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This study aimed to design a facile and efficient protocol for upgrading the performance indices of polysulfone (PS) membrane (porosity, hydrophilicity, pure water flux (PWF), surface charge, and fouling-resistance) by blending with newly synthesized poly(ionic) crosslinked chitosan Schiff bases (PICCSBs). The PS-PICCSBs mixed-matrix membranes (MMMs) have successfully fabricated and characterized based on spectral and microscopic analyses, porosity, zeta potential, water contact angle, and water uptake (wettability) measurements. The PWF, fouling-resistance against bovine serum albumin (BSA), as well as ion exchange capacity (IEC) against nitrate anion were studied. The wettability, hydrophilicity and overall porosity of new MMMs have greatly increased, in comparison to a pristine PS membrane (M 0 ). In addition, blending of PS with PICCSBs resulted in switching its surface from negatively- to positively-charged. The PWF of MMMs has increased to reach a maximum value of 238.6 L/m 2  h for MMM 1 (9.3-fold higher than M 0 ). Meanwhile, BSA rejection has declined from 96.62% for M 0 to 41.9% for MMM 1 . The fouling parameters results of MMMs indicated their low fouling propensity. The IEC of nitrate anions revealed that the nitrate uptake by MMM 1 is higher than that for M 0 and MMM 2 by 34% and 14%, respectively., Competing Interests: Declaration of competing interest All authors show no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

S-alkyltetrahydrothiophenium, [C n THT] + bis(trifluorosulfonyl)imide, [NTf 2 ] - room temperature ionic liquids (ILs) and tetraphenylborate, [BPh 4 ] - salts with alkyl chain lengths from C 4 to C 10 have been prepared. The ILs and salts were characterized and their purity verified by 1 H- and 13 C-nuclear magnetic resonance, elemental analysis, ion chromatography, Karl-Fischer titration, single crystal X-ray diffraction as well as thermogravimetric analysis. The experimentally determined density and viscosity decrease with increasing temperature. The experimental solubility of the [C n THT][NTf 2 ]-ILs in water (75 to 2.2 mg/L for C 4 to C 10 ) was modelled with very good agreement by Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT), based on the extremely low vapor pressures for the [C n THT][NTf 2 ]-ILs measured in this work (4.15 to 0.037 ⋅ 10 -7 ×p sat for C 4 to C 10 ). PC-SAFT is able to predict and correlate different thermodynamic properties by estimating the Helmholtz residual energy., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

We report an alternating-reduction approach by galvanic replacement and co-reduction to enable incorporation of Pd into Pt shell, and the obtained PtPd hollow nanocubes with an enhanced alloy effect and highly active {100} facets show high catalytic activity and superior durability in the methanol oxidation reaction.

In this work, a novel strategy for the straightforward synthesis of substituted phthalimides is described, which includes base-mediated Michael addition/intramolecular cyclization/[1,5]- H shift/cleavage of CS 2 /aromatization/nucleophilic acyl substitution reaction of 2-(4-oxo-2-thioxothiazolidin-5-ylidene)acetates and α , α -dicyanoolefines under ultrasound (US) irradiation. Some advantages of this method are as follows: having simple operation, easily accessible starting materials, chemoselective cascade process, synthetically useful yields, and green conditions by utilizing US irradiation as a source of energy and using ethanol as solvent.

Isocyanide-based consecutive Bargellini/Ugi multicomponent reactions as a combinatorial strategy have been developed for the synthesis of new class of pseudo-peptides. Via Bargellini reaction 3-carboxamido-isobutyric acids are prepared using acetone, chloroform, sodium hydroxide, and isocyanides. Then, using Ugi multicomponent reaction strategy, pseudo-peptides containing three amide bonds are synthesized using the Bargellini reaction product, aldehydes, amines, and isocyanides. This is an efficient and eco-friendly approach for easy access to wide variety of structurally diverse, drug-like pseudo-peptides from cheap and readily available precursors in high yields.

To improve our understanding of the chemistry of actinide complexes and to spur their development in the field of actinide markers, two new uranium complexes were synthesized using 8-hydroxyquinoline and 5,7-dichloro-8-hydroxyquinoline. The prepared complexes were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, ultraviolet-visible spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The impact of the electron-withdrawing group of the ligand on the photoluminescence spectra of the complexes in solution and in the solid state was scrutinized. The bandgap of the complexes was calculated using the density functional theory (DFT) method to investigate the effects of the electron-withdrawing groups on energy levels. The synthesized uranium complexes demonstrated appropriate levels of the lowest unoccupied molecular orbital energy, leading to favorable dye stability. The prepared uranium complexes showed blue fluorescent emission, and the sample with the most intense fluorescence was used to construct bluish-green organic light-emitting diodes using simple solution processing fabrication methods. Absorbance spectra, emission spectra, DFT-calculated energy levels, and comparisons of the fabricated organic light-emitting diodes indicated that the electron-withdrawing group was a key factor in photoluminescence behavior.

Glioblastoma (GBM) is the most aggressive malignant primary brain tumour in adulthood. Despite strong research efforts current treatment options have a limited impact on glioma stem-like cells (GSCs) which contribute to GBM formation, progression and chemoresistance. Invasive growth of GSCs is in part associated with epithelial-mesenchymal-like transition (EMT), a mechanism associated with CD73 in several cancers. Here, we show that CD73 regulates the EMT activator SNAIL1 and further investigate the role of enzymatic and non-enzymatic CD73 activity in GBM progression. Reduction of CD73 protein resulted in significant suppression of GSC viability, proliferation and clonogenicity, whereas CD73 enzymatic activity exhibited negative effects only on GSC invasion involving impaired downstream adenosine (ADO) signalling. Furthermore, application of phosphodiesterase inhibitor pentoxifylline, a potent immunomodulator, effectively inhibited ZEB1 and CD73 expression and significantly decreased viability, clonogenicity, and invasion of GSC in vitro cultures. Given the involvement of adenosine and A 3 adenosine receptor in GSC invasion, we investigated the effect of the pharmacological inhibition of A 3 AR on GSC maintenance. Direct A 3 AR inhibition promoted apoptotic cell death and impaired the clonogenicity of GSC cultures. Taken together, our data indicate that CD73 is an exciting novel target in GBM therapy. Moreover, pharmacological interference, resulting in disturbed ADO signalling, provides new opportunities to innovate GBM therapy.

