UV curable epoxy acrylate-clay nanocomposites

UV curable epoxy acrylates were reinforced with two different organically modified montmorillonites (MMTs) and an unmodified MMT. Conversion and rate of polymerization was monitored by real time infrared spectroscopy (RTIR) and photo-DSC. Microstructures were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and optical clarity. Optical clarity of the films containing clay was quite good as only a slight decrease was observed. Physical properties of the reinforced films were examined by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), hardness and tensile testing. Enhancements in glass transition temperature (T_g), thermal stability and mechanical properties were observed. The films reinforced with the unmodified MMT exhibit the most significant enhancements in properties.     

Synthesis of novel 3'-C-methylene thymidine and 5-methyluridine/cytidine H-phosphonates and phosphonamidites for new backbone modification of oligonucleotides

Novel 5'-O-DMT- and MMT-protected 3'-C-methylene-modified thymidine, 5-methyluridine, and 5-methylcytidine H-phosphonates 1-7 with O-methyl, fluoro, hydrogen, and O-(2-methoxyethyl) substituents at the 2'-position have been synthesized by a new effective strategy from the corresponding key intermediates 3'-C-iodomethyl nucleosides and intermediate BTSP, prepared in situ through the Arbuzov reaction. The modified reaction conditions for the Arbuzov reaction prevented the loss of DMT- and MMT-protecting groups, and directly provided the desired 5'-O-DMT- and/or MMT-protected 3'-C-methylene-modified H-phosphonates 1-6 although some of them were also prepared through the manipulation of protecting groups after the P-C bond formation. The modified Arbuzov reaction of 3'-C-iodomethyl-5-methylcytidine 53, prepared from its 5-methyluridine derivative 42, with BTSP provided the 5-methylcytidine H-phosphonate 54, which was further transferred to the corresponding 4-N-(N-methylpyrrolidin-2-ylidene)-protected H-phosphonate monomer 7. 5'-O-MMT-protected 3'-C-methylene-modified H-phosphonates 5, 3, and 7 were converted to the corresponding cyanoethyl H-phosphonates 50, 51, and 56 using DCC as a coupling reagent. One-pot three-step reactions of 50, 51, and 56 provided the desired 3'-C-methylene-modified phosphonamidite monomers 8-10. Some of these new 3'-methylene-modified monomers 1-10 have been successfully utilized for the synthesis of 3'-methylene-modified oligonucleotides, which have shown superior antisense properties including nuclease resistance and binding affinity to the target RNA.     

A one-pot synthesis of 1,4-dithiins and 1,4-benzodithiins from ketones using the recyclable reagent 1,1′-(ethane-1,2-diyl)dipyridinium bistribromide (EDPBT)

A novel access to 1,4-dithiins and 1,4-benzodithiins from the corresponding ketones in one-pot using the recyclable reagent, 1,1′-(ethane-1,2-diyl)dipyridinium bistribromide (EDPBT) is described. This method is mild, simple, environmentally benign and is applied successfully for the ring expansion of 1,3-dithiolane to 1,4-dithiins and the ring expansion associated with aromatisation of cyclic ketones with or without double bonds in the ring. The main feature of this method is that EDPBT acts as a promoter in the formation of 1,3-dithiolane and as a reagent in the ring expansion step. The spent reagent can be recovered, regenerated and reused.     

Synthesis of 2'-O-[2-[(N,N-dimethylamino)oxy]ethyl] modified nucleosides and oligonucleotides.

A versatile synthetic route has been developed for the synthesis of 2'-O-[2-[(N,N-dimethylamino)oxy]ethyl] (abbreviated as 2'-O-DMAOE) modified purine and pyrimidine nucleosides and their corresponding nucleoside phosphoramidites and solid supports. To synthesize 2'-O-DMAOE purine nucleosides, the key intermediate B (Scheme 1) was obtained from the 2'-O-allyl purine nucleosides (13a and 15) via oxidative cleavage of the carbon-carbon bond to the corresponding aldehydes followed by reduction. To synthesize pyrimidine nucleosides, opening the 2,2'-anhydro-5-methyluridine 5 with the borate ester of ethylene glycol gave the key intermediate B. The 2'-O-(2-hydroxyethyl) nucleosides were converted, in excellent yield, by a regioselective Mitsunobu reaction, to the corresponding 2'-O-[2-[(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)oxy]ethyl] nucleosides (18, 19, and 20). These compounds were subsequently deprotected and converted into the 2'-O-[2-[(methyleneamino)oxy]ethyl] derivatives (22, 23, and 24). Reduction and a second reductive amination with formaldehyde yielded the corresponding 2'-O-[2-[(N,N-dimethylamino)oxy]ethyl] nucleosides (25, 26, and 27). These nucleosides were converted to their 3'-O-phosphoramidites and controlled-pore glass solid supports in excellent overall yield. Using these monomers, modified oligonucleotides containing pyrimidine and purine bases were synthesized with phosphodiester, phosphorothioate, and both linkages (phosphorothioate and phosphodiester) present in the same oligonucleotide as a chimera in high yields. The oligonucleotides were characterized by HPLC, capillary gel electrophoresis, and ESMS. The effect of this modification on the affinity of the oligonucleotides for complementary RNA and on nuclease stability was evaluated. The 2'-O-DMAOE modification enhanced the binding affinity of the oligonucleotides for the complementary RNA (and not for DNA). The modified oligonucleotides that possessed the phosphodiester backbone demonstrated excellent resistance to nuclease with t(1/2) > 24 h.     

