Conspectus In this Account, we briefly discuss the recently discovered and rapidly developing superbase-promoted self-organization reactions of several equivalents of acetylenes and ketones to afford ...complex compounds that represent promising synthetic building blocks common in natural products. Notably, acetylenes play a special role in these reactions because of their dual (acting as an electrophile and a nucleophile) and flexible reactivity. These unique properties of acetylenes are elegantly expressed in superbasic media, where acetylenes are more deprotonated and their electrophilicity increases as a result of complexation with alkali metal cations, with simultaneous enhancement of the nucleophilic reactants due to desolvation. Under these conditions, acetylenes behave as a driving and organizing force toward other reactants. Various combinations of nucleophilic addition to the triple bond and acetylene deprotonation in the presence of other reactants with dual reactivity (e.g., ketones) enables the self-organization of complex molecular architectures that are inaccessible by conventional reactions. Herein we analyze recent achievements in this area concerning the reactions of acetylenes with ketones in superbasic KOH/DMSO-type systems that selectively afford synthetically and pharmaceutically valuable carbo- and heterocycles. Most of the reactions are triggered by the nucleophilic addition of deprotonated ketones (enolate anions) to acetylenes (superbase-catalyzed C-vinylation of ketones with acetylenes, which was recently introduced by our group into a toolkit of organic chemistry). The β,γ-ethylenic ketones thus formed can then take part in cascade processes with ketones and acetylenes to afford either carbocycles (e.g., hexahydroazulenones, acyl terphenyls, functionalized and cyclopentenols) or heterocycles (e.g., furans, benzoxepines, dioxabicyclo3.2.1octanes, and dioxadispiro5.1.5.2pentadecanes), depending on the structure of the reactants and the reaction conditions. Most of these compounds are selectively built from several equivalents of ketones and acetylenes in different combinations, and despite the presence of two or more asymmetric carbons in the products, they are generated as single diastereomers. When other nucleophiles (hydroxylamine, hydrazines, guanidine, and oximes) and ketones are involved in these self-organization processes, the intermediate β,γ-ethylenic ketones allow the formation of diverse heterocyclic systems (pyrroles, isoxazolines, pyrazolines, aminopyrimidines, and azabicyclo3.1.0hexanes). The discovered unique chemical transformations do not require transition metal catalysts and proceed under mild and operationally simple conditions. Most of these syntheses involve cascade addition reactions and therefore represent pot-, atom-, step-, and energy-saving processes that meet the requirements of green chemistry. The significance of the approach discussed herein is that it represents a viable alternative to existing classic and modern transition-metal-based catalytic syntheses of some fundamental carbo- and heterocycles. This is demonstrated by its employment of readily available, inexpensive starting materials like acetylenes and ketones and simple, widely accessible superbasic systems such as KOH/DMSO, which serves as a highly active universal catalyst and auxiliary. As shown in this Account, as this approach has developed, the number of preparatively attractive methods for the synthesis of diverse and potentially useful compounds has rapidly ballooned. The impressive experimental results presented in this Account will hopefully draw the attention of large circles of organic chemists involved in the design of rational and ecologically sound synthetic procedures and thus increase the application of these techniques in medicinal chemistry and materials science.
High entropy materials (HEMs) have emerged as a new class of materials with exceptional scientific and technological potential. Since discovery of high entropy alloys (HEAs) in 2004, the concept of ...high entropy has been enlarged to ceramic, sulfide, fluoride, and phosphide materials. Correspondingly, their nearly infinite compositional space has been expanded to refractories, lanthanides, and recently platinum group metals (PGMs). Among these types of alloys, PGM-based HEM nanoparticles (HEM-NPs) are of great scientific interest because of the ability to continuously tailor their properties by tuning the ratio of noble to non-noble metal species. Besides, the functional properties of bulk HEAs such as shape memory effect, magnetocaloric, and superconductivity are attracting more and more attentions. In this review, we discuss the progress in the PGM-based HEMs focusing on catalytic performance of nanoparticles and functional properties of bulk materials. We begin with the synthesis of HEM-NPs emphasizing on the ability of alloying immiscible elements into single phase NPs. Then, we summarize the reported catalytic/electrocatalytic applications of HEM-NPs for different types of reactions, including CO2/CO reduction reactions, CO oxidation, methanol oxidation, oxygen reduction reaction and electrochemical water splitting. We present a case-by-case discussion to clarify how various metal species can play distinct role in chemically complex structure of HEM-NPs under different reaction conditions. We further try to give a picture of the current state of shape memory, magnetocaloric, and superconductivity effects in the bulk PGM-based HEAs.