Multi-emitter luminescent metal-organic frameworks (LMOFs) possess multiple emission bands that can cover a wider spectral region, which is a prerequisite for white-light emitting and multi-dimensional ratiometric fluorescent sensing. By taking advantage of the structure features of MOFs (e.g. hybrid structure, porosity) and the various luminescence origins of LMOFs, different emission sources can be designed and combined with each other into a homogeneous solid-state LMOF phase with the desired emission properties. This feature article reviews the recent development of multi-emitter LMOFs, and focuses on the design strategies for creating multi-emitter LMOFs based on at least two emission centers. The design strategies are classified into and discussed along six categories: type I metal-linker emitters, Type II multi-metal emitters, Type III multi-linker emitters, Type IV chromophore@LMOF (chromophore incorporated into an already luminescent MOF), Type V chromophores@MOF (multi-chromophores embedded into a non-emissive MOF) and Type VI multi-heterostructure LMOF emitters. The new class of Type VI includes core-shell structured LMOF⊃LMOF and nanostructured LMOF/LMOF thin films on a substrate. The good spatial separation between the different emitters in their own but chemically linked LMOF phase can retain their emission properties with less interference with the other emitters.

On Wednesday 11 th March, 2020, the world health organization (WHO) announced novel coronavirus (COVID-19, also called SARS-CoV-2) as a pandemic. Due to time shortage and lack of either a vaccine and/or an effective treatment, many trials focused on testing natural products to find out potential lead candidates. In this field, an edible and folk medicinal Jordanian plant Crepis sancta (Asteraceae) was selected for this study. Phytochemical investigation of its enriched polyphenolic extract afforded four eudesmane sesquiterpenes (1-4) together with (6 S ,9 R )-roseoside (5) and five different methylated flavonols (6-10). Structure elucidation of isolated compounds was unambiguously determined based on HRESIMS, X-ray crystallography, and exhaustive 1D and 2D NMR experiments. All isolated compounds were assessed for their in vitro anti-inflammatory, antiallergic and in silico COVID-19 main protease (M pro ) inhibitory activities. Among the tested compounds, compounds 5-10 revealed potent anti-inflammatory, antiallergic and COVID-19 protease inhibitory activities. Chrysosplenetin (10) is considered as a promising anti-inflammatory and antiallergic lead structure adding to the phytotherapeutic pipeline. Moreover, its inhibitory activity against SARS-CoV-2 M pro , supported by docking and molecular dynamic studies, strengthens its potential as a lead structure paving the way toward finding out a natural remedy to treat and/or to control the current COVID-19 pandemic., Competing Interests: The authors declare that there is no conflict of interest., (This journal is © The Royal Society of Chemistry.)

The bifunctional linker 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid (H2mpba) was used for the synthesis of new (square lattice) sql 2D metal-organic frameworks (MOFs) [Cu(Hmpba)2]·L (L = DMF or ACN) in a solvent-mixture of dimethylformamide/water and acetonitrile/water. These sql 2D MOFs are supramolecular isomers of the lvt 3D network [Cu(Hmpba)2]·4MeOH·1H2O (lvt-MeOH) that was synthesized previously by Richardson and co-workers. All these frameworks are potentially porous structures with solvent molecules included in the channels of the as synthesized materials. After activation all three materials showed good CO2 adsorption capacity, demonstrated here for lvt-MeOH for the first time, with a saturation uptake of 113 cm3 g-1 (lvt-MeOH-act.), 111 cm3 g-1 (sql-DMF-act.) and 90 cm3 g-1 (sql-ACN-act.) at 195 K. The flexibility of the lvt-MeOH-act. network is evidenced by a gate-opening effect seen in the CO2 measurement at 195 K and under gravimetric high-pressure CO2 adsorption. According to the water and ethanol sorption measurements the new sql frameworks can be categorized as hydrophobic materials in contrast to the hydrophilic lvt framework. In the lvt-MeOH structure the crystal solvent can be replaced with water to yield the structurally authenticated water-only network lvt-H2O containing 3D arrays of S4-symmetric (H2O)20 clusters.

Porous materials such as MOFs are interesting candidates for gas separation and storage. An important parameter to gain deeper insights to the adsorption process of an adsorptive on an adsorbent is the isosteric enthalpy of adsorption, ΔHads which is defined as the heat to be released/required when an adsorptive binds to/detaches from the solid surface of an adsorbent. Two or three adsorption isotherms at different but close temperatures with ΔT ≤ 20 K for two and ΔT ≈ 10 K for three isotherms are the basis to derive the isosteric enthalpy of adsorption through the Clausius-Clapeyron approach or the virial analysis. This Perspective presents the procedure of the common (dual-site) Freundlich-Langmuir fit/Clausius-Clapeyron approach and the virial fit of the isotherms with usable Excel sheets and Origin files for the subsequent derivation of ΔHads. Exemplary adsorption isotherms of CO2, SO2 and H2 at two temperatures on MOFs are analyzed. The detailed computational description and comparison of the Clausius-Clapeyron approach and the virial analysis to determine ΔHads outlines the limitations of the two methods with respect to the available experimental data, especially at low pressure/low uptake values. It is emphasized that no extrapolation beyond the experimental data range should be done. The quality of the important and underlying isotherm fits must be checked and ensured with logarithmic-scale n/p isotherm plots for the (dual-site) Freundlich-Langmuir fit in the low-pressure region and through low standard deviations for the coefficients in the virial analysis.

We describe a holistic approach for achieving a nearly quantitative conversion for an enzymatic reaction while simultaneously increasing the long-term stability of the enzyme. The approach provided chemical control of bioreactions by utilizing newly synthesized tetrahydrothiophene-based ionic liquids (THT ILs). We showcased its power by using THT-ILs as additives at a low concentration (only 10 mmol L -1 ) in the alcohol dehydrogenase (ADH)-catalyzed synthesis of methylated 1-phenylethanol (Me-PE). We discovered an "odd-even" effect of the IL-cation chain length: Me-PE displayed beneficial interactions with THT ILs having odd-numbered chain lengths and deleterious interactions with those having even-numbered chain lengths. An intermolecular thermodynamic simulation of the bulk phase and critical micelle concentration investigations of the local surroundings of the THT-ILs proved the occurrence of these interactions, and these two methods confirmed the odd-even effect from different perspectives. Additionally, storing the ADH enzyme in pure THT IL at room temperature allowed for a boosted long-term stability of the enzyme (500 times greater than that in aqueous buffer) without the need for freezing., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

New metal-organic frameworks (MOF) with lanthanum(III), cerium(III), neodymium(III), europium(III), gadolinium(III), dysprosium(III), and holmium(III)] and the ligand precursor 1,3,5- tris( 4 -carboxyphenyl)- 2,4,6 -trimethylbenzene (H 3 L) were synthesized under solvothermal conditions. Single crystal x-ray analysis confirmed the formation of three-dimensional frameworks of [LnL(H 2 O) 2 ] n ·xDMF·yH 2 O for Ln = La, Ce, and Nd. From the nitrogen sorption experiments, the compounds showed permanent porosity with Brunauer-Emmett-Teller (BET) surface areas of about 400 m 2 /g, and thermal stability up to 500 °C. Further investigations showed that these Ln-MOFs exhibit catalytic activity, paving the way for potential applications within the field of catalysis.

