Berberis vulgaris (B. vulgaris) and Rhus coriaria (R. coriaria) have been documented to have various pharmacologic activities. The current study assessed the in vitro as well as in vivo inhibitory efficacy of a methanolic extract of B. vulgaris (MEBV) and an acetone extract of R. coriaria (AERC) on six species of piroplasm parasites. The drug-exposure viability assay was tested on three different cell lines, namely mouse embryonic fibroblast (NIH/3T3), Madin-Darby bovine kidney (MDBK) and human foreskin fibroblast (HFF) cells. Qualitative phytochemical estimation revealed that both extracts containing alkaloid, tannin, saponins and terpenoids and significant amounts of flavonoids and polyphenols. The GC-MS analysis of MEBV and AERC revealed the existence of 27 and 20 phytochemical compounds, respectively. MEBV and AERC restricted the multiplication of Babesia (B.) bovis, B. bigemina, B. divergens, B. caballi, and Theileria (T.) equi at the half-maximal inhibitory concentration (IC50) of 0.84 ± 0.2, 0.81 ± 0.3, 4.1 ± 0.9, 0.35 ± 0.1 and 0.68 ± 0.1 µg/mL and 85.7 ± 3.1, 60 ± 8.5, 90 ± 3.7, 85.7 ± 2.1 and 78 ± 2.1 µg/mL, respectively. In the cytotoxicity assay, MEBV and AERC inhibited MDBK, NIH/3T3 and HFF cells with half-maximal effective concentrations (EC50) of 695.7 ± 24.9, 931 ± 44.9, ˃1500 µg/mL and 737.7 ± 17.4, ˃1500 and ˃1500 µg/mL, respectively. The experiments in mice showed that MEBV and AERC prohibited B. microti multiplication at 150 mg/kg by 66.7% and 70%, respectively. These results indicate the prospects of these extracts as drug candidates for piroplasmosis treatment following additional studies in some clinical cases.

Adropin is a unique hormone encoded by the energy homeostasis-associated (Enho) gene. Adropin is produced in the liver and brain, and also in peripheral tissues such as in the heart and gastrointestinal tract. Furthermore, adropin is present in the circulatory system. A decade after its discovery, there is evidence that adropin may contribute to body weight regulation, glucose and lipid homeostasis, and cardiovascular system functions. In this review, we summarize and discuss the physiological, metabolic, and pathophysiological factors regulating Enho as well as adropin. Furthermore, we review the literature addressing the role of adropin in adiposity and type 2 diabetes. Finally, we elaborate on the role of adropin in the context of the cardiovascular system, liver diseases, and cancer.

The aim of this study was to analyze the binding interactions between a common antihypertensive drug (ramipril, R) and the widely distributed plant flavonoid quercetin (Q), in the presence of human serum albumin (HSA). From the observed fluorescence spectra of the (HSA + R) system we can assume that ramipril is also one of the Site 3 ligands—similar to fusidic acid—the binding of which has been proven by RTG crystallography. Our claim is supported by near-UV CD spectroscopy, microscale themophoresis and molecular modeling. The presence of R slightly inhibited the subsequent binding of Q to HSA and, on the contrary, the pre-incubation of HSA with Q caused a stronger binding of R, most likely due to allosteric interactions. At high concentrations, R is also able to displace Q from its binding site. The dissociation constant KD for the binding of R is more than hundredfold larger than for Q, which means that R is a very weak binder to HSA. The knowledge of qualitative and quantitative parameters of R, as well as the methods used in this study, are important for future research into HSA binding. This study shows the importance of implementing other methods for KD determination. Microscale thermophoresis has proved to be a novel, practical and accurate method for KD determination on HSA, especially in cases when fluorescence spectroscopy is unable to produce usable results.

