Novel redox-active hexaguanidine molecules with multiple redox states were synthesized by connecting three o-diguanidinobenzene units. In 2,3,6,7,14,15-hexaguanidino-triptycenes, the three redox-active o-diguanidinobenzene units are connected through C-C bonds to the sp3-hybridized bridgehead C atoms, and in 2,3,6,7,10,11-hexaguanidino-triphenylenes they are directly connected. The connectivity difference leads to different electronic coupling between the three redox-active o-diguanidinobenzene units, with homoconjugation being present in the triptycene, but not in the triphenylene compounds. Motivated by the appearance of an intense low-energy electronic transition, we especially analysed the effect of homoconjugation on the electronic structure and charge delocalization in the dicationic redox state of the triptycene derivatives. Then, several trinuclear high-spin cobalt (and copper) complexes were synthesized with the triphenylene and triptycene ligands, and the magnetic coupling and redox properties analysed. By choice of the coligands (hexafluoroacetylacetonate, trifluoroacetylacetonate and acetylacetonate), oxidation could be switched between metal- and ligand-centered redox events, leading to drastic changes in the magnetic or optical properties, especially as a consequence of homoconjugation in the triptycene derivatives.

Synthesis of highly functionalized spiro[4.4]nonane, and spiro[4.5]decane motifs by the reaction of dimethylacetylenedicarboxylate (DMAD) with 2-(2'-ketoalkyl)-1,3-indandiones, 2-(3'-ketoalkyl)-1,3-indandiones, respectively, has been developed by utilizing a catalytic amount of DABCO. The tertiary hydroxy-containing spiro[4.4]nonane products were converted into fully conjugated pentafulvene π-systems in an acidic medium via dehydration and unprecedented C-C bond rearrangement.

Although challenging, the distant C-H functionalization with precision is quite rewarding and has long been intriguing. Tailoring an appropriate template accomplishes the job but the prerequisite sets the limitation. We herein unveil our discovery of annulation of alkynes on to two distant (from directing group) C-H bonds through rollover cyclometallation assisted by conjugated C=C bond. The annulation follows a concomitant cyclization rewarding a rare triple C-H functionalization. The annulation is totally regioselective with an array of unsymmetrical alkynes, taking the leverage of an extended conjugation or a tertiary hydroxyl co-ordination. The mechanism is supported by control experiments, KIE & labelling studies and Mass spectrometry.

A metal-free one-pot process for the gem-difluoroolefination of amides is described. The reaction is based on interaction of generated in situ α-chloroiminium salts with difluorinated phosphorus ylide formed from difluorocarbene and triphenylphosphine. The olefination involves nucleophile-assisted dephosphorylation and proceeds within one hour at low temperature. The gem-difluoroenamines were used in further transformations leading to a variety of fluoroalkylated amines.

This study reports the design of a donor-acceptor (D-A) molecule with two fluorene units on each side of a benzothiadiazole moiety, which allows multiple intermolecular interactions to compete with one another so as to induce the evolution of the metastable 2D platelets to the stable 2D platelets during the self-assembly of the D-A molecule. Importantly, the living seeded self-assembly of metastable and stable 2D structures with precisely controlled sizes can be conveniently achieved using an appropriate supersaturated solution of the D-A molecule as the seeded growth medium that can temporarily hold the almost-proceeding spontaneous nucleation from competing with the seeded growth. The stable 2D platelets with smaller area sizes exhibit higher sensitivity to gaseous dimethyl sulfide, illustrating that the novel living self-assembly method provides more available functional structures with controlled sizes for practical applications. The key finding of this study is that the new living methodology is separated into two independent processes: the elaborate molecular design for various crystalline structures as seeds and the application of an appropriate supersaturated solution as the growth medium to grow the uniform structures with controlled sizes; this would make convenient and possible the living seeded self-assembly of rich 1D, 2D, and 3D architectures.

SARS-CoV-2 and its global spread have created an unprecedented public health crisis. The spike protein of SARS-CoV-2 has gained significant attention due to its crucial role in viral entry into host cells and its potential as both a prophylactic and a target for therapeutic interventions. Herein, we report the first successful total synthesis of the SARS-CoV-2 spike protein receptor binding domain (RBD), highlighting the key challenges and the strategies employed to overcome them. Appropriate utilization of advanced solid phase peptide synthesis and cutting-edge native chemical ligation methods have facilitated the synthesis of the protein molecule. We discuss problems encountered during the chemical synthesis and approaches taken to optimize the yield and the purity of the synthetic protein molecule. Furthermore, we demonstrate that the chemically synthesized spike RBD efficiently binds to the known mini-protein binder LCB1. The successful chemical synthesis of the spike RBD presented here can be utilized to gain valuable insights into SARS-CoV-2 spike RBD biology, advancing our understanding and aiding the development of intervention strategies to combat future coronavirus outbreaks. The modular synthetic approach described in this study can be effectively implemented in the synthesis of other mutated variants or enantiomer of spike RBD for mirror-image drug discovery.