The enantiopure Schiff bases (R or S)-N-1-(phenyl)ethyl-2,4-X1,X2-salicylaldimine (X1, X2 = Cl, Br, I) coordinate to copper(ii) and provide pseudotetrahedral bis[(S or R)-N-1-(phenyl)ethyl-(2,4-X1,X2-salicylaldiminato-κ2N,O)]-Δ/Λ-Cu(ii) (Λ/Δ-Cu-R or Δ/Λ-Cu-S). An induced Λ and Δ-chirality at-metal centre has been launched along the C2-axis of the molecule. Steric constraints brought by halogen substituents on the coordinating salicylal ring provide diastereoselectively Λ-Cu-R or Δ-Cu-S as major and Δ-Cu-R or Λ-Cu-S as minor diastereomers at solid-state, as evidenced by X-ray crystal structures and PXRD analyses. These results reveal inversion of induced chirality at-metal in comparison to the similar complexes without halogen substituents on the salicylal ring. Electronic circular dichroism (ECD) spectra show mirror-image relationships, confirming enantiomeric excess of the R or S-ligated complexes in solution. Comparisons of experimental and simulated ECD spectra suggest diastereomeric excess of Δ-Cu-R or Λ-Cu-S in solution which correspond to an inversion from the found solid-state Λ-Cu-R or Δ-Cu-S as major diastereomers. In addition, the optimized gas-phase structures also reveal Δ-Cu-R or Λ-Cu-S as slightly more stable than Λ-Cu-R or Δ-Cu-S. Thus, solid-state versus solution (or gas-phase) studies also indicate an interconversion of induced chirality (helicity inversion) at-metal from Λ-Cu-R or Δ-Cu-S to Δ-Cu-R or Λ-Cu-S. Thermal stability increases with the molecular weight of the complexes following Cl < ClBr < Br < I substituents. Hirshfeld surface analyses explore the strongest halogen (ortho)-halogen (para) interactions between two molecules in Λ-Cu-R3 or Δ-Cu-S3 at a distance shorter than the sum of the van der Waals radii of the two iodine atoms, provide a brilliant red spot on the dnorm surfaces. EPR spectra along with simulation suggest an axial symmetry with gz > gx,y > 2.0 and values for gz/Az ≥ 135 cm indicate pseudotetrahedral geometry for the complexes.

We report a systematic study on the possibility of forming mixed-linker metal-organic frameworks (MOFs) spanning between the aluminum MOFs CAU-23 and MIL-160 with their 2,5-thiophenedicarboxylate (TDC) and 2,5-furandicarboxylate (FDC) linkers, respectively. The planned synthesis of a mixed-linker MOF, combining TDC and FDC in the framework turned out to yield a rather largely intricate mixture of CAU-23 and MIL-160. This is due to the different opening angles of 150° for TDC versus 120° for FDC and the concomitant cis-trans versus cis-only OH-bridges in the infinite secondary building unit {Al(μ-OH)(O2C-)} chains. At the same time, the CAU-23 phase is accompanied by the polymorphic MIL-53-TDC phase with trans-only OH-bridges. The measurement of water vapor sorption isotherms was the method of choice to confirm the formation of mixed MOFs instead of mixed-linker phases. Thereby, the water sorption isotherms indicate the simultaneous formation of both MOF phases, albeit they do not exclude mixed-linker MOFs which may have formed at low levels of substitution. The differentiation via powder X-ray diffractometry (PXRD), IR-spectroscopy and nitrogen sorption was either not conclusive enough or impossible, due to similarities of the neat MOF phases. The synthesized MOF mixtures within the TDC : FDC ratios of 38 : 62 up to 82 : 18 exhibit two or three uptake steps in the water sorption isotherm, with the first two corresponding to an overlay from the individual water sorption isotherm of CAU-23 and MIL-160 and a third one from the additional MIL-53-TDC.

One of the most important self-defense strategies employed by bacteria to resist the action of antibiotics is a biofilm formation upon the infected surface. Thus, there is an urgent need to explore novel candidates that have potent antibacterial and anti-biofilm effects to tackle this challenge. In this endeavor, we have transformed shrimp shell wastes to N-methylated water-soluble chitosan thiomer (MWSCT) which was used as either a chelating agent or bio-reductant and capping agent for Ag(I) ions in the preparation of a Ag(I)MWSCT complex or silver nanocomposite (Ag(0)MWSCT), for targeting antibacterial and anti-biofilm applications. The antibacterial and anti-biofilm performance of the new methylated chitosan thiomer (MWSCT) and its silver architectures (Ag(I)MWSCT, Ag(0)MWSCT) were assessed in vitro against E. coli and S. aureus. These new materials have significant capacities to synergistically inhibit the proliferation of the targeted bacterial cells and biofilm formation, in a structure- and species-dependent manner. Ag(0)MWSCT emerged as the most potent compound in inhibiting the growth of bacterial strains (MIC E. coli / MIC S. aureus  = 0.05/ 0.34 μg/mL, 1.6-/ 2.5-times lower than that recorded for the clinical drug (ciprofloxacin, Cipro). Also, this nanocomposite showed the highest anti-biofilm effects (only 1.7% E. coli biofilm growth; 11.8% staphylococcal biofilm growth)., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this work, we synthesized two tailored phosphorescent Pt(II) complexes bearing a cyclometalating tridentate thiazole-based C^N*N pincer luminophore ( L ) and exchangeable chlorido ( [PtCl(L)] ) or cyanido ( [PtCN(L)] ) coligands. While both complexes showed photoluminescence from metal-perturbed ligand-centered triplet states ( 3 MP-LC), [PtCN(L)] reached the highest phosphorescence quantum yields and displayed a significant sensitivity toward quenching by 3 O 2 . We encapsulated them into two Zn-based metal-organic frameworks, namely, MOF-5 and ZIF-8 . The incorporation of the organometallic compounds in the resulting composites [PtCl(L)]@ZIF-8 , [PtCN(L)]@ZIF-8 , [PtCl(L)]@MOF-5 , and [PtCN(L)]@MOF-5 was verified by powder X-ray diffractometry, scanning electron microscopy, time-resolved photoluminescence spectroscopy and microscopy, as well as N 2 - and Ar-gas sorption studies. The amount of encapsulated complex was determined by graphite furnace atomic absorption spectroscopy, showing a maximum loading of 3.7 wt %. If compared with their solid state forms, the solid-solution composites showed prolonged 3 O 2 -sensitive excited state lifetimes for the complexes at room temperature, reaching up to 18.4 μs under an Ar atmosphere, which is comparable with the behavior of the complex in liquid solutions or even frozen glassy matrices at 77 K.