Functional properties of each enzyme strictly depend on immobilization protocol used for linking enzyme and carrier. Different strategies were applied to prepare the immobilized derivatives of Rhizomucor miehei lipase (RML) and chemically aminated RML (NH2-RML). Both RML and NH2-RML forms were covalently immobilized on glyoxyl sepharose (Gx-RML and Gx-NH2-RML), glyoxyl sepharose dithiothreitol (Gx-DTT-RML and Gx-DTT-NH2-RML), activated sepharose with cyanogen bromide (CNBr-RML and CNBr-NH2-RML) and heterofunctional epoxy support partially modified with iminodiacetic acid (epoxy-IDA-RML and epoxy-IDA-NH2-RML). Immobilization varied from 11% up to 88% yields producing specific activities ranging from 0.5 up to 1.9 UI/mg. Great improvement in thermal stability for Gx-DTT-NH2-RML and epoxy-IDA-NH2-RML derivatives was obtained by retaining 49% and 37% of their initial activities at 70 °C, respectively. The regioselectivity of each derivative was also examined in hydrolysis of fish oil at three different conditions. All the derivatives were selective between cis-5,8,11,14,17-eicosapentaenoic acid (EPA) and cis-4,7,10,13,16,19-docosahexaenoic acid (DHA) in favor of EPA. The highest selectivity (32.9 folds) was observed for epoxy-IDA-NH2-RML derivative in the hydrolysis reaction performed at pH 5 and 4 °C. Recyclability study showed good capability of the immobilized biocatalysts to be used repeatedly, retaining 50%–91% of their initial activities after five cycles of the reaction.

Novel flavanones that incorporate chromene motifs are synthesized via a one-step multicomponent reaction. The structures of the new chromenes are elucidated by using IR, 1H-NMR, 13C-NMR, 1H-1H COSY, HSQC, HMBC, and elemental analysis. The new compounds are screened for their in vitro antimicrobial and cytotoxic activities. The antimicrobial properties are investigated and established against seven human pathogens, employing the agar well diffusion method and the minimum inhibitory concentrations. A majority of the assessed derivatives are found to exhibit significant antimicrobial activities against most bacterial strains, in comparison to standard reference drugs. Moreover, their cytotoxicity is appraised against four different human carcinoma cell lines: human colon carcinoma (HCT-116), human hepatocellular carcinoma (HepG-2), human breast adenocarcinoma (MCF-7), and adenocarcinoma human alveolar basal epithelial cell (A-549). All the desired compounds are subjected to in-silico studies, forecasting their drug likeness, bioactivity, and the absorption, distribution, metabolism, and excretion (ADME) properties prior to their synthetic assembly. The in-silico molecular docking evaluation of all the targeted derivatives is undertaken on gyrase B and the cyclin-dependent kinase. The in-silico predicted outcomes were endorsed by the in vitro studies.

To enhance the versatility of organic azides in organic synthesis, a better understanding of their photochemistry is required. Herein, the photoreactivity of azidoisoxazole 1 was characterized in cryogenic matrices with IR and UV-Vis absorption spectroscopy. The irradiation (λ = 254 nm) of azidoisoxazole 1 in an argon matrix at 13 K and in glassy 2-methyltetrahydrofuran (mTHF) at 77 K yielded nitrosoalkene 3. Density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations were used to aid the characterization of nitrosoalkene 3 and to support the proposed mechanism for its formation. It is likely that nitrosoalkene 3 is formed from the singlet excited state of azidoisoxazole 1 via a concerted mechanism or from cleavage of an intermediate singlet nitrene that does not undergo efficient intersystem crossing to its triplet configuration.

The aim of this study was to develop a prodrug of ubiquinol-10 (UqH-10), the active form of ubiquinone-10 (Uq-10), for oral delivery. Bioavailability of UqH-10 is hampered by its high susceptibility to oxidation and water-insolubility. We prepared three novel N,N-dimethylglycine ester derivatives of UqH-10, including a 1-monoester (UqH-1-DMG), 4-monoester (UqH-4-DMG), and 1,4-bis-ester (UqH-DMG), and assessed their physicochemical properties in vitro and in vivo. UqH-DMG spontaneously formed an aqueous micelle solution comprising 20 nm particles at 36.5 °C. Cationic UqH-DMG formed nano-sized (5 nm) mixed-micelles with taurocholic acid. Reconversion of the derivatives to UqH-10 was accelerated in human liver microsomes. The oral bioavailability of UqH-10 after administration of UqH-derivatives or Uq-10 was determined in fasted and postprandial rats secreting normal and high levels of bile, respectively. In fasted rats, plasma UqH-10 after UqH-derivatives administration reached Cmax at 2–3 h and after Uq-10 administration, it remained low. The AUC0-24h of UqH-10 after UqH-derivatives administration was 2–3-fold higher than that after Uq-10 administration. In postprandial rats, the Tmax of UqH-10 after UqH-derivatives administration was an hour earlier than after Uq-10 administration. In conclusion, cationic UqH-derivatives are convenient prodrugs that enhance UqH-10 bioavailability by forming nanosized mixed-micelles with intestinal bile acids.

