Polystyrene resins with immobilized polyamines: Preparation,characterization, and ability to bind Cu(II) ions

Three polyamine ligands, ethylenediamine (EDA), diethylenetriamine (DTA), and triethylenetetramine (TETA), were bound to three chloromethylated “popcorn” polystyrene resins (16, 50, and 100% phenyl ring substitution) with the use of pyridine as the reaction medium. The rate of chloride displacement decreased with increasing molecular weight of the amine and higher degree of resin chloromethylation, while the extent of multiple attachments to the polymer matrix increased. The additional crosslinking, a result of multiple attachments, caused the polyamine resins to swell to a lesser extent in pyridine and water. The ability of the insoluble polyamine–polystyrene resins to chelate Cu²⁺ ions from dilute solutions (200 ppm) was determined at pH 5. With EDA resins the capacity for Cu²⁺ increased with increasing amount of the bound polyamine, with DTA it remained unchanged, while with TETA it was found to decrease.     

Understanding the factors controlling the photo-oxidation of natural DNA by enantiomerically pure intercalating ruthenium polypyridyl complexes through TA/TRIR studies with polydeoxynucleotides and mixed sequence oligodeoxynucleotides

Ruthenium polypyridyl complexes which can sensitise the photo-oxidation of nucleic acids and other biological molecules show potential for photo-therapeutic applications. In this article a combination of transient visible absorption (TrA) and time-resolved infra-red (TRIR) spectroscopy are used to compare the photo-oxidation of guanine by the enantiomers of [Ru(TAP)₂(dppz)]²⁺ in both polymeric {poly(dG-dC), poly(dA-dT) and natural DNA} and small mixed-sequence duplex-forming oligodeoxynucleotides. The products of electron transfer are readily monitored by the appearance of a characteristic TRIR band centred at ca. 1700 cm⁻¹ for the guanine radical cation and a band centered at ca. 515 nm in the TrA for the reduced ruthenium complex. It is found that efficient electron transfer requires that the complex be intercalated at a G-C base-pair containing site. Significantly, changes in the nucleobase vibrations of the TRIR spectra induced by the bound excited state before electron transfer takes place are used to identify preferred intercalation sites in mixed-sequence oligodeoxynucleotides and natural DNA. Interestingly, with natural DNA, while it is found that quenching is inefficient in the picosecond range, a slower electron transfer process occurs, which is not found with the mixed-sequence duplex-forming oligodeoxynucleotides studied.

Efficient electron transfer requires the complex to be intercalated at a G-C base-pair. Identification of preferred intercalation sites is achieved by TRIR monitoring of the nucleobase vibrations before electron transfer.     

A convenient synthesis of cis and trans 4-tert-butoxycarbonyl-substituted cyclohexylglycine

A novel synthesis of cis and trans substituted 4-tert-butoxycarbonyl cyclohexylglycines via asymmetric aminohydroxylation of vinyl styrene followed by reduction of the aromatic ring and subsequent oxidation is reported.     

13C-NMR relaxation studies of alkali metal cryptate complexes

The ¹³C spin-lattice relaxation times (T₁'s) of cryptands [2.1.1], [2.2.1] and [2.2.2] as well as those of the corresponding cryptate complexes with Li⁺, Na⁺, and K⁺ in CDCl₃ and CH₃OH:D₂O (90:10) were measured and the results are interpreted in terms of molecular compression and desolvation effects.     

STRUCTURE OF DYE AGGREGATES AND THE MECHANISM(S) OF PHOTOSENSITIZATION OF AgBr*,†

Abstract— This paper reports the present conclusions of an extended investigation on photo-sensitization of silver bromide. A general molecular packing structure for dye aggregates on the AgBr (111) surface is proposed. This structure, along with the observed spectral absorption displacements of small aggregates, is used to elucidate the phenomena of antisensitization and supersensitization. Supersensitization is seen as a partitioning of large dye aggregates into small aggregates by a deliberately added second component or by gaps between the aggregates. This partitioning isolates antisensitizing dye in a small fraction of the aggregates and minimizes its effect. The smallest aggregates are least likely to contain an antisensitizer, and show the highest quantum efficiency for photoconductivity and photographic action. Photoconductivity measurements establish that supersensitization occurs before the electron appears in the AgBr phase.
The question of direct electron injection vs. energy transfer as mechanisms for AgBr photosensitization is examined in terms of radiationless transfer to surface Ag₂S on AgBr. The absorption of surface Ag₂S is shown to be adequate for acceptance of Förster transfer from the dye, and surface Ag₂S is known to be photographically active. However, this mechanism is inefficient, and inadequate to account for observed high efficiency infrared sensitization. Direct electron injection is seen as the more probable mechanism for efficient dye sensitization of AgBr.     