A highly efficient photoenergy conversion is strongly dependent on the cumulative cascade efficiency of the photogenerated carriers. Spatial heterojunctions are critical to directed charge transfer and, thus, attractive but still a challenge. Here, a spatially ternary titanium-defected TiO 2 @carbon quantum dots@reduced graphene oxide (denoted as V Ti @CQDs@rGO) in one system is shown to demonstrate a cascade effect of charges and significant performances regarding the photocurrent, the apparent quantum yield, and photocatalysis such as H 2 production from water splitting and CO 2 reduction. A key aspect in the construction is the technologically irrational junction of Ti-vacancies and nanocarbons for the spatially inside-out heterojunction. The new "spatial heterojunctions" concept, characteristics, mechanism, and extension are proposed at an atomic-/nanoscale to clarify the generation of rational heterojunctions as well as the cascade electron transfer.

Covalent triazine frameworks (CTFs) are little investigated, albeit they are promising candidates for electrocatalysis, especially for the oxygen evolution reaction (OER). In this work, nickel nanoparticles (from Ni(COD) 2 ) were supported on CTF-1 materials, which were synthesized from 1,4-dicyanobenzene at 400 °C and 600 °C by the ionothermal method. CTF-1-600 and Ni/CTF-1-600 show high catalytic activity towards OER and a clear activity for the electrochemical oxygen reduction reaction (ORR). Ni/CTF-1-600 requires 374 mV overpotential in OER to reach 10 mA/cm 2 , which outperforms the benchmark RuO 2 catalyst, which requires 403 mV under the same conditions. Ni/CTF-1-600 displays an OER catalytic activity comparable with many nickel-based electrocatalysts and is a potential candidate for OER. The same Ni/CTF-1-600 material shows a half-wave potential of 0.775 V for ORR, which is slightly lower than that of commercial Pt/C (0.890 V). Additionally, after accelerated durability tests of 2000 cycles, the material showed only a slight decrease in activity towards both OER and ORR, demonstrating its superior stability., (Copyright © 2020, Öztürk et al.; licensee Beilstein-Institut.)

Metal-organic frameworks (MOFs) can contain open metal sites (OMS) or coordinatively unsaturated sites (CUS) or open coordination sites (OCS) when vacant Lewis acid sites on the metal ions or cluster nodes have been generated. This review combines for the first time all aspects of OMS in MOFs, starting from different preparation strategies over theoretical studies on the effects of OMS with host-guest interactions up to distinct OMS-MOF applications. In the experimental part the focus of this review is on MOFs with proven OMS formation which are not only invoked but are clearly verified by analytical methods.

The interfacial co-existence of oxygen and metal vacancies in metal oxide semiconductors and their highly efficient carrier transport have rarely been reported. This work reports on the co-existence of oxygen and titanium vacancies at the interface between TiO 2 and rGO via a simple two-step calcination treatment. Experimental measurements show that the oxygen and titanium vacancies are formed under 550 °C/Ar and 350 °C/air calcination conditions, respectively. These oxygen and titanium vacancies significantly enhance the transport of interfacial carriers, and thus greatly improve the photocurrent performances, the apparent quantum yield, and photocatalysis such as photocatalytic H 2 production from water-splitting, photocatalytic CO 2 reduction and photo-electrochemical anticorrosion of metals. A new "interfacial co-existence of oxygen and titanium vacancies" phenomenon, and its characteristics and mechanism are proposed at the atomic-/nanoscale to clarify the generation of oxygen and titanium vacancies as well as the interfacial carrier transport.

Fluoride-ion induced hydrolysis of imine (C[double bond, length as m-dash]N) bonds has not been documented in the literature, in spite of the numerous salicylidene-based fluoride sensors studied over the years. Herein, we have proposed a mechanism for fluoride-ion induced hydrolysis of salicylidene compounds (SL and CL1-3) based on 1 H-NMR, 19 F-NMR, LC-MS and UV-vis spectroscopy experiments., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The marine-derived fungus Aspergillus falconensis , isolated from sediment collected from the Canyon at Dahab, Red Sea, yielded two new chlorinated azaphilones, falconensins O and P ( 1 and 2 ) in addition to four known azaphilone derivatives ( 3 - 6 ) following fermentation of the fungus on solid rice medium containing 3.5% NaCl. Replacing NaCl with 3.5% NaBr induced accumulation of three additional new azaphilones, falconensins Q-S ( 7 - 9 ) including two brominated derivatives ( 7 and 8 ) together with three known analogues ( 10 - 12 ). The structures of the new compounds were elucidated by 1D and 2D NMR spectroscopy and HRESIMS data as well as by comparison with the literature. The absolute configuration of the azaphilone derivatives was established based on single-crystal X-ray diffraction analysis of 5 , comparison of NMR data and optical rotations as well as on biogenetic considerations. Compounds 1 , 3 - 9 , and 11 showed NF-κB inhibitory activity against the triple negative breast cancer cell line MDA-MB-231 with IC 50 values ranging from 11.9 to 72.0 µM.

We present a facile approach to encapsulate functional porous organic cages (POCs) into a robust MOF by an incipient-wetness impregnation method. Porous cucurbit[6]uril (CB6) cages with high CO 2 affinity were successfully encapsulated into the nanospace of Cr-based MIL-101 while retaining the crystal framework, morphology, and high stability of MIL-101. The encapsulated CB6 amount is controllable. Importantly, as the CB6 molecule with intrinsic micropores is smaller than the inner mesopores of MIL-101, more affinity sites for CO 2 are created in the resulting CB6@MIL-101 composites, leading to enhanced CO 2 uptake capacity and CO 2 /N 2 , CO 2 /CH 4 separation performance at low pressures. This POC@MOF encapsulation strategy provides a facile route to introduce functional POCs into stable MOFs for various potential applications., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Bottom-up and top-down approaches are described for the challenging synthesis of Fe/Al nanoparticles (NPs) in ionic liquids (ILs) under mild conditions. The crystalline phase and morphology of the metal nanoparticles synthesized in three different ionic liquids were identified by powder X-ray diffractometry (PXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), selected-area electron diffraction (SAED) and fast Fourier transform (FFT) of high-resolution TEM images. Characterization was completed by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) for the analysis of the element composition of the whole sample consisting of the NPs and the amorphous background. The bottom-up approaches resulted in crystalline FeAl NPs on an amorphous background. The top-down approach revealed small NPs and could be identified as Fe 4 Al 13 NPs which in the IL [OPy][NTf 2 ] yield two absorption bands in the green-blue to green spectral region at 475 and 520 nm which give rise to a complementary red color, akin to appropriate Au NPs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Combination of the polyimide 6FDA-mPD (6FDA = 4,4'-hexafluoroisopropylidene diphthalic anhydride and mPD = m-phenylenediamine) and crystallites of the metal-organic frameworks (MOFs) MIL-101(Cr) or MOF-199 (HKUST-1, Cu-BTC) produces mixed-matrix membranes (MMMs) with excellent dispersion and compatibility of the MOF particles within the polymer matrix. Permeation tests of a binary CO2/CH4 (50/50) gas mixture showed a remarkable increase of CO2 permeabilities for MIL-101(Cr)@6FDA-mPD and significantly higher selectivities for MOF-199@6FDA-mPD. The CO2 permeability increased from 10 (neat polymer) to 50 Barrer for the 24 wt% MIL-101(Cr)@6FDA-mPD membrane (with essentially constant selectivity) due to the high pore volume of MIL-101(Cr). The CO2/CH4 selectivity increased from 54 to 89 from the neat 6FDA-mPD polymer to the 24 wt% MOF-199@6FDA-mPD membrane, apparently due to the high CO2 adsorption capacity of MOF-199.

