Yasuyuki Nakamura

Cyclic porphyrin arrays as artificial photosynthetic antenna: synthesis and excitation energy transfer

Covalently linked cyclic porphyrin arrays have been explored in recent years as artificial photosynthetic antenna. In this review we present the fundamental aspects of covalently linked cyclic porphyrin arrays by highlighting recent progress. The major emphasis of this tutorial review lies on the synthetic method, the structure, and the excitation energy transfer (EET) of such arrays. The final cyclization steps were often performed with the aid of templates. Efficient EET along the wheel is observed in these cyclic arrays, but ultrafast EET processes with rates of <1 ps, which rival those in the natural LH2, are rare and have been identified only in cyclic arrays 30-32 composed of directly meso-meso linked porphyrins.

Organotellurium-Mediated Controlled/Living Radical Polymerization Initiated by Direct C−Te Bond Photolysis

UV-vis irradiation of an organotellurium chain transfer agent in the presence of vinyl monomers leads to the formation of highly controlled living polymers with predetermined number average molecular weights and narrow molecular weight distributions.

Role of the left atrium in adaptation of the heart to chronic mitral regurgitation in conscious dogs.

The manner in which the left atrium adapts to chronic mitral regurgitation and the role of the adapted left atrium as a modulator of excessive central blood volume were analyzed in seven conscious dogs, instrumented with high-fidelity pressure transducers and ultrasonic dimension gauges for measurement of left atrial and left ventricular pressure and cavity size. After obtaining data in a control situation, mitral regurgitation was produced by transventricular chordal sectioning. Heart rate was matched by right atrial pacing. In the “early” stage (7–14 days), left ventricular end-diastolic and mean left atrial pressures increased from 6 to 16 mm Hg and from 4 to 12 mm Kg, respectively. Both left ventricular end-diastolic segment length and left atrial diameter prior to atrial contraction increased by 7%. In the “late” stage (20–35 days), despite significant decreases in left ventricular filling pressure (11 mm Hg) and left atrial pressure (8 mm Hg), there was a continuous increase in left ventricular end-diastolic dimension (10%) and atrial end-diastolic diameter (10%). After the onset of mitral regurgitation, the left atrium performed greater work with a more enlarged cavity. Left atrial chamber stiffness was progressively decreased. These changes were associated with progressive increase in the left atrial diameter at zero stress, and there was a significant increase in the diameter of the left atrial myocyte. These results indicate that during chronic mitral regurgitation, the left atrium enlarges in size and mass, with a more potent booster action. The left atrial chamber becomes more compliant. Thus, the enlarged left atrium appears to exert an important compensatory mechanism in the case of excessive central blood volume by buffering pressure rise in the atrium and by providing an adequate ventricular filling volume.

Intramolecular Energy Transfer within Butadiyne-Linked Chlorophyll and Porphyrin Dimer-Faced, Self-Assembled Prisms

The synthesis and photophysical properties of butadiyne-linked chlorophyll and porphyrin dimers in toluene solution and in several self-assembled prismatic structures are described. The butadiyne linkage between the 20-positions of the macrocycles results in new electronic transitions polarized along the long axes of the dimers. These transitions greatly increase the ability of these dimers to absorb the solar spectrum over a broad wavelength range. Femtosecond transient absorption spectroscopy reveals the relative rate of rotation of the macrocycles around the butadiyne bond joining them. Following addition of 3-fold symmetric, metal-coordinating ligands, both macrocyclic dimers self-assemble into prismatic structures in which the dimers comprise the faces of the prisms. These structures were confirmed by small-angle X-ray scattering experiments in solution using a synchrotron source. Photoexcitation of the prismatic assemblies reveals that efficient, through-space energy transfer occurs between the macrocyclic dimers within the prisms. The distance dependence of energy transfer between the faces of the prisms was observed by varying the size of the prismatic assemblies through the use of 3-fold symmetric ligands having arms with different lengths. These results show that self-assembly of discrete macrocyclic prisms provides a useful new strategy for controlling singlet exciton flow in antenna systems for artificial photosynthesis and solar cell applications.

Two-Dimensionally Extended Porphyrin Tapes: Synthesis and Shape-Dependent Two-Photon Absorption Properties

We report the synthesis and characterization of L- and T-shaped porphyrin tapes as extensible structural motifs of two-dimensionally extended porphyrin tapes. The two-photon absorption (TPA) cross-section values (sigma((2))) for L- and T-shaped porphyrin tapes as well as those for linear trimeric and tetrameric porphyrin tapes were measured by an open-aperture Z-scan method at 2300 nm, a wavelength at which the one-photon absorption contribution is either zero or almost negligible. Under these conditions, the sigma((2)) values for the linear porphyrin tape trimer and tetramer were determined to be 18 500 and 41 200 GM, respectively. The sigma((2)) value for the L-shaped trimer was determined to be 8700 GM, which is only half that of the linear trimer, whereas the sigma((2)) value for the T-shaped tetramer was measured to be 35 700 GM. These results clearly indicate the dependence of the TPA cross-section on the molecular shape, which underscores the importance of directionality in the pi-conjugation pathway for the enhancement of TPA cross- section.

