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T K Kim

Publications and source records attributed to T K Kim.

At least 19 recordsLinked to original sources

Impulsive solvent heating probed by picosecond x-ray diffraction.

The time-resolved diffraction signal from a laser-excited solution has three principal components: the solute-only term, the solute-solvent cross term, and the solvent-only term. The last term is very sensitive to the thermodynamic state of the bulk solvent, which may change during a chemical reaction due to energy transfer from light-absorbing solute molecules to the surrounding solvent molecules and the following relaxation to equilibrium with the environment around the scattering volume. The volume expansion coefficient alpha for a liquid is typically approximately 1 x 10(-3) K(-1), which is about 1000 times greater than for a solid. Hence solvent scattering is a very sensitive on-line thermometer. The decomposition of the scattered x-ray signal has so far been aided by molecular dynamics (MD) simulations, a method capable of simulating the solvent response as well as the solute term and solute/solvent cross terms for the data analysis. Here we present an experimental procedure, applicable to most hydrogen containing solvents, that directly measures the solvent response to a transient temperature rise. The overtone modes of OH stretching and CH3 asymmetric stretching in liquid methanol were excited by near-infrared femtosecond laser pulses at 1.5 and 1.7 microm and the ensuing hydrodynamics, induced by the transfer of heat from a subset of excited CH3OH* to the bulk and the subsequent thermal expansion, were probed by 100 ps x-ray pulses from a synchrotron. The time-resolved data allowed us to extract two key differentials: the change in the solvent diffraction from a temperature change at constant density, seen at a very short time delay approximately 100 ps, and a term from a change in density at constant temperature. The latter term becomes relevant at later times approximately 1 mus when the bulk of liquid expands to accommodate its new temperature at ambient pressure. These two terms are the principal building blocks in the hydrodynamic equation of state, and they are needed in a self-consistent reconstruction of the solvent response during a chemical reaction. We compare the experimental solvent terms with those from MD simulations. The use of experimentally determined solvent differentials greatly improved the quality of global fits when applied to the time-resolved data for C2H4I2 dissolved in methanol.

Chemistry, Physical↗

Autoimmune pancreatitis: radiologic findings in 20 patients.

BACKGROUND: Autoimmune pancreatitis is a new clinical entity that is characterized by peculiar histopathologic and laboratory findings and by a dramatic clinical response to corticosteroid therapy. We evaluated the radiologic findings of autoimmune pancreatitis. METHODS: Computed tomographic, magnetic resonance imaging, endoscopic retrograde cholangiopancreatographic, and ultrasonographic findings of 20 patients with autoimmune pancreatitis in our hospital between November 2000 and December 2003 were retrospectively reviewed regarding changes and ancillary findings in the pancreatic parenchyma, the main pancreatic duct, peripancreatic vessels, and distal common bile duct. In addition, follow-up images were reviewed for changes in any abnormality seen on the initial examinations. RESULTS: Pancreatic parenchymal enlargement was invariably seen that was diffuse (n = 19) or focal (n = 1), with homogeneous contrast enhancement on computed tomography (n = 20) and magnetic resonance imaging (n = 15). Capsule-like rim enhancement was seen in six patients. There was focal (n = 18) or diffuse (n = 2) narrowing of the main pancreatic duct and it was usually multifocal (n = 17) in the former. Narrowing of the peripancreatic veins was seen in 14 patients. There was tapered (n = 15) or abrupt (n = 3) narrowing of the distal common bile duct in 18 patients, with contrast enhancement of the narrowed segment in eight. Invariably, changes in the pancreatic parenchyma, main pancreatic duct, peripancreatic vessels, and common bile duct were normalized on follow-up studies after steroid therapy. CONCLUSION: In this series, common radiologic findings of autoimmune pancreatitis were (a) diffuse pancreas enlargement, (b) multifocal narrowing of the main pancreatic duct, (c) narrowing of peripancreatic veins, and (d) tapered narrowing of the distal common bile duct with frequent contrast enhancement. These findings were usually reversible with steroid therapy.

Adult↗

Ultrafast x-ray diffraction of transient molecular structures in solution.

