Search Results (28)

Cyclo[48]carbon (C48) exhibits an aesthetically pleasant structure featuring a cyclic polyyne, and it serves as a prototypical medium-sized ring that moves us towards an understanding of its overall magnetic behavior in a challenging molecular shape through analysis of its induced magnetic field. The isotropic induced magnetic field (NICS) profile shows a strong deshielding region at the ring center and a shielding region near the carbon rim, indicating antiaromatic behavior. Under a perpendicular magnetic field, a pronounced deshielding cone extends from the ring center, whereas a parallel external field induces a localized shielding near the carbon backbone. This results in significant magnetic anisotropy above and below the ring plane, characteristic of its medium-sized cyclic structure. Decomposition of the magnetic shielding highlights that paramagnetic effects predominantly govern the magnetic response and anisotropy of C48, with diamagnetic contributions playing a minor role. These insights suggest that chemical modifications targeting frontier orbitals could effectively tune the magnetic properties of cyclo[48]carbon, providing a foundation for the design of substituted derivatives with tailored diamagnetic anisotropy for advanced material applications. Full article

Carbyne, a linear chain of carbon atoms, possesses extraordinary properties but has remained elusive due to its extreme instability. While encapsulation within carbon nanotubes stabilizes carbyne, a lack of synthetic control over its location has prevented practical use. Here, we introduce a spatially localized plasma jet technique that enables the guided spatially selective self-assembly of carbyne encapsulated within multiwalled carbon nanotube (carbyne@MWCNT) hybrids on graphite surfaces. This method uses intense, localized plasma energy to simultaneously grow nanotubes and synthesize carbyne within them, where the nanotube structure and carbyne encapsulation are governed by the localized heat flux distribution. Beyond confirming carbyne formation via its characteristic Raman mode, we discover its second-order vibrational spectrum, confirming anharmonic interactions between the chain and its nanotube container. This spatial control can be used to architect functional carbyne@MWCNT arrays, whose potential applications are discussed in detail. Full article

Employing some simple physics-inspired density-based information-theoretic approach (ITA) quantities to predict the electron correlation energies remains an open challenge. In this work, we expand the scope of the LR(ITA) (LR means linear regression) protocol to more complex systems, including (i) 24 octane isomers; (ii) polymeric structures, polyyne, polyene, all-trans-polymethineimine, and acene; (iii) molecular clusters, such as metallic Be_n and Mg_n, covalent S_n, hydrogen-bonded protonated water clusters H⁺(H₂O)_n, and dispersion-bound carbon dioxide (CO₂)_n, and benzene (C₆H₆)_n clusters. With LR(ITA), one can simply predict the post-Hartree-Fock (such as MP2 and coupled cluster) electron correlation energies at the cost of Hartree-Fock calculations, even with chemical accuracy. For large molecular clusters, we employ the linear-scaling generalized energy-based fragmentation (GEBF) method to gauge the accuracy of LR(ITA). Employing benzene clusters as an illustration, the LR(ITA) method shows similar accuracy to that of GEBF. Overall, we have verified that ITA quantities can be used to predict the post-Hartree-Fock electron correlation energies of various complex systems. Full article

In spite of the many chemical reports on polyacetylenes of the genus Artemisia, combined conclusions regarding their distribution and biological functions are widely missing. The aim of the present review was to arrange the diversity of polyacetylenes in the genus following biogenetic aspects and group them together into characteristic structural types. The co-occurrence of the dehydrofalcarinol type with the aromatic capillen-isocoumarin type represents a characteristic biogenetic trend, clearly segregating species of the subgenus Dracunculus from those of the subgenera Artemisia and Absinthium, distinguished by the spiroketal enol ether and/or linear triyne type. Various accumulation trends toward specific structures additionally contribute to a more natural species grouping within the subgenera. Biological activities were reported for all four structural types, ranging from antifungal, insecticidal, nematicidal, and cytotoxic properties to allelopathic effects. Of particular interest were their remarkable cytotoxic potencies, from which the very high values of dehydrofalcarin-3,8-diol may be associated with the pronounced affinity of this type to form extremely stable bonds to proteins acting in signaling pathways. The aromatic acetylene capillin inhibited the viability of various tumor cells in a dose- and time-dependent manner. Its potent apoptosis-inducing activity was induced via the mitochondrial pathway. A group of spiroketal enol ethers was identified as inhibitors of PMA-induced superoxide generation. Among them, the epoxide of the isovalerate ester exhibited the highest potency. The ecological impact of acetylene formation was made apparent by the allelopathic effects of DME of the linear triyne type, and the aromatic capillen by inhibiting seed germination and growth of widespread weeds. Full article

