Crystals of Diphenyl-Benzothiadiazole and Its Derivative with Terminal Trimethylsilyl Substituents: Growth from Solutions, Structure, and Fluorescence Properties.

Linear conjugated molecules consisting of benzothiadiazole (BTD) and phenyl rings are highly efficient organic luminophores. Crystals based on these compounds have great potential for use as light-emitting elements, in particular, scintillation detectors. This paper compares the peculiarities of growth, structure, and fluorescent properties of crystals based on 4,7-diphenyl-2,1,3-benzothiadiazole (P2-BTD) and its organosilicon derivative 4,7-bis(4-(trimethylsilyl)phenyl) BTD ((TMS-P)2-BTD). The conditions for the formation of centimeter-scale single crystals were found for the former, while it was possible to prepare also bulky faceted individual crystals for the latter. The structures of P2-BTD and (TMS-P)2-BTD crystals at 85 and 293 K were investigated by single-crystal X-ray diffraction. The crystal structure of P2-BTD has been refined (sp. gr. P1̅, Z = 4), and for (TMS-P)2-BTD crystals, the structure has been solved for the first time (sp. gr. P21/c, Z = 32). Experimental and theoretical investigations of the absorption-fluorescent properties of solutions and crystals of the molecules have been carried out. The luminophores are characterized by a large Stokes shift for both solutions and crystals with a high fluorescence quantum yield of 75-98% for solutions and 50-85% for the crystals. A solvatochromic effect was observed for solutions of both luminophores: an increase in the values of the fluorescence quantum yield and the excited state lifetime were established with increasing the solvent polarity. Fluorescence properties of solutions and crystals have been analyzed using the data on crystal structure and conformation structure of the molecules as well as density functional theory calculations of their electronic structure. The results have shown that the crystal packing of P2-BTD molecules exhibits uniformity in conformational states, while (TMS-P)2-BTD molecules display a variety of conformational structures in the crystals. This unique combination of features makes them a remarkable example among the other molecular systems for identifying the relationship between the structure and absorption-fluorescence properties through comparative analysis.

Nanoparticles of Push-Pull Triphenylamine-Based Molecules for Light-Controlled Stimulation of Neuronal Activity.

Organic semiconductor materials with a unique set of properties are very attractive for interfacing biological objects and can be used for noninvasive therapy or detection of biological signals. Here, we describe the synthesis and investigation of a novel series of organic push-pull conjugated molecules with the star-shaped architecture, consisting of triphenylamine as a branching electron donor core linked through the thiophene π-spacer to electron-withdrawing alkyl-dicyanovinyl groups. The molecules could form stable aqueous dispersions of nanoparticles (NPs) without the addition of any surfactants or amphiphilic polymer matrixes with the average size distribution varying from 40 to 120 nm and absorption spectra very similar to those of human eye retina pigments such as rods and green cones. Variation of the terminal alkyl chain length of the molecules forming NPs from 1 to 12 carbon atoms was found to be an efficient tool to modulate their lipophilic and biological properties. Possibilities of using the NPs as light nanoactuators in biological systems or as artificial pigments for therapy of degenerative retinal diseases were studied both on the model planar bilayer lipid membranes and on the rat cortical neurons. In the planar bilayer system, the photodynamic activity of these NPs led to photoinactivation of ion channels formed by pentadecapeptide gramicidin A. Treatment of rat cortical neurons with the NPs caused depolarization of cell membranes upon light irradiation, which could also be due to the photodynamic activity of the NPs. The results of the work gave more insight into the mechanisms of light-controlled stimulation of neuronal activity and for the first time showed that fine-tuning of the lipophilic affinity of NPs based on organic conjugated molecules is of high importance for creating a bioelectronic interface for biomedical applications.

Synthesis of Vinyl-Containing Polydimethylsiloxane in An Active Medium.

This research deals with the synthesis of copoly(methylvinyl)(dimethyl)siloxanes by the copolycondensation of dimethyldiethoxy- and methylvinyldimethoxysilane in an active medium, followed by thermal condensation in a vacuum. We achieved a range of copolymers exhibiting finely tuned molecular weights spanning between 1500 and 20,000 with regulated functional methylvinylsiloxane units. Analysis of the microstructure showed that the copolymerization predominantly formed products demonstrating a random distribution of units (R~1). However, an increase in the content of vinyl-containing monomers increases the R parameter, indicating an enhanced tendency towards alternating linkages within the copolymer matrix.

