Biomedical subjects
Publications and source records attributed to Dongho Kim.
A dodecameric porphyrin wheel was prepared by Ag(I)-promoted intramolecular coupling of a linear porphyrin dodecamer and was observed by scanning tunneling microscopy (STM). Efficient energy hopping along the array was revealed by femtosecond transient anisotropy measurements.
Excitation-energy transport (EET) phenomena in meso-meso directly linked Zn(II)porphyrin arrays in the singlet and triplet excited states were investigated with a view to electronic coupling strength and coherence length by steady-state and time-resolved spectroscopic measurements. To investigate energy transfer in the triplet states, we modified the Zn(II)porphyrin arrays with bromo substituents at both ends. The coupling strength of the Soret bands of the arrays was estimated to be about 2200 cm-1, and that of the Q bands is about 570 cm-1. The coherence length in the S1 state of the Zn(II)porphyrin arrays was determined to be 4-5 porphyrin units, which is comparable to that of the well-ordered two-dimensional circular structure B850 in the peripheral light-harvesting antenna (LH2) in photosynthetic purple bacteria. This indicates that the Zn(II)porphyrin arrays are well suited for mimicking natural light-harvesting antenna complexes. On the other hand, the rate of energy transfer in the triplet state is estimated to be on the order of 100 microseconds-1, and the very weak coupling between the triplet states (ca. 0.003 cm-1), indicates that the triplet excitation energy is essentially localized on a single porphyrin moiety.
On the basis of the Ag(I)-promoted coupling reaction of Zn(II) 5,15-diaryl porphyrin that gave a meso-meso-linked diporphyrin, we developed a variety of directly linked porphyrin arrays including linear, windmill, gridlike, cyclic, and box architectures. Electronic and excitonic interactions are thus fine tuned by placing porphyrin chromophores in well-defined arrangements. Photoexcited-state dynamics of these porphyrin arrays, as revealed by various ultrafast laser-based measurements, are pertinent to photosynthetic light-harvesting antenna in terms of very efficient excitation energy hopping over many porphyrins and lack of a defect that acts as energy sink. The conformational flexibility of a meso-meso-linked diporphyrin has also been used for the fine tuning of excitonic interactions as demonstrated by strapped meso-meso diporphyrins and reversible switching of energy transfer in a triporphyrin. Triply linked porphyrin arrays have also been explored, which exhibit an exceptionally low HOMO-LUMO gap as a result of a fully conjugated pi electronic system over a coplanar platform.
Femtosecond time-resolved transient absorption studies have been performed to investigate the photoinduced energy and electron-transfer processes in Zn(II)porphyrin-Zn(II)chlorin-fullerene triad in which energy and oxidation potential gradients are directed along the donor-acceptor-linked arrays. Fast energy transfer (approximately 450 fs) from photoexcited Zn(II)porphyrin to Zn(II)chlorin was observed upon selective photoexcitation of Zn(II)porphyrin unit in the triad. In a nonpolar solvent such as toluene, the energy transfer from the excited singlet state of Zn(II)chlorin to fullerene occurs and is followed by the formation of an intermediate state with a time constant of nanoseconds, which was attributed to the intramolecular exciplex between Zn(II)chlorin and fullerene. In benzonitrile, on the other hand, the photoexcitation of the triad results in the fast electron transfer (< 1 ps) from photoexcited Zn(II)chlorin to fullerene. The generated charge-separated species recombine with a time constant of approximately 12 ps. The relatively fast charge separation and charge recombination rates imply that the strong electronic coupling between Zn(II)chlorin and fullerene moieties is probably induced by the folded conformation between Zn(II)chlorin and fullerene moieties which enhances direct through-space interaction between the approximately contacted pi systems.
Electrical conduction measurements were made on two extreme types of directly linked porphyrin arrays by using nanoelectrodes. One type is the directly linked Zn(II)porphyrin arrays, consisting of 48 Zn(II)porphyrin moieties (Z48), and the other type is the completely flat, tape-shaped Zn(II)porphyrin arrays, consisting of eight Zn(II)porphyrin units (T8). The I-V curve for Z48 exhibits the diode-like behavior and the hysteresis depending on the voltage sweep direction presumably due to the conformational heterogeneity arising from the dihedral angle distribution in Z48. On the other hand, the I-V curve for T8 is nearly symmetric without any hysteresis, leading to the higher conductivity and the smaller band gap. These results illustrate that the stronger pi-electron conjugation in T8, as compared with that of Z48, results in better electrical conduction.
