Bulky Groups (bulky + groups)

Distribution by Scientific Domains
Chemistry75%

Selected Abstracts

Computational modeling of tetrahydroimidazo-[4,5,1-jk][1,4]-benzodiazepinone derivatives: An atomistic drug design approach using Kier-Hall electrotopological state (E-state) indices

JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 11 2008
Nitin S. Sapre
Abstract Quantitative structure-activity relationships (QSAR), based on E-state indices have been developed for a series of tetrahydroimidazo-[4,5,1-jk]-benzodiazepinone derivatives against HIV-1 reverse transcriptase (HIV-1 RT). Statistical modeling using multiple linear regression technique in predicting the anti-HIV activity yielded a good correlation for the training set (R2 = 0.913, R = 0.897, Q2 = 0.849, MSE = 0.190, F -ratio = 59.97, PRESS = 18.05, SSE = 0.926, and p value = 0.00). Leave-one-out cross-validation also reaffirmed the predictions (R2 = 0.850, R = 0.824, Q2 = 0.849, MSE = 0.328, and PRESS = 18.05). The predictive ability of the training set was also cross-validated by a test set (R2 = 0.812, R = 0.799, Q2 = 0.765, MSE = 0.347, F -ratio = 64.69, PRESS = 7.37, SSE = 0.975, and p value = 0.00), which ascertained a satisfactory quality of fit. The results reflect the substitution pattern and suggest that the presence of a bulky and electropositive group in the five-member ring and electron withdrawing groups in the seven-member ring will have a positive impact on the antiviral activity of the derivatives. Bulky groups in the six-member ring do not show an activity-enhancing impact. Outlier analysis too reconfirms our findings. The E-state descriptors indicate their importance in quantifying the electronic characteristics of a molecule and thus can be used in chemical interpretation of electronic and steric factors affecting the biological activity of compounds. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008 [source]

Rigid Bisphenanthrolines: Synthesis, Structure and Self-Assembly at a Solid,Liquid Interface,

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2006
Michael Schmittel
Abstract Several rigid linear bisphenanthrolines with and without bulky groups at the bisimine sites were synthesized. For three representatives, the solid-state structures were elucidated. Their potential for self-assembled monolayers was explored by scanning tunneling microscopy (STM) at the solid,liquid interface, and the resulting architectures were found to be promising candidates for templating metal-ion nanopatterns. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Gel point prediction of metal-filled castor oil-based polyurethanes system,

POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10-12 2002
Anil Srivastava
Abstract Prediction of gel point conversion and network formation is of great importance in polycondensation during synthesis as well as processing. It enables one to estimate the safe conversions for reactor operation without gelation and the cycle time during processing, and plays an important role in controlling the molding parameters used for reinforced reaction injection molding (RRIM), reaction injection molding (RIM) and compression molding. Theories of gelation have been extensively published in the literature and supported by experimental data for various polycondensation systems. However, most such studies relate to unfilled systems. In this work, metal-filled polyurethanes have been synthesized in bulk by reacting toluene di-isocyanate with castor oil and its polyols possessing different hydroxyl values. Metallic aluminum powder (10,40% by weight) was dispersed thoroughly in castor oil and its polyols before reacting at different temperatures (30,60,°C) in a moisture-free, inert environment. The gel point conversions were measured experimentally and an empirical model from the experimental data has been developed to predict the gelation behavior. The proposed model could be of immense importance in the paints, adhesives and lacquers industries, which use castor oil in bulk. From these experiments it was concluded that: (i) fine metal powder gives a rise in viscosity; (ii) metal fillers not only restrict the molecular motion due to the increase in viscosity, but also lower the conversion; (iii) the vegetable oil and its polyols have a number of bulky groups, which also impart the delay tendency in gel time; (iv) there is a change in gelation dynamics at 50,°C , this is due to the change in reactivity of di-isocyanates; (v) the presence of metal filler does not initiate the intermolecular condensation; (vi) there is a gap between theoretical and experimental gel point owing to the unequal reactivity of the secondary alcohol position; (vii) there is an inverse relationship of gel time with the reaction temperature and hydroxyl value of polyols. An empirical model based on process parameters, i.e., hydroxyl value, temperature, shape factor and filler concentration, has been derived and found to be adequate for the metal-filled system. The correlation coefficient on the data is on the lower side in some cases because the following were not taken into account: (i) the first-order kinetics followed by the reaction in the second half while it is tending towards gelation; (ii) the error in observing the gel point viscosity; (iii) errors in assuming the spherical shape of aluminum metal powder; (iv) errors due to failure to maintain the constant speed in agitation. Copyright © 2003 John Wiley & Sons, Ltd. [source]

Fine-Tuning the Dimerization of Tetraureacalix[4]arenes

CHEMISTRY - A EUROPEAN JOURNAL, Issue 15 2010
Yuliya Rudzevich Dr.
Abstract Calix[4]arenes substituted by four urea residues at their wide rim form hydrogen-bonded homo- and heterodimeric capsules in apolar solvents. If urea groups are covalently connected to loops or substituted by bulky residues, the dimerization may be restricted to those pairs in which the loops do not overlap and for which the residues are small enough to pass the loops. In the present study, we describe the dimerization properties of tetraureas with one, two (adjacent or opposite), three, or four loops and those bearing (additionally) up to four residues of different size: a=tolyl, b=3,5-di- tert -butylphenyl, c=4-propyloxy-3,5-di-(tert -butylphenyl)phenyl, and d=4-[tris-(4- tert -butylphenyl)methyl]phenyl. For compounds with four loops of different size (O(CH2)nO-chains with n=10, 14, and 20 connecting the m -positions of the urea phenyl residues) a clear "stepwise" sorting scheme could be established, in which the bulkiest residue d is excluded by all tetraloop compounds and the smallest residue a can pass only the smallest loops (n=10). The medium-sized residues b or c are tolerated by n=14 and 20 or only by n=20. Selectivities can be built up also on geometrical factors. A trisloop compound, for instance, combines only with a tetraurea bearing a single bulky residue and tetraureas with two bulky substituents in adjacent or opposite position are distinguished by the bisloop derivatives with adjacent or opposite loops. The impossibility to form a homodimer of a monoloop compound containing two bulky residues leads to its selective heterodimerization with a derivative bearing three bulky groups. Subtle effects for "borderline" cases, in which the dimerization or reorganization takes a longer time, are also discussed. [source]