Thioether-Containing Zirconium(Alkoxy)Siloxanes: Synthesis and Study of Dielectric and Mechanical Properties of Silica-Filled Polydimethylsiloxane Compositions Cured by Them.

A number of thioether-containing zirconium siloxanes, differing in their composition and metal atom shielding degree with a siloxy substituent, were synthesized and characterized. Synthesis of such compounds made it possible to evaluate the effect of sulfur atoms' presence in the cured compositions on their dielectric properties, as well as to evaluate their curing ability and influence on mechanical characteristics compared to the sulfur-free analogs obtained earlier. Studying a wide range of compositions differing in their content and ratio of metallosiloxane and silica components revealed that such systems are still typical dielectrics. At the same time, the introduction of thioether groups can provide increased dielectric constant and conductivity in comparison with previously obtained sulfur-free similar compositions in the <102 Hz frequency range (dielectric constant up to ~10-30 at frequency range 1-10 Hz). As before, the dielectric parameters increase is directly determined by the silica component proportion in the cured material. It is also shown that varying sulfur-containing zirconium siloxanes structure and functionality and its combination with previously obtained sulfur-free analogs, along with varying the functionality and rubber chain length, can be an effective tool for changing the dielectric and mechanical material parameters in a wide range (tensile strength 0.5-7 Mpa, elastic deformation 2-300%), which determine the prospects for the use of such cured systems as dielectric elastomers for various purposes.

Food Freshness Measurements and Product Distinguishing by a Portable Electronic Nose Based on Organic Field-Effect Transistors.

Determination of food freshness, which is the most ancient role of the human sense of smell, is still a challenge for compact and inexpensive electronic nose devices. Fast, sensitive, and reusable sensors are long-awaited in the food industry to replace slow, labor-intensive, and expensive bacteriological methods. In this work, we present microbiological verification of a novel approach to food quality monitoring and spoilage detection using an electronic nose based on organic field-effect transistors (OFETs) and its application for distinguishing products. The compact device presented is able to detect spoilage-related gases as early as at the 4 × 104 CFU g-1 bacteria count level, which is 2 orders of magnitude below the safe consumption threshold. Cross-selective sensor array based on OFETs with metalloporphyrin receptors were made on a single substrate using solution processing leading to a low production cost. Moreover, machine learning methods applied to the sensor array response allowed us to compare spoilage profiles and separate them by the type of food: pork, chicken, fish, or milk. The approach presented can be used to monitor food spoilage and distinguish different products with an affordable and portable device.

Spectrally Selective Full-Color Single-Component Organic Photodetectors Based on Donor-Acceptor Conjugated Molecules.

Photodetectors based on organic materials are attractive due to their tunable spectral response and biocompatibility, meaning that they are a promising platform for an artificial human eye. To mimic the photoelectric response of the human eye, narrowband spectrally-selective organic photodetectors are in great demand, and single-component organic photodetectors based on donor-acceptor conjugated molecules are a noteworthy candidate. In this work, we present single-component selective full-color organic photodetectors based on donor-acceptor conjugated molecules synthetized to mimic the spectral response of the cones and rods of a human eye. The photodetectors demonstrated a high responsivity (up to 70 mA/W) with a response time of less than 1 µs, which is three orders of magnitude faster than that of human eye photoreceptors. Our results demonstrate the possibility of the creation of an artificial eye or photoactive eye "prostheses".

Classical entanglement of twisted random light propagating through atmospheric turbulence [Invited].

We examine the impact of the atmospheric turbulence on a recently discovered type of classical entanglement of partially coherent beams endowed with a twist phase. We derive a compact analytical expression for the Schmidt number of a bi-orthogonal decomposition of the Wigner function of a twisted Gaussian Schell-model (TGSM) beam propagating through the turbulent atmosphere. We elucidate conditions for a TGSM source to generate a strongly classically entangled paraxial field over a desired propagation distance in the turbulent atmosphere. Our results will find applications to free-space optical communications and motivate further research into classical entanglement with random light.