Benzosiloles and their π-extended derivatives are present in many important advanced materials due to their excellent physical properties. Especially, they have found many potential applications in the development of novel electronic materials such as OLEDs, semiconductors and solar cells. In this review, we have summarized several main approaches to construct (di)benzosilole derivatives and (benzo)siloles fused to aromatic five- and six-membered heterocycles.

The fabrication and luminescent performance of novel phosphors Na2YMg2V3O12:Dy3+ were investigated by a conventional solid-state reaction method. Under near-UV light, the Na2YMg2V3O12 host self-activated and released a broad emission band (400–700 nm, with a peak at 524 nm) ascribable to charge transfer in the (VO4)3− groups. Meanwhile, the Na2YMg2V3O12:Dy3+ phosphors emitted bright yellow light within both the broad emission band of the (VO4)3- groups and the sharp peaks of the Dy3+ ions at 490, 582, and 663 nm at a quenching concentration of 0.03 mol. The emission of the as-prepared Na2YMg2V3O12:Dy3+ phosphors remained stable at high temperatures. The obtained phosphors, commercial Y2O3:Eu3+ red phosphors, and BaMgAl10O17:Eu2+ blue phosphors were packed into a white light-emitting diode (WLED) device with a near-UV chip. The designed WLED emitted bright white light with good chromaticity coordinates (0.331, 0.361), satisfactory color rendering index (80.2), and proper correlation to a color temperature (7364 K). These results indicate the potential utility of Na2YMg2V3O12:Dy3+ phosphor as a yellow-emitting phosphor in solid-state illumination.

Chitin biomass, a rich renewable resource, is the second most abundant natural polysaccharide after cellulose. Conversion of chitin biomass to high value-added chemicals can play a significant role in alleviating the global energy crisis and environmental pollution. In this review, the recent achievements in converting chitin biomass to high-value chemicals, such as 5-hydroxymethylfurfural (HMF), under different conditions using chitin, chitosan, glucosamine, and N-acetylglucosamine as raw materials are summarized. Related research on pretreatment technology of chitin biomass is also discussed. New approaches for transformation of chitin biomass to HMF are also proposed. This review promotes the development of industrial technologies for degradation of chitin biomass and preparation of HMF. It also provides insight into a sustainable future in terms of renewable resources.

Summary of main observation and conclusion

The catalytic asymmetric 1,3‐dipolar [3 + 2] cycloaddition of azomethine ylides with stilbenes has been established, affording structurally diverse pyrrolidines bearing four contiguous stereocenters with stereo‐diversity in generally high yields and good to excellent stereoselectivities (up to 98% yield, 99:1 dr, >99% ee). Meanwhile, this strategy allowed the formal synthesis of antitumor drug RG7388 (Phase III clinical study) and its analogues in high efficiency.

