sections. When hydrogel degradability was blocked, comparable Brillouin frequency shifts of the MCF-7 spheroids were found in both compliant and stiff hydrogels, along with similar levels of growth-induced compressive stress. Under low compressive stress, single cells or free multicellular aggregates showed consistently lower Brillouin frequency shifts compared to spheroids growing within hydrogels. Thus, the spheroids’ mechanical properties were modulated by matrix stiffness and degradability as well as multicellularity, and also to the associated level of compressive stress felt by tumor spheroids. Spheroids generated from a panel of invasive breast, prostate and pancreatic cancer cell lines within degradable stiff hydrogels, showed higher Brillouin frequency shifts and less cell invasion compared to those in compliant hydrogels. Taken together, our findings contribute to a better understanding of the interplay between cancer cells and microenvironment mechanics and degradability, which is relevant to better understand cancer progression.