Abstract The sensitivity of Photoelectron Circular Dichroism (PECD) in the angular distribution of photoelectrons, a recent chiral technique, to detect chirality in pure hydrocarbons is investigated in a number of benchmark molecules. It is found that a very large chiral signal is expected, surpassing most current examples, giving a sure fingerprint of absolute configuration. On the other hand, the sensitivity to specific isomers or closely related molecules is relatively modest.

Abstract Dicyano-functionalized benzene and naphthalene anion derivatives exhibit a relatively rich population of electronically excited states in stark contrast to many assumptions regarding the photophysics of anions in general. The present work has quantum chemically analyzed the potential electronically excited states of closed-shell anions created by replacing hydrogen atoms with valence bound lone pairs in benzene and naphthalene difunctionalized with combinations of -CN and -C2H. Dicyanobenzene anion derivatives can exhibit dipole-bound excited states as long as the cyano groups are not in para position to one another. This also extends to cyanoethynylbenzene anions as well as deprotonated dicyano- and cyanoethynylnaphthalene anion derivatives. Diethynyl functionalization is less consistent. While large dipole moments are created in some cases for deprotonation on the -C2H group itself, the presence of electronically excited states beyond those that are dipole-bound is less consistent. Beyond these general trends, 2-cyanonaphthalene-34 gives strong indication for exhibiting a quadrupole-bound excited state, and the 1-cyanoethynylnaphthalene-29 and -36 anion derivatives are shown to possess as many as two valence-bound excited states and one dipole-bound excited state. These photophysical properties may have an influence on regions where polycyclic aromatic hydrocarbons are known to exist such as in various astrochemical environments or even in combustion flames.

Abstract Nowadays, durable protective coatings receive more attention in the field of conservation for several reasons (they are cost effective, time consuming, more resistance, etc.). Hence, this study was focused on producing a multi-functional, durable coating to protect different stone materials, especially, Lecce stone, bricks, and marble. For this purpose, ZrO2 -doped-ZnO-PDMS nanocomposites (PDMS, polydimethylsiloxane used as the binder) were synthesized by in situ reaction (doped nanoparticles were inserted into the polymer matrix during the synthesis of PDMS)and the performances of resulting coatings were examined by handling different experimental analyses. In particular, the study aimed to evaluate the durability properties of the coating along with the self-cleaning effect. As a result, the durability of the nanocomposite coating with respect to the well-known PDMS coating was assessed after exposure to two different ageing cycles: solar ageing (300 W, 1000 h) and humid chamber ageing (RH > 80%, T = 22 ± 3◦C, desiccator, 2 years). All the results were in good agreement with each other providing that newly prepared nanocomposite coating can be used as a durable protective coating for different stone materials.

Abstract Nitro compounds are an important class of organic molecules with broad application in organic synthesis, medicinal chemistry, and materials science. Among the variety of methodologies available for their synthesis, the direct oxidation of primary amines represents an attractive alternative route. Efforts towards the development of oxidative procedures for the synthesis of nitro derivatives have spanned over the past decades, leading to a wide variety of protocols for the selective oxidative conversion of amines to nitro derivatives. Methods for the synthesis of nitroarenes via oxidation of aryl amines, with particular emphasis on recent advances in the field, are summarised in this review.

Abstract The aim of this study was to evaluate whether the application of two pre-harvest relicitors—methyl-jasmonate (MeJ) and benzothiadiazole (BTH)—to Monastrell grapes, at two maturation stages, affected the composition and structure of the skin cell walls (SCWs) to differing extents.This study was conducted in 2016–2017 on Vitis vinifera L. cv Monastrell. A water suspension of MeJ and BTH, and a mixture of both, was applied at veraison and mid-ripening. The composition of the berry SCW was analyzed. Environmental conditions caused substantial changes in SCW composition,especially at high temperatures. Indeed, a reduction of approximately 50% in the biosynthesis of hemicellulose, proteins and total phenols was observed, accompanied by a slight increase in cellulose and lignin. However, the application of the treatments also caused changes in some SCW constituents: increases in the concentration of phenols, proteins and lignin were observed, especially when the MeJ and MeJ + BTH treatments were applied at veraison. Likewise, a reduction in uronic acids was observed in the MeJ + BTH treatment applied at veraison. These changes in the SCWs could affect their structural characteristics, and therefore influence grape handling in the field and in the winery. Further studies are needed to determine the extent to which MeJ and BTH treatments affect other skin characteristics.

