Rational Design of a Uranyl Metal–Organic Framework for the Capture and Colorimetric Detection of Organic Dyes

A new uranyl containing metal–organic framework, RPL-1 : [(UO₂)₂(C₂₈H₁₈O₈)] ^. H₂O (RPL for Radiochemical Processing Laboratory), was prepared, structurally characterized, and the solid-state photoluminescence properties explored. Single crystal X-ray diffraction data reveals the structure of RPL - 1 consists of two crystallographically unique three dimensional, interpenetrating nets with a 4,3-connected tbo topology. Each net contains large pores with an average width of 22.8 Å and is formed from monomeric, hexagonal bipyramidal uranyl nodes that are linked via 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (TCPB) ligands. The thermal and photophysical properties of RPL-1 were investigated using thermogravimetric analysis and absorbance, fluorescence, and lifetime spectroscopies. The material displays excellent thermal stability and temperature dependent uranyl and TCPB luminescence. The framework is stable in aqueous media and due to the large void space (constituting 76 % of the unit cell by volume) can sequester organic dyes, the uptake of which induces a visible change to the color of the material.     

Synthesis,Characterization and Evaluation of the Antibacterial and Antitumor Activity of HalogenatedSalen Copper (II) Complexes derived from Camphoric Acid

Platinum metal complexes are the most common chemotherapeutics currently used in cancer treatment. However, the frequent adverse effects, as well as acquired resistance by tumor cells, urge the development of effective alternatives. In the recent past, copper complexes with Schiff base ligands have emerged as good alternatives, showing interesting results. Accordingly, and in continuation of previous studies in this area, three new camphoric acid-derived halogenated salen ligands and their corresponding Cu (II) complexes were synthesized and their antitumor activity was evaluated in order to determine the influence of the type and number of halogens present (Br, Cl). The in vitro cytotoxic activity was screened against colorectal WiDr and LS1034 and against breast MCF-7 and HCC1806 cancer cell lines. The results proved the halogenated complexes to be very efficient, the tetrachlorinated Cu (II) complex being the most promising, presenting IC₅₀ of 0.63–1.09 μM for the cell lines studied. The complex also shows selectivity to colorectal cancer cells compared to non-tumor colon cells. It is worth highlighting that the tetrachlorinated Cu (II) complex, our most efficient complex, shows a significantly more powerful antitumor effect than the reference drugs currently used in conventional chemotherapy. The halogenated salen and corresponding complexes were also screened for their antimicrobial activity against four bacterial species-Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa-and four fungal species-Candida albicans, Candida glabrata, Aspergillus fumigatus and Alternaria alternata. The compounds were found to exhibit moderate to strong antibacterial activity against the bacterial strains studied. NMR studies and theoretical calculations provided some insight into the structure of the ligands and copper complexes. Considering the results presented herein, our work validates the potential use of copper-based chemotherapeutics as alternatives for cancer treatment.     

Single‐Site Zeolite‐Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry

A family of HY zeolite‐supported cationic organoiridium carbonyl complexes was formed by reaction of Ir(CO)₂(acac) (acac=acetylacetonate) to form supported Ir(CO)₂ complexes, which were treated at 298 K and 1 atm with flowing gas‐phase reactants, including C₂H₄, H₂, ¹²CO, ¹³CO, and D₂O. Mass spectrometry was used to identify effluent gases, and infrared and X‐ray absorption spectroscopies were used to characterize the supported species, with the results bolstered by DFT calculations. Because the support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, these were characterized by a high degree of uniformity, which allowed a precise determination of the species involved in the replacement, for example, of one CO ligand of each Ir(CO)₂ complex with ethylene. The supported species include the following: Ir(CO)₂, Ir(CO)(C₂H₄)₂, Ir(CO)(C₂H₄), Ir(CO)(C₂H₅), and (tentatively) Ir(CO)(H). The data determine a reaction network involving all of these species.     

Photobiological Interactions of Blue Light and Photosynthetic Photon Flux: Effects of Monochromatic and Broad‐Spectrum Light Sources

Photosynthesis (Pn) and photomorphogenesis (Pm) are affected by light quality, light intensity and photoperiod. Although blue light (BL) is necessary for normal development, it is less efficient in driving Pn than other wavelengths of photosynthetically active radiation. The effects of BL on Pm are highly species dependent. Here we report the interacting effects of BL and photosynthetic photon flux (PPF) on growth and development of lettuce, radish and pepper. We used light‐emitting diode (LED) arrays to provide BL fractions from 11% to 28% under broad‐spectrum white LEDs, and from 0.3% to 92% under monochromatic LEDs. All treatments were replicated three times at each of two PPFs (200 and 500 μmol m^?2 s^?1). Other than light quality, environmental conditions were uniformly maintained across chambers. Regardless of PPF, BL was necessary to prevent shade‐avoidance responses in radish and lettuce. For lettuce and radish, increasing BL reduced stem length, and for both species, there were significant interactions of BL with PPF for leaf expansion. Increasing BL reduced petiole length in radish and flower number in pepper. BL minimally affected pepper growth and other developmental parameters. Pepper seedlings were more photobiologically sensitive than older plants. Surprisingly, there were few interactions between monochromatic and broad‐spectrum light sources.