Glioblastoma (GBM) is an aggressive disease with currently no satisfying treatment option available. GBM cells with stem cell properties are thought to be responsible for the initiation and propagation of the disease, as well as main contributors to the emergence of therapy resistance. In this work, we developed a novel method to synthesize fluorescent gold nanoparticles as potential drug and gene delivery systems for GBM therapy, able to penetrate three-dimensional stem cell selected patient-derived GBM neurosphere systems in vitro. By using polyethylene imine (PEI) as a stabilizer and reducing agent, as well as fluorescein isothiocyanate (FITC) as a fluorescent marker, our fully in-house developed fluorescent gold nanoparticles (AuPEI-FITC NPs) with core sizes between 3 and 6 nm were obtained via a fast microwave-assisted reaction. Cytotoxicity, adsorption and internalization of AuPEI-FITC NPs into the cell lines JHH520, 407 and GBM1 were investigated using the cellular growth assay and fluorescence-activated cell sorting (FACS) analysis. AuPEI-FITC NPs showed no apparent cytotoxicity and an uptake in cells of up to ~80%. A differentiation between surface-bound and internalized AuPEI-FITC NPs was possible by quenching extracellular signals. This resulted in a maximal internalization degree of 61%, which depends highly on the synthesis method of the nanoparticles and the cell type tested. The best internalization was found for AuPEI-FITC1 which was prepared in a one pot reaction from KAuCl 4 , PEI and FITC. Thus, appropriately synthesized AuPEI-FITC NPs show great potential as vehicles to transport DNA or drugs in GBM cells., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier Inc. All rights reserved.)

An Erlotinib triphenylphosphane gold(I) conjugate has been prepared from AuCl(PPh 3 ) and its crystal structure has been established by X-ray diffraction, showing a metallo-helicate formation. IC 50 values of the new gold conjugate were calculated towards a panel of human tumor cell lines representative of breast (MCF-7, MDA-MB-231) and colon (HT-29) cancer cells. Overall, the gold conjugate exhibited higher cytotoxic activity than that of Erlotinib against the cancer cells studied. Particularly, the antiproliferative effect of the conjugate demonstrated to be 68-fold higher than Erlotinib in highly metastatic and triple negative MDA-MB-231 cell line. The gold conjugate caused DNA damage, reactive oxygen species (ROS) increase and induced apoptosis. Flow cytometry analysis showed that the conjugate induces significant arrest in S and G 2 /M phases primarily, whereas Erlotinib, as an inhibitor of epidermal growth factor receptor (EGFR), blocks G 1 /S transition and increases G 1 cell population., Competing Interests: Declaration of competing interest There is no interest conflict in this paper., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Cell surface engineering is an emerging technology to encapsulate cells in order to enhance their functions. However, methods for reversible encapsulation of cells with abiotic functionalities are rare. Herein, we describe a phenylboronic acid based click reaction for encapsulation of single yeast cells using mesoporous silica nanoparticles (MSNs). This encapsulation does not impact natural growth of the cells and leads to a significant enhancement of cell survival in a variety of hostile environments. Owing to the glucose-responsiveness of the boronate ester bond between cell surface polysaccharides and B(OH) 2 -grafted MSNs, encapsulation was reversible by addition or removal of glucose. This effort offers living cells effective protection under harsh conditions and enables reversible assembling-detaching of abiotic functions.

Nano/microsized MIL-101Cr was synthesized by microwave heating of emulsions for the use as a composite with Matrimid mixed-matrix membranes (MMM) to enhance the performance of a mixed-gas-separation. As an example, we chose CO 2 /CH 4 separation. Although the incorporation of MIL-101Cr in MMMs is well-known, the impact of nanosized MIL-101Cr in MMMs is new and shows an improvement compared to microsized MIL-101Cr under the same conditions and mixed-gas permeation. In order to reproducibly obtain nanoMIL-101Cr microwave heating was supplemented by carrying out the reaction of chromium nitrate and 1,4-benzenedicarboxylic acid in heptane-in-water emulsions with the anionic surfactant sodium oleate as emulsifier. The use of this emulsion with the phase inversion temperature (PIT) method offered controlled nucleation and growth of nanoMIL-101 particles to an average size of <100 nm within 70 min offering high apparent BET surface areas (2,900 m 2 g -1 ) and yields of 45%. Concerning the CO 2 /CH 4 separation, the best result was obtained with 24 wt.% of nanoMIL-101Cr@Matrimid, leading to 32 Barrer in CO 2 permeability compared to six Barrer for the neat Matrimid polymer membrane and 21 Barrer for the maximum possible 20 wt.% of microMIL-101Cr@Matrimid. The nanosized filler allowed reaching a higher loading where the permeability significantly increased above the predictions from Maxwell and free-fractional-volume modeling. These improvements for MMMs based on nanosized MIL-101Cr are promising for other gas separations., (Copyright © 2019 Gruber, Nuhnen, Lerch, Nießing, Klopotowski, Herbst, Karg and Janiak.)