A series of dinuclear rare‐earth metal alkyl complexes {[μ‐η2:η1:η1‐3‐(LNCH)(CH2SiMe3)Ind]RE(CH2SiMe3)(THF)}2 (L1 = 2‐tBuC6H4, RE = Y, Gd, Dy, Er, Yb; L2 = 2,4,6‐Me3C6H2, RE = Dy, Er; Ind = indolyl) and {[μ‐η2:η1:η1‐3‐(LNCH2)Ind]RE(CH2SiMe3)(THF)}2 (L1, RE = Y, Dy, Er, Yb; L2, RE = Er, Yb) bearing 3‐arylamido functionalized indolyl ligands having diverse bonding modes with metal ions were synthesized either by the insertion reaction of the imino group to the RE‐C bond or by the alkane elimination reaction. In the preparation of above complexes, rare‐earth metal alkyl complexes [μ‐η5:η1:η1‐3‐(L2NCH)(CH2SiMe3)Ind]Gd(CH2SiMe3)(THF)}2 with a μ‐η5:η1:η1 coordination mode to the gadolinium ion and {[μ‐η3:η1:η1‐3‐(L2NCH2)Ind]Dy(CH2SiMe3)(THF)}2 with a μ‐η3:η1:η1 coordination mode to the dysprosium ion were unexpectedly isolated. The reactions of 3‐(L2N=CH)Ind with Er(CH2SiMe3)3(THF)2 at room temperature, generated a tetranuclear imino‐indolyl erbium intermediate {[μ‐η1:η1‐3‐(L2N=CH)Ind]Er(CH2SiMe3)2(THF)}4, which can transform into the amido functionalized indolyl erbium complex in hot toluene. Moreover, the reactivities of the newly synthesized ytterbium complex with N‐heterocyclic compounds were investigated, affording the corresponding products of the mixed pyridyl‐indolyl, imidazolyl‐indolyl, and ortho‐metalated complexes. The yttrium complexes showed a high regioselectivity and steroselectivity for the isoprene polymerization with 1, 4‐trans selectivity up to 91.7% and 1, 4‐cis selectivity up to 96.1%, respectively in the presence of cocatalysts.

We report the synthesis, photophysics, electrochemistry and electrochemiluminescence (ECL) of two dqp (dqp = 2,6‐di(quinoline‐8‐yl)pyridine) based ruthenium(II) complexes, bearing either a n ‐butyl ester (1) or the corresponding carboxylic acid functionality (2). The complexes were prepared from [Ru(dqp)(MeCN) 3 ][PF 6 ] 2 by reaction with the dqp precursor using microwave irradiation. In both cases, photoluminescence spectra present strong 3 MLCT‐based red/near‐infrared (NIR) emissions centred at about 700 nm. The photoluminescence quantum yields were 6.4% and 7.4% for 1 and 2 respectively while the excited state lifetimes were 3.92 µs and 2.00 µs. Both complexes are ECL active, although ECL efficiency (Φ ECL­ ) of 1 was substantially higher than 2 , due to its more favourable electrochemical properties. Importantly, 1 also gave strong ECL in aqueous media, which is rare for near‐infrared emitters. The results suggest the possibility of very interesting ECL sensing applications for this class of emitter in biological media.

Operando analyses have provided several breakthroughs in the construction of high‐performance materials and devices, including energy storage systems. However, despite the advances in electrode engineering, the formidable issues of lithium intercalation and deintercalation kinetics cannot be investigated via planar observations. Thus, we propose the side‐view operando observation by optical microscopy of a graphite anode based on its color changes during electrochemical lithiation. Since the graphite color varies according to the optical energy gap during lithiation and delithiation, we could study the corresponding charge/discharge kinetics; in addition, our cell configuration uses liquid electrolytes similarly to commercial cells, allowing practical applications. Furthermore, this side‐view observation has showed that microscale spatial variations in rate and composition control the insertion and desertion, revealing the kinetics through the whole electrode. The results of this study could enhance the fundamental understanding of the kinetics of battery materials.

The hydroxycinnamic acids, p ‐coumaric acid ( p CA) and ferulic acid (FA), add diversity to the portfolio of products produced by grass‐fed lignocellulosic biorefineries. The level of lignin‐bound p CA in Zea mays was modified by alteration of PMT expression. The biomass was processed in a lab‐scale alkaline‐pretreatment biorefinery process and the data was used for a baseline technoeconomic analysis to determine where to direct our future research efforts in coupling plant design to biomass utilization processes. We concluded that future plant engineering efforts should focus on strategies that ramp up predominantly one type of hydroxycinnamate ( p CA or FA) and suppress accumulation of the other. The technoeconomic analysis indicated that target extraction titers of one hydroxycinnamic acid need to be >50 g/kg biomass, at least a five‐fold higher than our observed titers for the impure p CA/FA product mixture from wild‐type maize. The technical challenge for process engineers is to develop a viable process requiring more than 80% reduction in the isolation costs.

The practical application of high-capacity transition-metal sulfide anodes has been hampered by the poor rate capability and cycling performance. As recently reported in Matter, Yang and co-workers have developed a robust micro-truss structural Cu1.81S material with excellent mechanical strength for high-performance sodium-ion batteries.

