Spin—rotational relaxation study of molecular reorientation in the presence of internal extended rotational diffusion

Molecular reorientation in the presence of internal rotation is investigated and an analytical expression for the spin—rotational rate of a nucleus attached to the internal rotor is obtained in terms of the internal angular-momentum correlation time. A model of a symmetric-top molecule undergoing anisotropic rotational diffusion is extended to include a modified extended diffusion of internal rotation. The result is applied to liquid toluene and the internal angular-momentum correlation time is evaluated from the ¹³C nuclear spin—rotational relaxation rate of the methyl carbon. A comparison with the previous result on the dipole—dipole relaxation data is made and the consistency of the present theory is discussed.     

Scaffold-based molecular design with a graph generative model

Searching for new molecules in areas like drug discovery often starts from the core structures of known molecules. Such a method has called for a strategy of designing derivative compounds retaining a particular scaffold as a substructure. On this account, our present work proposes a graph generative model that targets its use in scaffold-based molecular design. Our model accepts a molecular scaffold as input and extends it by sequentially adding atoms and bonds. The generated molecules are then guaranteed to contain the scaffold with certainty, and their properties can be controlled by conditioning the generation process on desired properties. The learned rule of extending molecules can well generalize to arbitrary kinds of scaffolds, including those unseen during learning. In the conditional generation of molecules, our model can simultaneously control multiple chemical properties despite the search space constrained by fixing the substructure. As a demonstration, we applied our model to designing inhibitors of the epidermal growth factor receptor and show that our model can employ a simple semi-supervised extension to broaden its applicability to situations where only a small amount of data is available.

We propose a scaffold-based graph generative model for designing novel drug candidates that include the desired scaffold as a substructure.     

Tricarbonyl(dialkylamidocyclohexa-1,3-diene)iron: Preparation,Isomerization and Stereochemistry

The direct reaction of iron pentacarbonyl with diethylamidocyclohexadiene gave three isomeric tricarbonyliron complexes, 1, 2 and 3. Only 1 isomerized to give 2 under acidic conditions, whereas 3 remained unchanged. The chemical properties of the tricarbonyl(amidocyclohexadiene)iron complexes differed from those of the tricarbonyl(carboxycyclohexadiene)iron complexes. Complex 3 which underwent no hydride abstraction with triphenylmethyl hexafluorophosphate, has an exo stereochemistry.     

Derivation of class II force fields. VIII. Derivation of a general quantum mechanical force field for organic compounds

A class II valence force field covering a broad range of organic molecules has been derived employing ab initio quantum mechanical "observables." The procedure includes selecting representative molecules and molecular structures, and systematically sampling their energy surfaces as described by energies and energy first and second derivatives with respect to molecular deformations. In this article the procedure for fitting the force field parameters to these energies and energy derivatives is briefly reviewed. The application of the methodology to the derivation of a class II quantum mechanical force field (QMFF) for 32 organic functional groups is then described. A training set of 400 molecules spanning the 32 functional groups was used to parameterize the force field. The molecular families comprising the functional groups and, within each family, the torsional angles used to sample different conformers, are described. The number of stationary points (equilibria and transition states) for these molecules is given for each functional group. This set contains 1324 stationary structures, with 718 minimum energy structures and 606 transition states. The quality of the fit to the quantum data is gauged based on the deviations between the ab initio and force field energies and energy derivatives. The accuracy with which the QMFF reproduces the ab initio molecular bond lengths, bond angles, torsional angles, vibrational frequencies, and conformational energies is then given for each functional group. Consistently good accuracy is found for these computed properties for the various types of molecules. This demonstrates that the methodology is broadly applicable for the derivation of force field parameters across widely differing types of molecular structures. Copyright 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1782-1800, 2001     

Hard form factors for meson-baryon strong couplings as derived from deep inelastic lepton scattering

