Microwave-Assisted Lignin Extraction-Utilizing Deep Eutectic Solvents to Their Full Potential.

The current research intended to investigate the suitability of different choline-chloride-based deep eutectic solvents for their role in microwave lignin extraction. Lignin, a widely spread biopolymer in plants and woody structures, is a valuable replacement for fossil-fuel-based materials. While some promising applications have been trialled already, the extraction of this material from its matrix still causes problems. Here, we highlight an efficient and fast method to extract lignin from untreated larch bark with deep eutectic solvents in a standard domestic microwave. We developed a straightforward, green methodology, which can be used on various reaction scales, with materials available to many researchers. Lignin was extracted within only 30 min of microwave irradiation in yields of up to 96%. Compared to traditional deep eutectic extraction by conventional heating, the reaction time was cut by 87% and the energy costs were reduced by 93.5%. The hydrogen bond donors were exchanged and different types, namely acid-based, hydroxyl-based and amide-based donor systems, were evaluated for their suitability concerning microwave lignin extraction. This study presents a novel approach towards energy-efficient and green lignin valorisation, without the inherent need for costly equipment.

Surface-confined formation of conjugated porphyrin-based nanostructures on Ag(111).

Porphyrin-based oligomers were synthesized from the condensation of adsorbed 4-benzaldehyde-substituted porphyrins through the formation of CC linkages, following a McMurry-type coupling scheme. Scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy data evidence both the dissociation of aldehyde groups and the formation of CC linkages. Our approach provides a path for the on-surface synthesis of porphyrin-based oligomers coupled by CC bridges - as a means to create functional conjugated nanostructures.

Structural effects of meso-halogenation on porphyrins.

The use of halogens in the crystal engineering of supramolecular porphyrin assemblies has been a topic of strong interest over the past decades. With this in mind we have characterized a series of direct meso-halogenated porphyrins using single crystal X-ray crystallography. This is accompanied by a detailed conformational analysis of all deposited meso-halogenated porphyrins in the CSD. In this study we have used the Hirshfeld fingerprint plots together with normal-coordinate structural decomposition and determined crystal structures to elucidate the conformation, present intermolecular interactions, and compare respective contacts within the crystalline architectures. Additionally, we have used density functional theory calculations to determine the structure of several halogenated porphyrins. This contrasts conformational analysis with existing X-ray structures and gives a method to characterize samples that are difficult to crystallize. By using the methods outlined above we were able to deduce the impact a meso halogen has on a porphyrin, for example, meso-halogenation is dependent on the type of alternate substituents present when forming supramolecular assemblies. Furthermore, we have designed a method to predict the conformation of halogenated porphyrins, without need of crystallization, using DFT calculations with a high degree of accuracy.

Synthesis, crystal structure, and ADME prediction studies of novel imidazopyrimidines as antibacterial and cytotoxic agents.

In the present study, a novel series of polyfunctionalized imidazopyrimidines 6a-u and 9a-d were efficiently constructed by a domino reaction between 2-imino-6-substituted-2,3-dihydropyrimidin-4(1H)-ones 4a-d or 8a-c and 2-bromoacetophenones 5a-i under mild basic conditions. The synthesized series were screened for their antibacterial activity against Staphylococcus aureus and Bacillus subtilis as Gram-positive (+) bacteria, as well as against Gram-negative (-) bacteria Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, and Salmonella typhi. Most of the synthesized derivatives of imidazopyrimidines 6 and 9 showed remarkable selectivity against Gram(-) bacteria over the Gram(+) ones. Compounds 6c, 6f, and 6g displayed potent and broad-spectrum antibacterial activity against all tested strains. Compounds 6f and 6g displayed promising inhibitory activity on GryB ATPase from E. coli with IC50 = 1.14 and 0.73 µM, respectively. Simultaneously, some of the synthesized imidazopyrimidines were screened for their antiproliferative activity against 60 cancer cell lines at a concentration of 10 µM. Compound 9d showed potent activity against most of the tested cell lines, with a mean growth inhibition of 37%. The ADME (absorption, distribution, metabolism, and excretion) prediction study demonstrated that the synthesized hits have, in addition to their promising chemotherapeutic activity, acceptable pharmacokinetic properties, and a drug-likeness nature to be further developed.

Hydrogels: soft matters in photomedicine.

Photodynamic therapy (PDT), a shining beacon in the realm of photomedicine, is a non-invasive technique that utilizes dye-based photosensitizers (PSs) in conjunction with light and oxygen to produce reactive oxygen species to combat malignant tissues and infectious microorganisms. Yet, for PDT to become a common, routine therapy, it is still necessary to overcome limitations such as photosensitizer solubility, long-term side effects (e.g., photosensitivity) and to develop safe, biocompatible and target-specific formulations. Polymer based drug delivery platforms are an effective strategy for the delivery of PSs for PDT applications. Among them, hydrogels and 3D polymer scaffolds with the ability to swell in aqueous media have been deeply investigated. Particularly, hydrogel-based formulations present real potential to fulfill all requirements of an ideal PDT platform by overcoming the solubility issues, while improving the selectivity and targeting drawbacks of the PSs alone. In this perspective, we summarize the use of hydrogels as carrier systems of PSs to enhance the effectiveness of PDT against infections and cancer. Their potential in environmental and biomedical applications, such as tissue engineering photoremediation and photochemistry, is also discussed.

Cubane Cross-Coupling and Cubane-Porphyrin Arrays.

Herein, an improved methodology for aryl-cubane cross-coupling is reported. The peculiarities of the cubane core and its behavior during cross-coupling conditions were analyzed, while the versatility of this adapted Baran cross-coupling methodology was demonstrated by the synthesis of various aryl-cubane systems, including coupling products of cubanes and porphyrins. Furthermore, arm extension of alkynyl-cubanes by Sonogashira reactions is demonstrated, showcasing the first proof of the stability of the cubane core in the presence of palladium catalysts.