Thermal Analysis of Cobalt(II) Salts with some Carboxylic Acids

The thermal analysis of CoC₂O₄·2H₂O, Co(HCOO)₂·2H₂O and Co(CH₃COO)₂·4H₂O was carried out with simultaneous TG-DTG-DTA measurements under non-isothermal conditions in air and argon atmospheres. The intermediates and the end products of decomposition were characterised by X-ray diffraction and IR and UV-VIS spectroscopy. The decomposition of the studied compounds occur in several stages. The first stage of dissociation of each compound is dehydration both in air and argon. The next stages differ in air and argon. The final product of the decomposition of each compound in air is Co₃O₄. In argon it is a mixture of Co and CoO for cobalt(II) oxalate and cobalt(II) formate but CoO for cobalt(II) acetate. This revised version was published online in August 2006 with corrections to the Cover Date.     

Use of short columns and high flow rates for rapid gradient reversed-phase chromatography

Summary Rapid analyses were performed using reversed-phase liquid chromatography with short (20–100 mm) columns swept by fast yet shallow gradients, and the results compared with those obtained with 150 mm columns and slow gradients. The resolution losses incurred with shorter columns were minimised by employing elevated flow rates, to ensure that comparable mean retention factors were experienced by individual analytes during gradients run on different columns. This conserves gradient steepness. High quality performance was obtained with turn-around times of 5–10 minutes. An overall 5-fold enhancement in the rate of information generation was obtained. The relevance of instrumental parameters and of column and packing dimensions, upon the potential for improved performance is discussed. Some implications for the rapidly developing technique of capillary electrochromatography are briefly indicated.     

Chemical modification of the surface of cellulosic fibres. 2. Introduction of alkenyl moieties via condensation reactions involving isocyanate functions

Various cellulosic substrates including powders, long fibres and sheets were treated with isocyanates bearing an alkenyl function in a non-swelling medium. These heterogeneous reactions introduced a small but significant number of polymerizable moieties at the surface of the cellulose. In a second step, the free radical polymerization of styrene or methyl methacrylate was carried out in the presence of these modified cellulosics. It was shown that the alkenyl functions appended onto their surface took part in the chain growth thus giving a continuous path of covalent bonds between the solid substrate and the polymer matrix. 0969--0239 © 1998 Blackie Academic & Professional     

Dielectric and dynamic mechanical relaxation studies on poly(aryl ether ketone)s

The relaxation behavior of four amorphous poly(aryl ether ketone)s was investigated using dielectric relaxation spectroscopy and dynamic mechanical analysis. The temperature dependence of the relaxation times of the glass transition process and the cooperative nature of this process were unaffected by changes in polymer structure. The temperature location of the loss peaks for all polymers progressed smoothly between the low frequency of the mechanical measurements and the higher frequencies of the dielectric probe. Differences were observed in mechanical activation energy and dielectric relaxation strength for one polymer which contained a significant concentration of meta linkages, compared with the para-linked polymers, while relaxation broadness was generally greater in the dynamic mechanical mode. Changes in chemical structure had little effect on the shape, intensity, and location of the β-relaxation peak, the main observation being that the Arrhenius activation energy measured by dynamic mechanical analysis was significantly higher than that calculated from the dielectric data. The dielectric β-relaxation was sensitive to absorbed moisture. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 851–859, 1998     

Swelling of polyacrylamide gels in polyacrylamide solutions

Swelling behavior of polyacrylamide (PAAm) and polyacrylamide-co-polyacrylic acid (PAAm-co-PAAc) gels was investigated in aqueous solutions of monodisperse PAAms with molecular weights (M_w) ranging from 1.5 × 10³ to 5 × 10⁶ g/mol. The volume of the gels decreases as the PAAm concentration in the external solution increases. This decrease becomes more pronounced as the molecular weight of PAAm increases. The classical Flory–Huggins (FH) theory correctly predicts the swelling behavior of nonionic PAAm gels in PAAm solutions. The polymer–polymer interaction parameter χ₂₃ was found to decrease as the molecular weight of PAAm increases. The swelling behavior of PAAm-co-PAAc gels in PAAm solutions deviates from the predictions of the FH theory. This is probably due to the change of the ionization degree of AAc units depending on the polymer concentration in the external solution. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1313–1320, 1998     

Synthesis and characterization of a family of biodegradable poly(ester amide)s derived from glycine