As stimulated by earlier attempts for obtaining theNN andN form factors from the deep inelastic lepton scattering data, we extend the analysis by taking into account effects of additional mesons including, , ,K, andK ^*, with the coupling constants fixed by the lowenergy nucleon-nucleon and hyperon-nucleon scattering data. Contrary to an earlier claim that the NN andN form factor must be very soft (e.g., with the cutoff mass less than 500 MeV in the monopole form), we find, for example, that with all form factors parametrized in the dipole form, a universal cutoff mass of 1150 MeV in the/N sector and 1400 MeV in the/ sector yields predictions in excellent agreement with recently published neutrino data on the momentum fractions carried by thes, , and¯d quarks, as well as consistent with the sea-to-valence ratio extracted from the CDHS data and the Femilab E615 experiment. Similar results can also be obtained by using exponential cutoffs for all couplings, or by using monopole forms for some vertices while retaining dipole forms for the rest. The success of the mesonexchange picture in generating the strangeness content in a proton suggests an alternative understanding of the origin of sea quarks in the proton.We wish to thank G. Garvey, K. Holinde, L.-C. Liu, M. B. Johnson, M. Strikman, A. W. Thomas and Jochen Wambach for helpful conversations. W-Y. P. Hwang wishes to acknowledge the Alexander von Humboldt Foundation for a fellowship to visit Jülich for conducting research. His research works was also supported in part by the National Science Council of the Republic of China. The work of G. E. Brown is supported in part by a Humboldt award, in part by NATO Grant RG85/0093, and in part by the U.S. Department of Energy.     

Dense stars with exotic configurations

In this paper, we consider dense stars with configurations expected from the SU(3)_C×SU(2)_W× U(1) standard model of strong and electroweak interactions. Following a recent suggestion that strange matter, a form of (uds) quark matter, may be the true ground state of hadronic matter, we investigate the prospect for the existence of dense stars consisting partially, or entirely, of strange matter by comparing the relative stability between neutron matter and strange matter. It is found that the restriction on the maximum star mass holds in all cases, including a pure strange star, a pure neutron star, and a neutron star with a quark core. It is also found that the choice of both the bag constantB and the strong coupling constant _s has a decisive effect on the relative stability between strange matter and neutron matter. For currently accepted values of (B, _s), anA= dense starcannot consist entirely,nor partially, of strange matter. Nevertheless, such conclusion may be subject to change if corrections ofO ( _s ² ) or other effects are taken into account. Finally, we use the framework of Tolman, Oppenheimer, and Volkoff to analyze two cases of boson stars: gluon stars and stars consisting of massive scalar particles (massive bosons). It is found that, in the case of gluon stars, the presence of the bag constant in the QCD vacuum yields results very similar to that found in quark stars. On the other hand, soliton stars consisting of massive bosons exist if there is some background pressure which plays the role similar to the bag constant for lowering the matter pressure. The stability problem for both gluon stars and soliton stars is briefly discussed.     

Singular perturbed Markov chains and exact behaviors of simulated annealing processes

We study asymptotic properties of discrete and continuous time generalized simulated annealing processesX(·) by considering a class of singular perturbed Markov chains which are closely related to the large deviation of perturbed diffusion processes. Convergence ofX(t) in probability to a setS ₀ of desired states, e.g., the set of global minima, and in distribution to a probability concentrated onS ₀ are studied. The corresponding two critical constants denoted byd and withd are given explicitly. When the cooling schedule is of the formc/logt, X(t) converges weakly forc>0. Whether the weak limit depends onX(0) or concentrates onS ₀ is determined by the relation betweenc, d, and . Whenc>, the expression for the rate of convergence for each state is also derived.     

Annular Functions and Gap Series

If f(z) = c_kz^nk, where n_k+1/n_k q > 1, and f(z) is analyticin |z| < 1, the f(z) is an annular function if and only ifsup |c_k| = . This answers a question posed by L. R. Sons andD.M. Campbell simplifies the proofs of many known examples ofannular functions. Present address: Dept. of Mathematical Sciences, McMaster University,Hamilton, Ontario, Canada L8S4K1     

Development of β-hydroxyamide/titanium complexes for catalytic enantioselective silylcyanation of aldehydes

A highly enantioselective addition of trimethylsilylcyanide to aldehydes catalyzed by chiral titanium complexes is described. The chiral titanium complexes were prepared in situ from Ti(OⁱPr)₄ and β-hydroxyamide ligands, that could easily be synthesized from ketopinic acid and C₂ symmetrical chiral diamines in a small number of steps.