Electronically coupled porphyrin arrays are suitable for artificial light harvesting antenna in light of a large absorption cross-section and fast excitation energy transfer (EET). Along this line, an artificial energy transfer model system has been synthesized, comprising of an energy donating meso-meso linked Zn(II) porphyrin array and an energy accepting 5,15-bisphenylethynylated Zn(II) porphyrin linked via a 1,4-phenylene spacer. This includes an increasing number of porphyrins in the meso-meso linked Zn(II) porphyrin array, 1, 2, 3, 6, 12, and 24 (Z1A, Z2A, Z3A, Z6A, Z12A, and Z24A). The intramolecular singlet-singlet EET processes have been examined by means of the steady-state and time-resolved spectroscopic techniques. The steady-state fluorescence comes only from the acceptor moiety in Z1A-Z12A, indicating nearly the quantitative EET. In Z24A that has a molecular length of ca. 217 A, the fluorescence comes largely from the acceptor moiety but partly from the long donor array, indicating that the intramolecular EET is not quantitative. The transient absorption spectroscopy has provided the EET rates in real time scale: (2.5 ps)(-1) for Z1A, (3.3 ps)(-1) for Z2A, (5.5 ps)(-1) for Z3A, (21 ps)(-1) for Z6A, (63 ps)(-1) for Z12A, and (108 ps)(-1) for Z24A. These results have been well explained by a revised Förster equation (Sumi formula), which takes into account an exciton extending coherently over several porphyrin pigments in the donor array, whose length is not much shorter than the average donor-acceptor distance. Advantages of such strongly coupled porphyrin arrays in light harvesting and transmission are emphasized in terms of fast EET and a large absorption cross-section for incident light.
A systematic series of ITO electrodes modified chemically with self-assembled monolayers (SAMs) of porphyrins and porphyrin-fullerene dyads have been designed to provide valuable insight into the development of artificial photosynthetic devices. First the ITO and gold electrodes modified chemically with SAMs of porphyrins with a spacer of the same number of atoms were prepared to compare the effects of energy transfer (EN) quenching of the porphyrin excited singlet states by the two electrodes. Less EN quenching was observed on the ITO electrode as compared to the EN quenching on the corresponding gold electrode, leading to remarkable enhancement of the photocurrent generation (ca. 280 times) in the porphyrin SAMs on the ITO electrode in the presence of the triethanolamine (TEA) used as a sacrificial electron donor. The porphyrin (H(2)P) was then linked with C(60) which can act as an electron acceptor to construct H(2)P-C(60) SAMs on the ITO surface in the presence of hexyl viologen (HV(2+)) used as an electron carrier in a three electrode system, denoted as ITO/H(2)P-C(60)/HV(2+)/Pt. The quantum yield of the photocurrent generation of the ITO/H(2)P-C(60)/HV(2+)/Pt system (6.4%) is 30 times larger than that of the corresponding system without C(60): ITO/H(2)P-ref/HV(2+)/Pt (0.21%). Such enhancement of photocurrent generation in the porphyrin-fullerene dyad system is ascribed to an efficient photoinduced ET from the porphyrin singlet excited state to the C(60) moiety as indicated by the fluorescence lifetime measurements and also by time-resolved transient absorption studies on the ITO systems. The surface structures of H(2)P and H(2)P-C(60) SAMs on ITO (H(2)P/ITO and H(2)P-C(60)/ITO) have been observed successfully in molecular resolution with atomic force microscopy for the first time.
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A series of zinc(II) porphyrin-imide dyads (ZP-Im), in which an electron donating ZP moiety is directly connected to an electron accepting imide moiety in the meso position, have been prepared for the examination of energy gap dependence of intramolecular electron transfer reactions with large electronic coupling. The nearly perpendicular conformation of the imide moiety towards the porphyrin plane has been revealed by Xray crystal structures. The energy gap for charge separation, 1ZP* - Im --> ZP+ - Im-, is varied by changing the electron accepting imide moiety to cover a range of about 0.8 eV in DMF. Definitive evidence for electron transfer has been obtained in three solvents (toluene, THF, and DMF) through picosecond-femtosecond transient absorption studies, which have allowed us to determine the rates of photoinduced charge separation, 1ZP* - Im --> ZP+ - Im-, and subsequent thermal charge recombination ZP+ - Im- --> ZP - Im. The free-energy gap dependence (energy gap law) has been probed from the normal to the nearly top region for the charge separation rate alone, and only the inverted region for the charge recombination rate. Although both of the energy gap dependencies can be approximately reproduced by means of the simplified semiclassical equation, when we take into consideration the effect of the high frequency vibrations replaced by one mode of averaged frequency, many features, including the effects of solvent polarity and the electron tunneling matrix element on the energy gap law, differ considerably from those of the previously studied porphyrin-quinone systems, which have weaker interchromophore electronic interactions.
Femtosecond fluorescence anisotropy measurements for a variety of cyclic porphyrin arrays such as Zn(II)porphyrin m-trimer and hexamer are reported along with o-dimer and monomer as reference molecules. In the porphyrin arrays, a pair of porphyrin moieties are joined together via triphenyl linkage to ensure cyclic and rigid structures. Anisotropy decay times of the porphyrin arrays can be well described by the Förster incoherent excitation hopping process between the porphyrin units. Exciton coupling strengths of 74 and 264 cm(-1) for the m-trimer and hexamer estimated from the observed excitation energy hopping rates are close to those of B800 and B850, respectively, in the LH2 bacterial light-harvesting antenna. Thus, these cyclic porphyrin array systems have proven to be useful in understanding energy migration processes in a relatively weak interaction regime in light of the similarity in overall structures and constituent chromophores to natural light-harvesting arrays.