Electromagnetic pollution could harm sensitive electronic equipment due to the rising use of electronic devices and communication infrastructure. The supercapacitor's electrochemical performance should be enhanced, and electromagnetic damage should be prevented. This study proposes NiCo2O4/CF composites for supercapacitors and microwave absorption. They are made by combining hydrothermal and annealing processes. Dense NiCo2O4 nanoneedles were uniformly grown on the outer layer of carbon foam (CF) as a growth skeleton, preventing the agglomeration of NiCo2O4. The composite had a specific capacitance of 537.5 F/g at 1 A/g. When the current density was set to 1 A/g, the supercapacitor that used NiCo2O4/CF as the cathode had a specific capacitance of 70.7 F/g, and when the current density was increased to 10 A/g, the original specific capacitance of 87.2% could still be maintained after 5000 charge-discharge cycles. At a power density of 3695.5 W/kg, an energy density of 22.1 Wh/kg could be maintained. Furthermore, we performed a microwave absorption test and determined its reflection loss curve for various sample thicknesses. Recombination enhanced the composite material's microwave absorption capability by greatly reducing the dielectric loss and the magnetic loss.

The changed interaction between S−Nb−S in [NbO]_6−x-xS structure, and the constructed [NbO]_6−x-xS structure realized the regulation of charge density change and spontaneous polarization. S-doping weakens the S−Nb−S interaction in the [NbO]_6−x-xS structure, which effectively improves the performance of the pyro-photo-electric synergistic water splitting system.

Abstract

Pyroelectric materials in the field of photoelectrochemical (PEC) water splitting still face the problems of difficult low spontaneous polarization intensity and excessive carrier recombination. Based on the above problems, we altered the interaction between S−Nb−S in the [NbO]_6−x-xS structure, and the constructed [NbO]_6−x-xS structure achieved the regulation of charge density change and spontaneous polarization. The results show that under the stimulation of light and temperature fluctuations, the current density of the NS-4 photoanode is as high as 0.574 mA/cm² at 1.23 V_RHE, which is about 1.59 times higher than the pure NaNbO₃ current density value, and the NS −4 photoanode achieves IPCE value of 16.08 %. The first-principles density-functional theory calculations (DFT) reveal the principle of the [NbO]_6−x-xS structure for the suppression function of the carrier recombination and the improvement function of the pyroelectric effect. The analysis shows that the S-doping leads to the weakening of S−Nb−S interactions in the [NbO]_6−x-xS structure, which improves the pyroelectric effect and suppresses the photo/pyro-generated carrier recombination, and effectively enhances the performance of the pyro-photo-electric synergistic water splitting system. This work promotes the development of pyroelectric materials in the field of photoelectrochemical water splitting.

Computational screening of 2D materials composed of 3d transition metal and hexaamine dipyrazino quinoxalineas efficient catalysts for carbon dioxide reduction reactions.

Abstract

Transition metals and organic ligands combine to form metal-organic frameworks (MOFs), which possess distinct active sites, large specific surface areas and stable porous structures, giving them considerable promise for CO₂ reduction electrocatalysis. In the present study, using spin polarisation density-functional theory, a series of 2D MOFs constructed from 3d transition metal and hexamethylene dipyrazoline quinoxaline(HADQ) were investigated. The calculated binding energies between HADQ and metal atoms for the ten TM-HADQ monolayers were strong sufficient to stably disperse the metal atoms in the HADQ monolayers. Of the ten catalysts tested, seven (Sc, Ni, Cu, Zn, Ti, V and Cr) exhibited high CO₂ reduction selectivity, while Mn, Fe and Co required pH values above 2.350, 6.461 and 6.363, respectively, to exhibit CO₂ reduction selectivity. HCOOH was the most important producer for Sc, Zn, Ni and Mn, while CH₄ was the main producer for Ti, Cr, Fe and V. Cu and Co were less selective, producing HCHO, CH₃OH, and CH₄ simultaneously at the same rate-determining step and limiting potential. The Cu-HADQ catalyst had a high overpotential for the HCHO product (1.022 V), while the other catalysts had lower overpotentials between 0.016 V and 0.792 V. Thus, these results predict TM-HADQ to show excellent activity in CO₂ electrocatalytic reduction and to become a promising electrocatalyst for CO₂ reduction.

Binary metallic CuCo₅S₈ is successfully synthesized and evaluated as a CA-free anode in sodium-ion batteries. Because of the metallic properties of the material, the CA-free anode exhibits superior rate and cyclic performances. The high electrode density and multi-electron transfer during the charge-discharge process enable CuCo₅S₈ anode to display an outstanding volumetric capacity.

Abstract

With the rapid improvement of compact smart devices, fabricating anode materials with high volumetric capacity has gained substantial interest for future sodium-ion batteries (SIBs) applications. Herein, a novel bimetal sulfide CuCo₅S₈ material is proposed with enhanced volumetric capacity due to the intrinsic metallic electronic conductivity of the material and multi-electron transfer during electrochemical procedures. Due to the intrinsic metallic behavior, the conducting additive (CA) could be removed from the electrode fabrication without scarifying the high rate capability. The CA-free CuCo₅S₈ electrode can achieve a high volumetric capacity of 1436.4 mA h cm⁻³ at a current density of 0.2 A g⁻¹ and 100 % capacity retention over 2000 cycles in SIBs, outperforming most metal chalcogenides, owing to the enhanced electrode density. Reversible conversion reactions are revealed by combined measurements for sodium systems. The proposed new strategy offers a viable approach for developing innovative anode materials with high-volumetric capacity.