A series of aliphatic poly(ester amide)s derived from 1,6-hexanediol, glycine, and diacids with a variable number of methylenes (from 2 to 8) have been synthesized and characterized. Infrared spectroscopy shows that the studied polymers present a unique kind of hydrogen bond that is established between their amide groups. Thermal properties as melting, glass transition, and decomposition temperatures are reported. The data indicate that all the polymers are highly crystalline. Thus, different kinds of spherulites (positive and/or negative) were obtained depending on the preparation conditions and on the polymer samples. Moreover, all the polymers crystallized from dilute diol solutions as ribbonlike crystals where a regular folding habit and a single hydrogen bond direction could be deduced. A test of enzymatic hydrolysis was employed to assess the potential biodegradability of these polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1271–1282, 1998     

Syntheses and biological activities of α-methoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil and its polymers

The new monomer, α-methoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil (METFU), was synthesized by the reaction of 5-fluorouracil (5-FU) and exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (ETA) in order to prepare polymers containing 5-FU moiety. Poly(α-methoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil) [poly(METFU)], poly(α-methoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouraci-co-acrylic acid) [poly(METFU-co-AA)], and poly(α-methoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil-co-vinyl acetate) [poly(METFU-co- VAc)] were synthesized by photopolymerizations using 2,2-dimethoxy-2-phenylacetophenone (DMP) as an initiator. The synthesized METFU and the polymers were identified by FTIR and ¹H-NMR spectroscopies. The contents of METFU in poly(METFU-co-AA) and poly(METFU-co-VAc) determined by elemental analysis were 52 and 60 mol %, respectively. The average molecular weights and polydispersity indices determined with GPC were as follows: M n = 9,400, M w = 11,400 M w/M n = 1.21 for poly(METFU), M n = 14,400, M w = 26,800, M w/M n = 1.86 for poly(METFU-co-AA), and M n = 23,100, M w = 33,000, M w/M n = 1.43 for poly(METFU-co-VAc). The in vitro cytotoxicities of samples were evaluated with mouse mammary carcinoma (FM3A), mouse leukemia (P388), and human histiocytic lymphoma (U937) as cancer cell lines, and mouse liver cells (AC2F) as a normal cell line. The in vivo antitumor activities of synthesized polymers against mice bearing the sarcoma 180 tumor cell line were greater than those of 5-FU at concentrations of 0.8 and 80 mg/kg. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2177–2184, 1998     

On Bonding,Structure, and Stability of Ternary Hydrides A2MH2 (A = Li,Na; M = Pd,Pt)

Bonding, structure, and stability of solid A₂MH₂ with A = Li, Na; M = Pd, Pt were investigated with a relativistically corrected density-functional approach, which reliably describes the trends among these four compounds. In order to examine the influence of the ligands (A) and of the crystalline environment, calculations were also made for free A₂MH₂ molecules and MH₂^2– ions. The free MH₂^2– complex is held together by strong bonds between formally closed shell atomic units because of strong M-d,s hybridization. The M–H bonds are further stabilized by the alkali metal ion ligands and by the crystal surrounding. The crystal field expands the H–A distance and enhances the H–A polarity. Relativistic effects contribute to M–H bonding in the solid state. The experimentally determined bond lengths and their trends are in accordance with theory. Due to relativistic and lanthanide effects, the Pt–H bond length becomes nearly as short as the Pd–H one. The small Li ion causes a distortion of the Li₂PtH₂ crystal resulting in an even shorter Pt–H bond length. In the gas-phase, A₂PtH₂ is more stable against dissociation than A₂PdH₂. The stability of the solid compounds is strongly influenced by the cohesive energy of the metal M, and also by the nature of the alkali metal. The evaluated enthalpies of formation favor increasing stability of solid A₂MH₂ against disproportionation into M and AH from Pt to Pd and from Li to Na. This is in agreement with experimental findings. The assignment of the experimental vibrational excitations should be reconsidered.     

The Use of Non-Splitting Injection Techniques for Trace Analysis in Narrow-Bore Capillary Gas Chromatography

The use of hot splitless, cold splitless, and on-column injections for trace analysis in narrow-bore capillary GC is evaluated. Despite the low flow rates for the columns used, the required splitless times for splitless injections can be surprisingly short if liners with a small inside diameter are used. On-column injection can be applied by using an appropriate normal-bore precolumn coupled to the narrow-bore analytical column using a specially designed low dead volume column connector. The effects of the experimental conditions such as sample volume, injection temperature, and initial oven temperature on peak focusing and the discrimination and degradation behavior of the analytes are discussed. The possibilities to obtain sensitive and fast separations are illustrated by various applications.     

AStudyontheInfluenceofCu￣2￣＋，Cd￣2￣＋andPb￣2￣＋onTripleHelixPoly（A：2I）

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