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Polymer reactivity can be sterically hindered under certain conditions when the functional group is close to the polymer chain or in a sterically hindered environment or reaction involves a small molecule reactant that is bulky. Several examples illustrate this effect:

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ll(O) =

1. The a-chymotrypsin-catalyzed hydrolysis of the p-nitroanilide group in acrylamide copolymers with monomer I proceeds with a rate comparable to that of the monomer



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C# Converting existed excel file to pdf - MSDN - Microsoft
Hi,. We'd like to convert existed excel file to pdf, how do we do that in our C# windows form project? Thanks for help. Jason. Moved by Leo Liu ...

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when n 5. The rate decreases sharply with decreasing value of n as the reactive site becomes progressively closer to the polymer backbone and less accessible to the bulky a-chymotrypsin catalyst [Fu and Morawetz, 1976]. The reaction rate is not, however, affected by the molecular weight of the copolymer [Drobnik et al., 1976]. 2. Hydrogenation of cyclododecene using the polymeric rhodium catalyst II occurs at a rate 5 times slower than does cyclohexene [Mathur and Williams, 1976; Mathur et al., 1980]. The low-molecular-weight homolog III shows no difference in catalytic activity toward the two cycloalkenes.

2" {cos 0-

CH2 P(C6H5)2

. O}

3. Compounds n-C4H9I and n-C18H37I react at the same rate with pyridine, but n-C4H9I is almost fourfold more reactive than n-C18H37I toward poly(4-vinylpyridine) [Grieg and Sherrington, 1978].

{ 0 -. O} .





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This is a package of an Example Project for NpoiExcel. As a free C# excel API, it can enable developers to edit, copy, create, print and convert Excel files which ...

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Polymer reactions involving the conversion of uncharged functional groups to charged groups often exhibit a decrease in reactivity with conversion. Thus the quaternization of poly(4-vinylpyridine) becomes progressively slower with increasing conversion, since reaction proceeds with the buildup and concentration of charge on the polymer molecule [Noah et al., 1974; Sawage and Loucheux, 1975]. An unreactive pyridine group is less reactive by a factor of 3 when neighboring pyridine groups have reacted. This autoretardation behavior is not observed for the small molecule homolog, such as 4-ethylpyridine, since unreacted molecules are separated from reacted 4-ethylpyridine by solvent.

(C.66)

9-2

Now notice that to rotate the coordinate axes by {} round keeping r fixed is the same as to rotate r by -{} round kf~eping the coordinate axes fixed. Moreover, as (cos {} /2+0 sin {} /2)(cos (}/2+0sin {} /2) = 1, the time component does not change and we can write

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ScreenUpdating = false; // Make the process silent excelApplication.DisplayAlerts = false; // Open the workbook that you wish to export to PDF excelWorkbook ...

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The same phenomenon is responsible for the decrease in the ionization constant of a polymeric acid such as poly(acrylic acid) with increasing degree of ionization [Kawaguchi et al., 1990, 1992; Morawetz and Wang, 1987]. This effect is somewhat moderated for acrylic acid ethylene copolymers, since charge density on the ionized polymer is decreased. The basicity

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~ + nsin ~ },

9-3

(C.67)

of a polymeric base such as poly(4-vinylpyridine) or poly(vinyl amine) decreases with increasing protonation of nitrogen [Lewis et al., 1984; Satoh et al., 1989]. These autoretardation effects are partially alleviated by the addition of salts that shield the charge on the polymer. Charge on a polymer molecule can also affect reactivity by altering the concentration of the small molecule reactant within the polymer domains. The reaction of a charged polymer with a charged reactant results in acceleration for oppositely charged species and retardation when the charges are the same. For example, the rate constant for the KOH saponi cation of poly(methyl methacrylate) decreases by about an order of magnitude as the reaction proceeds [Plate, 1976]. Partially reacted poly(methyl methacrylate) (IV) repells hydroxide ion, while

unreacted polymer does not. The concentration of OH within the polymer domains decreases progressively with increasing conversion. Acceleration of reactivity is observed for the SN2 reaction of poly(4-vinylpyridine) and a-bromoacetate ion when the polymer is partially protonated [Ladenheim et al., 1959]. The positive charge on the polymer attracts and concentrates a-bromoacetate ion within the polymer domains.

which is the formula discovered by Cayley. Last but not least, let us obtain an explicit formula for a simple Lorentz transformation, say a Lorentz boost. An arbitrary Lorentz transformation (excluding reflections) can be obtained by applying a boost and then an ordinary three-dimensional rotation. In vector notation, a Lorentz boost can be written as [48, 566] r' = r + (-y .- 1)(r . v)v - f3'Yctv, (C.68) (C.69)

9-4

ct' = 'Y{ ct - f3r v},

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