The development of new antibiotics with unique mechanisms of action is paramount to combating the growing threat of antibiotic resistance. Recently, based on inspiration from natural products, an asymmetrical polyacetylene core structure was examined for its bioactivity and found to have differential specificity for different bacterial species based on the substituents around the conjugated alkyne. This research further probes the structural requirements for bioactivity through a systematic synthesis and investigation of new compounds with variable carbon chain length, alkynyl subunits, and alcohol substitution. Furthermore, the research examines the activity of the new compounds towards the inhibition of biofilm formation. Overall, several key new polyyne compounds have been identified in both decreasing bacterial viability and in disrupting pre-formed biofilms. These properties are key in the fight against bacterial infections and will be helpful in the further development of new antibiotic agents. Full article

Polyyne is an sp-hybridized linear carbon chain (LCC) with alternating single and triple carbon–carbon bonds. Polyyne is very reactive; thus, its structure can be easily damaged through a cross-linking reaction between the molecules. The longer the polyyne is, the more unstable it becomes. Therefore, it is difficult to directly synthesize long polyynes in a solvent. The encapsulation of polyynes inside carbon nanotubes not only stabilizes the molecules to avoid cross-linking reactions, but also allows a restriction reaction to occur solely at the ends of the polyynes, resulting in long LCCs. Here, by controlling the diameter of single-walled carbon nanotubes (SWCNTs), polyynes were filled with high yield below room temperature. Subsequent annealing of the filled samples promoted the reaction between the polyynes, leading to the formation of long LCCs. More importantly, single chiral (6,5) SWCNTs with high purity were used for the successful encapsulation of polyynes for the first time, and LCCs were synthesized by coalescing the polyynes in the (6,5) SWCNTs. This method holds promise for further exploration of the synthesis of property-tailored LCCs through encapsulation inside different chiral SWCNTs. Full article

Laser synthesis of polyyne molecules C${}_{2n}$H${}_2$ (n > 2) in liquid hydrocarbons is a complex process in which intense pulsed radiation decomposes the initial carbon-containing substance (the hydrocarbon solvent itself or the solid carbon particles in a suspension). Notwithstanding the fact that the mechanism of pulsed laser ablation in liquids (PLAL) is widely accepted, the effect of the laser parameters on laser-driven polyyne formation is still not understood in detail. Here, we report a study of the polyyne yield as a function of the laser field intensity and exposure dose. Several carbon-containing liquids, including pure n-hexane, pure ethanol, and graphite powder suspended in ethanol, were treated with tightly focused picosecond IR radiation (wavelength of 1064 nm, pulse duration of 10 ps). The synthesis rate was characterized by UV-vis optical absorption spectroscopy. The yields of the polyynes were found to vary in exact accordance with the value of the absorbed laser energy, following specific nonlinear or linear laws. The influence of the laser intensity on the partial concentration of polyynes in the solution was analyzed. Full article