Phenothiazines are of potential use as dye sensitizers in Grätzel-type dye sensitized solar cells (DSSC). Plasmonic nanoparticles like gold nanoparticles can enhance the power conversion efficiency of these solar cells. In this work near-infrared surface-enhanced Raman spectroscopy (NIR-SERS) is used to investigate the interaction between six novel phenothiazine-merocyanine dyes containing the three different functional groups rhodanine, 1,3-indanedione and cyanoacylic acid with plasmonic nanomaterials, to decide if the incorporation of plasmonic nanoparticles could enhance the efficiency of a Grätzel-type solar cell. The studies were carried out in the solution state using spherical and rod-shaped gold nanostructures. With KCl induced agglomerated spherical gold nanoparticles, forming SERS hot spots, the results showed low detection limits between 0.1 μmol L -1 for rhodanine containing phenothiazine dyes, because of the formation of Au-S bonds and 3 μmol L -1 for cyanoacrylic acid containing dyes, which formed H-aggregates in the watery dispersion. Results with gold nanorods showed similar trends in the SERS measurements with lower limits of detection, because of a shielding effect from the strongly-bound surfactant. Additional fluorescence studies were carried out to determine if the incorporation of nanostructures leads to fluorescence quenching. Overall we conclude that the addition of gold nanoparticles to rhodanine and 1,3-indanedione containing phenothiazine merocyanine dyes could enhance their performance in Grätzel-type solar cells, because of their strong interactions with plasmonic nanoparticles., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The most contracted cerium(iv)-based metal-organic framework (MOF) with fcu topology incorporating an alkyne-based linker, namely acetylenedicarboxylate (ADC), was synthesized under green conditions in water at room temperature and thoroughly characterized. The structure of this new MOF, denoted as Ce-HHU-1, was determined from powder X-ray diffraction data and Rietveld refinement and is made up of octahedral [Ce 6 O 4 (OH) 4 ] 12+ clusters, each of which is connected to other inorganic units by twelve ADC linkers to give a porous network with fcu topology analogous with UiO-66. The permanent microporosity of Ce-HHU-1 was confirmed by nitrogen sorption, meanwhile its high hydrophilicity was displayed by a type I water vapor sorption isotherm. The adsorption of CO 2 in Ce-HHU-1 features a remarkably high zero-coverage isosteric heat of adsorption of 47 kJ mol -1 , attributed to the presence of the -C[triple bond, length as m-dash]C- triple-bond in the framework. The latter also allows for Ce-HHU-1 to capture and irreversibly chemisorb Br 2 vapors, as well as both chemi- and physisorb I 2 vapors in an effective manner, making this material potentially applicable for air cleaning from toxic halogen vapors.

Starting from substituted alkynones, α-pyrones and/or 1 H -pyridines were generated in a Michael addition-cyclocondensation with ethyl cyanoacetate. The peculiar product formation depends on the reaction conditions as well as on the electronic substitution pattern of the alkynone. While electron-donating groups furnish α-pyrones as main products, electron-withdrawing groups predominantly give the corresponding 1 H -pyridines. Both heterocycle classes fluoresce in solution and in the solid state. In particular, dimethylamino-substituted α-pyrones, as donor-acceptor systems, display remarkable photophysical properties, such as strongly red-shifted absorption and emission maxima with daylight fluorescence and fluorescence quantum yields up to 99% in solution and around 11% in the solid state, as well as pronounced emission solvatochromism. Also a donor-substituted α-pyrone shows pronounced aggregation-induced emission enhancement., (Copyright © 2019, Breuer et al.; licensee Beilstein-Institut.)

Covalent triazine framework CTF-1 and polysulfone (PSF) are used to form mixed-matrix membranes (MMMs) with 8, 16, and 24 wt% of the porous filler material CTF-1. Studies on permeability and selectivity are carried out concerning the gases O 2 , N 2 , CO 2 , and CH 4 . CO 2 permeability of the synthesized MMMs increases by 5.4 Barrer in comparison to the pure PSF membrane. The selectivity remains unchanged for O 2 /N 2 and CO 2 /CH 4 but was found to be increased for CO 2 /N 2 . Further, comparisons to theoretical models for permeability prediction yield a permeability for CTF-1 which is about six times higher than the permeability of PSF. The inverse of the sum of the free fractional volumes (FFV) of the polymer and the filler correlate linearly to the logarithm of the permeabilities of the gases which conversely indicates that the porosity of the filler contributes to the gas transport through the membrane., (Copyright © 2019 Dey, Bügel, Sorribas, Nuhnen, Bhunia, Coronas and Janiak.)

A new porous coordination polymer (PCP/MOF), ZRTE-10 , based on a tetrahedral 1,3,5,7-tetra(carboxyphenyl)benzene ligand (H 4 L 4 ) was synthesized using formic or acetic acids as modulators. The low symmetry ( C 2/ c ) framework, [Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (L 4 )(HL 4 ) 2 (OH) 2 (H 2 O) 2 ], is built upon a rare 10-connected Zr 6 cluster. Two-thirds of the ligands bear one nondeprotonated carboxy group, and the framework has a complex trinodal 3,4,10-c, {4 14 .6 24 .8 7 }{4 3 } 2 {4 5 .6}, underlying net. Supercritical CO 2 drying and mild degassing at 120 °C yielded a porous material with S BET = 1190 m 2 . When heated up to ∼200 °C, -1 . When heated up to ∼200 °C, ZRTE-10 converts to another crystalline framework, ZRTE-11 . The latter was identified to be identical to the expected fluorite ( flu ) observed previously for other tetrahedral ligands. The high symmetry ( I 4/m) framework is built upon 8-connected Zr 6 clusters and has a formula of [Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) 4 (L 4 ) 2 ]. The complicated trinodal network of ZRTE-10 and the simple flu net in ZRTE-11 are topologically interrelated via the operation of the merging of two neighbor three-connected nodes to one four-connected one. The thermally induced conversion of ZRTE-10 proceeds with expulsion of one ligand per Zr 6 node in the pores of the framework, resulting in a relatively low S BET = 585 m 2 g -1 for the activated H 4 L 4 @ ZRTE-11 . A mixed ligand approach for ZRTE-10,11 was attempted using 1,3,5-tetra(carboxyphenyl)benzene (H 3 L 3 ), which is a truncated analog of H 4 L 4 with one missing branch. The monocrystalline sample of ZRTE-10 obtained in small yields demonstrated only minor inclusion of H 3 L 3 . However, the high-yielding (∼80%) procedure with HCl as a modulator allows near proportional incorporation of the ligands. The formed materials are semiamorphous with powder XRDs intermediary between pure ZRTE-10 and -11 . Thermal treatment of the semiamorphous materials increases their crystallinity and allows S BET = 400-550 m 2 g -1 surface areas to be reached for pure H 4 L 4 and H 3 L 3 or their mixture alike. The approach proposes a viewpoint on the H 3 L 3 trifunctional ligand as a model of a ligand platform, suitable for bearing a large functionality on the fourth "truncated" branch. The significance of ZRTE-10 as a material for postsynthetic introduction of metal-based cluster functionality and as a model of functionality encapsulation, an alternative to the ship-in-the-bottle method, is discussed.

Two new eremophilane-type sesquiterpenes, carperemophilanes A and B (1-2), three new maleimide-bearing compounds, carpesiumaleimides A-C (3-5), along with a known sesquiterpene, carabrol (6), were isolated from the ethanol extract of Carpesium abrotanoides L. Their structures were elucidated by analysis of their NMR and MS data as well as by comparison with the literature. The absolute configuration of carperemophilane A (1) was determined by single-crystal X-ray diffraction analysis. All isolated compounds (1-6) were evaluated in vitro for cytotoxicity against two human cancer cell lines MDA-MB-231 and HGC-27 using the MTT method. Compounds 1, 2 and 6 showed cytotoxic activities with IC 50 values ranging from 7.45 to 37.35 μM., (Copyright © 2019. Published by Elsevier B.V.)

