Luminescent Metallo‐Supramolecular Polymers

Luminescent metallo‐supramolecular polymers are a type of functional supramolecular architectures which integrates the advantages of emission, metal‐coordination, supramolecular chemistry as well as polymeric properties to realize advanced functions. Due to the abundant stimuli‐responsiveness of supramolecular assemblies and the light‐emitting properties, they have been widely applied as chemo‐sensors, light‐emitting devices, contrast agents for bio‐imaging, etc. In this review, we classify luminescent metallo‐supramolecular polymers based on the types of species (lanthanides, organometallic compounds, oligomer or polymer‐based ligands, small‐molecule‐based organic ligands) used to generate the luminescence and summarize recent developments of luminescent metallo‐supramolecular polymers. We mainly focus on the functions and applications of luminescent metallo‐supramolecular polymers and hope to give our reader a snapshot of research on luminescent metallo‐supramolecular polymers and encourage more scientists to devote into this promising area.     

The two-photon excitation cross section of 6MAP, a fluorescent adenine analogue

6MAP is a fluorescent analogue of adenine that undergoes Watson-Crick base pairing and base stacking in double-stranded DNA. The one-photon absorption spectrum of 6MAP is characterized by a maximum around 330 nm with moderate quantum yield fluorescence centered at about 420 nm. To take advantage of this probe for confocal and single-molecule microscopy, it would be advantageous to be able to excite the analogue via two photons. We report the first determination of the two-photon excitation cross section and spectrum for 6MAP from 614 to 700 nm. The power dependence of the fluorescence indicates that emission results from the absorption of two photons. The one-photon and two-photon emission line shapes are identical within experimental error. A study of the concentration dependence of the fluorescence yield for one-photon excitation shows no measurable quenching up to about 5 microM. The maximum in the two-photon excitation spectrum gives a two-photon cross section, delta(TPE), of 3.4 +/- 0.1 Goeppert-Mayer (G.M.) at 659 nm, which correlates well with the one-photon absorption maximum. This compares quite favorably with cross sections of various naturally fluorescent biological molecules such as flavins and nicotiamide. In addition, we have also obtained the two-photon-induced fluorescence emission spectrum of quinine sulfate. It is approximately the same as that for one-photon excitation, suggesting that two-photon excitation of quinine sulfate may be used for calibration purposes.     

Novel Pb(II), Zn(II), and Cd(II) coordination polymers constructed from ferrocenyl-substituted carboxylate and bipyridine-based ligands

Treatment of two kinds of ferrocenyl-substituted carboxylate ligands (3-ferrocenyl-2-crotonic acid, HOOC-CH=(CH(3))CFc (Fc=(eta(5)-C(5)H(5))Fe(eta(5)-C(5)H(4))) or O-ferrocecarbonyl benzoic acid, o-HOOCC(6)H(4)COFc with Pb(OAc)(2).3H(2)O, Zn(OAc)(2).2H(2)O, or Cd(OAc)(2).2H(2)O) resulted in four novel ferrocene-containing coordination polymers [[Pb(mu(2)-eta(2)-OOCCH=(CH(3))CFc)(2)].MeOH](n) (1), [[Zn(o-OOCC(6)H(4)COFc)(2)(4,4'-bipy)(H(2)O)(2)].2MeOH.2H(2)O](n) (4,4'-bipy = 4,4'-bipyridine) (2), [[Cd(o-OOCC(6)H(4)COFc)(2)(bpe)(MeOH)(2)].2H(2)O](n) (bpe = 1,2-bis(4-pyridyl)ethene) (3), and [Pb(o-OOCC(6)H(4)COFc)(eta(2)-o-OOCC(6)H(4)COFc)(bpe)](n)() (4). Their crystal structures have been characterized by single X-ray determinations. In polymer 1, Pb(II) ions are bridged by tridentate FcC(CH(3))=CHCOO(-) anions, forming an infinite chain [Pb(mu(2)-eta(2)-OOC=CH(CH(3))CFc)(2)](n). In polymers 2-4, there are three kinds of components, metal ions, o-FcCOC(6)H(4)COO(-) units, and organic bridging ligands. The bipyridine-based ligands connect metal ions leading to a one-dimensional chain with o-FcCOC(6)H(4)COO(-) units acting as monodentate or chelate ligands in the side chain. Such coordination polymers containing ferrocenyl-substituted carboxylate and bipyridine-based ligands are very rare. The solution-state differential pulse voltammetries of polymers 1-4 were determined. The results indicate that the half-wave potential of the ferrocenyl moieties is influenced by the Pb(II) ions in polymer 1 and strongly influenced by Zn(II), Cd(II), or Pb(II) ions in polymers 2-4. The thermal properties of the four polymers were also investigated.     

