Correlation as a determinant of configurational entropy in supramolecular and protein systems

Details

• Personal Author:
  Fedorowicz A ; Fenley AT ; Gilson MK ; Hnizdo, Vladimir ; Killian BJ ; Sharp DS
• Description:
  For biomolecules in solution, changes in configurational entropy are thought to contribute substantially to the free energies of processes like binding and conformational change. In principle, the configurational entropy can be strongly affected by pairwise and higher-order correlations among conformational degrees of freedom. However, the literature offers mixed perspectives regarding the contributions that changes in correlations make to changes in configurational entropy for such processes. Here we take advantage of powerful techniques for simulation and entropy analysis to carry out rigorous in silico studies of correlation in binding and conformational changes. In particular, we apply information-theoretic expansions of the configurational entropy to well-sampled molecular dynamics simulations of a model host-guest system and the protein bovine pancreatic trypsin inhibitor. The results bear on the interpretation of NMR data, as they indicate that changes in correlation are important determinants of entropy changes for biologically relevant processes and that changes in correlation may either balance or reinforce changes in first-order entropy. The results also highlight the importance of main-chain torsions as contributors to changes in protein configurational entropy. As simulation techniques grow in power, the mathematical techniques used here will offer new opportunities to answer challenging questions about complex molecular systems. [Description provided by NIOSH]
• Subjects:
  Coal Coal Mining Environmental Monitoring Ergonomics Mining Occupational Health Safety Stress, Psychological
• Keywords:
  Binding-energy Molecular-biology Molecular-structure Proteins
• ISSN:
  1089-5647
• Document Type:
  Text
• Funding:
  Contract
• Genre:
  Journal Article
• Place as Subject:
  California ; Florida ; OSHA Region 3 ; OSHA Region 4 ; OSHA Region 9 ; West Virginia
• CIO:
  National Institute for Occupational Safety and Health (NIOSH)
• Division:
  HELD - Health Effects Laboratory Division
• Topic:
  Workplace Safety & Health
• Location:
  North America
• Volume:
  118
• Issue:
  24
• NIOSHTIC Number:
  nn:20044594
• Citation:
  J Phys Chem B 2014 Jun; 118(24):6447-6455
• Contact Point Address:
  Vladimir Hnizdo, National Institute for Occupational Safety and Health, 1095 Willowdale Road, Morgantown, West Virginia 26505
• Email:
  hnizdo2044@gmail.com
• Federal Fiscal Year:
  2014
• Peer Reviewed:
  True
• Source Full Name:
  Journal of Physical Chemistry B
• Collection(s):
  National Institute for Occupational Safety and Health
• Main Document Checksum:
  urn:sha-512:a0a953365d2edcd8e92299cf531da1ce338b8e4181baf6afef085f15c0e18a0a2c92c1ef6e524e83823bd149551f44618db06c29d97bcdeaeaea3b737c524434
• Download URL:
  https://stacks.cdc.gov/view/cdc/200263/cdc_200263_DS1.pdf
• File Type:
  [PDF - 1.38 MB ]