We report direct structural evidence of the bridged radical (CH2ICH2.) in a polar solution, obtained using time-resolved liquid-phase x-ray diffraction. This transient intermediate has long been hypothesized to explain stereo-chemical control in many association and/or dissociation reactions involving haloalkanes. Ultrashort optical pulses were used to dissociate an iodine atom from the haloethane molecule (C2H4I2) dissolved in methanol, and the diffraction of picosecond x-ray pulses from a synchrotron supports the following structural dynamics, with approximately 0.01 angstrom spatial resolution and approximately 100 picosecond time resolution: The loss of one iodine atom from C2H4I2 leads to the C-I-C triangular geometry of CH2ICH2.. This transient C2H4I then binds to an iodine atom to form a new species, the C2H4I-I isomer, which eventually decays into C2H4 + I2. Solvent dynamics were also extracted from the data, revealing a change in the solvent cage geometry, heating, and thermal expansion.

Computer Simulation↗

Cerebral fat embolism: diffusion-weighted magnetic resonance imaging findings.

PURPOSE: To demonstrate the diffusion-weighted (DWI) magnetic resonance imaging (MRI) findings, and the follow-up MRI findings, of cerebral fat embolism in the acute stage. MATERIAL AND METHODS: The initial DWI and clinical findings of six patients with cerebral fat embolism were retrospectively evaluated. The finding of DWI with a b-value of 1000 s/mm2 (b=1000) was compared with that of DWI with a b-value of 0 s/mm2 (b=0). In three patients who underwent follow-up MRI, the interval change of the lesion on T2-weighted images was investigated. RESULTS: The characteristic DWI finding of cerebral fat embolism in the acute stage was multiple, hyperintense, dot-like lesions disseminated in the brain. These lesions were distributed dominantly in the bilateral border-zone areas. Some lesions had an ancillary location including the cortex, deep white matter, basal ganglia, and cerebellum. The lesions were more intense and numerous in DWI (b=1000) than in DWI (b=0). The findings on the follow-up T2-weighted images were multiple confluent hyperintense lesions in the white matter with progression since the initial MRI. CONCLUSION: DWI could be a sensitive tool for detecting cerebral fat embolism in the acute phase. It is recommended that DWI be included in the initial evaluation of cerebral fat embolism with MRI.

Adult↗

Correlation of the condition of the patellar articular cartilage and patellofemoral symptoms and function in osteoarthritic patients undergoing total knee arthroplasty.

We sought to determine the degree of correlation between the condition of the patellar articular cartilage and patellofemoral symptoms and function in osteoarthritic patients undergoing total knee arthroplasty. The depth of the osteoarthritic lesion, as graded by the Outerbridge classification and its size and location were assessed to determine the condition of the patellar cartilage in 80 consecutive osteoarthritic knees undergoing total knee arthroplasty. The association between the condition of the cartilage and patellofemoral symptoms and function was investigated by correlation analysis. The depth and size of the lesion had a significant but weak correlation with anterior knee pain (r = -0.300 and -0.289; p = 0.007 and 0.009, respectively), whereas location had no significant association (p > 0.05). None had a significant association with patellofemoral functional parameters (chair-rising, stair-climbing, and quadriceps power) (p > 0.05). Our study indicates that patellofemoral symptoms and function are not completely determined by the condition of the cartilage. Caution should be taken when the symptoms and functional limitations are attributed to a lesion in the patellofemoral joint in making a decision regarding patellar resurfacing in total knee arthroplasty.

Aged↗

Oxetane modified, conformationally constrained, antisense oligodeoxyribonucleotides function efficiently as gene silencing molecules.

Incorporation of nucleosides with novel base-constraining oxetane (OXE) modifications [oxetane, 1-(1',3'-O-anhydro-beta-d-psicofuranosyl nucleosides)] into antisense (AS) oligodeoxyribonucleotides (ODNs) should greatly improve the gene silencing efficiency of these molecules. This is because OXE modified bases provide nuclease protection to the natural backbone ODNs, can impart T(m) values similar to those predicted for RNA-RNA hybrids, and not only permit but also accelerate RNase H mediated catalytic activity. We tested this assumption in living cells by directly comparing the ability of OXE and phosphorothioate (PS) ODNs to target c-myb gene expression. The ODNs were targeted to two different sites within the c-myb mRNA. One site was chosen arbitrarily. The other was a 'rational' choice based on predicted hybridization accessibility after physical mapping with self-quenching reporter molecules (SQRM). The Myb mRNA and protein levels were equally diminished by OXE and PS ODNs, but the latter were delivered to cells with approximately six times greater efficiency, suggesting that OXE modified ODNs were more potent on a molar basis. The rationally targeted molecules demonstrated greater silencing efficiency than those directed to an arbitrarily chosen mRNA sequence. We conclude that rationally targeted, OXE modified ODNs, can function efficiently as gene silencing agents, and hypothesize that they will prove useful for therapeutic purposes.

