Preparation of α,ω‐telechelic hexyl acrylate polymers with ?OH, ?COOH,and ?NH2 functional groups by RAFT

The design, synthesis, and use of two new, stable, functionalized chain transfer agents (CTA's) containing OH and amine end groups for the RAFT polymerization is reported: 2‐hydroxyethoxy‐carbonylphenylmethyl dithiobenzoate and 2‐(2‐(tert‐butoxycarbonyl)ethylamino)‐2‐oxo‐1‐phenylethyl benzodithioate, respectively. The RAFT polymerization of n‐hexyl acrylate (HA) using those CTA's, were compared to several other functionalized dithiobenzoate esters reported in the literature containing COOH and Ester groups. The performances of the dithiobenzoates were compared in terms of kinetics and molecular weight distribution control. Good control in polymerization of n‐hexyl acrylate with a linear increase of M_n with conversion mantaining polydispersity indices (PDI) below 1.1 was obtained by use of the new functionalized CTA's developed and also by use of some other CTA's tested, to produce well‐defined linear polymers with one specific chain‐end functionality: ? OH, ? COOH or Amine. Using a postpolymerization reaction with functionalized azocompounds in a 5 to 1 ratio, α,ω‐telechelic polymers, with ? OH or ? COOH as functional group at the second end were obtained. By using this synthetic strategy α,ω‐homotelechelic and heterotelechelic polymers were readily prepared. The chemical availability of functional end‐groups in the telechelics was demonstrated by reaction with methacrylic anhydride. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3033–3051, 2010     

Synthesis of thermosensitive guar‐based hydrogels with tunable physico‐chemical properties by click chemistry

Thermosensitive guar‐based hydrogels are obtained in water solutions by copper‐catalyzed 1,3‐dipolar cycloaddition between alkyne‐functionalized guars and α,ω‐diazido‐poly[(ethylene glycol)‐co‐(propylene glycol)]. Characterization by TGA, HR‐MAS ¹H NMR, and rheology have shown that hydrogels with tunable physico‐chemical properties, such as crosslinking density, viscoelasticity, swelling ratio, and so forth, could be obtained by varying the guar molar mass, the degree of alkyne functionality, the guar/crosslinker weight ratio, and the reaction temperature. Based on swelling measurements, it has been shown that the thermal sensitiveness of guar‐based hydrogels is fast, reversible, and intimately related to the weight fraction of the thermosensitive crosslinker in the network. Finally, the monitoring of doxorubicin hydrochloride release has demonstrated the potential of these hydrogels as temperature‐dependent drug release devices. The robust, efficient, and orthogonal approach described herein represents a general approach towards the development of well‐controlled guar‐based hydrogels using α,ω‐diazido crosslinkers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2733–2742, 2010     

A new titanium (IV) complex bearing phenoxyimine‐fluorene ligand and its use as catalyst for ethylene homo‐ and copolymerization

A new titanium (IV) complex bearing phenoxyimine‐fluorene ligand was prepared and its behaviors in ethylene homo‐ and copolymerization with 1‐hexene, 1‐octene, and norbornene in the presence of modified methylaluminoxane (MMAO) were studied respectively. The effects of various polymerization conditions including polymerization temperature, ethylene pressure and the concentration of comonomer on the catalytic activities and properties of the resultant polymer were investigated. The broad molecular weight distribution of resulting polymer indicated that the multiple active species were formed during polymerization. Such complex showed good catalytic activities in ethylene homo‐ and copolymerizations and good capabilities of incorporating various comonomers into polyethylene backbone. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1617–1621, 2010     

Combination of Dispersive Liquid‐Liquid Microextraction with Flame Atomic Absorption for Determination of Trace Ni and Co in Water Samples and Vitamin B12

A dispersive liquid‐liquid microextraction method based on the dispersion of 1,2‐dichlorobenzene as an extraction solvent into an aqueous phase in the presence of ethanol as a dispersive solvent for the preconcentration of Co²⁺ and Ni²⁺ ions is discussed. 1‐Nitroso 2‐naphtol was used as a chelating agent prior to the extraction and the preconcentrated analyte was determined by flame atomic absorption spectrometry. The effect of various experimental parameters including the extraction and dispersive solvent type and volume, pH, amount of the chelating agent, etc. on the microextraction and complex formation was investigated for finding the optimum conditions. The enhancement factors were about 61.9 and 51.8, the calibration graphs were linear in the range of 10‐150 μgL^?1 and 10‐250 μgL^?1 with detection limits of 2.42 μgL^?1 and 1.59 μgL^?1, and RSD (n = 5) of 3.08% and 2.17% for cobalt and nickel, respectively. The method was successfully applied to the determination of Co and Ni in water and vitamin B₁₂.     

Verticillane‐Type Diterpenoids and an Eudesmanolide‐Type Sesquiterpene from the Formosan Soft Coral Cespitularia hypotentaculata

Four new diterpenes, cespihypotins W–Z ( 1 – 4 ), having the verticillane skeleton and characterized by an α,β‐unsaturated γ‐hydroxycyclopentanone moiety, and a new eudesmanolide‐type sesquiterpene, cespilactam A ( 5 ), containing an α,β‐unsaturated γ‐lactam residue, were isolated from the AcOEt‐soluble fraction of the Taiwanese soft coral Cespitularia hypotentaculata. The structure and relative configuration of these metabolites was elucidated through extensive interpretation of MS, COSY, HSQC, HMBC, and NOESY experiments and by comparison of their NMR data with those of related compounds.     

A New Dimeric Alkaloid from the Leaf of Psychotria calocarpa

Psychotriasine was isolated from the leaves of Psychotria calocarpa (Rubiaceae). The structure was established by spectroscopic methods including 2D‐NMR analysis. To the best of our knowledge, psychotriasine is the first example of a dimeric tryptamine‐related alkaloid that contains a free N^α‐methyltryptamine unit in the molecule.     

New Coumarins and Triterpenes from Calophyllum inophyllum

Four new coumarins, 1 – 4 , and two new triterpenes, 5 and 6 , along with nine known compounds have been identified from the leaves of Calophyllum inophyllum on the basis of spectroscopic analyses and chemical methods. The structure of apetalolide ( 7 ), previously reported from C. apetalum, was revised by means of 2D‐NMR, and the absolute configuration of the known compound inophyllum D ( 8 ) was established by a modified Mosher's method.     

High‐spin states in tetrahedral X4 clusters (X = H,Li, Na,K)

The high‐spin electronic states for lithium, sodium, and potassium four‐atom clusters were studied. In particular, we performed coupled cluster geometry optimization of the quintet state in tetrahedral geometry. The quintet state of these systems is characterized by having all the valence electron unpaired, giving rise to the so‐called no‐pair bonding. Single‐point full configuration interaction computations on the equilibrium geometries for the various clusters are also presented. The analysis of the valence orbitals in a localized representation confirms the importance of the p atomic orbitals to explain this unusual type of bond. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010