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By Sherman H. C.

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Extra info for An Investigation of the Chemical Nature of Two Typical Enzymes Pancreatic and Malt Amylases

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Like in the case of the ylides, no d-orbital participation is needed to describe the bonding in these compounds. Rather, the delocalized 3c–4e model can again be used [33], which also accounts for the positive charge at the central phosphorus atom, in accordance with the ylidic resonance structure (IIC Scheme 5). P P a b Scheme 2 Phosphenium cations (a) and phosphide ions (b) P C IA Scheme 3 Ylide and ylene bonding description with σ4,λ5-P P C IB Aromatic Phosphorus Heterocycles P 31 P E E: CR2, NR, O, S E E: CR, N Scheme 4 Possible participation of ylides in π-systems P CH2 P H2C H2C CH2 P H2C IIB IIA CH2 IIC Scheme 5 Bis-methylene-phosphorane-type bonding with the usual notations and resonance structures E P P E E: CR2, NR, O, S E: CR, N Scheme 6 Possible participation of bis-methylene-phosphorane-type bonding in π-systems Like ylides, bis-methylene-phosphoranes can also be built into π-systems in different ways (see Scheme 6), with one of the P=E bonds in an exocyclic position, or with the entire 3c–4e π-system incorporated into the cyclic delocalization.

Wiley, Chichester, p 283 28. Wiley, New York 29. Matos MAR, Miranda MS, Monte MJS, Santos LMNBF, Morais VMF, Chickos JS, Umnahanant P, Liebman JF (2007) J Phys Chem A 111:11152 30. Temprado M, Roux MV, Umnahanant P, Zhao H, Chickos JS (2005) J Phys Chem B 109: 12590 31. Roux MV, Jiménez P, Dávalos JZ, Temprado M, Liebman JF (2003) J Chem Thermodyn 35: 803 32. Roux MV, Jiménez P, Dávalos JZ, Turrión C, Afeefy HY, Liebman JF (1998) J Chem Soc Faraday 94:887 33. Roux MV, Temprado M, Dávalos JZ, Jiménez P, Hosmane RS, Liebman JF (2002) Phys Chem Chem Phys 4:3611 34.

The enthalpy of formation of purine (XLVIII), with its four nitrogens dispersed through both rings, has been measured in recent times [78], and chronicled in the archive [15] with yet a later value [79]. These two values inexplicably differ by over 2000 kJ mol−1. In the absence of a value for the enthalpy of sublimation we are hesitant to discuss this species further, other than to note two estimates from a paper more than 100 years old [80] that straddle the results in [78] by ca. ±20 kJ mol−1.

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An Investigation of the Chemical Nature of Two Typical Enzymes Pancreatic and Malt Amylases by Sherman H. C.


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