Molecular structure and puckering potential of gas-phase 1-pyrroline as determined by microwave and infrared spectroscopy

The microwave spectrum of 1-pyrroline has been measured from 8 to 48 GHz. The transitions have been assigned to those of the ground state and the four lowest excited states of the ring-puckering vibration of monomer, which is a five-membered ring molecule with one CN double bond. The trimer, which exists in the liquid phase, has not been detected in the gas phase. The geometrical structure of the monomer has been estimated by an ab initio calculation and the trimer by a molecular mechanics calculation. The former is consistent with the experimental rotational constants. A gas-phase infrared spectrum has also been measured, and the ring-puckering potential has been determined by an analysis of the combination bands of the ring-puckering mode and the ring-stretching modes. The potential is described using a puckering coordinate, z, as V(z) = az² + bz⁴, where $\text{a = ?3.358(16) × 10}{}^4\text{cm}{}^{\mathrm{?1}}\text{A}\text{?}{}^{\mathrm{?2}}$ and $\text{b = 1.345(9) × 10}{}^6\text{cm}{}^{\mathrm{?1}}\text{A}\text{?}{}^{\mathrm{?4}}$; these values are intermediate of the corresponding values for cyclopentene and 1-pyrazoline. The nuclear quadrupole coupling constants, χ_aa = ?4.39(10), χ_bb = 1.04(10), and χ_cc = 3.35(10) MHz, have been determined by an analysis of well-resolved hyperfine splittings. These constants have been reproduced by an ab initio calculation with a 4-31G(N¹) basis set.     

Almost Complex Structures Which Are Compatible with Kähler or Symplectic Structures

In this note we prove that half of all homotopy classes of almost complex structures on M is not compatible with any symplectic structure for a certain class of oriented compact 4-manifolds M. In particular, half of all homotopy classes of almost complex structures on an oriented 4-manifold is not compatible to any Kähler structure.     

Structure of consistent ground state: Re—derivation of RPA vacuum and inclusion of higher RPA effects

Here is presented a method to determine the consistent ground state (CGS ) which satisfies the so-called killer condition for the excitation operator. This method may be called an extended application of the procedure employed by Weiner and Goscinski in deriving the random phase approximation (RPA ) vacuum. The RPA vacuum is derived by solving the recurrence formula of the configuration coefficients of a multiconfigurational state vector. The role of boson approximation to the primitive p-h excitation operator is also investigated and by using the present formalism the cluster-expansion-type CGS is derived as the RPA vacuum under the boson approximation. Inclusion of the effects of a higher RPA in the CGS leads to the simultaneous equations of the configuration coefficients of the CGS . In including the effect of the second RPA , only the symmetry-broken CGS can exist. When the third RPA effect is involved instead of the second RPA , there can be a symmetry-adapted CGS , in which the picture of electron pairs acquired in the standard RPA vacuum is modified. Thus the exact CGS vectors are analytically obtained in the case of simple model systems of two or four electrons.     

Carbon chemical shifts of 1,1-diphenylethylene and α-methylstyrene dimer dianions

The natural abundance C-13 NMR spectra of 1,1-diphenylethylene and α-methylstyrene dimer dianions have been obtained using the proton noise decoupling technique. The extra negative charge distributions in the carbanions have been discussed and compared with those obtained from the proton chemical shifts. The chemical shifts of the two ortho carbons in a phenyl ring are equivalent to each other for the former carbanion but not for the latter.     

Concepts of probabilistic sets

In the field of pattern recognition or decision making theory, the important subjects are as follows: (1) ambiguity of property of objects, (2) variety of character of objects, (3) subjectivity of observers, (4) evolution of knowledge of observers (i.e. learning). Considering these points, the concept of probabilistic set is proposed. It is based on both probability theory and fuzzy concepts. A probabilistic set on a total space is defined by a point wise measurable function from a parameter space (which is a probability space) to a characteristic space (which is a measurable space). It is shown that the family of all probabilistic sets constitutes a complete pseudo-Boolean algebra. Moment analysis is possible by using a probability measure of the parameter space. Other useful concepts are also mentioned such as probabilistic mappings and expected cardinal numbers.     

Hadroproduction of heavy quark flavors in QCD

Within the framework of perturbative QCD, we investigate the hadroproduction of charmed particles via two-gluon as well as quark-pair annihilation. The total production cross section is found to be sensitive to the choice of the scale parameter Q² and in general not free from non-perturbative effects. Charmed-particle production in the high-p_T region is also studied.     

Potential application of poly(N-isopropylacrylamide) gel containing polymeric micelles to drug delivery systems

We have investigated rapidly thermo-responsive NIPA gel containing polymer surfactant PMDP (NIPA-PMDP gel) as a potential drug carrier using (+)-l-ascorbic acid as a model drug. In the NIPA-PMDP gel system micelles of polymer surfactant PMDP are trapped by the entanglement of polymer chains inside the gel networks. Therefore, in principle the gel system tightly stores targeted drug in the micelles and rapidly releases controlled amount of the drug by switching on-off of external stimuli such as temperature or infrared laser beam. In our investigation on release profile, the NIPA-PMDP gel system showed completely different releasing behavior from that of the conventional NIPA gel. The NIPA-PMDP gel released rapidly all loaded (+)-l-ascorbic acid above the phase transition temperature (ca. 34 degrees C), while slowly released the corresponding amount of the drug below the temperature. In contrast, the conventional NIPA gel released more slowly limited amount of the drug above the phase transition temperature while similarly did to the NIPA-PMDP gel below the temperature. The release profile of the NIPA-PMDP gel seems to be governed by only kinetics of volume phase transition of the gel network but not by the hydrophobic domains of the micelles probably because of too hydrophilic nature of (+)-l-ascorbic acid.     

Chemical reactivities of the cation and anion of M@C82 (M = Y, La, and Ce)

The chemical reduction and oxidation of M@C82 (M = Y, La, and Ce) afford the corresponding anion and cation, respectively, which show unique and interesting chemical reactivities. It is found that the successful reversible gain or loss of electrons by ionization is useful for controlling the stability and reactivity of M@C82 toward both nucleophiles and electrophiles.