Structurally stable beams in the turbulent atmosphere: dark and antidark beams on incoherent background [Invited].

We demonstrate analytically and verify numerically that recently discovered, and experimentally realized, partially coherent dark and antidark beams are structurally stable on propagation in a statistically homogeneous, isotropic random medium, such as the turbulent atmosphere. The dark/antidark beams defy diffraction in free space, and they manifest themselves as dark/bright notches/bumps against an incoherent background. The structure of a bump/notch remains invariant on propagation of the beam through the random medium, while the peak amplitude of the bump/notch decays with the propagation distance in the medium at a rate dependent on the strength of the medium turbulence. We also evaluate numerically the scintillation index of such beams and show that it is significantly lower than that of generic, low-coherence Gaussian Schell-model beams. The combination of structural stability and low scintillations makes partially coherent dark/antidark beams very promising candidates for information transfer and optical communications through atmospheric turbulence.

Classical entanglement of twisted random light propagating through atmospheric turbulence [Invited]: publisher's note.

This publisher's note corrects the title of the article J. Opt. Soc. Am. A39, C1 (2022)JOAOD60740-323210.1364/JOSAA.465410 appearing in the 100 Years of Emil Wolf feature issue.

Synthesis and Photophysical Properties of Novel Meta-Conjugated Organic Molecules with 1,3,5-Benzene Branching Units.

The synthesis and photophysical investigation of three novel meta-conjugated molecules based on 3,1,2-benzothiadiazole and thiophene-2,5-diyl derivatives linked through 1,3,5-benzene branching units are described. Each of them is a symmetrical molecule with two branching units, four identical lateral thiophene-containing fragments, and one central benzothiadiazole-containing fragment. To study the effect of the chemical structure on their photophysical properties, the molecules with different linearly conjugated lateral and central fragments due to incorporation of additional thiophene rings were synthesized and compared. It was shown that absorption spectra of the meta-conjugated molecules can be represented as a sum of absorption bands of model compounds for their peripheral and central fragments containing a common benzene ring being branched at the 1,3,5-benzene unit in the meta-conjugated molecules. Therefore, they cannot be considered simply as isolated π-conjugated systems of their peripheral and central fragments. Instead, DFT calculations showed that several transitions between the orbitals located in different regions of the meta-conjugated molecule are responsible for the formation of their absorption spectra, and they strongly depend on the degree of their overlapping. Theoretical absorption spectra reconstructed from the DFT data demonstrated a good agreement with the experimental results: the transitions with larger oscillator strength correspond to the bands with higher molar extinction coefficients and vice versa. It was shown that luminescence spectral maxima of the meta-conjugated molecules monotonically shift to the lower energy from 489 to 540 and 613 nm with increasing the number of thiophene rings in the peripheral and central fragments, respectively. However, luminescence quantum yield of the meta-conjugated molecules critically depends on the length of linearly conjugated fragments in its structure decreasing from 24% to 1.3% with increasing the number of thiophene rings in the lateral fragments but increasing to 90% in the molecule with more thiophene rings in both types of the fragments. The results obtained are well correlated to the ratio of radiative and nonradiative deactivation rate constants of the meta-conjugated molecules that indicates a high rate of internal conversion between the excited states corresponding to different fragments of the molecule. The CV measurements allowed estimating the HOMO, LUMO, and bandgap values of the target and model compounds, which confirm the presence of meta-conjugation within the molecules investigated. Thus, connection of linearly conjugated fragments through meta-positions (meta-conjugation) of a benzene ring leads to an intermediate option between fully conjugated and nonconjugated molecules due to partial delocalization of electron density through the 1,3,5-substituted benzene branching center.

A new linear phenyloxazole-benzothiadiazole luminophore: crystal growth, structure and fluorescence properties.