Abstract Strain-induced on-surface transformations provide an appealing route to steer the selectivity towards desired products. Here, we demonstrate the selective on-surface synthesis of extended all-trans poly(2,6-pyridine) chains on Au(111). By combining high-resolution scanning tunneling and atomic force microscopy, we revealed the detailed chemical structure of the reaction products. Density functional theory calculations indicate that the synthesis of extended covalent structures is energetically favored over the formation of macrocycles, due to the minimization of internal strain. Our results consolidate the exploitation of internal strain relief as a driving force to promote selective on-surface reactions.

Abstract There is great contemporary interest in using cleaner technologies through green chemistry and utilizing biopolymers as raw material. Pectin is found on plant cell walls, and it is commonly extracted from fruit shells, mostly apples or citrus fruits. Pectin has applications in many areas of commercial relevance; for this reason, it is possible to find available information about novel methods to transform pectin and pursuing enhanced features, with the structuring of biopolymer microspheres being highly cited to enhance its activity. The structuring of polymers is a technique that has been growing in recent decades, due to its potential for diverse applications in various fields of science and technology. Several techniques are used for the synthesis of microspheres, such as ionotropic gelation,extrusion, aerosol drying, or emulsions, with the latter being the most commonly used method based on its reproducibility and simplicity. The most cited applications are in drug delivery, especially for the treatment of colon diseases and digestive-tract-related issues. In the industrial field, it is used for protecting encapsulated compounds; moreover, the environmental applications mainly include the bioremediation of toxic substances. However, there are still many possibilities for expanding the use of this biopolymer in the environmental field.

Abstract K[(18-crown-6)-bis(tetrahydrofuran)anthracenide] was independently prepared by three groups, and its structure described by two of them. The third structure description, though listed in the Cambridge Crystallographic Data Centre (CSD) collection, contains no space group or atomic coordinates, but the cell constants leave no doubt that it is the same species as the two others, which were reported in 2006 and 2016. The compound crystallizes in space group P21 , with Z0 = 2.0 atT = 123 K and R = 4.91% (I), and at 100 K and R = 4.44% (II); both impressive results in their individual quality and agreement, despite differences in experimental methods and the temperature of data collection. A more detailed examination of the published data for (I) and (II) reveals that the correct description for this very unusual, and thus far unique substance, is that it contains a radical anion crystallizing as a kryptoracemate rather than as a simple example of a Sohncke space group with Z0 = 2.0. The anthracenide anions present in (I) and (II) are virtually identical; in contrast, the internal pair of cationic species differ from one another in the dissymmetry of the flexible tetrahydrofuran ligands, having significantly different internal and external torsional angles. The two THF molecules attached to the K(crown-ether) cations are not centrosymmetrically related, and this is what makes this portion of the asymmetric unit responsible for the crystal being a kryptoracemate. Our presentation will be based on the more fully documented sample (II), unless specifically stated.

