Microwave plasma CVD-grown graphene–CNT hybrids for enhanced electron field emission applications

The growth and electron emission characteristics were investigated from a hybrid structure of multiwalled carbon nanotubes (MWCNTs) and multilayer layer graphene (MLG) deposited on silicon substrate coated with iron catalyst and an interlayer of aluminium. The hybrid structures were synthesized in a two-step process by microwave plasma-enhanced chemical vapour deposition technique. The formation of MWCNTs takes place by absorption and precipitation of carbon radicals into the catalyst particles. Thereafter, ample carbon forms MLG on tip of the MWCNTs resulting in a MLG-MWCNTs hybrid nanostructure. MLG was observed to grow branching out of the tips and sidewalls of the MWCNTs and is expected to attach by Van der Walls bonds. Transmission electron microscopy and micro-Raman spectroscopy confirmed the crystalline nature of the hybrid structures. Electron emission studies were carried out using a diode-type field emission setup. The enhancement factor was found to be ~3,500 for bare MWCNTs, ~4,070 to ~5,000 for hybrid structures and ~6,500 for N-doped MLG-MWCNTs hybrid structures. Modification in the defects structure and enhancement of emission sites are suggested to be responsible for the increase of the field emission characteristics.     

Silica nanowires: Growth,integration, and sensing applications

This review (with 129 refs.) gives an overview on how the integration of silica nanowires (NWs) into micro-scale devices has resulted, in recent years, in simple yet robust nano-instrumentation with improved performance in targeted application areas such as sensing. This has been achieved by the use of appropriate techniques such as di-electrophoresis and direct vapor-liquid-growth phenomena, to restrict the growth of NWs to site-specific locations. This also has eliminated the need for post-growth processing and enables nanostructures to be placed on pre-patterned substrates. Various kinds of NWs have been investigated to determine how their physical and chemical properties can be tuned for integration into sensing structures. NWs integrated onto interdigitated micro-electrodes have been applied to the determination of gases and biomarkers. The technique of directly growing NWs eliminates the need for their physical transfer and thus preserves their structure and performance, and further reduces the costs of fabrication. The biocompatibility of NWs also has been studied with respect to possible biological applications. This review addresses the challenges in growth and integration of NWs to understand related mechanism on biological contact or gas exposure and sensing performance for personalized health and environmental monitoring. Figure

Silica nanowires decorated micro-electrodes for sensing application     

Synthesis of Polysubstituted Pyrazolo[3,4‐b]pyridine‐3‐Carbohydrazide and Pyrazolo[3,4‐d]pyridazine Derivatives

5‐Amino‐4‐formyl pyrazole carboxylate gave facile reactions with malononitrile, hydrazine, and ketones in the presence of piperidine furnished substituted pyrazolo[3,4‐b]pyridines and pyrazolo[3,4‐b]quinolones. The pyridazine sulfonamides were obtained by the reaction of 5‐chloro 4‐formyl pyrazole carboxylate with sulfonamide derivatives.     

Prospective virtual screening for novel p53–MDM2 inhibitors using ultrafast shape recognition

The p53 protein, known as the guardian of genome, is mutated or deleted in approximately 50 % of human tumors. In the rest of the cancers, p53 is expressed in its wild-type form, but its function is inhibited by direct binding with the murine double minute 2 (MDM2) protein. Therefore, inhibition of the p53–MDM2 interaction, leading to the activation of tumor suppressor p53 protein presents a fundamentally novel therapeutic strategy against several types of cancers. The present study utilized ultrafast shape recognition (USR), a virtual screening technique based on ligand–receptor 3D shape complementarity, to screen DrugBank database for novel p53–MDM2 inhibitors. Specifically, using 3D shape of one of the most potent crystal ligands of MDM2, MI-63, as the query molecule, six compounds were identified as potential p53–MDM2 inhibitors. These six USR hits were then subjected to molecular modeling investigations through flexible receptor docking followed by comparative binding energy analysis. These studies suggested a potential role of the USR-selected molecules as p53–MDM2 inhibitors. This was further supported by experimental tests showing that the treatment of human colon tumor cells with the top USR hit, telmisartan, led to a dose-dependent cell growth inhibition in a p53-dependent manner. It is noteworthy that telmisartan has a long history of safe human use as an approved anti-hypertension drug and thus may present an immediate clinical potential as a cancer therapeutic. Furthermore, it could also serve as a structurally-novel lead molecule for the development of more potent, small-molecule p53–MDM2 inhibitors against variety of cancers. Importantly, the present study demonstrates that the adopted USR-based virtual screening protocol is a useful tool for hit identification in the domain of small molecule p53–MDM2 inhibitors.     

