Preparation and properties of poly(imide-oxoisoindolobenzothiadiazine dioxides)

New thermally stable poly(imide-oxoisoindolobenzothiadiazine dioxides) (PIOD) have been prepared by the three-step cyclopolycondensation reaction of diaminobenzenesulfonamides with aromatic tetracarboxylic dianhydrides. The polymerization proceeded through the formation of poly(amic acid-sulfonamides) (PAAS), followed by cyclodehydration to yield polyimide-sulfonamides (PIS), which were subsequently converted to PIOD at 300°C. PAAS having inherent viscosities in the range of 0.1–0.5 in N-methyl-2-pyrrolidone (NMP) were obtained in approximately quantitative yield. PIOD were insoluble in most organic solvents, whereas PAAS and PIS were soluble in NMP and dimethyl sulfoxide. Differential thermal analysis and thermogravimetric analysis indicated that PIOD began to decompose at 460°C in air. The cyclodehydration of the model compounds was also investigated.     

Atomic one- and two-electron subshell moments in position and momentum spaces

For 357 subshells of the 53 neutral atoms He through Xe in their ground states, the two-electron intracule (relative motion) <u ^k > _nl and extracule (center-of-mass motion) <R ^k > _nl subshell moments in position space are examined as well as their counterparts <v ^k > _nl and <P ^k > _nl in momentum space, where n and l are the principal and azimuthal quantum numbers of the atomic subshell, respectively. It is clarified that between the intracule and extracule moments the “2 ^k -rule” is strictly valid, which means <u ^k > _nl = 2 ^k <R ^k > _nl and <v ^k > _nl = 2 ^k <P ^k > _nl for any nl subshell. Theoretical analysis also proves that for a particular case of k = +2, two relations <u ²> _nl = (N _nl −1)<r ²> _nl and <v ²> _nl = (N _nl −1)<p ²> _nl hold exactly, where N _nl (≥2) is the number of electrons in the subshell nl, and <r ^k > _nl and <p ^k > _nl are the familiar one-electron subshell moments in position and momentum spaces, respectively. The latter equality establishes a new and rigorous relation between the second electron-pair moments in momentum space and the total energy of an atom through the virial theorem. For k=+1, −1, and −2, the numerical Hartree-Fock results for the 357 subshells show that there are approximate but accurate linear relations between <u ^k > _nl and <r ^k > _nl and between <v ^k > _nl and <p ^k > _nl , in which the proportionality constant in each space depends on n,l, and k. Received: 27 April 1998 / Accepted: 29 May 1998 / Published online: 28 August 1998     

Cyclophanes as hosts for aromatic and aliphatic guests

A series of water-soluble cyclophanes, made by connecting two diarylmethane units and two bridging chains via four nitrogens, were found to provide hydrophobic cavities of definite shape and size for forming inclusion complexes with various organic compounds in aqueous solution. Some chemical modifications of these cyclophanes are described.This paper is dedicated to Professor D. J. Cram to celebrate his honor in receiving the 1987 Nobel Prize in Chemistry.     

Kinetic study of the electron-transfer oxidation of the phenolate anion of a vitamin E model by molecular oxygen generating superoxide anion in an aprotic medium

Electron-transfer reduction of molecular oxygen (O2) by the phenolate anion (1-) of a vitamin E model, 2,2,5,7,8-pentamethylchroman-6-ol (1H), occurred to produce superoxide anion, which could be directly detected by a low-temperature EPR measurement. The rate of electron transfer from 1- to O2 was relatively slow, since this process is energetically unfavourable. The one-electron oxidation potential of 1- determined by cyclic voltammetric measurements is sufficiently negative to reduce 2,2-bis(4-tert-octylphenyl)-1-picrylhydrazyl radical (DOPPH*) to the corresponding one-electron reduced anion, DOPPH-, suggesting that 1- can also act as an efficient radical scavenger.     

Ratiometric direct detection of nitric oxide based on a novel signal-switching mechanism

A novel fluorescent probe, which could be the first example of a ratiometric molecular probe for direct monitoring of NO production, has been developed using a 'spin-exchange' mechanism.     

Medium-size Gaussian basis sets for hydrogen through argon

Summary Medium-sized Gaussian basis sets are reoptimized for the ground states of the atoms from hydrogen through argon. The composition of these basis sets is (4s), (5s), and (6s) for H and He, (9s5p) and (12s7p) for the atoms Li to Ne, and (12s8p) and (12s9p) for the atoms Na to Ar. Basis sets for the² P states of Li and Na, and the³ P states of Be and Mg are also constructed since they are useful in molecular calculations. In all cases, our energies are lower than those obtained previously with Gaussian basis sets of the same size.     

Average electron momenta in many-electron atoms

In many-electron atoms, the average electron momentum p represents the mean momentum of a single electron when all the electron motions are averaged. If any two electrons are considered simultaneously, however, the average momentum p splits into two different momenta, low momentum p_< and high momentum p_>. For the 102 atoms He through Lr in their ground states, the momenta p_< and p_> are systematically examined at the Hartree–Fock limit level. It is also shown that the sum p_>+p_< and the difference p_>–p_< of the two momenta constitute upper and lower bounds to the electron-pair relative momentum p₁₂=|p₁–p₂| and to the electron-pair center-of-mass momentum P=|p₁+p₂|/2. The tightness of the bounds is discussed for the 102 atoms.     

Endo- and aminopeptidase activities of rat cathepsin H.

Employing soluble denatured protein substrates and their derivatives, the proteolytic activity of rat cathepsin H was investigated. The enzyme showed aminopeptidase activity which sequentially released amino acid from the N-terminal of the substrate. The aminopeptidase activity did not act on N alpha-acetylated peptides and showed moderate ionic-strength dependence when methionyl-methylcoumarylamide was employed as a substrate. These results indicate that the activity essentially requires an N-terminal free amino group of the substrate and recognizes it electrostatically to some extent. On the other hand, the enzyme was also indicated to exhibit endopeptidase activity by employing appropriate N alpha-acetylated peptide substrates. In contrast to the aminopeptidase activity, the endopeptidase activity showed rather strict specificity, preferring hydrophobic residues at P2 and P3 sites. Because of the broad specificity and high efficiency of the aminopeptidase activity, it was difficult to directly observe endopeptidase activity in the digestion of large peptide substrates with a free alpha-amino terminal. Thus, this is the first experimental evidence that indicates endopeptidase activity by assigning internal peptide bonds cleaved by this activity. From this data, we proposed a model of the binding site of this enzyme.