Abstract The micellar properties of the anionic surfactant, sodium dodecyl sulfate (SDS) are modified by the biologically active amino acids. Amino acids (AAs) have experienced a variety of interactions and are proposed to influence SDS micelles due to their nominated hydrophobic interactions. The present study determines the critical micellar concentration (CMC) of SDS in aqueous solutions as well as in amino aqueous solutions. Three amino acids (glutamic acid, histidine, and tryptophan) are considered here. The conductometric measurements were carried out using a wide range of SDS concentrations at different temperatures. Surface tension experiments have also been applied to estimate many surface parameters including surface excess concentration (Γmax), surface occupied area per surfactant molecule (Amin), surface tension at CMC (γcmc), surface pressure at CMC (Πcmc) and Gibbs free energy of adsorption (∆G◦ads), enthalpy ∆H◦m and the critical packing parameter(CPP). Interestingly, CMC values of SDS in water and in aqueous amino acids estimated by the surface tension method are comparable with the corresponding values obtained by the conductance method. The thermodynamic parameters of SDS micellization were also evaluated in both presence and absence of AAs. The additives of AAs work to reduce the CMC values, as well as the SDS thermodynamic parameters. This reduction is highly dependent on the hydrophobicity of the AA side chain. Negative values of ∆G◦m, ∆H◦m elucidate that micellization of SDS in the presence of amino acids is thermodynamically spontaneous and exothermic. The outcomes here might be utilized for pharmaceutical applications to stabilize proteins and inhibit protein aggregation.

Abstract Enantiopure N-heterocyclic carbene half-sandwich metal complexes of the general formula [Cp*M(CˆC:)I] (M = Rh, Ir; CˆC: = NI-NHC; NI-H = Naphthalimide; NHC = N-heterocyclic carbene) are reported. The rhodium compound was obtained as a single isomer displaying six membered metallacycle and was resolved on chiral column chromatography to the corresponding enantiomers (S)-[Cp*Rh(CˆC:)I] (S)-2 and (R)-[Cp*Rh(CˆC:)I] (R)-2. The iridium congener, however, furnishes a pair of regioisomers, which were resolved into (S)-[Cp*Ir(CˆC:)I] (S)-3 and (R)-[Cp*Ir(CˆC:)I] (R)-3 and (S)-[Cp*Ir(CˆC:)I] (S)-4 and (R)-[Cp*Ir(CˆC:)I] (R)-4. These regioisomers differ from each other, only by the size of the metallacycle; five-membered for 3 and six-membered for 4. The molecular structures of (S)-2 and (S)-4 are reported. Moreover, the chiroptical properties of these compounds are presented and discussed. These compounds display exceptional stable configurations at the metal center in solution with enantiomerization barrier ∆G6= up to 124 kJ/mol. This is because the nature of the naphthalimide-NHC clamp ligand and the iodide ligand contribute to their configuration’s robustness. In contrast to related complexes reported in the literature, which are often labile in solution.

Abstract The use of organic additives presents the greatest versatility and control of zeolite synthesis in order to prepare novel architectures for desired applications. Despite this prospect, there is little clarity of how organic additives are involved in framework assembly and the range of behaviours that are available. To address this issue, we have considered zeolites RHO and ZK-5 which can both be prepared using 18-crown-6 ether as an additive. Previously, this additive has shown to employ different structure directing behaviours to assemble a variety of zeolites. We have used high resolution powder X-ray diffraction and Rietveld refinement to determine structural models for zeolites RHO and ZK-5 with 18-crown-6 ether occluded in the framework. In doing so, we can observe the identity, location and orientation of the occluded additive and reason the structure directing behaviour in synthesis. We report that the isolated 18-crown-6 ether molecule is involved in the assembly of zeolite RHO, and for zeolite ZK-5 it is the K+ coordinated macrocation. In both cases the relevant additive is disordered in the framework, suggesting that they behave as space-filling species that stabilise the formation of the α-cage.

Abstract Molecular motors convert light and thermal energies into mechanical work, offering good opportunities to design novel molecular devices. Among them, molecular motors alternate a photoisomerization and a thermal helix inversion to achieve unidirectional rotation. The rotational speed is limited by the helix inversion step, which in turn is governed by a barrier in the electronic ground state. In this work, we systematically study the solvation effect on the thermal process of selected molecular motors, comparing reaction barriers obtained from both density functional theory (DFT) in the isolated system and umbrella sampling within a hybrid quantum mechanics/molecular mechanics (QM/MM) model in solution. We find more prominent solvation effects on those molecular motors with larger dipole moments. The results could provide insight into how to functionalize molecular motors to speed up their rotation.