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•Recent advances in PGM-based high entropy materials is reviewed.•The current state and challenges of the synthesis of HEM-NPs are reported.•Catalytic/electrocatalytic properties of HEM-NPs are reviewed considering their intrinsic multicomponent nature.•Mechanical and shape memory properties of PGM-based HEAs are discussed.•The realm of PGM-based HEAs has been expanded to superconductivity and magnetocaloric effects.
During the last 30 years, knowledge of the essential role that pyrrole structures play in the chemistry of living organisms, drug design, and the development of advanced materials has increased. ...Correspondingly, research on the diverse issues of synthetic, theoretical, and applied chemistry has snowballed. Devoted to the latest achievements of this
Numerous physiological functions rely on distinguishing temperature through temperature-sensitive transient receptor potential channels (thermo-TRPs). Although the function of thermo-TRPs has been ...studied extensively, structural determination of their heat- and cold-activated states has remained a challenge. Here, we present cryo-EM structures of the nanodisc-reconstituted wild-type mouse TRPV3 in three distinct conformations: closed, heat-activated sensitized and open states. The heat-induced transformations of TRPV3 are accompanied by changes in the secondary structure of the S2-S3 linker and the N and C termini and represent a conformational wave that links these parts of the protein to a lipid occupying the vanilloid binding site. State-dependent differences in the behavior of bound lipids suggest their active role in thermo-TRP temperature-dependent gating. Our structural data, supported by physiological recordings and molecular dynamics simulations, provide an insight for understanding the molecular mechanism of temperature sensing.
Infrared and THz optics has many promising practical applications such as in spectroscopy, diagnostic, optical metrology, sensing, and many others. Due to limited number of IR radiation sources, the ...frequency down-conversion processes are widely used for obtaining infrared radiation. Among them, the most applicable method is a generation of wave with difference frequency under the three-waves interaction in a medium with quadratic nonlinear response. Below we propose a new effective tool for three times decreasing frequency of the incident pulse based on three-waves interaction in a medium with the quadratic susceptibility. At such interaction, a medium’s response inherent cubic non-linearity appears due to so-called cascading SHG. The frequency down-conversion process possesses two stable modes. This is shown using multi-scale method. For each of the modes, the analytical solution is developed in the framework of the long pulse duration approximation without using the pump energy non-depletion approximation. The computer simulation results confirm those of analytical analysis. We show that the conversion efficiency of the incidentpump pulse energy achieves about 70%, if the low frequency wave incident intensity equals zero, or almost 100%, if the incident intensity of the low frequency wave is non-zero. The developed theoretical approach may be applied to other processes of the frequency down-conversion.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
An interaction of laser pulse, containing a few cycles, with substance is a modern problem, attracting attention of many researches. The frequency conversion is a key problem for a generation of such ...pulses in various ranges of frequencies. Adequate description of such pulse interaction with a medium is based on a slowly evolving wave approximation (SEWA), which has been proposed earlier for a description of propagation of the laser pulse, containing a few cycles, in a medium with cubic nonlinear response. Despite widely applicability of the frequency conversion for various nonlinear optics problems solutions, SEWA has not been applied and developed for a theoretical investigation of the frequency doubling process until present time. In this study the set of generalized nonlinear Schrödinger equations describing a second harmonic generation of the super-short femtosecond pulse is derived. The equations set contains terms, describing the pulses self-steepening, and the second order dispersion (SOD) of the pulse, a diffraction of the beam as well as mixed derivatives. We propose the transform of the equations set to a type, which does not contain both the mixed derivatives and time derivatives of the nonlinear terms. This transform allows us to derive the integrals of motion of the problem: energy, spectral invariants and Hamiltonian. We show the existence of two specific frequencies (singularities in the Fourier space) inherent to the problem. They may cause an appearance of non-physical absolute instability of the problem solution if the spectral invariants are not taken into account. Moreover, we claim that the energy preservation at the laser pulses propagation may not occur if these invariants do not preserve. Developed conservation laws, in particular, have to be used for developing of the conservative finite-difference schemes, preserving the conservation laws difference analogues, and for developing of adequate theory of the modulation instability of the laser pulses, containing a few cycles.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
