Zinc (II) and AIEgens: The “Clip Approach” for a Novel Fluorophore Family. A Review

Aggregation-induced emission (AIE) compounds display a photophysical phenomenon in which the aggregate state exhibits stronger emission than the isolated units. The common term of “AIEgens” was coined to describe compounds undergoing the AIE effect. Due to the recent interest in AIEgens, the search for novel hybrid organic–inorganic compounds with unique luminescence properties in the aggregate phase is a relevant goal. In this perspective, the abundant, inexpensive, and nontoxic d¹⁰ zinc cation offers unique opportunities for building AIE active fluorophores, sensing probes, and bioimaging tools. Considering the novelty of the topic, relevant examples collected in the last 5 years (2016–2021) through scientific production can be considered fully representative of the state-of-the-art. Starting from the simple phenomenological approach and considering different typological and chemical units and structures, we focused on zinc-based AIEgens offering synthetic novelty, research completeness, and relevant applications. A special section was devoted to Zn(II)-based AIEgens for living cell imaging as the novel technological frontier in biology and medicine.     

Biosynthesis of Zinc Oxide Nanoparticles from Acacia nilotica (L.) Extract to Overcome Carbapenem-Resistant Klebsiella Pneumoniae

Recently, concerns have been raised globally about antimicrobial resistance, the prevalence of which has increased significantly. Carbapenem-resistant Klebsiella pneumoniae (KPC) is considered one of the most common resistant bacteria, which has spread to ICUs in Saudi Arabia. This study was established to investigate the antibacterial activity of biosynthesized zinc oxide nanoparticles (ZnO-NPs) against KPC in vitro and in vivo. In this study, we used the aqueous extract of Acacia nilotica (L.) fruits to mediate the synthesis of ZnO-NPs. The nanoparticles produced were characterized by UV-vis spectroscopy, zetasizer and zeta potential analyses, X-ray diffraction (XRD) spectroscopy, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM). The antimicrobial activity of ZnO-NPs against KPC was determined via the well diffusion method, and determining minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC), the results showed low MIC and MBC when compared with the MIC and MBC of Imipenem and Meropenem antibiotics. The results of in vitro analysis were supported by the results upon applying ZnO-NP ointment to promote wound closure of rats, which showed better wound healing than the results with imipenem ointment. The biosynthesized ZnO-NPs showed good potential for use against bacteria due to their small size, applicability, and low toxicity to human cells.     

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)₂TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures.     

Adding Value in Production of Multifunctional Polylactide (PLA)–ZnO Nanocomposite Films through Alternative Manufacturing Methods

Due to the added value conferred by zinc oxide (ZnO) nanofiller, e.g., UV protection, antibacterial action, gas-barrier properties, poly(lactic acid) (PLA)–ZnO nanocomposites show increased interest for utilization as films, textile fibers, and injection molding items. The study highlights the beneficial effects of premixing ZnO in PLA under given conditions and its use as masterbatch (MB), a very promising alternative manufacturing technique. This approach allows reducing the residence time at high processing temperature of the thermo-sensitive PLA matrix in contact of ZnO nanoparticles known for their aptitude to promote degradation effects onto the polyester chains. Various PLA–ZnO MBs containing high contents of silane-treated ZnO nanoparticles (up to 40 wt.% nanofiller specifically treated with triethoxycaprylylsilane) were produced by melt-compounding using twin-screw extruders. Subsequently, the selected MBs were melt blended with pristine PLA to produce nanocomposite films containing 1–3 wt.% ZnO. By comparison to the more traditional multi-step process, the MB approach allowed the production of nanocomposites (films) having improved processing and enhanced properties: PLA chains displaying higher molecular weights, improved thermal stability, fine nanofiller distribution, and thermo-mechanical characteristic features, while the UV protection was confirmed by UV-vis spectroscopy measurements. The MB alternative is viewed as a promising flexible technique able to open new perspectives to produce more competitive multifunctional PLA–ZnO nanocomposites.     