Two-Level Finite Element Iterative Algorithm Based on Stabilized Method for the Stationary Incompressible Magnetohydrodynamics

In this paper, based on the stabilization technique, the Oseen iterative method and the two-level finite element algorithm are combined to numerically solve the stationary incompressible magnetohydrodynamic (MHD) equations. For the low regularity of the magnetic field, when dealing with the magnetic field sub-problem, the Lagrange multiplier technique is used. The stabilized method is applied to approximate the flow field sub-problem to circumvent the inf-sup condition restrictions. One- and two-level stabilized finite element algorithms are presented, and their stability and convergence analysis is given. The two-level method uses the Oseen iteration to solve the nonlinear MHD equations on a coarse grid of size H, and then employs the linearized correction on a fine grid with grid size h. The error analysis shows that when the grid sizes satisfy h=O(H2), the two-level stabilization method has the same convergence order as the one-level one. However, the former saves more computational cost than the latter one. Finally, through some numerical experiments, it has been verified that our proposed method is effective. The two-level stabilized method takes less than half the time of the one-level one when using the second class Nédélec element to approximate magnetic field, and even takes almost a third of the computing time of the one-level one when adopting the first class Nédélec element.     

The Biosynthesis Related Enzyme,Structure Diversity and Bioactivity Abundance of Indole-Diterpenes: A Review

Indole diterpenes are a large class of secondary metabolites produced by fungi, possessing a cyclic diterpenoid backbone and an indole moiety. Novel structures and important biological activity have made indole diterpenes one of the focuses of synthetic chemists. Although the discovery, identification, structural diversity, biological activity and especially structure–activity relationship of indole diterpenes have been reported in some papers in recent years, they are absent of a systematic and comprehensive analysis, and there is no elucidation of enzymes related to this kind of natural product. Therefore, it is necessary to summarize the relevant reports to provide new perspectives for the following research. In this review, for the first time, the function of related synthases and the structure–activity relationship of indole diterpenes are expounded, and the recent research advances of them are emphasized.     

Tetrabromobisphenol Exposure Impairs Bovine Oocyte Maturation by Inducing Mitochondrial Dysfunction

Tetrabromobisphenol (TBBPA) is the most widely used brominated flame retardant in the world and displays toxicity to humans and animals. However, few studies have focused on its impact on oocyte maturation. Here, TBBPA was added to the culture medium of bovine cumulus–oocyte complexes (COCs) to examine its effect on oocytes. We found that TBBPA exposure displayed an adverse influence on oocyte maturation and subsequent embryonic development. The results of this study showed that TBBPA exposure induced oocyte meiotic failure by disturbing the polar-body extrusion of oocytes and the expansion of cumulus cells. We further found that TBBPA exposure led to defective spindle assembly and chromosome alignment. Meanwhile, TBBPA induced oxidative stress and early apoptosis by mediating the expression of superoxide dismutase 2 (SOD2). TBBPA exposure also caused mitochondrial dysfunction, displaying a decrease in mitochondrial membrane potential, mitochondrial content, mtDNA copy number, and ATP levels, which are regulated by the expression of pyruvate dehydrogenase kinase 3 (PDK3). In addition, the developmental competence of oocytes and the quality of blastocysts were also reduced after TBBPA treatment. These results demonstrated that TBBPA exposure impaired oocyte maturation and developmental competence by disrupting both nuclear and cytoplasmic maturation of the oocyte, which might have been caused by oxidative stress induced by mitochondrial dysfunction.     

The Amomum tsao-ko Essential Oils Inhibited Inflammation and Apoptosis through p38/JNK MAPK Signaling Pathway and Alleviated Gentamicin-Induced Acute Kidney Injury

The clinical application of gentamicin may lead to acute kidney injury (AKI), and the nephrotoxicity of gentamicin is related to the pathological mechanism of several oxidative and inflammatory cytokines. Plant-derived essential oils have good anti-inflammatory and antioxidant properties. This study aimed to clarify the protective effect of Amomum tsao-ko essential oils (AOs) on gentamicin-induced AKI in rats and its possible mechanism. The rat AKI model was induced by intraperitoneal injection of gentamicin. After 14 days of oral AO treatment, the renal function and pathological changes of the kidney tissues were evaluated, and the level of kidney tissue oxidative stress was detected. The content of inflammatory cytokines was measured by ELISA. The expression of ERK1/2, JNK1/2, p38, NF-κB, caspase-3, and Bax/Bcl-2 proteins were estimated by Western blot analysis. The results showed that taking AO reduced the contents of serum urea and creatinine in AKI rats and improve the pathological changes and oxidative stress of the kidney tissue in rats. At the same time, AO reduced inflammation and apoptosis during AKI by regulating the MAPK pathway. The data show that AO has a protective effect on the kidneys and may be a potential drug for treating kidney injury.     