Imidazolo‐dC Metal‐Mediated Base Pairs: Purine Nucleosides Capture Two Ag+ Ions and Form a Duplex with the Stability of a Covalent DNA Cross‐Link

8‐Phenylimidazolo‐dC (^phImidC, 2 ) forms metal‐mediated DNA base pairs by entrapping two silver ions. To this end, the fluorescent “purine” 2′‐deoxyribonucleoside 2 has been synthesised and converted into the phosphoramidite 6 . Owing to the ease of nucleobase deprotonation, the new Ag⁺‐mediated base pair containing a “purine” skeleton is much stronger than that derived from the pyrrolo‐ [3,4‐d]pyrimidine system (^phPyrdC, 1 ). The silver‐mediated ^phImidC–^phImidC base pair fits well into the DNA double helix and has the stability of a covalent cross‐link. The formation of such artificial metal base pairs might not be limited to DNA but may be applicable to other nucleic acids such as RNA, PNA and GNA as well as other biopolymers.     

Control of Regioselectivity over Gold Nanocrystals of Different Surfaces for the Synthesis of 1,4‐Disubstituted Triazole through the Click Reaction

Gold nanocubes, octahedra, and rhombic dodecahedra were examined for facet‐dependent catalytic activity in the formation of triazoles. Rhombic dodecahedra gave 100 % regioselective 1,4‐triazoles. The product yield was increased by decreasing the particle size. However, a mixture of 1,4‐ and 1,5‐triazoles was obtained in lower yields when cubes and octahedra of similar sizes were used. The lowest Au‐atom density on the {110} surface and largest unsaturated coordination number of surface Au atoms may explain their best catalytic efficiency and product regioselectivity. Various spectroscopic techniques were employed to verify the formation of the Au–acetylide intermediate and establish the reaction mechanism, in which phenylacetylene binds to the Au {110} surface through the terminal‐binding mode to result in the exclusive formation of 1,4‐triazoles. The smallest rhombic dodecahedra can give diverse 1,4‐disubstituted triazoles in good yields by coupling a wide variety of alkynes and organic halides.     

The mechanism of 1,4 alkyl group migration in hypervalent halonium ylides: the stereochemical course

Rhodium(II)-acetate-catalyzed decomposition of either 1,3-cyclohexanedione phenyliodonium ylide or 5,5-dimethyl-1,3-cyclohexanedione phenyliodonium ylide in the presence of alkyl halides yields the corresponding 3-alkoxy-2-halocyclohex-2-enones via a 1,4 alkyl group migration shown to be concerted and intramolecular. In the case of (S)-alpha-phenethyl chloride, the rearrangement proceeds with essentially 88.6% retention of configuration. Theoretical calculations at the B3LYP/6-31G level reveal an activation energy of 5.4 kcal/mol for the process. A Claisen-like rearrangement occurs in the case where allylic halides, such as dimethylallyl or methallyl chorides, are used. The mechanistic pathway proposed for these processes involves addition of the halogen atom of the alkyl or allyl halide to the rhodium carbenoid from the iodonium ylide to yield a halonium intermediate that undergoes halogen to oxygen group migration. Aryl halides, such as chloro-, bromo-, iodo-, and fluorobenzene, behave differently under the same reaction conditions, yielding the product of electrophilic aromatic substitution, namely, the 2-(4-halophenyl) 1,3-cyclohexanedione.     

Back Cover: Ligand-Free Ultrasmall Recyclable Iridium(0) Nanoparticles for Regioselective Aromatic Hydrogenation of Phosphine Oxide Scaffolds: An Easy Access to New Phosphine Ligands (Angew. Chem. Int. Ed. 39/2023)

Herein, we developed the recyclable ligand-free iridium (Ir)-hydride based Ir⁰ nanoparticles (NPs) for the first regioselective partial hydrogenation of P^V-substituted naphthalenes. Both the isolated and in situ generated NPs are catalytically active. A control nuclear magnetic resonance (NMR) study revealed the presence of metal-surface-bound hydrides, most likely formed from Ir⁰ species. A control NMR study confirmed that hexafluoroisopropanol as a solvent was accountable for substrate activation via hydrogen bonding. High-resolution transmission electron microscopy of the catalyst supports the formation of ultrasmall NPs, and X-ray photoelectron spectroscopy confirmed the dominance of Ir⁰ in the NPs. The catalytic activity of NPs is broad as showcased by highly regioselective aromatic ring reduction in various phosphine oxides or phosphonates. The study also showcased a novel pathway toward preparing bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl (H₈-BINAP) and its derivatives without losing enantioselectivity during catalytic events.