• Journal of the Korea Institute of Military Science and Technology
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• v.3 no.1
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• pp.164-175
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• 2000

Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

• Journal of KIISE:Software and Applications
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• v.30 no.5_6
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• pp.444-453
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• 2003

Recently, a great interest of bio-technology(BT) is concentrated and the image analysis technique for electrophoresis gels is highly requested to analyze genetic information or to look for some new bio-activation materials. For this purpose, the location and quantity of each band in a lane should be measured. In most of existing techniques, the approach of peak searching in a profile of a lane is used. But this peak is improper as the representative of a band, because its location does not correspond to that of the brightest pixel or the center of gravity. Also, it is improper to measure band quantity in most of these approaches because various enhancement processes are commonly applied to original images to extract peaks easily. In this paper, we adopt an approach to measure accumulated brightness as a band quantity in each band region, which Is extracted by not using any process of changing relative brightness, and the gravity center of the region is calculated as a band location. Actually, we first extract lanes with an entropy-based threshold calculated on a gel-image histogram. And then, three other methods are proposed and applied to extract bands. In the MER method, peaks and valleys are searched on a vertical search line by which each lane is bisected. And the minimum enclosing rectangle of each band is set between successive two valleys. On the other hand, in the RG-1 method, each band is extracted by using region growing with a peak as a seed, separating overlapped neighbor bands. In the RG-2 method, peaks and valleys are searched on two vertical lines by which each lane is trisected, and the left and right peaks nay be paired up if they seem to belong to the same band, and then each band region is grown up with a peak or both peaks if exist. To compare above three methods, we have measured the location and amount of bands. As a result, the average errors in band location of MER, RG-1, and RG-2 were 6%, 3%, and 1%, respectively, when the lane length is normalized to a unit value. And the average errors in band amount were 8%, 5%, and 2%, respectively, when the sum of band amount is normalized to a unit value. In conclusion, RG-2 was shown to be more reliable in the accuracy of measuring the location and amount of bands.