A series of meso-meso-linked diporphyrins S(n) strapped with a dioxymethylene group of various length were synthesized by intramolecular Ag(I)-promoted coupling of dioxymethylene-bridged diporphyrins B(n), for n=10, 8, 6, 5, 4, 3, 2, and 1. Shortening of the strap length causes a gradual decrease in the dihedral angle between the porphyrins and increasing distortion of porphyrin ring, as suggested by MM2 calculations and (1)H NMR studies. This trend has been also suggested by X-ray crystallographic studies on the corresponding Cu(II) complexes of nonstrapped diporphyrin 2 Cu, and strapped diporphyrins S(8)Cu, S(4)Cu, and S(2)Cu. The absorption spectrum of relatively unconstrained diporphyrins S(10) strapped with a long chain exhibits split Soret bands at 414 and 447 nm and weak Q(0,0)- and prominent Q(1,0)-bands, both of which are similar to those of nonstrapped diporphyrin 2. Shortening of the strap length causes systematic changes in the absorption spectra, in which the intensities of the split Soret bands decrease, the absorption bands at about 400 nm and > 460 nm increase in intensity, and a prominent one-band feature of a Q-band is changed to a distinct two-band feature with concurrent progressive red-shifts of the lowest Q(0,0)-band. The fluorescence spectra also exhibit systematic changes, roughly reflecting the changes of the absorption spectra. The strapped diporphyrins S(n) are all chiral and have been separated into enantiomers over a chiral column. The CD spectra of the optically active S(n) display two Cotton effects at 430-450 and at about 400 nm with the opposite signs. The latter effect can be explained in terms of oblique arrangement of m( perpendicular 1) and m( perpendicular 2) dipole moments, while the former effect cannot be accounted for within a framework of the excition coupling theory. The resonance Raman (RR) spectra taken for excitation at 457.9 nm are variable among S(n), while the RR spectra taken for excitation at 488.0 nm are constant throughout the S(n) series. These photophysical properties can be explained in terms of INDO/S-SCI calculations, which have revealed charge transfer (CT) transitions accidentally located close in energy to the excitonic Soret transitions. This feature arises from a close proximity of the two porphyrins in meso-meso-linked diporphyrins. In addition to the gradual red-shift of the exciton split Soret band, the calculations predict that the high-energy absorption band at about 400 nm, the lower energy Cotton effect, and the RR spectra taken for excitation at 457.9 nm are due to the CT states which are intensified upon a decrease in the dihedral angle.
The novel fused Zn(II)porphyrin arrays (Tn, porphyrin tapes) in which the porphyrin macrocycles are triply linked at meso-meso, beta-beta, beta-beta positions have been investigated by steady-state and time-resolved spectroscopic measurements along with theoretical MO calculations. The absorption spectra of the porphyrin tapes show a systematic downshift to the IR region as the number of porphyrin pigments increases in the arrays. The fused porphyrin arrays exhibit a rapid formation of the lowest excited states (for T2, approximately 500 fs) via fast internal conversion processes upon photoexcitation at 400 nm (Soret bands), which is much faster than the internal conversion process of approximately 1.2 ps observed for a monomeric Zn(II)porphyrin. The relaxation dynamics of the lowest excited states of the porphyrin tapes were accelerated from approximately 4.5 ps for the T2 dimer to approximately 0.3 ps for the T6 hexamer as the number of porphyrin units increases, being explained well by the energy gap law. The overall photophysical properties of the porphyrin tapes were observed to be in a sharp contrast to those of the orthogonal porphyrin arrays. The PPP-SCI calculated charge-transfer probability indicates that the lowest excited state of the porphyrin tapes (Tn) resembles a Wannier-type exciton closely, whereas the lowest excited state of the directly linked porphyrin arrays can be considered as a Frenkel-type exciton. Conclusively, these unique photophysical properties of the porphyrin tapes have aroused much interest in the fundamental photophysics of large flat organic molecules as well as in the possible applications as electric wires, IR sensors, and nonlinear optical materials.
Cryotherapy is a treatment modality that uses a technique to selectively freeze tissue and thereby cause controlled tissue destruction. The procedure involves placement of multiple small diameter probes through the perineum into the prostate tissue at selected spatial intervals. Transrectal ultrasound is used to properly position the cylindrical probes before activation of the liquid Argon cooling element, which lowers the tissue temperature below -40 degrees Centigrade. Tissue effect is monitored by transrectal ultrasound changes as well as thermocouples placed in the tissue. The computer-based cryotherapy simulation system mimics the major surgical steps involved in the procedure. The simulated real-time ultrasound display is generated from 3-D ultrasound datasets where the interaction of the ultrasound with the instruments as well as the frozen tissue is simulated by image processing. The thermal and mechanical simulations of the tissue are done using a modified finite-difference/finite-element method optimized for real-time performance. The simulator developed is a part of a comprehensive training program, including a computer-based learning system and hands-on training program with a proctor, designed to familiarize the physician with the technique and equipment involved.