Clustering analysis of different hop varieties according to their essential oil composition measured by GC/MS

This study describes the analysis of total hops essential oils from 18 cultivated varieties of hops, five of which were bred in Lithuania, and 7 wild hop forms using gas chromatography-mass spectrometry. The study sought to organise the samples of hops into clusters, according to 72 semi-volatile compounds, by applying a well-known method, k-means clustering analysis and to identify the origin of the Lithuanian hop varieties. The bouquet of the hops essential oil was composed of various esters, terpenes, hydrocarbons and ketones. Monoterpenes (mainly β-myrcene), sesquiterpenes (dominated by β-caryophyllene and α-humulene) and oxygenated sesquiterpenes (mainly caryophyllene oxide and humulene epoxide II) were the main compound groups detected in the samples tested. The above compounds, together with a-muurolene, were the only compounds found in all the samples. Qualitative and quantitative differences were observed in the composition of the essential oils of the hop varieties analysed. For successful and statistically significant clustering of the data obtained, expertise and skills in employing chemometric analysis methods are necessary. The result is also highly dependent on the set of samples (representativeness) used for segmentation into groups, the technique for pre-processing the data, the method selected for partitioning the samples according to the similarity measures chosen, etc. To achieve a large and representative data set for clustering analysis from a small number of measurements, numerical simulation was applied using the Monte Carlo method with normal and uniform distributions and several relative standard deviation values. The grouping was performed using the k-means clustering method, employing several optimal number of clusters evaluation techniques (Davies-Bouldin index, distortion function, etc.) and different data pre-processing approaches. The hop samples analysed were separated into 3 and 5 clusters according to the data filtering scenario used. However, the targeted Lithuanian hop varieties were clustered identically in both cases and fell into the same group together with other cultivated hop varieties from Ukraine and Poland.     

Preparation and characterization of Y1−xPrxBa2Cu3O7−δ single crystals

We present a reliable method for growing single crystals of Y_1−xPr_xBa₂Cu₃O_7−δ high-T_c superconductors in ZrO₂ crucibles. This method results in crystals with greatly improved superconducting properties compared to crystals grown with the previously reported methods which use Al₂O₃ crucibles. We describe techniques for crystal growth in both Al₂O₃ and ZrO₂ crucibles using an excess of BaCo₃ and CuO as the flux. The crystals were characterized by means of DC magnetic-susceptibility measurements, electrical-resistivity measurements, and electron microprobe analysis. The effects of Al contamination on the conditions for crystal growth and on the superconducting properties of the crystals are found to be quite significant.     

A degree problem for the compositum of two number fields*

The triplet (a, b, c) of positive integers is said to be compositum-feasible if there exist number fields K and L of degrees a and b, respectively, such that the degree of their compositum KL equals c. We determine all compositum-feasible triplets (a, b, c) satisfying a ≤ b and b ∈ {8, 9}. This extends the classification of compositum-feasible triplets started by Drungilas, Dubickas, and Smyth [5]. Moreover, we obtain several results related to triplets of the form (a, a, c). In particular, we prove that the triplet (n, n, n(n ? 2)) is not compositum-feasible, provided that n ≥ 5 is an odd integer.

     

Control of light polarization by acousto-optic diffraction from leaky acoustic wave in LiNbO₃

The acousto-optic control of light polarization due to diffraction by leaky acoustic waves in ZX-LiNbO? has been demonstrated. The randomly polarized light of 633 nm wavelength is converted by the anisotropic diffraction into two beams with mutually orthogonal polarizations, the relative intensities of which depend on the light incidence angle and acoustic frequency. Variation in acoustic frequency from 108 to 112 MHz rotates the polarization of the output optical beam by 90°. The acousto-optic control is accomplished entirely by electronic means and can be applied for implementation of fast polarization converters.     

Light Engineering and Silicon Diffractive Optics Assisted Nonparaxial Terahertz Imaging

The art of light engineering unveils a world of possibilities through the meticulous manipulation of photonic properties such as intensity, phase, and polarization. Precision control over these properties finds application in a variety of fields spanning communications, light–matter interactions, laser direct writing, and imaging. Terahertz (THz) range, nestled between microwaves and infrared light, stands out for its remarkable ability to propagate with minimal losses in numerous dielectric materials and compounds, making THz imaging a powerful tool for noninvasive control and inspection. In this study, a rational framework for the design and optimal assembly of nonparaxial THz imaging systems is established. The research is centered on lensless photonic systems composed solely of high-resistivity silicon-based nonparaxial elements such as the Fresnel zone plate, the Fibonacci lens, the Bessel axicon, and the Airy zone plate, all fabricated using laser ablation technology. Through a comprehensive examination through illumination engineering and scattered light collection from raster-scanned samples in a single-pixel detector scheme, the imaging systems are evaluated via diverse metrics including contrast, resolution, depth of field, and focus. These findings chart an exciting course toward the development of compact and user-friendly THz imaging systems where sensors and optical elements seamlessly integrate into a single chip.     