运用综合手段研究铅锌硫化物精矿的氧化和鉴定其产物

南京关口每年从国外进口铅、锌精矿达几百万吨,随着我国国民经济的发展,作为重要有色金属来源的该矿种的进口量仍将逐年增加。硫化物精矿在运输和储存过程中都有可能发生氧化,由此导致金属品位的波动是常见现象,然而此前在这方面的报导甚少。为此,作者以铅锌硫化物精矿为例对其进行了模拟状态下的氧化实验并采用能谱、光学显微镜、化学物相分析、X射线衍射分析、扫描电镜等手段对氧化前及氧化后的样品进行了鉴定。结果表明,在模拟精矿储运条件下两种精矿的氧化皆甚为明显,铅精矿为1.5%,而锌精矿达到了14.5%,由此引起的品位变化是不可忽视的。鉴于有色金属硫化物精矿在储运过程中呈现了它们的易氧化性并对品位产生影响,所以有关这类矿产品的商贸过程中涉及取样、样品加工和保管、公证等问题,均应在科学实验基础上规范化。     

Sequential separation of Cu(II)/Ni(II)/Fe(II) from strong-acidic pickling wastewater with a two-stage process based on a bi-pyridine chelating resin

A self-synthesized bi-pyridine chelating resin (PAPY) could separate Cu(II)/Ni(II)/Fe(II) sequentially from strong-acidic pickling wastewater by a two-stage pH-adjusted process, in which Cu(II), Ni(II), and Fe(II) were successively preferred by PAPY. In the first stage (pH 1.0), the separation factor of Cu(II) over Ni(II) reached 61.43 in Cu(II)-Ni(II)-Fe(II) systems. In the second stage (pH 2.0), the separation factor of Ni(II) over Fe(II) reached 92.82 in Ni(II)-Fe(II) systems. Emphasis was placed on the selective separation of Cu(II) and Ni(II) in the first-stage. The adsorption amounts of Cu(II) onto PAPY were 1.2 mmol/g in the first stage, while those of Ni(II) and Fe(II) were lower than 0.3 mmol/g. Cu(II) adsorption was hardly affected by Ni(II) with the presence of dense Fe(II), but Cu(II) inhibited Ni(II) adsorption strongly. Part of preloaded Ni(II) could be replaced by Cu(II) based on the replacement effect. Compared with the absence of Fe(II), dense Fe(II) could obviously enhance the separation of Cu(II)-Ni(II). More than 95.0% of Cu(II) could be removed in the former 240 BV (BV for bed volume of the adsorbent) in the fixed-bed adsorption column process with the flow rate of 2.5 BV/h. As proved by X-ray photoelectron spectrometry (XPS) and density functional theory (DFT) analyses, Cu(II) exerted a much stronger deprotonation and chelation ability toward PAPY than Ni(II) and Fe(II). Thus, the work shows a great potential in the separation and purification of heavy metal resources from strong-acidic pickling wastewaters.     

Porphyrin N-Pincer Pd(II)-Complexes in Water: A Base-Free and Nature-Inspired Protocol for the Oxidative Self-Coupling of Potassium Aryltrifluoroborates in Open-Air

Metalloporphyrins (and porphyrins) are well known as pigments of life in nature, since representatives of this group include chlorophylls (Mg-porphyrins) and heme (Fe-porphyrins). Hence, the construction of chemistry based on these substances can be based on the imitation of biological systems. Inspired by nature, in this article we present the preparation of five different porphyrin, meso-tetraphenylporphyrin (TPP), meso-tetra(p-anisyl)porphyrin (TpAP), tetrasodium meso-tetra(p-sulfonatophenyl)porphyrin (TSTpSPP), meso-tetra(m-hydroxyphenyl)porphyrin (TmHPP), and meso-tetra(m-carboxyphenyl)porphyrin (TmCPP) as well as their N-pincer Pd(II)-complexes such as Pd(II)-meso-tetraphenylporphyrin (PdTPP), Pd(II)-meso-tetra(p-anisyl)porphyrin (PdTpAP), Pd(II)-tetrasodium meso-tetra(p-sulfonatophenyl)porphyrin (PdTSTpSPP), Pd(II)-meso-tetra(m-hydroxyphenyl)porphyrin (PdTmHPP), and Pd(II)-meso-tetra(m-carboxyphenyl)porphyrin (PdTmCPP). These porphyrin N-pincer Pd(II)-complexes were studied and found to be effective in the base-free self-coupling reactions of potassium aryltrifluoroborates (PATFBs) in water at ambient conditions. The catalysts and the products (symmetrical biaryls) were characterized using their spectral data. The high yields of the biaryls, the bio-mimicking conditions, good substrate feasibility, evading the use of base, easy preparation and handling of catalysts, and the application of aqueous media, all make this protocol very attractive from a sustainability and cost-effective standpoint.     

