Low temperature X-ray crystallographic structures of two lamotrigine analogues: (I) 2-methyl,3-amino, 5-imino-6-(2,3-dichlorophenyl)-1,2,4-triazine water solvate and (II) 2-methyl,3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine isethionate, hemi-hydrate

The X-ray crystal structures of two lamotrigine derivatives (I) 2-methyl, 3-amino, 5-imino-6-(2, 3-dichlorophenyl)-1,2,4-triazine, C10H9Cl2N5, as the hemi hydrate and (II) 2-methyl,3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine, C10H10Cl2N5, as the isethionate-water solvate, have been carried out at liquid nitrogen temperature. A detailed comparison of the two structures is given. Both are monoclinic and centrosymmetric, with (I) in space group C2/c, and (II) in space group P2(1)/n. For (I) the unit cell dimensions are a = 19.5466(10), b = 7.5483(4), c = 15.7861(8) angstrom, beta = 91.458(3)degrees, volume = 2328.4(2) angstrom(3), Z = 8, density = 1.590 Mg/m(3); for (II). For (II) the unit cell dimensions are a = 6.0566(2), b = 11.0084(4) c = 23.9973(9) angstrom, beta = 92.587(3)degrees, volume = 1598.35(10) angstrom(3), Z = 4, density = 1.597 Mg/m(3). For (I) final R indices [I > 2sigma(I)] are R1 = 0.0356, wR2 = 0.0782 and R indices (all data) are R1 = 0.0424, wR2 = 0.0817. For (II) final R indices [I > 2sigma(I)] are R1 = 0.0380, wR2 = 0.0871 and R indices (all data) R1 = 0.0558, wR2 = 0.0949. Both structures have a molecule of water of crystallization and (II) also includes a solvated CH3SO3. Comparisons are made between the two structures. Structure (I) is very unusual in having a = NH group at position C5' on the triazine ring. No other examples of this particular substitution, which is usually -NH2, have been reported.

Convenient synthetic routes to bidentate and monodentate 2-, 3- and 4-pyridyl phosphines: potentially useful ligands for water-soluble complex catalysts

The monodentate and bidentate pyridyl phosphines, PR3 and R2P(CH2)2PR2, where R=3- or 4-pyridyl can be prepared in high yields by treatment of butyllithium/TMEDA/3- or 4-bromopyridine with PCl3 or Cl2P(CH2)2PCl2 at low temperature. 1,2-Bis(di-2-pyridylphosphino)ethane is conveniently synthesised by an alternative route involving reaction of 1,2-dibromoethane with lithium di-2-pyridylphosphide.

Water

The Water chapter of the Poor Choices report.

Kinetic studies of water uptake and loss in glass-ionomer cements

The water sorption and desorption behaviour of three commercial glass-ionomer cements used in clinical dentistry have been studied in detail. Cured specimens of each material were found to show slight but variable water uptake in high humidity conditions, but steady loss in desiccating ones. This water loss was found to follow Fick's law for the first 4-5 h. Diffusion coefficients at 22 degrees C were: Chemflex 1.34 x 10(-6) cm(2) s(-1), Fuji IX 5.87 x 10(-7) cm(2) s(-1), Aquacem 3.08 x 10(-6) cm(2) s(-1). At 7 degrees C they were: Chemflex 8.90 x 10(-7) cm(2) s(-1), Fuji IX 5.04 x 10(-7) cm(2) s(-1), Aquacem 2.88 x 10(-6) cm(2) s(-1). Activation energies for water loss were determined from the Arrhenius equation and were found to be Chemflex 161.8 J mol(-1), Fuji IX 101.3 J mol(-1), Aquacem 47.1 J mol(-1). Such low values show that water transport requires less energy in these cements than in resin-modified glass-ionomers. Fick's law plots were found not to pass through the origin. This implies that, in each case, there is a small water loss that does not involve diffusion. This was concluded to be water at the surface of the specimens, and was termed "superficial water". As such, it represents a fraction of the previously identified unbound (loose) water. Superficial water levels were: Chemflex 0.56%, Fuji IX 0.23%, Aquacem 0.87%. Equilibrium mass loss values were shown to be unaffected by temperature, and allowed ratios of bound:unbound water to be determined for all three cements. These showed wide variation, ranging from 1:5.26 for Chemflex to 1:1.25 for Fuji IX.