Abstract A slight modification of the synthetic procedure resulted in a new (Cc) polymorph of vinylic tellurium-trichloride Z-Cl(Ph)C=C(Ph)TeCl3 (1, β-form) which is stabilized by Te· · · Cl chalcogen bonds, assembling its molecules into the zigzag chains. Such a packing motive is in contrast to the known (Pca21) polymorph of Z-Cl(Ph)C=C(Ph)TeCl3 (1, α-form, CCDC refcode: BESHOW), which is built upon Te· · · π(Ph) chalcogen bonded chains. We noted a similar case of [Te· · · halogen] vs.[Te· · · π(Ph)] supramolecular synthon polymorphism in its triiodide congener Z-l(Ph)C=CPh(TeI3)(2, α and β-polymorphic forms). Quantum chemical calculations of the intermolecular interaction and lattice energies for 1α–β and 2α–β supported the assumption that α is thermodynamic while β is a kinetic form. Kinetic forms 1β and 2β are isostructural (Cc), while the thermodynamic forms 1α (Pca21) and 2α (P21/c) are not and feature an unusual example of long-range supramolecular synthon module isomerism. In other words, 1α–2α pairs demonstrate very similarly to isostructural Te· · · πPh ChB stabilized chains, which are further packed differently relative to each other, following different angular geometry of type-I Cl· · · Cl and type-II I· · · I halogen bonding. These structural considerations are backed by quantum chemical calculations that support the proposed hierarchy of primary and secondary supramolecular synthons and the assignment of α and β as thermodynamic and kinetic forms, respectively.

Abstract Bulk heterojunction organic solar cells (BHJs) are competitive within the emerging photovoltaic technologies for solar energy conversion because of their unique advantages. Their development has been boosted recently by the introduction of nonfullerene electron acceptors (NFAs), to be used in combination with a polymeric electron donor in the active layer composition. Many of the recent advances in NFAs are attributable to the class of fused-ring electron acceptors (FREAs), which is now predominant, with one of the most notable examples being formed with a fused five-member-ring indaceno[1,2-b:5,6-b0]dithiophene (IDT) core. Here, we propose a novel and more sustainable synthesis for the IDT core. Our approach bypasses tin derivatives needed in the Stille condensation, whose byproducts are toxic and difficult to dispose of, and it makes use of cascade reactions, effectively reducing the number of synthetic steps.

Abstract Viruses, and in particular, RNA viruses, dominate the WHO’s current list of ten global health threats. Of these, we review the widespread and most common HIV, influenza virus, and SARS-CoV-2 infections, as well as their possible prevention by vaccination and treatments by pharma cotherapeutic approaches. Beyond the vaccination, we discuss the virus-targeting and host-targeting drugs approved in the last five years, in the case of SARS-CoV-2 in the last one year, as well as new drug candidates and lead molecules that have been published in the same periods. We share our views on vaccination and pharmacotherapy, their mutually reinforcing strategic significance in combating pandemics, and the pros and cons of host and virus-targeted drug therapy. The COVID-19 pandemic has provided evidence of our limited armamentarium to fight emerging viral diseases. Novel broad-spectrum vaccines as well as drugs that could even be applied as prophylactic treatments or in early phases of the viremia, possibly through oral administration, are needed in all three areas. To meet these needs, the use of multi-data-based precision medicine in the practice and innovation of vaccination and drug therapy is inevitable.