Synthesis of Calcium Silicate Hydrate from Coal Gangue for Cr(VI) and Cu(II) Removal from Aqueous Solution

Both the accumulation of coal gangue and potentially toxic elements in aqueous solution have caused biological damage to the surrounding ecosystem of the Huainan coal mining field. In this study, coal gangue was used to synthesize calcium silicate hydrate (C-S-H) to remove Cr(VI) and Cu(II)from aqueous solutions and aqueous solution. The optimum parameters for C-S-H synthesis were 700 °C for 1 h and a Ca/Si molar ratio of 1.0. Quantitative sorption analysis was done at variable temperature, C-S-H dosages, solution pH, initial concentrations of metals, and reaction time. The solution pH was precisely controlled by a pH meter. The adsorption temperature was controlled by a thermostatic gas bath oscillator. The error of solution temperature was controlled at ± 0.3, compared with the adsorption temperature. For Cr(VI) and Cu(II), the optimum initial concentration, temperature, and reaction time were 200 mg/L, 40 °C and 90 min, pH 2 and 0.1 g C-S-H for Cr(VI), pH 6 and 0.07 g C-S-H for Cu(II), respectively. The maximum adsorption capacities of Cr(VI) and Cu(II) were 68.03 and 70.42 mg·g⁻¹, respectively. Furthermore, the concentrations of Cu(II) and Cr(VI) in aqueous solution could meet the surface water quality standards in China. The adsorption mechanism of Cu(II) and Cr(VI) onto C-S-H were reduction, electrostatic interaction, chelation interaction, and surface complexation. It was found that C-S-H is an environmentally friendly adsorbent for effective removal of metals from aqueous solution through different mechanisms.     

Effectiveness of the Oxygenation over Classical Protonolysis Reactions: A Case of Alkylzinc Complexes Incorporating an Aminoalcoholate Ligand

Alkylzinc aminoalcoholates have emerged as powerful catalysts in organic synthesis and polymerization processes. Despite extensive research, difficulties in the rational design of these catalytic systems and in-depth understanding of their modes of action have hitherto been encountered. Most of the major obstacles stem largely from the relatively limited knowledge of the structure-activity relationship of zinc catalysts. In fact, the key active species are often generated in situ via the protonolysis of the alkylzinc precursors, which precludes their isolation and detailed characterization. Herein, the effectiveness of the oxygenation over the classical protonolysis in the synthesis of zinc alkylperoxides stabilized by an aminoalcoholate ligand is demonstrated. The controlled oxygenation of a tert-butylzinc complex incorporating a pridinolum (prinol) ligand leads to well-defined a dinuclear adduct of a (prinol)ZnOOtBu moiety with the parent tBuZn(prinol) complex and a novel dimer [tBuOOZn(prinol)]₂ with terminal alkylperoxide groups. The observed reaction outcomes strongly depend on the reaction conditions. Although sparse examples of heteroleptic adducts of the [RZn(L)]_x[ROOZn(L)]_y-type are known, the herein reported homoleptic [ROOZn(L)]_x aggregate is unprecedented. Strikingly, comparative studies involving reactions between tBuZn(prinol) and tert-butylhydroperoxide or ethanol revealed that the respective seemingly simple zinc alkylperoxides, or zinc alkoxides, respectively, are not accessible via the classical alcoholysis. We believe that these game-changing results concerning multifaceted chemistry of organozinc aminoalcoholates should pave the way for more rational development of various Zn-based catalytic systems.