Cell Division↗

Circular dichroism in angle-resolved photoemission spectra of under- and overdoped Pb-Bi2212.

We use angle-resolved photoemission with circularly polarized excitation to demonstrate that in the 5 x 1 superstructure-free (Pb,Bi)(2)Sr(2)CaCu(2)O(8+delta) (Pb-Bi2212) material there are no signatures of time-reversal symmetry breaking in the sense of the criteria developed earlier [Nature (London) 416, 610 (2002)]]. The dichroic signal retains reflection antisymmetry as a function of temperature and doping and in all mirror planes, precisely defined by the experimental dispersion at low energies. The obtained results demonstrate that the signatures of time-reversal symmetry violation in pristine Bi2212, as determined by angle-resolved photoemission spectroscopy, are not a universal feature of all cuprate superconductors.

Journal Article↗

Accuracy of magnetic resonance cholangiopancreatography for locating hepatolithiasis and detecting accompanying biliary strictures.

BACKGROUND AND STUDY AIMS: Magnetic resonance cholangiopancreatography (MRCP) is rapidly replacing diagnostic endoscopic retrograde cholangiopancreatography (ERCP) in various pancreaticobiliary diseases. This study was designed to evaluate the accuracy of MRCP in detection of hepatolithiasis and accompanying biliary strictures. PATIENTS AND METHODS: A prospective study over 2 years was conducted in 66 patients with primary intrahepatic stones. All patients with hepatolithiasis underwent percutaneous transhepatic cholangioscopy (PTC) within 2 weeks of the MRCP examination. The MRCP findings were compared with those of PTC as the reference standard for assessing the location of intrahepatic stones and the presence or absence of accompanying biliary strictures. RESULTS: The sensitivity, specificity, and accuracy of MRCP for detecting and locating intrahepatic stones were 97 %, 99 %, and 98 %, respectively. The sensitivity, specificity, and accuracy of MRCP for detecting and locating intrahepatic bile duct strictures were 93 %, 97 %, and 97 %, respectively. During PTC, six of the 66 patients (9 %) were found on histology to have intraductal cholangiocarcinoma in stone-bearing ducts, which had not been suspected on MRCP. CONCLUSIONS: In this study, MRCP allowed intrahepatic stones and accompanying biliary strictures to be located accurately. MRCP may therefore be able to replace diagnostic ERCP in patients with primary intrahepatic stones. However, MRCP had a limited ability to reveal concurrent intraductal cholangiocarcinoma associated with hepatolithiasis.

Bile Ducts, Intrahepatic↗

Fluorescence in situ hybridization analysis of nitrifiers in piggery wastewater treatment reactors.

Fluorescence in situ hybridization (FISH) was performed to analyze the nitrifying microbial communities in an activated sludge reactor (ASR) and a fixed biofilm reactor (FBR) for piggery wastewater treatment. Heterotrophic oxidation and nitrification were occurring simultaneously in the ASR and the COD and nitrification efficiencies depend on the loads. In the FBR nitrification efficiency also depends on ammonium load to the reactor and nitrite was accumulated when free ammonia concentration was higher than 0.2 mg NH3-N/L. FISH analysis showed that ammonia-oxidizing bacteria (NSO1225) and denitrifying bacteria (RRP1088) were less abundant than other bacteria (EUB338) in ASR. Further analysis on nitrifying bacteria in the FBR showed that Nitrosomonas species (NSM156) and Nitrospira species (NSR1156) were the dominant ammonia-oxidizing and nitrite-oxidizing bacteria, respectively, in the piggery wastewater nitrification system.

Animals↗

Doping dependence of the mass enhancement in (Pb,Bi)2Sr2CaCu2O8 at the antinodal point in the superconducting and normal states.