Left ventricular regional wall stress in dilated cardiomyopathy

Left ventriculography with simultaneous pressure micromanometry was performed in 11 normal control subjects and 17 patients with dilated cardiomyopathy (DCM). Left ventricular silhouettes in the right anterior oblique projection were divided into eight areas, and regional wall stress was computed by Janzs method in each area excluding the two most basal areas. Wall stress was higher in DCM patients than in control subjects (p less than 0.01). The percent area changes from end diastole to end systole in each area were lower in DCM patients than in control subjects (mean for six areas, 22 +/- 14% versus 54 +/- 9%, respectively, p less than 0.01), but the coefficient of variation for the percent area changes in the six areas of the left ventricle in DCM patients was greater than that in control subjects (32 +/- 17% versus 15 +/- 4%, respectively, p less than 0.01), indicating regional differences in hypokinesis. There was a significant negative correlation between end-systolic regional wall stress and percent area change (r = -0.60 to -0.86, p less than 0.05) in each area. Thus, excessive regional afterload may play an important role in causing regional hypokinesis in DCM.

Photoinduced Switching from Living Radical Polymerization to a Radical Coupling Reaction Mediated by Organotellurium Compounds

An efficient and simple method for the synthesis of symmetric macromolecules by photoinduced switching from radical polymerization to a radical coupling reaction is reported. Structurally well-defined telechelic polyisoprenes and ABA-triblock copolymers were prepared by successive organotellurium-mediated living radical polymerization (TERP) under thermal conditions, followed by a polymer-end radical coupling reaction under photoirradiation.

Importance of left ventricular systolic function in the assessment of left ventricular diastolic function with doppler transmitral flow velocity recording

To study the effect of left ventricular systolic function on the Doppler transmitral flow velocity pattern, Doppler echocardiographic variables were correlated with hemodynamic indexes in 11 control subjects and 58 patients with heart disease. All underwent cardiac catheterization performed with use of a Millar micromanometer. The time constant of left ventricular isovolumetric pressure decrease and left ventricular end-diastolic myocardial stiffness was calculated. The 58 patients were classified into two groups according to ejection fraction: group I (n = 30; ejection fraction greater than 55%) and group II (n = 28; ejection fraction less than 50%). Compared with the control subjects, patients in group I had impairment only of left ventricular relaxation (time constant 47 +/- 9 vs. 38 +/- 3 ms; p less than 0.01), whereas patients in group II had, in addition to impaired left ventricular relaxation (time constant 52 +/- 11 vs. 38 +/- 3 ms; p less than 0.01), increased preload, increased pulmonary capillary pressure (12 +/- 8 vs. 5 +/- 3 mm Hg; p less than 0.01) and increased myocardial stiffness (2,018 +/- 980 vs. 1,050 +/- 218 g/cm2; p less than 0.01). In group I, there was a significant partial correlation coefficient between the time constant and deceleration half-time (r = 0.54). In group II, a strong correlation existed between myocardial stiffness and peak atrial filling velocity (r = -0.71) and between myocardial stiffness and the ratio of peak atrial to peak rapid filling velocity (r = -0.71).(ABSTRACT TRUNCATED AT 250 WORDS)

Synthesis of meso-β doubly linked porphyrin tapesElectronic supplementary information (ESI) available: 1H NMR spectra. See http://www.rsc.org/suppdata/cc/b3/b302032k/

The oxidation of 5,15-bis(3,5-di-tert-butylphenyl) Ni(II)-porphyrin 1b with Sc(OTf)3 and DDQ led to production of meso-beta doubly linked Ni(II)-porphyrin tapes that have large pi-electronic communications over the arrays.

Doppler echocardiographic transmitral peak early velocity does not directly reflect hemodynamic changes in humans : importance of normalization to mitral stroke volume

Doppler echocardiographic transmitral peak early velocity normalized to the time-velocity integral during diastole is equivalent to volumetric peak filling rate normalized to stroke volume. To compare the pathophysiologic validity of normalized and nonnormalized peak early flow velocity, pulsed Doppler echocardiography with simultaneous high fidelity left ventricular pressure measurements was performed in 52 patients with coronary artery disease. Left ventricular loading conditions were changed by intravenous administration of norepinephrine in 15 patients and synthetic atrial natriuretic polypeptide in 15 others. Norepinephrine increased nonnormalized and normalized peak early flow velocities in association with significantly elevated end-diastolic, peak systolic and mitral valve opening pressures and decelerated the time constant of left ventricular isovolumetric pressure decline. Atrial natriuretic polypeptide did not change either nonnormalized or normalized peak early flow velocity, despite significant reductions in end-diastolic, peak systolic and mitral valve opening pressure and an accelerated time constant. Normalized peak early flow velocity showed the highest univariate correlation with long-term change in mitral valve opening pressure (n = 52, r = 0.67, p less than 0.0001). It provided a modest univariate correlation (n = 30, r = 0.74, p less than 0.0001) with immediate change in mitral valve opening pressure during norepinephrine infusion, whereas this correlation was lower (n = 30, r = 0.57, p less than 0.001) during polypeptide infusion. However, multivariate regression analysis relating normalized peak velocity with long- and short-term changes in end-diastolic, peak systolic and mitral valve opening pressures, time constant and constant of left ventricular chamber stiffness improved the correlation coefficients (r = 0.80 to 0.85, all p less than 0.0001). In contrast, neither univariate nor multivariate correlations of nonnormalized velocity with long- and short-term changes in these hemodynamic variables were satisfactory. Thus, nonnormalized peak early flow velocity does not directly reflect underlying hemodynamic changes in humans. Normalization to mitral stroke volume clarifies the dependence of peak early flow velocity on the determinants of early diastolic filling. When left ventricular early diastolic filling is evaluated by Doppler echocardiography, normalized peak early flow velocity should be taken into consideration.