Correction for 'Synthesis of hydrophobic and hydrophilic TiO2 nanofluids for transformable surface wettability and photoactive coating' by Jie Hu et al., Chem. Commun., 2019, 55, 9275-9278.

Confinement of noble nanometals in a zeolite matrix is a promising way to special types of catalysts that show significant advantages in size control, site adjustment, and nano-architecture design. The beauty of zeolite-confined noble metals lies in their unique confinement effects on a molecular scale, and thus enables spatially confined catalysis akin to enzyme catalysis. In this Minireview, the confined synthesis strategies of zeolite-confined noble metals will be briefly discussed, showing the processes, advantages, features, and mechanisms. The confined catalysis carried on zeolite-confined noble metals will be summarized, and great emphasis will be paid to the confinement effects involving size, encapsulation, recognition, and synergy. Great progress of atomic sites in the size effect, supercage stabilization in the encapsulation effect, site adsorption in the recognition effect, and cascade reaction in the synergy effect are highlighted. This Minireview is concluded with challenges and opportunities in terms of the synthesis of zeolite-confined noble metals and their applications to design multifunctional catalysts with high catalytic activity, selectivity, and stability., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two azaphilone pigments (1 and 2), two dihydrobenzofurans (3 and 4), two macrodiolides (5 and 6), and a dimeric alkyl aromatic constituent (7) were isolated from the goose dung-derived fungus Coniella fragariae. Compounds 1-3 proved to be new natural products. Coniellins H and I (1 and 2) feature a tetracyclic core and an aldehyde group at C-5, which is unusual for azaphilone derivatives. The X-ray structure of pyrenophorin (5) is reported for the first time. Pyrenophorin (5) showed strong cytotoxicity against several cancer cell lines with IC 50 values ranging from 0.07 to 7.8 μM., (Copyright © 2019 Elsevier B.V. All rights reserved.)

NiGa is a catalyst for the semihydrogenation of alkynes. Here we show the influence of different dispersion times before microwave-induced decomposition of the precursors on the phase purity, as well as the influence of the time of microwave-induced decomposition on the crystallinity of the NiGa nanoparticles. Microwave-induced co-decomposition of all-hydrocarbon precursors [Ni(COD) 2 ] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in the ionic liquid [BMIm][NTf 2 ] selectively yields small intermetallic Ni/Ga nanocrystals of 5 ± 1 nm as derived from transmission electron microscopy (TEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and supported by energy-dispersive X-ray spectrometry (EDX), selected-area energy diffraction (SAED) and X-ray photoelectron spectroscopy (XPS). NiGa@[BMIm][NTf 2 ] catalyze the semihydrogenation of 4-octyne to 4-octene with 100% selectivity towards ( E )-4-octene over five runs, but with poor conversion values. IL-free, precipitated NiGa nanoparticles achieve conversion values of over 90% and selectivity of 100% towards alkene over three runs.

New acetylenedicarboxylate (ADC) and chlorofumarate (Fum-Cl) based hafnium-metal-organic frameworks have been synthesized by alternatively reacting acetylenedicarboxylic acid in DMF or water with appropriate hafnium salt, in the presence of acetic acid modulator. The two materials of respective ideal formulas [Hf 6 O 4 (OH) 4 (ADC) 6 ] (Hf-HHU-1) and [Hf 6 O 4 (OH) 4 (Fum-Cl) 6 ] (Hf-HHU-2) have been structurally characterized by powder X-ray diffraction to be UiO-66 isostructural, consisting of octahedral [Hf 6 O 4 (OH) 4 ] 12+ secondary building units each connected to other units by 12 ADC or Fum-Cl linkers into a microporous network with fcu topology. This structure was confirmed by Rietveld refinement. Hf-HHU-2 is formed by in situ hydrochlorination of acetylenedicarboxylic acid to chlorofumarate. Its presence has been determined by combined Raman spectroscopy, solid-state NMR, scanning electron microscopy, energy dispersive X-ray and X-ray photoelectron spectroscopies. Hf-HHU-1 and Hf-HHU-2 exhibit very high hydrophilicity as revealed by their water sorption profiles, meanwhile Hf-HHU-2 adsorbs CO 2 with an isosteric heat of 39 kJ mol -1 . Hf-HHU-2 also adsorbs molecular iodine vapor exclusively as polyiodide anions due to grafted chloro-functions on the pores surface. It has been observed that defective nanodomains with reo tolopology can be introduced in the structure of Hf-HHU-2 by variation of the linker to metal-salt molar ratio.

Graphene quantum dots (GQDs) are a promising next generation nanomaterial with manifold biomedical applications. For real world applications, comprehensive studies on their influence on the functionality of primary human cells are mandatory. Here, we report the effects of GQDs on the transcriptome of CD34 + hematopoietic stem cells after an incubation time of 36 hours. Of the 20 800 recorded gene expressions, only one, namely the selenoprotein W, 1, is changed by the GQDs in direct comparison to CD34 + hematopoietic stem cells cultivated without GQDs. Only a meta analysis reveals that the expression of 1171 genes is weakly affected, taking into account the more prominent changes just by the cell culture. Eight corresponding, weakly affected signaling pathways are identified, which include, but are not limited to, the triggering of apoptosis. These results suggest that GQDs with sizes in the range of a few nanometers hardly influence the CD34 + cells on the transcriptome level after 36 h of incubation, thereby demonstrating their high usability for in vivo studies, such as fluorescence labeling or delivery protocols, without strong effects on the functional status of the cells.

Two modified TiO 2 nanofluids were developed, with either hydrophobic or hydrophilic properties. The hydrophobic TiO 2 nanofluid, embedded in an organo-silyl salt, could be transformed into a hydrophilic TiO 2 nanofluid by exchange of the chloride with an organo-sulphonate ion. Both modified TiO 2 nanofluids exhibited high fluidity, thermal stability and photoactivity.

A proof-of-concept strategy for significant enhancement of hydrogen evolution reaction (HER) performance of transition metals via construction of a metal/semiconductor Schottky junction is presented. The decoration of low-cost commercial TiO 2 nanoparticles on the surface of microscale Co dendrites causes a significant charge transfer across the Co/TiO 2 Schottky interface and enhances the local electron density at the Co surface, confirmed by X-ray photoelectron spectroscopy results and density functional theory calculations. The Co/TiO 2 Schottky catalyst displays superior HER activity with a turnover frequency of 0.052 s -1 and an exchange current density of 79 μA cm -2 , which are about 4.3 and 4.0 times greater than that of pristine Co, respectively. Moreover, the Co/TiO 2 Schottky catalyst displays excellent electrochemical durability for long-term operation in both alkaline solution and high saline solution. Theoretical calculations suggest that the Schottky junction plays an important role to optimize hydrogen adsorption free energy (Δ G H* ) by tuning the electronic structure, which enhances the performance for HER of the Co/TiO 2 Schottky catalyst. This study of modulating the electronic structure of the catalysts via the Schottky junction could provide valuable insights for designing and synthesizing low-cost, high-performance electrocatalysts.