In this issue of Chem, Kondo and co-workers report a facile soft-chemical method for the preparation of layered, electrically conductive hydrogen boride, which is short-range order but amorphous as a result of the geometrical frustration of the terminal B–H bonds. This work offers an alternative route to two-dimensional (2D) boron materials.

Ruthenium PNP pincer complexes bearing supplementary cyclometalated C,N‐bound ligands have been prepared and fully characterized for the first time. By replacing CO and H‐ as ancillary ligands in such complexes, additional electronic and steric modifications of this actual class of catalysts are possible. The advantages of the new catalysts are demonstrated in the general α‑alkylation of ketones with alcohols following a hydrogen autotransfer protocol. Herein, various aliphatic and benzylic alcohols were applied as green alkylating agents for ketones bearing aromatic, heteroaromatic or aliphatic substituents as well as cyclic ones. Mechanistic investigations revealed that during catalysis Ru carboxylate complexes are predominantly formed while neither the PNP nor the CN ligand are released from the catalyst in significant amounts.

Copper efflux oxidase (CueO) from Escherichia coli is a special bacterial laccase due to its fifth copper binding site. Herein, it is discovered that the fifth Cu occupancy plays a crucial and favorable role of electron relay in bioelectrocatalytic oxygen reduction. By substituting the residues at the four coordinated positions of the fifth Cu, 11 beneficial variants are identified with ≥2.5‐fold increased currents at ‐250 mV (up to 6.13 mA cm‐2). Detailed electrocatalytic characterization suggests the microenvironment of the fifth Cu binding site governs the electrocatalytic current of CueO. Additionally, further electron transfer analysis assisted by molecular dynamics (MD) simulation demonstrates that an increase in localized structural stability and a decrease of distance between the fifth Cu and the T1 Cu are two main factors contributing to the improved kinetics of CueO variants. It may guide a novel way to tailor laccases and perhaps other oxidoreductases for bioelectrocatlaytic applications.

We here compare the properties as well as solid state structures, singlet fission, and OFET performance of three tetrafluoropentacenes (1,4,8,11: 10 , 1,4,9,10: 11 , 2,3,9,10: 12 ). The novel compounds 10 and 11 were synthesized from the corresponding 6,13‐etheno‐bridged precursors by reaction with dimethyl 1,2,4,5‐tetrazine‐3,6‐dicarboxylate at elevated temperatures in high purity. While most of the molecular properties of the compounds are similar, their chemical reactivity and crystal structures differ considerably. Isomer 10 undergoes the orbital symmetry forbidden thermal [4 + 4] dimerization, while 11 and 12 are much less reactive. The latter isomers crystallize in a herringbone motif, but 10 prefers π‐π stacking. While the energy of the first electric dipole allowed optical transition varies only within 370 cm ‒1 (0.05 eV) for the neutral compounds, this amounts to roughly 1600 cm ‒1 (0.20 eV) for radical cations and 1300 cm ‒1 (0.16 eV) for dications. Transient spectroscopy of films of 11 and 12 reveals singlet fission time constants (91 ± 11 fs, 73 ± 3 fs, respectively) that are shorter than for pentacene (112 ± 9 fs). OFET devices constructed from 11 and 12 show close to ideal TFT characteristics with electron mobilities of 2×10 ‐3 cm 2 /(Vs) and 6×10 ‐2 cm 2 /(Vs), respectively.

A SeO3 centered lacunary Keggin‐type heteropolyoxovanadate (hetero‐POV) K6H2[SeV10O28(SeO3)3]·14H2O (1) was isolated by one‐pot reaction of KVO3 and SeO2 under acidic condition. X‐ray studies revealed that it comprised a single {VO5}‐capped trivacant B‐α‐type Keggin ion [SeV9O33(VO)]14‒ with its lacunary sites decorated by three {SeO3} pyramids. Interestingly, this new basic hetero‐POV building block was further used as precursor to assembly with different transtion metal (TM) ions, yielding a series of TM‐sandwiched POVs K6H8[(SeV10O28(SeO3)3)2(M(H2O)4)]·24H2O (M2+ = Mn2+ (2), Co2+ (3), Zn2+ (4)). All four compounds were characterised by single‐crystal X‐ray structure analysis, IR, XPS, EPR, and 51V NMR spectroscopy. Importantly, three TM‐sandwiched derivatives exhibited effective catalytic activity for the heterogeneous oxidative desulfurization of sulfides at room temperature.