Synthesis of chimeric oligonucleotides containing phosphodiester, phosphorothioate, and phosphoramidate linkages

[reaction: see text] H-Phosphonate monomers of 2'-O-(2-methoxyethyl) ribonucleosides have been synthesized. Oxidation of oligonucleotide H-phosphonates has been optimized to allow the synthesis of oligonucleotides containing either 2'-deoxy or 2'-O-(2-methoxyethyl) ribonucleoside residues combined with three different phosphate modifications in the backbone, i.e., phosphodiester (PO), phosphorothioate (PS), and phosphoramidate (PN). Phosphodiester linkages were introduced by oxidation with a cocktail of 0.1 M Et(3)N in CCl(4)/Pyr/H(2)O (5:9:1) without affecting phosphorothioate or phosphoramidate linkages. For the synthesis of phosphoramidate-modified oligonucleotides, N(4)-acetyl deoxycytidine-3'-H-phosphonate monomers were used to avoid transamination during the oxidation step.     

Aromaticity interplay between quinodimethanes and C(60) in diels-alder reactions: insights from a theoretical study

A theoretical study is performed of the Diels-Alder reactions of various o-quinodimethanes (QDM) with C(60) by the AM1 model and limited ab initio and DFT techniques. All reactions are shown to proceed through a concerted transition state possessing a considerable net aromaticity as evidenced from bond orders and magnetic criteria such as the magnetic susceptibility exhaltations (MSE) and nucleus independent chemical shifts (NICS) and produce different kinds of aromatic stabilized fullerene cycloadducts. Computations show that a strong LUMO-dienophile control of C(60) is realized by the influence of pyramidalization, but its high reactivity over alkene appears to be governed by the global aromaticity on fullerene rather than its strain. The aromatic functionalization occurring in QDM upon cycloaddition drastically increases the reaction rate and exothermicity of all QDM-C(60) reactions as compared to the butadiene-C(60) reaction. In fact, the simultaneously existing aromatic destabilization in fullerene indicates its opposite effect to the resonance stabilization in diene; it is thus fully restricted when the gained aromaticity is transmitted from the nucleophilic QDM to the fullerene electrophile in a push-pull manner. However, the overall aromaticity effect shown by the aromatization as well as the aromaticity of C(60) seems to accelerate these reactions at an increased rate.     

Exchange interactions in some low-dimensional metal dithiolene complexes

Low-dimensional systems are formed by planar metal dithiolene complexes which stack as columnar structures in the solid state. Stronger interactions among units within a chain leads to highly anisotropic magnetic properties. The magnetic effects are a manifestation of exchange interaction,J and can be studied through detailedepr techniques in conjunction with magnetic susceptibility and x-ray crystal structure. A brief review of such studies carried out mostly in our laboratory is presented along with the relevant background materials.     

DAPPA grafted polymer: an efficient solid phase extractant for U(VI), Th(IV) and La(III) from acidic waste streams and environmental samples

A new class of polymeric resin has been synthesized by grafting Merrifield chloromethylated resin with (dimethyl amino-phosphono-methyl)-phosphonic acid (MCM-DAPPA), for the preconcentration of U(VI), Th(IV) and La(III) from both acidic wastes and environmental samples. The various chemical modification steps involved during grafting process are characterized by FT-IR spectroscopy, ³¹P and ¹³C-CPMAS (cross-polarized magic angle spin) NMR spectroscopy and CHNS/O elemental analysis. The water regain capacity data for the grafted polymer are obtained from thermo-gravimetric (TG) analysis. The influence of various physico-chemical parameters during the quantitative extraction of metal ions by the resin phase are studied and optimized by both static and dynamic methods. The significant feature of this grafted polymer is its ability to extract both actinides and lanthanides from high-level acidities as well as from near neutral conditions. The resin shows very high sorption capacity values of 2.02, 0.89 and 0.54 mmol g⁻¹ for U(VI), 1.98, 0.63 and 0.42 mmol g⁻¹ for Th(IV) and 1.22, 0.39 and 0.39 mmol g⁻¹ for La(III) under optimum pH, HNO₃ and HCl concentration, respectively. The grafted polymer shows faster phase exchange kinetics (<5 min is sufficient for 50% extraction) and greater preconcentration ability, with reusability exceeding 20 cycles. During desorption process, all the analyte ions are quantitatively eluted from the resin phase with >99.5% recovery using 1 M (NH₄)₂CO₃, as eluent. The developed grafted resin has been successfully applied in extracting Th(IV) from high matrix monazite sand, U(VI) from sea water and also U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. The analytical data obtained from triplicate measurements are within 3.9% R.S.D. reflecting the reproducibility and reliability of the developed method.