Angle-resolved photoemission spectroscopy is used to study the mass renormalization of the charge carriers in the high-T(c) superconductor (Pb,Bi)2Sr2CaCu2O8 in the vicinity of the (pi,0) point in the superconducting and the normal states. Using matrix element effects at different photon energies and due to a high momentum and energy resolution the bonding and the antibonding bands could be separated in the whole dopant range. A huge coupling to a bosonic collective mode is observed below T(c) for both bands, in particular, for the underdoped case. Above T(c), a weaker coupling to a continuous spectrum of modes is detected.

Journal Article↗

Anomalous enhancement of the coupling to the magnetic resonance mode in underdoped Pb-Bi2212.

High-resolution angle-resolved photoemission with variable excitation energies is used to disentangle bilayer splitting effects and intrinsic (self-energy) effects in the electronic spectral function near the (pi,0) point of differently doped (Pb,Bi)(2)Sr(2)CaCu(2)O(8+delta). In contrast to overdoped samples, where intrinsic effects at the (pi,0) point are virtually absent, we find in underdoped samples intrinsic effects in the superconducting-state (pi,0) spectra of the antibonding band. This intrinsic effect is present only below the critical temperature and weakens considerably with doping. Our results give strong support for models which involve a strong coupling of electronic excitations with the resonance mode seen in inelastic neutron scattering experiments.

Journal Article↗

[Results of repair of SLAP lesion].

The surgical repair of SLAP lesions has become increasingly more common as the techniques and instrumentation have improved. However, there are few studies examining the results of repair of SLAP lesions. The goals of this paper are to summarize the recommended treatment for SLAP lesions and to report upon the studies available to date which report the results of SLAP repair.

Arthroscopy↗

Diffusion-limited extraction of organic ions by a track-membrane interfaced vacuum inlet.

Glycerol-wetted track membranes (polyethylene terephthalate) were used to interface a low-vacuum facility (approximately (10(-3) Torr) to an ambient pressure liquid analyte. High-field charge extraction conditions were routinely maintained between the liquid samples and a grid collector. The latter was positioned just near to the vacuum-facing side of such membranes. Upon establishing a steady-state charge extraction regime, the collector currents were monitored and recorded at various solute concentration levels. The collector currents, which depend on solute concentration, were found to agree with recent theoretical treatments of such processes. Both positively- and negatively-charged species from organic solutions were routinely extracted. Ion injection for the low- and the high-mobility species has favored the diffusion-limited and the evaporation-limited schemes, respectively. Variable concentrations of 1-pyrenoyl-methylpyridinium bromide as well as naphthylacetic and anthracenecarboxylic acids in glycerol were used.

Journal Article↗

Origin of the peak-dip-hump line shape in the superconducting-state (pi,0) photoemission spectra of Bi2Sr2CaCu2O8.

From detailed high-resolution measurements of the photon energy dependence of the (pi,0) superconducting-state photoemission spectrum of the bilayer Bi high-temperature superconductors, we show that the famous peak-dip-hump line shape is dominated by a superposition of spectral features originating from different electronic states which reside at different binding energies, but are each describable by essentially identical single-particle spectral functions. The previously identified bilayer-split CuO2 bands are the culprit: with the "superconducting" peak being due to the antibonding band, while the hump is mainly formed by its bonding bilayer-split counterpart.

Journal Article↗

Accuracy of CT in local staging of gallbladder carcinoma.

PURPOSE: To evaluate the accuracy of CT for staging gallbladder cancers, especially the T-factor of the TNM staging system. MATERIAL AND METHODS: CT investigations of 100 patients with surgically proven gallbladder cancers were retrospectively analyzed. Dynamic helical CT was performed in 16 patients and conventional CT in the remaining 84. On CT, three radiologists attempted tumor staging for these patients; the majority opinion was used for final decision. According to CT protocols (dynamic helical CT vs. conventional CT) and each tumor type (thickened wall/intraluminal mass/massive), the accuracy of CT staging was compared. The CT staging was correlated with the surgico-pathologic results. RESULTS: The overall accuracy of CT for staging gallbladder cancers was 71%; it was 79% for T1 and T2 tumors, 46% for T3 tumors, and 73% for T4 tumors. For all three readers, the poorest accuracy was obtained in T3 tumors. No statistically significant difference was noted in the accuracy between the groups undergoing conventional CT and dynamic helical CT. A statistically significant difference was noted in the accuracy for staging thickened wall and intraluminal mass types of tumors (p<0.05); the highest accuracy was obtained in the intraluminal mass type (89%) and the massive type (83%), while it was 54% in the thickened wall type. CONCLUSION: The accuracy of tumor staging with CT in patients with gallbladder cancer depends on the morphological type of tumor. The poorest result is obtained in the thickened wall type.