CgL1 laccase from Corynebacterium glutamicum was encapsulated into the metal-organic framework (MOF) ZIF-8 which was synthesized in a rapid enzyme friendly aqueous synthesis, the fastest in situ encapsulation of laccases reported to date. The obtained enzyme/MOF, i. e. laccase@ZIF-8 composite showed enhanced thermal (up to 70 °C) and chemical (N,N-dimethylformamide) stability, resulting in a stable heterogenous catalyst, suitable for high temperature reactions in organic solvents. Furthermore, the defined structure of ZIF-8 produced a size selective substrate specificity, so that substrates larger than the pore size were not accepted. Thereby, 2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) was used to verify that the enzyme is immobilized inside the MOF versus the outside surface. The enzyme@MOF composite was analyzed by atomic absorption spectroscopy (ASS) to precisely determine the enzyme loading to 2.1 wt%., Competing Interests: The authors declare no conflict of interest., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

3-Triazolylquinoxalines can be readily synthesized by applying two complementary synthetic protocols starting from heterocyclic π nucleophiles or (hetero)aryl glyoxylic acids in a consecutive four- or five-component reaction. Conceptually, the sequential use of a single cuprous salt for alkynylation and Cu-catalyzed alkyne-azide cycloaddition (CuAAC) in a one-pot fashion sets the stage for activation-alkynylation-cyclocondensation-CuAAC or glyoxylation-alkynylation-cyclocondensation-CuAAC sequences in good yields. The diversity-oriented generation of differently substituted 3-triazolylquinoxalines is an excellent entry to tunable emission solvatorchromic fluorophores with triazole ligation. The electronic structure, corroborated by DFT and TD-DFT calculations, rationalizes the charge transfer character of relevant absorptions and large Stokes shifts as well as the electronic innocence of the triazole substituents., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Efficient use of energy for cooling applications is a very important and challenging field in science. Ultra-low temperature actuated (T driving  < 80 °C) adsorption-driven chillers (ADCs) with water as the cooling agent are one environmentally benign option. The nanoscale metal-organic framework [Al(OH)(C 6 H 2 O 4 S)] denoted CAU-23 was discovered that possess favorable properties, including water adsorption capacity of 0.37 g H2O /g sorbent around p/p 0  = 0.3 and cycling stability of at least 5000 cycles. Most importantly the material has a driving temperature down to 60 °C, which allows for the exploitation of yet mostly unused temperature sources and a more efficient use of energy. These exceptional properties are due to its unique crystal structure, which was unequivocally elucidated by single crystal electron diffraction. Monte Carlo simulations were performed to reveal the water adsorption mechanism at the atomic level. With its green synthesis, CAU-23 is an ideal material to realize ultra-low temperature driven ADC devices.

A chemical investigation of the endophyte Penicillium sp. (strain ZO-R1-1), isolated from roots of the medicinal plant Zingiber officinale, yielded nine new indole diterpenoids (1-9), together with 13 known congeners (10-22). The structures of the new compounds were elucidated by 1D and 2D NMR analysis in combination with HRESIMS data. The absolute configuration of the new natural products 1, 3, and 7 was determined using the TDDFT-ECD approach and confirmed for 1 by single-crystal X-ray determination through anomalous dispersion. The isolated compounds were tested for cytotoxicity against L5178Y, A2780, J82, and HEK-293 cell lines. Compound 1 was the most active metabolite toward L5178Y cells, with an IC 50 value of 3.6 μM, and an IC 50 against A2780 cells of 8.7 μM. Interestingly, 1 features a new type of indole diterpenoid scaffold with a rare 6/5/6/6/6/6/5 heterocyclic system bearing an aromatic ring C, which is suggested to be important for the cytotoxic activity of this natural product against L5278Y and A2780 cells.

Two new rtl-MOFs rtl-[Cu(HIsa-az-dmpz)] and rtl-[Zn(HIsa-az-dmpz)] have been synthesized by using the new bifunctional ligand 5-(4-(3,5-dimethyl-1H-pyrazolyl)azo)isophthalic acid (H 3 Isa-az-dmpz). Both frameworks are potentially porous structures with DMF molecules included in the channels of the as synthesized materials. The flexible MOF rtl-[Cu(HIsa-az-dmpz)] undergoes a reversible phase change into a closed form upon activation. Consequently, rtl-[Cu(HIsa-az-dmpz)] shows S-shaped Type F-IV adsorption profiles or a gate-opening effect at cryogenic temperatures with high saturation uptakes of 360 cm 3 g -1 for N 2 at 77 K and 310 cm 3 g -1 for CO 2 at 195 K. These profiles together with the reversibility could be reproduced upon repeated measurements on the same materials. The gravimetric high-pressure CO 2 adsorption shows a gate-opening at ∼10 bar with an uptake of 332 mg g -1 . rtl-[Zn(HIsa-az-dmpz)] undergoes an irreversible transformation into a non-porous phase upon activation.

A metal-organic gel (metallogel) based on the new tetracarboxyl ligand N 1 , N 4 -(diterephthalic acid)terephthalamide in combination with chromium(III) has been converted into its xero- and aerogel and demonstrated to have excellent specific sorption properties for dyes in its metallogel state, where fuchsine is adsorbed faster than the two other dyes, calcein and disulfine blue, and for water, sulfur dioxide and carbon dioxide in its xero- and aerogel state. The metallogel showed very good shape retention and could be extruded from molds in designed shapes. In a rheology experiment, the storage modulus was determined to be 1440 Pa, and the metallogel is elastic up to 3 Hz, breaking at strains higher than 0.3%. Additional metallogels utilizing the same ligand with a wide range of metal ions (Al(III), Fe(III), Co(III), In(III), and Hg(II)) have also been synthesized, and the aluminum and mixed aluminum-chromium derivative were also converted into its aerogel. The highly porous Cr, Al, and AlCr metal-organic aerogels proved stable against water vapor in a physisorption experiment and were used to model breakthrough curves for SO 2 /CO 2 gas mixtures with the idealized adsorbed solution theory from their physisorption isotherms. The breakthrough simulation utilized SO 2 /CO 2 equivalencies from a real world application and showed effective retention of SO 2 from the gas mixture. Furthermore, the materials in this work exhibit the highest SO 2 uptake values for metal-organic aerogels so far (up to 116.8 cm 3 g -1 , or 23.4 wt %).