Electrospray ionization mass spectrometric detection of self-assembly of a crown ether complex directed by π-stacking interactions

The self-assembly of ligand-metal-ligand sandwich complexes involving a novel quinoxaline-containing crown ether, 1, was studied by electrospray ionization mass spectrometry (ESI-MS). Donor-acceptor π-stacking interactions between the electron-poor quinoxaline group of 1 and electron-rich benzene groups from benzo- or dibenzo-18-crown-6 were found to significantly enhance the formation of mixed-ligand sandwich complexes with a free energy gain of up to 17 kJ/mol relative to sandwich formation involving macrocycles without such aromatic functionalities. The relative intensities of the sandwich complexes were greatest with the alkali metals Na⁺, K⁺, and Rb⁺ as well as with the ammonium ion in equimolar concentrations with the macrocycles. The preferential formation of the mixed-ligand sandwich complexes demonstrated that donor-acceptor π-stacking interactions contribute to the assembly of molecular structures and can be monitored by ESI-MS.     

Synthesis of multi-1,10-phenanthroline ligands with 1,3-phenylene linkers and their lithium complexes

The synthesis of two multisite ligands containing four and five 1,10-phenanthroline (phen) chelates in line, respectively, is presented. The connectors are 1,3-phenylene linkers. The two ligands were prepared following multistep procedures, the two key reactions being the Suzuki coupling reaction between aromatic nuclei and the nucleophilic addition of aryllithium derivatives onto a phen fragment. The coordination chemistry of both ligands with Li+ ions was very clean and selective, whereas their reaction with copper(I) led to intractable mixtures of insoluble complexes. The tetraphen and the pentaphen compounds afforded almost quantitatively the four- and five-lithium double-stranded helical complexes, respectively. The helical systems are probably highly wound, as indicated by NMR measurements. The pronounced strain of the 5-Li+ complex is reflected by the easy loss of a lithium cation, as shown by electrospray mass spectrometry.     

Electrochemical and photochemical approaches for the synthesis of the C28–C38 fragment of okadaic acid

Okadaic acid, a potent and selective inhibitor of Protein Phosphatases 1 and 2A (PP1 and PP2A), is widely used as a probe for various biochemical processes. We describe herein two innovative methods for the synthesis of the terminal C28–C38 fragment of the natural polyether. Suárez photochemical oxidative cyclization and electrochemical oxidation of malonates to their ketals equivalents have been successfully applied for the assembly of the key spiroketal core.     

Structural and optical characterizations of rare earth pentaphosphates LnP5O14 (Ln = La, Gd) synthesized by the sol–gel process

The sol–gel chemistry route has successfully been used to prepare samples of LnP₅O₁₄ (Ln = La, Gd) pentaphosphates from lanthanides chlorides and phosphorous pentoxide dissolved in isopropanol. Crystallized powders of single phase were obtained after calcination of gels at 350 °C. The structural characterizations of materials were investigated by means of X-ray diffraction as well as infrared and Raman spectroscopies, whereas their thermal behavior has been studied by differential thermal analyse and thermogravimetric analyses. Powders morphology was analyzed by means of scanning electron microscopy and laser granulometry. The photoluminescence properties of the Eu³⁺ ions in sol–gel derived LaP₅O₁₄ and GdP₅O₁₄ samples were investigated and compared with homologous samples synthesized by the conventional solid state reaction.     

Controlled Synthesis of Thorium and Uranium Oxide Nanocrystals

Very little is known about the size and shape effects on the properties of actinide compounds. As a consequence, the controlled synthesis of well‐defined actinide‐based nanocrystals constitutes a fundamental step before studying their corresponding properties. In this paper, we report on the non‐aqueous surfactant‐assisted synthesis of thorium and uranium oxide nanocrystals. The final characteristics of thorium and uranium oxide nanocrystals can be easily tuned by controlling a few experimental parameters such as the nature of the actinide precursor and the composition of the organic system (e.g., the chemical nature of the surfactants and their relative concentrations). Additionally, the influence of these parameters on the outcome of the synthesis is highly dependent on the nature of the actinide element (thorium versus uranium). By using optimised experimental conditions, monodisperse isotropic uranium oxide nanocrystals with different sizes (4.5 and 10.7 nm) as well as branched nanocrystals (overall size ca. 5 nm), nanodots (ca. 4 nm) and nanorods (with ultra‐small diameters of 1 nm) of thorium oxide were synthesised.     

Characterization of a Smartphone Camera's Response to Ultraviolet A Radiation

As part of a wider study into the use of smartphones as solar ultraviolet radiation monitors, this article characterizes the ultraviolet A (UVA; 320–400 nm) response of a consumer complementary metal oxide semiconductor (CMOS)‐based smartphone image sensor in a controlled laboratory environment. The CMOS image sensor in the camera possesses inherent sensitivity to UVA, and despite the attenuation due to the lens and neutral density and wavelength‐specific bandpass filters, the measured relative UVA irradiances relative to the incident irradiances range from 0.0065% at 380 nm to 0.0051% at 340 nm. In addition, the sensor demonstrates a predictable response to low‐intensity discrete UVA stimuli that can be modelled using the ratio of recorded digital values to the incident UVA irradiance for a given automatic exposure time, and resulting in measurement errors that are typically less than 5%. Our results support the idea that smartphones can be used for scientific monitoring of UVA radiation.     

Self‐Assembled PAA‐Based Nanoparticles as Potential Gene and Protein Delivery Systems

A series of nanoparticles is prepared via layer‐by‐layer assembly of oppositely charged, synthetic biocompatible polyamidoamine polymers as potential carriers. Particle size, surface charge and internal chain mobility are quantified as a function of the polymer type and number of layers. The effect of addition of surfactant is examined to simulate the effects of nanoparticle dissolution. The cyctotoxicity of these particles (in epithelia and murine cell lines) are orders of magnitude lower than polyethyleneimine controls. Stable nanoparticles may be prepared from mixtures of strongly, oppositely charged polymers, but less successfully from weakly charged polymers, and, given their acceptable toxicity characteristics, such modularly designed constructs show promise for drug and gene delivery.

     

Experimental and theoretical studies of Diels-Alder dimerization of 1,2,3,4,5-pentachlorocyclopentadiene and of Diels-Alder cycloaddition of polychlorinated cyclopentadienes to norbornadiene

Diels-Alder cyclodimerization of 1,2,3,4,5-pentachlorocyclopentadiene (1) affords 2a as the exclusive reaction product. Diels-Alder cycloaddition of 1 to norbornadiene also proceeds stereoselectively to produce a single [4+2] cycloadduct, 4c. The structures of 2a and 4c were established unequivocally via application of single crystal X-ray crystallographic techniques. The origins of the observed diastereofacial selectivity in each of these cycloaddition processes have been investigated by application of semiempirical (AM1 Hamiltonian) and ab initio (Hartree-Fock 3-21G*) calculations. The computational results thereby obtained, which are based upon consideration of the kinetically favored transition state for each of the two cycloaddition reactions studied, are consistent with experiment. These semiempirical and ab initio methods also have been used to investigate the mechanisms of the Diels-Alder reactions that have been used to prepare aldrin and isodrin (7 and 8, respectively). The results thereby obtained suggest that isodrin formation via Diels-Alder cycloaddition of cyclopentadiene to 1,2,3,4,7,7-hexachloronorbornadiene proceeds with kinetic control of product stereochemistry.