Mechanistic Insights into the Photoisomerization of N,N′-Disubstituted Indigos

N,N′-disubstituted indigos are photoswitchable molecules that have recently caught the attention due to their addressability by red-light. When alkyl and aryl groups are utilized as the N-substituents, the thermal half-lives of Z isomers can be tuned independently while maintaining the advantageous red-shifted absorption spectra. To utilize these molecules in real-world applications, it is of immense importance to understand how their molecular structures as well as the environment influence their switching properties. To this end, we probed their photoisomerization mechanism by carrying out photophysical and computational studies in solvents of different polarities. The fluorescence and transient absorption experiments suggest for more polar excited and transition states, which explains the bathochromic shifts of absorption spectra and shorter thermal half-lives. On the other hand, the quantum chemical calculations reveal that in contrast to N-carbonyl groups, N-alkyl and N-aryl substituents are not strongly conjugated with the indigo chromophore and can thus serve as a tool for tuning the thermal stability of Z isomers. Both approaches are combined to provide in-depth understandings of how indigos undergo photoswitching as well as how they are influenced by N-substituent and the chemical surroundings. These mechanistic insights will serve as guiding principles for designing molecules eyeing broader applications.     

Binding affinities in the SAMPL3 trypsin and host–guest blind tests estimated with the MM/PBSA and LIE methods

We have estimated affinities for the binding of 34 ligands to trypsin and nine guest molecules to three different hosts in the SAMPL3 blind challenge, using the MM/PBSA, MM/GBSA, LIE, continuum LIE, and Glide score methods. For the trypsin challenge, none of the methods were able to accurately predict the experimental results. For the MM/GB(PB)SA and LIE methods, the rankings were essentially random and the mean absolute deviations were much worse than a null hypothesis giving the same affinity to all ligand. Glide scoring gave a Kendall's τ index better than random, but the ranking is still only mediocre, τ = 0.2. However, the range of affinities is small and most of the pairs of ligands have an experimental affinity difference that is not statistically significant. Removing those pairs improves the ranking metric to 0.4-1.0 for all methods except CLIE. Half of the trypsin ligands were non-binders according to the binding assay. The LIE methods could not separate the inactive ligands from the active ones better than a random guess, whereas MM/GBSA and MM/PBSA were slightly better than random (area under the receiver-operating-characteristic curve, AUC = 0.65-0.68), and Glide scoring was even better (AUC = 0.79). For the first host, MM/GBSA and MM/PBSA reproduce the experimental ranking fairly good, with τ = 0.6 and 0.5, respectively, whereas the Glide scoring was considerably worse, with a τ = 0.4, highlighting that the success of the methods is system-dependent.     

Experimental characterization of temperature‐dependent electron transport in single‐wall multi‐tube carbon nanotube transistors

Current–voltage, radio‐frequency (RF) and noise characteristics of single‐wall multi‐tube carbon nanotube (CNT) transistors were measured at cryogenic temperatures. Compared to an ambient temperature (T_a) of 300 K, only a slight drain current increase at T_a = 77 K was observed. In addition, a weak dependence of the maximum value of the current gain cut‐off frequency (f_T) on T_a was obtained, indicating that f_T is rather limited by the device intrinsic quantum and extrinsic capacitances than by an improved mobility due to reduced optical phonon scattering at low T_a. A noise analysis of the devices at T_a = 10 K reveals that the noise factor (NF) improvement at very low temperatures is related to the reduced Nyquist noise of all resistive transistor noise contributors. Since the main noise source in CNTFETs is the shot noise, NF remains comparatively high even at T_a = 10 K.

     

Nanometer-scale probing of optical and thermal near-fields with an apertureless NSOM

We have used a home-made apertureless near-field scanning optical microscope (ANSOM) for mapping nanometric steps between SiC and gold regions under visible (λ=655 nm) and infrared (λ=10.6 μm) illumination. The images, obtained with a signal demodulation at the tip oscillation frequency and at higher harmonics, clearly show optical contrasts with a subwavelength resolution of about 30 nm. Other images recorded in the visible on a YBa₂Cu₃O₇ crystal indicate that the tip used in our experiments is able to reveal polarization effects. We also present a near-field thermal optical microscope (NTOM) which operates without any external illumination. In this new kind of microscope, the laser source which is usually used to excite the evanescent waves, is replaced by a simple heating of the sample. The electromagnetic radiation locally scattered by the tip comes from the thermal radiation. Our results with this new technique prove a 200 nm lateral resolution.     

Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid host–guest binding energies

We have estimated free energies for the binding of nine cyclic carboxylate guest molecules to the octa-acid host in the SAMPL4 blind-test challenge with four different approaches. First, we used standard free-energy perturbation calculations of relative binding affinities, performed at the molecular-mechanics (MM) level with TIP3P waters, the GAFF force field, and two different sets of charges for the host and the guest, obtained either with the restrained electrostatic potential or AM1-BCC methods. Both charge sets give good and nearly identical results, with a mean absolute deviation (MAD) of 4 kJ/mol and a correlation coefficient (R ²) of 0.8 compared to experimental results. Second, we tried to improve these predictions with 28,800 density-functional theory (DFT) calculations for selected snapshots and the non-Boltzmann Bennett acceptance-ratio method, but this led to much worse results, probably because of a too large difference between the MM and DFT potential-energy functions. Third, we tried to calculate absolute affinities using minimised DFT structures. This gave intermediate-quality results with MADs of 5–9 kJ/mol and R ² = 0.6–0.8, depending on how the structures were obtained. Finally, we tried to improve these results using local coupled-cluster calculations with single and double excitations, and non-iterative perturbative treatment of triple excitations (LCCSD(T0)), employing the polarisable multipole interactions with supermolecular pairs approach. Unfortunately, this only degraded the predictions, probably because of a mismatch between the solvation energies obtained at the DFT and LCCSD(T0) levels.