Accurate determination of pyridine-poly(amidoamine) dendrimer absolute binding constants with the OPLS-AA force field and direct integration of radial distribution functions

OPLS-AA force field and direct integration of intermolecular radial distribution functions (RDF) were employed to calculate absolute binding constants of pyridine molecules to amino group (NH2) and amide group hydrogen atoms in and first generation poly(amidoamine) dendrimers in chloroform. The average errors in the absolute and relative association constants, as predicted with the calculations, are 14.1% and 10.8%, respectively, which translate into ca. 0.08 and 0.06 kcal/mol errors in the absolute and relative binding free energies. We believe that this level of accuracy proves the applicability of the OPLS-AA, force field, in combination with the direct RDF integration, to reproducing and predicting absolute intermolecular association constants of low magnitudes (ca. 0.2-2.0 range).     

Synthesis and thermal characteristics of bisimides. I

Ten structurally different bisimide resins were prepared by reacting maleic anhydride/citraconic anhydride and benzophenone tetracarboxylic dianhydride with aromatic diamines and fused aromatic structures or heterocyclic groups. The amines included were 1,5-diaminonaphthalene, 2,5-bis(p-aminophenyl)1,3,4-oxadiazole, 3,3-bis(p-aminophenyl)phthalide, 9,9-bis(p-aminophenyl)fluorene. and 10,10-bis(p-aminophenyl)anthrone. These monomers were characterized by infrared (IR). ¹H-NMR, mass spectroscopy, and elemental analysis. Thermal polymerization of these monomers was investigated by differential scanning calorimetry. Broad exothermic peaks were observed for a temperature range of 225–380°C. Temperature of exothermic peak position was influenced by the presence of substituents at the olefinic bond, and in biscitraconimides it was 40–50°C lower than in the corresponding bismaleimides. Anaerobic char yields of cured bisimide resins ranged from 44 to 64%. Oxadiazole-containing bisimides had low thermal stability. Increase in formula weight between the imide groups did not influence the char yields in a systematic manner. Graphite cloth laminates with two of these bisimide resins were fabricated and tested for a number of physical properties. Their limiting oxygen index was 70–72%.     

A direct synthesis of denbinobin

Denbinobin was made in seven steps from quinone 3. The cyclization of aldehyde 12 using P₄-tBu and the oxidation of a hindered alcohol with MnO₂ were key steps.     

A gas chromatographic determination of residues of eleven insecticides and two metabolites on olive tree leaves

A gas chromatographic (GC) method was developed and statistically validated for the simultaneous determination of residues of pyrethroid, endosulfan, and organophosphorus insecticides and some of their metabolites on olive tree leaves. Pesticide residues were extracted by static extraction with acetone-dichloromethane. After evaporation of the extract to dryness and redissolution in acetone, the organophosphorus insecticides were determined by GC with nitrogen-phosphorus detection. Another portion of the extract, after solvent change to acetonitrile, was cleaned up on an Alumina-N cartridge and analyzed for insecticides sensitive to electron-capture detection (ECD), i.e., pyrethroids and endosulfan and its metabolite. Recoveries of the organophosphorus insecticides ranged from 80.7 to 93.3% with relative standard deviations (RSDs) of < or = 7.2%; recoveries of the ECD-sensitive insecticides ranged from 71.6 to 89.5% with RSDs of < or = 11.6%. The method was used to analyze 26 samples of olive tree leaves from organic olive groves all over Greece, and the results confirmed the viability of the method for routine analysis. Residues of fenthion and fenthion sulfoxide were found in one and 3 samples, respectively, and their identities were confirmed by GC with mass spectrometry.     

Self-assembly of phosphate fluorosurfactants in carbon dioxide

Anionic phosphodiester surfactants, possessing either two fluorinated chains (F/F) or one hydrocarbon chain and one fluorinated chain (H/F), were synthesized and evaluated for solubility and self-assembly in liquid and supercritical carbon dioxide. Several surfactants, of both F/F and H/F types and having varied counterions, were found to be capable of solubilizing water-in-CO2 (W/C), via the formation of microemulsions, expanding upon the family of phosphate fluorosurfactants already found to stabilize W/C microemulsions. Small-angle neutron scatteringwas used to directly characterize the microemulsion particles at varied temperatures, pressures, and water loadings, revealing behavior consistent with previous results on W/C microemulsions.