Laser ablation of a bulk graphite target in water using femtosecond laser pulses (pulse width ≤ 190 fs) was performed to investigate the synthesis of polyynes and carbon-based nanomaterials and compare them with the well-studied cases of longer pulse (picosecond or nanosecond) ablations. The laser ablation products were characterized using UV-vis absorption spectroscopy, Raman spectroscopy, X-ray diffraction, and transmission electron microscopy, whereas the induced plasma plumes were characterized using laser-induced breakdown spectroscopy. Carbon-based nanomaterials and short-chain polyynes (C₆H₂ and C₈H₂) are formed in the solutions as proven by their characteristic absorption band at ~262 nm and peaks in the region of 190–240 nm as well as at around 2100 cm⁻¹ in the Raman spectra, respectively. Polyynes (C₈H₂) are present in the solutions that are produced under an ablation that is carried out in two intervals with a short pause between them, which is contrary to a continuous ablation that is performed for the same total time duration. The ablation products have a hexagonal graphite crystal structure. The carbon-based nanomaterials consist of large non-spherical and small spherical nanoparticles as well as sheet-like structures. The results of the study were compared with previous studies and discussed based on those studies. Full article

Resistive sensing responses of the thin films obtained by dehydrohalogenation of polyvinylidene chloride (PVDC) and polyvinylidene chloride–polyvinyl chloride (PVDC-PVC) copolymer were investigated. The structure of the samples was studied by transmission electron microscopy, Fourier-transform infrared spectroscopy and Raman spectroscopy. The analyses demonstrate the formation of a porous structure based on polyyne–polyene chains. The formation of a foam-like oxidized sp-rich structure was observed for the samples obtained via the chemical treatment of the PVDC. However, a loose film with a developed structure and a lower fraction of sp-hybridized carbon was observed for KOH-treated PVDC-PVC. The resistive sensing responses of both of the dehydrohalogenated structures were measured for various concentrations of acetone, acetic acid, ammonia hydroxide, methanol, ethanol, benzene and water. The interplay between the efficiency of the dehydrohalogenation of the films, their structure and sensing selectivity is discussed. Full article

We report on the formation of the field-effect transistor based on a polyyne–polyene structure. Polyvinylidene chloride (PVDC) drop casting and its subsequent dehydrochlorination in KOH solution allowed for the formation of porous polyyne–polyene material, which was analyzed via transmission electron microscopy, Fourier-transform infrared spectroscopy, and Raman spectroscopy, revealing the presence of sp- and sp²-hybridized chained fragments in the structure. The polyyne–polyene-based field-effect transistor showed a transconductance of 3.2 nA/V and a threshold voltage of −0.3 V. The obtained results indicate that polyyne–polyene-based transistors can be used as discrete elements of molecular electronics and that subsequent studies can be aimed toward the development of selective polyyne–polyene-based gas sensors with tunable sensitivity. Full article

The formation of polyene-polyyne-based nanocomposites by dehydrohalogenation of the drop-cast-deposited polyvinylidene fluoride, assessment and ion-induced tailoring of their gas sensing properties are reported. The investigated structure was analyzed by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy, transmission electron microscopy and Fourier-transform infrared spectroscopy, revealing the thickness-dependent incomplete dehydrofluorination of the structure and its porosity induced by KOH treatment. The polyene-polyyne structures modified by low-energy Ar⁺ were studied by SEM and Raman spectroscopy, which showed the morphology variation, the shortening of chains and the graphitization of samples. The resistive gas sensing properties of the samples were analyzed at room temperature, revealing selective sensing of ammonia vapor by non-irradiated sample and the enhancement of the sensing properties for ethanol and water vapor after ion irradiation. With the ion dose enlargement, the change in the sensing response from electrical conductivity increase to decrease was observed for ammonia and ethanol, allowing us to discuss the origin and tunability of the sensing mechanism of the samples. Full article