We discuss an effective time-dependent THz spectroscopy method for the detection and identification of a substance with an inhomogeneous surface using a broadband THz signal reflected from the ...substance. We show that a successful and reliable identification can be made using the single long-duration THz signal, which contains not only the main reflected pulse, but also several sub-pulses. The method does not use averaging of the measured THz signals over the viewing angles and scanning over the surface area, which significantly increases the signal processing speed. The identification is based on the method of spectral dynamics analysis together with the integral correlation criteria (ICC). We compare the absorption spectral dynamics of a substance under analysis with the corresponding dynamics for a standard substance from database. For reliable and effective substance detection, we propose to use several ICC simultaneously in different time intervals, which contain not only the main pulse of the reflected THz signal, but also the sub-pulses. This way, one can detect and identify the substance in the sample with high probability. As examples of identification, we used the THz signals reflected from the plastic explosive PWM C4 with both rough and concave surface. We show that the main pulse, reflected from the inhomogeneous surface of the sample, contains information about its absorption frequencies.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
The publications covering new, transition metal-free cross-coupling reactions of pyrroles with electrophilic haloacetylenes in solid medium of metal oxides and salts to regioselectively afford ...2-ethynylpyrroles are discussed. The reactions proceed at room temperature without catalyst and base under solvent-free conditions. These ethynylation reactions seem to be particularly important, since the common Sonogashira coupling does not allow ethynylpyrroles with strong electron-withdrawing substituents at the acetylenic fragments to be synthesized. The results on the behavior of furans, thiophenes, and pyrazoles under the conditions of these reactions are also provided. The reactivity and structural peculiarities of nucleophilic addition to the activated acetylene moiety of the novel C-ethynylpyrroles are considered.
We discuss an effective tool for the detection and identification of substances in ternary mixtures with similar spectral properties using a broadband reflected THz signal. Nowadays, this is an ...urgent problem; its effective solution is still far off. Two ternary mixtures of the explosives (RDX+TNT+HMX and RDX+TNT+PETN) were used as the examples for demonstration of the efficiency of the method proposed. The identification is based on the pulsed THz spectroscopy. We follow the spectral intensities together with the use of integral correlation criteria. They use the spectral line dynamics of the THz pulse reflected from the substance under investigation and that of the standard THz signal from database. In order to increase the accuracy and reliability of the identification, we analyze the partial non-overlapping time intervals, containing the main pulse of the reflected THz signal and the sequential sub-pulses. The main pulse is shown to contain information about high absorption frequencies (ν > 2.6 THz) of the mixture components. In the sub-pulses, the absorption frequencies of the components are detected in the range of low (ν < 2.6 THz) and high (ν > 2.6 THz) frequencies. The opportunity of distinguishing the mixtures with similar spectral properties is also shown.
We investigate the effectiveness of using the Rosenbrock method for numerical solution of 1D nonlinear Schrödinger equation (or the set of equations) with artificial boundary conditions (ABCs). We ...compare the computer simulation results obtained during long time interval at using the finite-difference scheme based on the Rosenbrock method and at using the conservative finite-difference scheme. We show, that the finite-difference scheme based on the Rosenbrock method is conditionally conservative one. To combine the advantages of both numerical methods, we propose new implicit and conditionally conservative combined method based on using both the conservative finite-difference scheme and conditionally conservative Rosenbrock method and investigate its effectiveness. The combined method allows decreasing the computer simulation time in comparison with the corresponding computer simulation time at using the Rosenbrock method. In practice, the combined method is effective at computation during short time interval, which does not require an asymptotic stability property for the finite-difference scheme. We generalize also the combined method with ABCs for 2D case.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
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