The Reactions of 2,2,2-Trichloro-1-phenylethanone with O,C and S Nucleophiles

The reactions of 2,2,2-trichloro-1-phenylethanone with various oxygen, carbon and sulfur nucleophiles were investigated with a view of widening the use of trichloroethanones as acylating agents.     

Copper-containing dendromesogens: the influence of the metal on the mesomorphism

The synthesis and liquid crystalline behaviour of the first and second generations of a dendrimeric structure based on poly(propyleneimine)(DAB-dendr(NH₂)_x) are reported. 4-(4-n-Alkoxybenzoyloxy)salicylaldehydes are used as mesogenic moieties attached at the peripheral amino groups of the dendrimers giving rise to dendromesogens with four and eight mesogenic branches. From these dendromesogens, considered as organic ligands, were prepared six metal-containing dendrimers which incorporate two or four copper atoms in their structures. All the dendrimeric ligands and three of the metal-containing dendrimers exhibit liquid crystalline properties which were studied by optical microscopy, DSC, X-ray diffraction and EPR spectroscopy.     

Assembling a Phthalocyanine and Perylenediimide Donor–Acceptor Hybrid through a Platinum(II) Diacetylide Linker

In a novel electron‐donor–acceptor conjugate, phthalocyanine (Pc) and perylenediimide (PDI) are connected through a trans‐platinum(II) diacetylide linker to yield Pc‐Pt‐PDI 1 . In the ground state, the presence of Pt^II disrupts the electronic communication between the two electroactive components, as revealed by UV/Vis spectroscopy and electrochemical studies. The photophysical behavior of 1 is compared with that of the corresponding Pc‐PDI electron‐donor–acceptor conjugate 2 in terms of charge separation and charge recombination. The insertion of Pt^II between Pc and PDI impacts the results in a longer‐lived Pc ^{. +}/PDI ^{. ?} radical ion‐pair state. In addition, the intermediately formed Pc triplet excited state is formed with higher quantum yields in 1 than in 2 .     

Dimensional Matching of Polycyclic Aromatics with Rectangular Metallacycles: Insertion Modes Determined by [C?H⋅⋅⋅π] Interactions

A family of Pd^II/Pt^II dinuclear receptors, designed to give a smooth increase in their cavity lengths (from 7.46–13.78 Å), is presented. Their inclusion complexes with a representative set of polycyclic aromatic substrates (naphthalene, carbazol, pyrene, and benzo[a]pyrene), were characterized and studied in aqueous solution and the solid state. By taking into account the dimensions of both receptors and substrates, an excellent complementarity was found between the size of the receptors and their ability to complex a given substrate. Furthermore, this dimensional matching results in specific binding modes depending on the ability of the guest to establish stabilizing [C? H???π] interactions with the host.     

Enzyme‐Responsive Silica Mesoporous Supports Capped with Azopyridinium Salts for Controlled Delivery Applications

The preparation of a new capped silica mesoporous material, Rh‐Azo‐S , for on‐command delivery applications in the presence of target enzymes is described. The material consists of nanometric mesoporous MCM‐41‐like supports loaded with Rhodamine B and capped with an azopyridine derivative. The material was designed to show “zero delivery” and to display a cargo release in the presence of reductases and esterases, which are usually present in the colon, mainly due to intestinal microflora. The opening and cargo release of Rh‐Azo‐S in vitro studies were assessed and seen to occur in the presence of these enzymes, whereas no delivery was noted in the presence of pepsine. Moreover, Rh‐Azo‐S nanoparticles were used to study controlled Rhodamine B dye delivery in intracellular media. HeLa cells were employed for testing the “non”‐toxicity of nanoparticles. Moreover, delivery of the dye in these cells, through internalization and enzyme‐mediated gate opening, was confirmed by confocal microscopy. Furthermore, the nanoparticles capped with the Azo group and loaded with a cytotoxic camptothecin ( CPT ) were also prepared (solid CPT‐Azo‐S ) and used as delivery nanodevices in HeLa cells. When this solid was employed, the cell viability decreased significantly due to internalization of the nanoparticles and delivery of the cytotoxic agent.     

Synthesis of 3-iodothiophenes via iodocyclization of (Z)-thiobutenynes

A simple synthesis of 3-iodothiophenes was demonstrated using a wide range of (Z)-thioenynes. The key step in the iodocyclofunctionalization was the selective reduction of the triple bond in (Z)-thioenynes by the addition of iodine as an electrophilic agent. The 3-iodothiophenes were obtained in good to excellent yields of 61–92%. The 3-iodothiophenes were used as substrates in Sonogashira cross-coupling reactions to obtain thiophene acetylenes.     

Application of the single comparator method to instrumental photon activation analysis

Journal of Radioanalytical and Nuclear Chemistry - Instrumental photon activation analysis (IPAA) is nondestructive and multi-elemental analysis method like instrumental neutron activation...     

Chemical Composition of Volatile Compounds in Apis mellifera Propolis from the Northeast Region of Pará State,Brazil

Propolis is a balsamic product obtained from vegetable resins by exotic Africanized bees Apis mellifera L., transported and processed by them, originating from the activity that explores and maintains these individuals. Because of its vegetable and natural origins, propolis is a complex mixture of different compound classes; among them are the volatile compounds present in the aroma. In this sense, in the present study we evaluated the volatile fraction of propolis present in the aroma obtained by distillation and simultaneous extraction, and its chemical composition was determined using coupled gas chromatography, mass spectrometry, and flame ionization detection. The majority of compounds were sesquiterpene and hydrocarbons, comprising 8.2–22.19% α-copaene and 6.2–21.7% β-caryophyllene, with additional compounds identified in greater concentrations. Multivariate analysis showed that samples collected from one region may have different chemical compositions, which may be related to the location of the resin’s production. This may be related to other bee products.     

Twist-Bend Nematic Glasses: The Synthesis and Characterisation of Pyrene-based Nonsymmetric Dimers

A selection of pyrene-based liquid crystal dimers have been prepared, containing either methylene-ether or diether linked spacers of varying length and parity. All the diether linked materials, CBOnO.Py (n=5, 6, 11, 12), exhibit conventional nematic and smectic A phases, with the exception of CBO11O.Py which is exclusively nematic. The methylene-ether linked dimer, CBnO.Py, with an even-membered spacer (n=5) was solely nematogenic, but odd-members (n=6, 8, 10) exhibited both nematic and twist-bend nematic phases. Replacement of the cyanobiphenyl fragment by cyanoterphenyl giving CT6O.Py, gave elevated melting and nematic-isotropic transition temperatures, and SmA and SmC_A phases were observed on cooling the nematic phase. Intermolecular face-to-face associations of the pyrene moieties drive glass formation, and all these materials have a glass transition temperature at or above room temperature. The stability of the glassy twist-bend nematic phase allowed for its study using AFM, and the helical pitch length, P_TB, was measured as 6.3 and 6.7 nm for CB6O.Py and CB8O.Py, respectively. These values are comparable to the shortest pitch of a twist-bend nematic phase measured to date.