Adult↗

Synthesis and biological evaluation of novel A-ring modified hexacyclic camptothecin analogues.

Eleven A-ring modified hexacyclic analogues of camptothecin (CPT) containing a 1,4-oxazine ring were synthesized from 10-hydroxycamptothecin (11a) and 7-ethyl-10-hydroxycamptothecin (3) (SN-38) in four to five steps and were subjected to the biological tests such as cytotoxicity, topoisomerase I (Topo I) inhibitory activity, acetylcholinesterase (AChE) inhibition, and stability in human plasma. Four compounds 15a, 15b, 16a, and 16c were about 2-fold more potent than topotecan and as potent as CPT toward human cancer cell lines A549, H128, WiDr, MKN45, SK-OV-3, and SK-BR-3 in vitro, even though the most active compound 15b was slightly less potent than SN-38. The potency of Topo I inhibition of these compounds showed relatively good correlation with their cytotoxicity. Most of the compounds exhibited AChE inhibitory activity weaker (9 +/- 2 to 20 +/- 3%) than CPT (23 +/- 5%) or topotecan (20 +/- 4%) and similar to SN-38 (13 +/- 2%), indicating that they might have little effect on causing early diarrhea. The stability of lactone forms of these compounds in human plasma seemed to be much higher than that of CPT and similar to that of topotecan but lower than that of SN-38. Among the new hexacyclic CPT analogues, compound 15b showed higher antitumor activity against human tumor xenograft, WiDr, in nude mice compared to that of SN-38. The most promising compound 15b has been selected for further development.

Animals↗

Synthesis and phosphodiesterase 5 inhibitory activity of novel phenyl ring modified sildenafil analogues.

New sildenafil analogues containing an ether ring fused into the phenyl moiety, 6a--d and 7a--d, were efficiently synthesized from the readily available starting materials, 1a--d and 2, in five steps. Ab initio calculations indicated that introduction of a cyclic ether to the phenyl group might enhance the co-planarity of the molecule. The torsional angles were calculated to be 2--3 degrees for the 5-membered cyclic ether derivatives, 6a, 6c, 7a, and 7c, and 12--16 degrees for the 6-membered ones, 6b, 6d, 7b, and 7d. On the other hand, sildenafil showed the least co-planarity with the torsional angle of 23 degrees compared with the target compounds, 6a--d and 7a--d. In the enzyme assay, however, the in vitro PDE 5 inhibitory activity was found out to be inversely related to the degree of co-planarity. In other words, the least planar sildenafil showed the highest activity, and the most planar 5-membered cyclic ether derivatives were least active by 100--200-fold compared with sildenafil. Our study clearly demonstrated that the open chain 2'-alkoxy group of the phenyl ring, although less effective for inducing the co-planarity, seemed to act as a much better lipophilic requirement than the cyclic alkoxy moiety.

3',5'-Cyclic-GMP Phosphodiesterases↗

Synthesis and phosphodiesterase 5 inhibitory activity of new 5-phenyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one derivatives containing an N-acylamido group phenyl ring.

New sildenafil analogues with an N-acylamido group at the 5'-position of the phenyl ring, 6a--e, were prepared from the readily available starting compound 2 in four straightforward steps. Enzyme assays demonstrated that all the target compounds 6a-e showed higher PDE5 inhibitory activities than sildenafil. It was observed that the PDE5 inhibitory activity was enhanced as the chain length of R group increased, but introduction of the branched alkyl groups such as isopropyl (6d) and cyclohexyl (6e) resulted in the drop of potency compared with 6c. In particular the N-butyrylamido derivative 6c exhibited the highest PDE5 inhibitory activity, and was about 6-fold more potent than sildenafil. However, all the compounds exhibited somewhat weak selectivity (1--3-fold) over PDE6, indicating that the compounds 6a--e have intrinsically lower selectivity than sildenafil.

Phosphodiesterase Inhibitors↗