Synthesis and biological evaluation of cis-restrained carbocyclic combretastatin A-4 analogs: Influence of the ring size and saturation on cytotoxic properties

Combretastatin A-4 (CA-4) is a highly cytotoxic natural product and several derivatives have been prepared which underwent clinical trial. These investigations revealed that the cis-stilbene moiety of the natural product is prone to undergo cis/trans isomerization under physiological conditions, reducing the overall activity of the drug candidates. Herein, we report the preparation of cis-restrained carbocyclic analogs of CA-4. The compounds, which differ by the size and hybridization of the carbocyclic ring have been evaluated for their cytotoxic properties and their ability to inhibit tubulin polymerization. Biological data, supported by molecular docking studies, identified cyclobutenyl and cyclobutyl derivatives of the natural product as highly promising drug candidates.     

Substrate specificity and products of side-reactions catalyzed by jasmonate:amino acid synthetase (JAR1)

Jasmonate:amino acid synthetase (JAR1) is involved in the function of jasmonic acid (JA) as a plant hormone. It catalyzes the synthesis of several JA-amido conjugates, the most important of which appears to be JA-Ile. Structurally, JAR1 is a member of the firefly luciferase superfamily that comprises enzymes that adenylate various organic acids. This study analyzed the substrate specificity of recombinant JAR1 and determined whether it catalyzes the synthesis of mono- and dinucleoside polyphosphates, which are side-reaction products of many enzymes forming acyl approximately adenylates. Among different oxylipins tested as mixed stereoisomers for substrate activity with JAR1, the highest rate of conversion to Ile-conjugates was observed for (+/-)-JA and 9,10-dihydro-JA, while the rate of conjugation with 12-hydroxy-JA and OPC-4 (3-oxo-2-(2Z-pentenyl)cyclopentane-1-butyric acid) was only about 1-2% that for (+/-)-JA. Of the two stereoisomers of JA, (-)-JA and (+)-JA, rate of synthesis of the former was about 100-fold faster than for (+)-JA. Finally, we have demonstrated that (1) in the presence of ATP, Mg(2+), (-)-JA and tripolyphosphate the ligase produces adenosine 5'-tetraphosphate (p(4)A); (2) addition of isoleucine to that mixture halts the p(4)A synthesis; (3) the enzyme produces neither diadenosine triphosphate (Ap(3)A) nor diadenosine tetraphosphate (Ap(4)A) and (4) Ap(4)A cannot substitute ATP as a source of adenylate in the complete reaction that yields JA-Ile.     

Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes

CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in combination with their outstanding thermal and chemical stability, and low densities. However, their insoluble nature causes problems in their processing since usually applied techniques such as spin coating are not available. Especially for membrane applications, where the processing of CMP as thin films is desirable, the processing problems have hindered their commercial application.Here we describe the interfacial synthesis of CMP thin films on functionalized substrates via molecular layer-by-layer (l-b-l) synthesis. This process allows the preparation of films with desired thickness and composition and even desired composition gradients.The use of sacrificial supports allows the preparation of freestanding membranes by dissolution of the support after the synthesis. To handle such ultra-thin freestanding membranes the protection with sacrificial coatings showed great promise, to avoid rupture of the nanomembranes. To transfer the nanomembranes to the desired substrate, the coated membranes are upfloated at the air-liquid interface and then transferred via dip coating.     

Engineering Mixed Ionic Electronic Conduction in La0.8Sr0.2MnO3+δ Nanostructures through Fast Grain Boundary Oxygen Diffusivity

Nanoionics has become an increasingly promising field for the future development of advanced energy conversion and storage devices, such as batteries, fuel cells, and supercapacitors. Particularly, nanostructured materials offer unique properties or combinations of properties as electrodes and electrolytes in a range of energy devices. However, the enhancement of the mass transport properties at the nanoscale has often been found to be difficult to implement in nanostructures. Here, an artificial mixed ionic electronic conducting oxide is fabricated by grain boundary (GB) engineering thin films of La_0.8Sr_0.2MnO_3+δ. This electronic conductor is converted into a good mixed ionic electronic conductor by synthesizing a nanostructure with high density of vertically aligned GBs with high concentration of strain‐induced defects. Since this type of GBs present a remarkable enhancement of their oxide‐ion mass transport properties (of up to six orders of magnitude at 773 K), it is possible to tailor the electrical nature of the whole material by nanoengineering, especially at low temperatures. The presented results lead to fundamental insights into oxygen diffusion along GBs and to the application of these engineered nanomaterials in new advanced solid state ionics devices such are micro‐solid oxide fuel cells or resistive switching memories.     