A new linear luminophore consisting of five conjugated units of oxazole, phenylene and a central benzothiadiazole fragment, 4,7-bis[4-(1,3-oxazol-5-yl)phenyl]-2,1,3-benzothiadiazole, has been synthesized and characterized. Needle-like single-crystal samples up to 10 mm in length were obtained by physical vapor transport. The crystal structure was determined at 95 K and 293 K using single-crystal X-ray diffraction. With decreasing temperature, the space group P21/n does not change, but the unit-cell volume of the crystal decreases. The presence of intra- and intermolecular hydrogen bonds was established. Melting parameters (Tm = 305.5°C, ΔHm = 52.2 kJ mol-1) and the presence of a liquid-crystalline mesophase (TLC = 336.3°C, ΔHLC = 1.4 kJ mol-1) were determined by differential scanning calorimetry and in situ thermal polarization optical microscopy studies. The presence of linear chains of hydrogen bonds ensures high stability of the crystal structure in a wide temperature range. The luminophore is characterized by a large Stokes shift (5120-5670 cm-1) and a high quantum yield of fluorescence, reaching 96% in solutions (λmax = 517 nm) and 27% in thin crystalline films (λmax = 529 nm). The calculated absorption and emission spectra are in good agreement with the experimental data. Because of the excellent optical properties and high thermal stability, the new linear luminophore has great potential for application in organic photonics and optoelectronic devices.

Biorecognition Layer Based On Biotin-Containing [1]Benzothieno[3,2-b][1]benzothiophene Derivative for Biosensing by Electrolyte-Gated Organic Field-Effect Transistors.

Requirements of speed and simplicity in testing stimulate the development of modern biosensors. Electrolyte-gated organic field-effect transistors (EGOFETs) are a promising platform for ultrasensitive, fast, and reliable detection of biological molecules for low-cost, point-of-care bioelectronic sensing. Biosensitivity of the EGOFET devices can be achieved by modification with receptors of one of the electronic active interfaces of the transistor gate or organic semiconductor surface. Functionalization of the latter gives the advantage in the creation of a planar architecture and compact devices for lab-on-chip design. Herein, we propose a universal, fast, and simple technique based on doctor blading and Langmuir-Schaefer methods for functionalization of the semiconducting surface of C8-BTBT-C8, allowing the fabrication of a large-scale biorecognition layer based on the novel functional derivative of BTBT-containing biotin fragments as a foundation for further biomodification. The fabricated devices are very efficient and operate stably in phosphate-buffered saline solution with high reproducibility of electrical properties in the EGOFET regime. The development of biorecognition properties of the proposed biolayer is based on the streptavidin-biotin interactions between the consecutive layers and can be used for a wide variety of receptors. As a proof-of-concept, we demonstrate the specific response of the BTBT-based biorecognition layer in EGOFETs to influenza A virus (H7N1 strain). The elaborated approach to biorecognition layer formation is appropriate but not limited to aptamer-based receptor molecules and can be further applied for fabricating several biosensors for various analytes on one substrate and paves the way for "electronic tongue" creation.

In Situ Coupling Applied Voltage and Synchrotron Radiation: Operando Characterization of Transistors.

A compact voltage application setup has been developed for in situ electrical testing of organic field effect transistors in combination with X-ray scattering studies at a synchrotron beamlines. Challenges faced during real condition in-operando test of newly developed OFETs originated an idea of creation of a new setup which excludes number of factors that make experiments complicated. The application of the setup is demonstrated on a prototype of an organic transistors based on α,ω-dihexyl-α-quaterthiophene molecules. The new setup allows to monitor material structural changes by X-ray scattering under applied voltage conditions and their direct correlations. The versatile setup eliminates possible shadowing effects and short circuits due to misalignment of the contacts. The electrical stability of the prototypes was characterized by the application of different voltage values. Corresponding structural changes were monitored by grazing X-ray scattering technique before, during and after the voltage was applied. The selected oligothiophene material with proved transistor properties shows high stability and directional anisotropy under applied voltage conditions. Thanks to a compact and flexible design of the setup, different type of small dimension devices could be studied under external voltage conditions at various synchrotron beamlines.

Twist phase and classical entanglement of partially coherent light.

We demonstrate that the presence of a twist phase in a random light beam leads to classical entanglement between phase space degrees of freedom of the beam. We find analytically the bi-orthogonal decomposition of the Wigner function of a twisted Gaussian Schell-model (TGSM) source and quantify its entanglement by evaluating the Schmidt number of the decomposition. We show that (i) classical entanglement of a TGSM source vanishes concurrently with the twist in the fully coherent limit and (ii) entanglement dramatically increases as the source coherence level decreases. We also show that the discovered type of classical entanglement of a Gaussian Wigner function does not degrade on beam propagation in free space.