We propose a latent energy transfer process in traditional Eu3+, Tb3+‐doped phosphors and present a new class of Eu3+, Tb3+‐doped Na4CaSi3O9 phosphors, enabled by luminescence decay dynamics that optimize the electron‐transfer energy process. Compared with other Eu3+, Tb3+‐doped phosphors, the as‐synthesized Eu3+, Tb3+‐doped Na4CaSi3O9 phosphors show improved large‐scale tunable emission color from green to red upon UV excitation, controlled by the Tb3+/Eu3+ doping ratio. Detailed spectroscopic measurements in the VUV‐UV‐vis region were used to determine the Eu3+‐O2‐ charge transfer energy, 4f‐5d transition energies and the energies of 4f excited multiplets of Eu3+ and Tb3+ with different 4fN electronic configurations. The Tb3+→Eu3+ energy transfer pathway in the co‐doped sample was systematically investigated, employing luminescence decay dynamics analysis to elucidate the relevant energy transfer mechanism in combination with the appropriate model simulation. To demonstrate their application potential, a prototype white light‐emitting diode (WLED) device was successfully fabricated using the yellow luminescence NCSO:0.03Tb3+,0.05Eu3+ phosphor with high thermal stability and a BaMgAl10O17:Eu2+ phosphor in combination with a near‐UV chip. These findings open up a new avenue to realize and develop multifunctional high‐performance phosphors by manipulating the energy transfer process for practical applications.

Lack of new antibiotics and increasing antimicrobial resistance are the main concerns of healthcare community nowadays, which necessitate the search for novel antibacterial agents. Recently, we discovered the cystobactamids ‐ a novel natural class of antibiotics with broad‐spectrum antibacterial activity. In this work, we describe a concise total synthesis of cystobactamid 507, the identification of the bioactive conformation using non‐covalently bonded rigid analogs, the first structure–activity relationship (SAR) study for cystobactamid 507 leading to new analogs with high metabolic stability, superior topoisomerase IIA inhibition, antibacterial activity and, importantly, stability toward the resistant factor AlbD. Deeper insight into the mode of action revealed that the cystobactamids employ DNA minor groove binding as part of the drug–target interaction without showing significant intercalation. By designing a new analog of cystobactamid 919‐2 we finally demonstrated that these findings could be further exploited to obtain more potent hexapeptides against Gram‐negative bacteria.

A supramolecular complex (1×C60) was prepared by assembling (C60‐Ih)[5,6]fullerene (C60) with the dinuclear Tb3+ triple‐decker complex [(TPP)Tb(Pc)Tb(TPP)] (1: Tb3+ = trivalent terbium ion, Pc2− = phthalocyaninato, TPP2− = tetraphenylporphyrinato) with quasi‐D4h symmetry to investigate the relationship between the coordination symmetry and single‐molecule magnet (SMM) properties. Tb3+‐Pc triple‐decker complexes (Tb2Pc3) have an important advantage over Tb3+‐Pc double‐decker complexes (TbPc2) since the magnetic relaxation processes correspond to the Zeeman splitting when there are two 4f spin systems. At 1.8 K, 1 and 1·C60 undergo different magnetic relaxations, and the changes in the ground state affect the spin dynamics. Although 1 and 1·C60 relax via QTM in a zero applied magnetic field (H), H dependencies of the magnetic relaxation times (τ) for H > 1500 Oe are similar. On the other hand, for H < 1500 Oe, the τ values have different behaviors since the off‐diagonal terms affect the magnetic relaxation mechanism. From temperature and H dependences of τ, spin‐phonon interactions along with direct and Raman mechanisms explain the spin dynamics. We believe that a supramolecular method can be used to control the magnetic anisotropy along the C4 rotation axis and the spin dynamic properties in dinuclear Ln3+‐Pc multiple‐decker complexes.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.