Surface Cleaning and Passivation Using (NH4)2S Treatment for Cu(In,Ga)Se2 Solar Cells: A Safe Alternative to KCN

With the aim of developing a safe alternative to the KCN etchant for the removal of Cu_xSe secondary phases at the surface of Cu(In,Ga)Se₂ (CIGSe) absorber, a method based on ammonium sulfide (AS) chemical treatment is proposed. Although lower etching rates are observed compared with the KCN reference solution, the AS solution is found to selectively etch Cu_xSe phases. In addition, it allows modifying the surface chemical state of the CIGSe absorber by incorporation of sulfur. As a consequence, the minority carrier lifetime located close to the surface of the absorber is found to be improved. Furthermore, it is demonstrated that optimizing the AS treatment time induces a remarkable enhancement in the electrical performances of the CIGSe‐based solar cells.     

Cistus creticus subsp. eriocephalus as a Model for Studying Plant Physiological and Metabolic Responses to Environmental Stress Factors

Variations in physiology and metabolic products of Cistus creticus subsp. eriocephalus along an altitudinal gradient (350–750 m.a.s.l.) within the Monti Lucretili Regional Natural Park (central Italy) were studied. The results showed that the phenol production was in relationship with the net photosynthetic rates and the chlorophyll content. In particular, the increasing caffeic acid (CA) content with altitude suggested its role in providing an additional photo‐protection mechanism, by its ability to consume photochemical reducing power and acting as an alternative C‐atom sink under high light conditions. The metabolic production was tested by high performance thin layer chromatography (HPTLC) fingerprint analysis, highlighting the potential of this technique in biologic studies.     

CuSbSe2 as a Potential Photovoltaic Absorber Material: Studies from Theory to Experiment

CuSbSe₂ appears to be a promising absorber material for thin‐film solar cells due to its attractive optical and electrical properties, as well as earth‐abundant, low‐cost, and low‐toxic constituent elements. However, no systematic study on the fundamental properties of CuSbSe₂ has been reported, such as defect physics, material, optical, and electrical properties, which are highly relevant for photovoltaic application. First, using density functional theory calculations, CuSbSe₂ is shown to have benign defect properties, i.e., free of recombination‐center defects, and flexible defect and carrier concentration which can be tuned through the control of growth condition. Next, systematic material, optical, and electrical characterizations uncover many unexplored fundamental properties of CuSbSe₂ including band position, temperature‐dependent band gap energy, Raman spectrum, and so on, thus providing a solid foundation for further photovoltaic research. Finally, a prototype CuSbSe₂‐based thin film solar cell is fabricated by a hydrazine solution process. The systematic theoretical and experimental investigation, combined with the preliminary efficiency, confirms the great potential of CuSbSe₂ for thin‐film solar cell applications.     

Fine‐Tuning the Sn Content in CZTSSe Thin Films to Achieve 10.8% Solar Cell Efficiency from Spray‐Deposited Water–Ethanol‐Based Colloidal Inks

Thin film solar cells with Al/ITO/ZnO/CdS/CZTSSe/Mo‐glass structure are fabricated employing a fast and low‐cost preparation procedure using an aqueous ink deposited by nonpyrolytic spray, followed by high temperature crystallization and selenization steps. Capacitance–voltage measurements on previously reported devices with >8% efficiency under 1 sun irradiation show a charge carrier density of the order of 10¹⁷ cm^?3. Moreover, admittance spectroscopy indicates the presence of mid‐bandgap defects that are tentatively attributed to a Sn deficit in the film. In order to reduce the number of these deep defects within the active layer of our solar cells, the Sn content is tuned in the precursor ink. Their morphology, elemental composition, crystal phases, capacitance–voltage profiling, admittance, photoluminescence, and photovoltaic performances are characterized. The results indicate that tuning the Sn content offers a strong leverage upon some key properties of the active layer, in particular the grain size, and the charge carrier and defect density. By employing this leverage to optimize the performance of our CZTSSe layers, the cell performances are increased to 10.0% without antireflection coating (ARC) and to 10.8% (on 0.25 cm²) with an ARC.