Optical coherence encryption with structured random light.

Information encryption with optical technologies has become increasingly important due to remarkable multidimensional capabilities of light fields. However, the optical encryption protocols proposed to date have been primarily based on the first-order field characteristics, which are strongly affected by interference effects and make the systems become quite unstable during light-matter interaction. Here, we introduce an alternative optical encryption protocol whereby the information is encoded into the second-order spatial coherence distribution of a structured random light beam via a generalized van Cittert-Zernike theorem. We show that the proposed approach has two key advantages over its conventional counterparts. First, the complexity of measuring the spatial coherence distribution of light enhances the encryption protocol security. Second, the relative insensitivity of the second-order statistical characteristics of light to environmental noise makes the protocol robust against the environmental fluctuations, e.g, the atmospheric turbulence. We carry out experiments to demonstrate the feasibility of the coherence-based encryption method with the aid of a fractional Fourier transform. Our results open up a promising avenue for further research into optical encryption in complex environments.

Airy beams on incoherent background.

We present a class of diffraction-free partially coherent beams, each member of which comprises a finite-power, non-accelerating Airy bump residing on a statistically homogeneous, Gaussian-correlated background. We examine free-space propagation of soft apertured realizations of the proposed beams and show that their evolution is governed by two spatial scales: the coherence width of the background and the aperture size. A relative magnitude of these factors determines the practical range of propagation distances over which the novel beams can withstand diffraction. The proposed beams can find applications to imaging and optical communications through random media.

Temporal Boundary Solitons and Extreme Superthermal Light Statistics.

We discover the formation of a temporal boundary soliton (TBS) in close proximity of a temporal boundary, moving in a nonlinear optical medium, upon high-intensity pulse collision with the boundary. We show that the emergent TBS is unstable to perturbations caused by the cross-phase modulation between the TBS and the other soliton products of the collision and that such instability triggers colossal intensity fluctuations of the reflected pulse ensemble with unprecedented magnitudes of the normalized autocorrelation function for an even weakly fluctuating input pulse.

Fully integrated ultra-sensitive electronic nose based on organic field-effect transistors.

Modern solid-state gas sensors approaching ppb-level limit of detection open new perspectives for process control, environmental monitoring and exhaled breath analysis. Organic field-effect transistors (OFETs) are especially promising for gas sensing due to their outstanding sensitivities, low cost and small power consumption. However, they suffer of poor selectivity, requiring development of cross-selective arrays to distinguish analytes, and environmental instability, especially in humid air. Here we present the first fully integrated OFET-based electronic nose with the whole sensor array located on a single substrate. It features down to 30 ppb limit of detection provided by monolayer thick active layers and operates in air with up to 95% relative humidity. By means of principal component analysis, it is able to discriminate toxic air pollutants and monitor meat product freshness. The approach presented paves the way for developing affordable air sensing networks for the Internet of Things.

Universal self-similar asymptotic behavior of optical bump spreading in random medium atop incoherent background: reply.

In his comment [Opt. Lett.45, 3510 (2020)OPLEDP10.1364/OL.385246], Charnotskii claims that the cross-spectral densities recently studied in Opt. Lett.45, 698 (2020)OPLEDP10.1364/OL.385246 of partially coherent beams atop a statistical background do not satisfy the non-negative definiteness requirement. We argue that Charnotskii's claim stems from his misunderstanding of the non-negative definiteness concept as applied to the model of Opt. Lett.45, 698 (2020)OPLEDP10.1364/OL.385246.

Vortex preserving statistical optical beams.

We establish a general form of the cross-spectral density of statistical sources that generate vortex preserving partially coherent beams on propagation through any linear ABCD optical system. We illustrate our results by introducing a class of partially coherent vortex beams with a closed form cross-spectral density at the source and demonstrating the beam vortex structure preservation on free space propagation and imaging by a thin lens. We also show the capacity of such vortex preserving beams of any state of spatial coherence to trap nanoparticles with the refractive index smaller than that of a surrounding medium.