The kinetics of water loss from zinc phosphate and zinc polycarboxylate dental cements

The water desorption behaviour of three different zinc oxide dental cements (two polycarboxylates, one phosphate) has been studied in detail. Disc-shaped specimens of each material were prepared and allowed to lose water by being subjected to a low humidity desiccating atmosphere over concentrated sulfuric acid. In all three cements, water loss was found to follow Fick's second law for at least 6 h (until M(t)/M(infinity) values were around 0.5), with diffusion coefficients ranging from 6.03 x 10(-8 )cm(2 )s(-1) (for the zinc phosphate) to 2.056 x 10(-7 )cm(2 )s(-1) (for one of the zinc polycarboxylates, Poly F Plus). Equilibration times for desorption were of the order of 8 weeks, and equilibrium water losses ranged from 7.1% for zinc phosphate to 16.9% and 17.4% for the two zinc polycarboxylates.

Water transport in resin-modified glass-ionomer dental cement

Water uptake and water loss have been studied in a commercial resin-modified glass-ionomer cement, Fuji II LC, under a variety of conditions. Uptake was generally non-Fickian, but affected by temperature. At room temperature, the equilibrium water uptake values varied from 2.47 to 2.78% whereas at low temperature (12 degrees C), it varied from 0.85 to 1.18%. Cure time affected uptake values significantly. Water uptake was much lower than in conventional glass-ionomer restorative cements exposed to water vapor. Loss of water under desiccating conditions was found to be Fickian for the first 5 h loss at both 22 and 12 degrees C. Diffusion coefficients were between 0.45 and 0.76 x 10( -7) cm(2)/s, with low temperature diffusion coefficients slightly greater than those at room temperature. Plotting water loss as percentage versus s(-(1/2)) allowed activation energies to be determined from the Arrhenius equation and these were found to be 65.6, 79.8, and 7.7 kJ/mol respectively for 30, 20, and 10 s cure times. The overall conclusion is that the main advantage of incorporating HEMA into resin-modified-glass-ionomers is to alter water loss behavior. Rate of water loss and total amount lost are both reduced. Hence, resin-modified glass-ionomers are less sensitive to water loss than conventional glass-ionomers.

Water transport in zinc oxy-chloride cements

The water uptake and water loss behaviour in three different formulations of zinc oxy-chloride cement have been studied in detail. Specimens of each material were subjected to a high humidity atmosphere (93% RH) over saturated aqueous sodium sulfate, and a low humidity desiccating atmosphere over concentrated sulfuric acid. In high humidity, the cement formulated from the nominal 75% ZnCl2 solutions gained mass, eventually becoming too sticky to weigh further. The specimens at 25% and 50% ZnCl2 by contrast lost mass by a diffusion process, though by 1 week the 50% cement had stated to gain mass and was also too sticky to weigh. In low humidity, all three cements lost mass, again by a diffusion process. Both water gain and water loss followed Fick's law for a considerable time. In the case of water loss under desiccating conditions, this corresponded to values of Mt/MĄ well above 0.5. However, plots did not go through the origin, showing that there was an induction period before true diffusion began. Diffusion coefficients varied from 1.56 x 10-5 (75% ZnCl2) to 2.75 x 10-5 cm2/s (50% ZnCl2), and appeared to be influenced not simply by composition. The drying of the 25% and 50% ZnCl2 cements in high humidity conditions occurred at a much lower rate, with a value of D of 2.5 x 10-8 cm2/s for the 25% ZnCl2 cement. This cement was found to equilibrate slowly, but total water loss did not differ significantly from that of the cements stored under desiccating conditions. Equilibration times for water loss in desiccating conditions were of the order of 2-4 hours, depending on ZnCl2 content; equilibrium water losses were respectively 28.8 [25% ZnCl2], 16.2 [50%] and 12.4 [75%] which followed the order of ZnCl2 content. It is concluded that the water transport processes are strongly influenced by the ZnCl2 content of the cement.