Abstract The development of widely applicable methods for the synthesis of C-C-bonded nanostructures on inert and insulating surfaces is a challenging yet rewarding milestone in the field of on-surface synthesis. This would enable studies of nearly unperturbed covalent nanostructures with unique electronic properties as graphene nanoribbons (GNR) and π-conjugated 2D polymers. The prevalent Ullmann-type couplings are almost exclusively carried out on metal surfaces to lower the temperature required for initial dehalogenation well below the desorption threshold. To overcome the necessity for the activation of monomers on the target surface, we employ a recently developed Radical Deposition Source (RaDeS) for the direct deposition of radicals onto inert surfaces for subsequent coupling by addition reactions. The radicals are generated en route by indirect deposition of halogenated precursors through a heated reactive tube, where the dehalogenation reaction proceeds. Here, we use the ditopic 6,11-diiodo-1,2,3,4-tetraphenyltriphenylene (DITTP) precursor that afforded chevron-like GNR on Au(111) via the usual two-staged reaction comprised of monomer-coupling into covalent polymers and subsequent formation of an extended GNR by intramolecular cyclodehydrogenation (CDH). As a model system for inert surfaces, we use Ag(111) passivated with a closed monolayer of chemisorbed iodine that behaves in an inert manner with respect to dehalogenation reactions and facilitates the progressive coupling of radicals into extended covalent structures. We deposit the DITTP-derived biradicals onto both iodine-passivated and pristine Ag(111) surfaces. While on the passivated surface, we directly observe the formation of covalent polymers, on pristine Ag(111) organometallic intermediates emerge instead. This has decisive consequences for the further progression of the reaction: heating the organometallic chain directly on Ag(111) results in complete desorption, whereas the covalent polymer on iodine-passivated Ag(111) can be transformed into the GNR. Yet, the respective CDH proceeds directly on Ag(111) after thermal desorption of the iodine passivation. Accordingly, future work is aimed at the further development of approaches for the complete synthesis of GNR on inert surfaces.

Abstract This paper presents a review of selected tunnel stability models that have been developed and used in calculating the minimum tunnel face pressure as described by original authors. Further more, this paper provides a comparison of required tunnel face pressure obtained from analytical models, based either on limit equilibrium method or the limit analysis method (upper bound theorem) and numerical models using the finite element method. The numerical results are presented in charts for the comparative study to discuss the influence of cover depth to tunnel diameter ratio (C/D), internal friction of the soil (ϕ), and cohesion (c) on normalized support pressure (pu/γD) for each model. To verify the accuracy of the selected models, a comparison of the results of seven tunnel stability models with the results of the physical models is carried out. In a ground composed of two layers, a comparison of the required tunnel face pressure is presented. The results show that the wedge–silo models provide higher support pressure than the conical block models. Moreover, the support pressure using the conical block models is only dependent on the friction angle and not on the C/D ratio. Finally, the results of wedge-silo models indicate more significant dependence of the required support pressure on the C/D ratio especially for the lower friction angle.

Abstract Concrete is increasingly utilized in the construction field in Southern Nevada. This area has an arid and hot summer and freezing cold winter conditions. These extreme conditions affect the properties of fresh concrete, which can cause cracking. Hot weather conditions may adversely affect both fresh and hardened concrete properties. Even though practices can minimize the detrimental effects, good quality control of fresh concrete, from mixing to finishing, is crucial under hot weather conditions. The objective of the present study is to evaluate the seasonal consistency of concrete quality, considering strength and slump properties. Another objective of this research is to determine the relationship between the seasonal air temperature variations and those of freshly batched concrete. Results indicate that strength and slump remain constant with varying air and concrete temperatures during pour. Additionally, during the hot season (air temperature above 27 ◦C (80 ◦F)), fresh concrete’s temperature is lower than the air’s temperature, in contrast during the cold season (air temperature below 16 ◦C (60 ◦F)), fresh concrete’s temperature is higher than the air’s temperature.Fresh concrete temperature and air temperature are similar in the range of 60 to 80 ◦F. Therefore, to limit the use of additional water or admixtures it is recommended to pour concrete when the air temperature is in the range of 16◦ and 27 ◦C (60 to 80 ◦F).