Due to the increase in multidrug-resistant microorganisms, the investigation of novel or more efficient antimicrobial compounds is essential. The World Health Organization issued a list of priority multidrug-resistant bacteria whose eradication will require new antibiotics. Among them, Acinetobacter baumannii, Pseudomonas aeruginosa, and Enterobacteriaceae are in the “critical” (most urgent) category. As a result, major investigations are ongoing worldwide to discover new antimicrobial compounds. Burkholderia, specifically Burkholderia sensu stricto, is recognized as an antimicrobial-producing group of species. Highly dissimilar compounds are among the molecules produced by this genus, such as those that are unique to a particular strain (like compound CF66I produced by Burkholderia cepacia CF-66) or antimicrobials found in a number of species, e.g., phenazines or ornibactins. The compounds produced by Burkholderia include N-containing heterocycles, volatile organic compounds, polyenes, polyynes, siderophores, macrolides, bacteriocins, quinolones, and other not classified antimicrobials. Some of them might be candidates not only for antimicrobials for both bacteria and fungi, but also as anticancer or antitumor agents. Therefore, in this review, the wide range of antimicrobial compounds produced by Burkholderia is explored, focusing especially on those compounds that were tested in vitro for antimicrobial activity. In addition, information was gathered regarding novel compounds discovered by genome-guided approaches. Full article

Matricaria recutita L., German chamomile, is one of the most widely used medicinal plants, whose efficacy has been proven in numerous studies. However, its roots have attracted only little interest so far, since mainly above-ground plant parts are used for medicinal purposes. To broaden the knowledge of chamomile roots, a profound phytochemical characterization was performed along with a bioactivity screening of corresponding root extracts. While volatile constituents such as chamomillol and polyynes were detected using GC-MS, HPLC-MSⁿ analyses revealed the occurrence of four coumarin glycosides, more than ten phenolic acid esters and five glyceroglycolipids. Furthermore, the antioxidant activity of the extracts was evaluated. Polar extracts revealed IC₅₀ values ranging from 13 to 57 µg/mL in the DPPH radical scavenging assay, which is in the same range as reported for chamomile flower extracts. In addition, superoxide radical scavenging potential and mild antibacterial effects against S. aureus und B. subtilis were demonstrated. Moreover, to assess interspecies variation in chamomile roots, extracts of M. recutita were compared to those of M. discoidea DC. Interestingly, the latter revealed stronger antioxidant activity. The presented results aim at the valorization of chamomile roots, previously discarded as by-product of chamomile flower production, as a sustainable source of bioactive phytochemicals. Full article

Polyynes are alternations of single and triple bonds between carbon atoms, while cumulenes are successions of double bonds. Since the triple bond is the strongest bond between two carbon atoms, recent preoccupations included synthesizing and condensing cyclic polyynes and cumulenes and their clusters. Density functional theory calculations predicted stable monocyclic rings formation for a number of C atoms equal to or higher than 16. Alternative to the series of Carbon atoms are alternations of Boron and Nitrogen. Large rings (such as those of 24 atoms) can be crossed and thus small clusters can be formed. Patterns of three crosses seem to further stabilize the atomic ensemble. Clusters of $4C_{24}$ and $4B_{12}{N}_{12}$ (96 atoms) as well as $4C_{26}$ (104 atoms) have been designed, and their conformation has been studied here. Full article

Highly unsaturated chain molecules are interesting due to their potential application as nanowires and occurrence in interstellar space. Here, we focus on predicting the electronic spectra of polyynic nitriles HC_2m+1N (m = 0–13) and dinitriles NC_2n+2N (n = 0–14). The results of time-dependent density functional theory (TD-DFT) calculations are compared with the available gas-phase and noble gas matrix experimental data. We assessed the performance of fifteen functionals and five basis sets for reproducing (i) vibrationless electronic excitation energies and (ii) vibrational frequencies in the singlet excited states. We found that the basis sets of at least triple-ζ quality were necessary to describe the long molecules with alternate single and triple bonds. Vibrational frequency scaling factors are similar for the ground and excited states. The benchmarked spectroscopic parameters were shown to be acceptably reproduced with adequately chosen functionals, in particular ωB97X, CAM-B3LYP, B3LYP, B971, and B972. Select functionals were applied to study the electronic excitation of molecules up to HC₂₇N and C₃₀N₂. It is demonstrated that optical excitation leads to a shift from the polyyne- to a cumulene-like electronic structure. Full article