Shikonin as a WT1 Inhibitor Promotes Promyeloid Leukemia Cell Differentiation

This study aims to observe the differentiating effect of shikonin on Wilms’ tumor 1 (WT1)-positive HL-60 cells and investigate the fate of the differentiated leukemia cells. WT1 overexpression unaffected cell viability but promoted resistance to H₂O₂-induced DNA injury and cell apoptosis. The binding of shikonin to the WT1 protein was confirmed by molecular docking and drug affinity reaction target stability (DARTS). Shikonin at the non-cytotoxic concentration could decrease the WT1 protein and simultaneously reduced the CD34 protein and increased the CD11b protein in a dose-dependent manner in normal HL-60 cells but not in WT1-overexpressed HL-60 cells. Shikonin unaffected HL-60 cell viability in 48 h. However, it lasted for 10 days; could attenuate cell proliferation, mitochondrial membrane potential (MMP), and self-renewal; prevent the cell cycle; promote cell apoptosis. In a mouse leukemia model, shikonin could decrease the WT1 protein to prevent leukemia development in a dose-dependent manner. In this study, we also confirmed preliminarily the protein–protein interactions between WT1 and CD34 in molecular docking and CO-IP assay. Our results suggest that: 1. shikonin can down-regulate the WT1 protein level for leukemia differentiation therapy, and 2. the interaction between WT1 and CD34 proteins may be responsible for granulocyte/monocyte immaturity in HL-60 cells.     

Enhancing Bioactive Saponin Content of Raphanus sativus Extract by Thermal Processing at Various Conditions

Pickled radish (Raphanus sativus) is a traditional Asian ingredient, but the traditional method takes decades to make this product. To optimize such a process, this study compared the saponin content of pickled radishes with different thermal processing and traditional processes (production time of 7 days, 10 years, and 20 years) and evaluated the effects of different thermal processes on the formation of radish saponin through kinetics study and mass spectrometry. The results showed that increasing the pickling time enhanced the formation of saponin in commercial pickled radishes (25 °C, 7 days, 6.50 ± 1.46 mg g⁻¹; 3650 days, 23.11 ± 1.22 mg g⁻¹), but these increases were lower than those induced by thermal processing (70 °C 30 days 24.24 ± 1.01 mg g⁻¹). However, it was found that the pickling time of more than 10 years and the processing temperature of more than 80 °C reduce the saponin content. Liquid chromatography–mass spectrometry (LC-MS) analysis showed that the major saponin in untreated radish was Tupistroside G, whereas treated samples contained Asparagoside A and Timosaponin A1. Moreover, this study elucidated the chemical structure of saponins in TPR. The findings indicated that thermal treatment could induce functional saponin conversion in plants, and such a mechanism can also be used to improve the health efficacy of plant-based crops.     

By-Product of the Red Ginseng Manufacturing Process as Potential Material for Use as Cosmetics: Chemical Profiling and In Vitro Antioxidant and Whitening Activities

Red ginseng (RG), which is obtained from heated Panax ginseng and is produced by steaming followed by drying, is a valuable herb in Asian countries. Steamed ginseng dew (SGD) is a by-product produced in processing red ginseng. In the present study, phytochemical profiling of extracts of red ginseng and steamed ginseng dew was carried out using gas chromatography-mass spectrometry (GC-MS) and rapid resolution liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry (RRLC-Q-TOF-MS) analysis. Additionally, antioxidant activities (DPPH, ·OH, and ABTS scavenging ability) and whitening activities (tyrosinase and elastase inhibitory activity) were analyzed. Phytochemical profiling revealed the presence of 66 and 28 compounds that were non-saponin components in chloroform extracts of red ginseng and steamed ginseng dew (RG-CE and SGD-CE), respectively. Meanwhile, there were 20 ginsenosides identified in n-butanol extracts of red ginseng and steamed ginseng dew (RG-NBE and SGD-NBE). By comparing the different polar extracts of red ginseng and steamed ginseng dew, it was found that the ethyl acetate extract of red ginseng (RG-EAE) had the best antioxidant capacity and whitening effect, the water extract of steamed ginseng dew (SGD-WE) had stronger antioxidant capacity, and the SGD-NBE and SGD-CE had a better whitening effect. This study shows that RG and SGD have tremendous potential to be used in the cosmetic industries.