Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study.

We establish a reliable quantum-mechanical approach to evaluate the vibrational properties of donor-acceptor molecular crystals. The anthracene-PMDA (PMDA = pyromellitic dianhydride) crystal, where anthracene acts as the electron donor and PMDA as the electron acceptor, is taken as a representative system for which experimental non-resonance Raman spectra are also reported. We first investigate the impact that the amount of nonlocal Hartree-Fock exchange (HFE) included in a hybrid density functional has on the geometry, normal vibrational modes, electronic coupling, and electron-vibrational (phonon) couplings. The comparison between experimental and theoretical Raman spectra indicates that the results based on the αPBE functional with 25%-35% HFE are in better agreement with the experimental results compared to those obtained with the pure PBE functional. Then, taking αPBE with 25% HFE, we assign the vibrational modes and examine their contributions to the relaxation energy related to the nonlocal electron-vibration interactions. The results show that the largest contribution (about 90%) is due to electron interactions with low-frequency vibrational modes. The relaxation energy in anthracene-PMDA is found to be about five times smaller than the electronic coupling.

Erbium: YAG versus holmium:YAG lithotripsy.

PURPOSE: We test the hypothesis that erbium:YAG (Er:YAG) lithotripsy is more efficient than holmium:YAG (Ho:YAG) lithotripsy. MATERIALS AND METHODS: Human calculi composed of greater than 97% calcium oxalate monohydrate and cystine were studied. Calculi were irradiated in water using Er:YAG or Ho:YAG lasers. Er:YAG lithotripsy was done with a 425 microm sapphire optical fiber at a pulse energy of 50 mJ at 10 Hz. Ho:YAG lithotripsy was performed with a 365 microm low hydroxy optical fiber at a pulse energy of 500 mJ at 10 Hz or a 425 microm sapphire optical fiber at a pulse energy of 50 mJ at 10 Hz. Fragmentation was defined as the initial stone mass minus the final dominant fragment mass and normalized for incident laser fluence (energy per unit area of fiber tip). RESULTS: Mean fragmentation plus or minus standard deviation for calcium oxalate monohydrate was 38 +/- 27 mg for Er:YAG and 22 +/- 6 for Ho:YAG (low hydroxy silica fiber) versus 5 +/- 1 for Ho:YAG (sapphire fiber, p = 0.001). When fragmentation was normalized for incident laser fluence given different optical fiber sizes, mean fragmentation efficiency was 53.6 +/- 38.7 g-microm2/J for Er:YAG lithotripsy compared with 22.6 +/- 6.4 for Ho:YAG (low hydroxy silica fiber) lithotripsy (p = 0.04). Mean cystine fragmentation was 15 +/- 3 mg for Er:YAG versus 9 +/- 1 for Ho:YAG (sapphire fiber, p = 0.0005). CONCLUSIONS: Er:YAG lithotripsy is more efficient than Ho:YAG lithotripsy.

Laser lithotripsy and cyanide.

BACKGROUND AND PURPOSE: Holmium:YAG lithotripsy of uric acid calculi produces cyanide. The laser and stone parameters required to produce cyanide are poorly defined. In this study, we tested the hypotheses that cyanide production: (1) varies with holmium:YAG power settings; (2) varies among holmium:YAG, pulsed-dye, and alexandrite lasers; and (3) occurs during holmium:YAG lithotripsy of all purine calculi. MATERIALS AND METHODS: Holmium:YAG lithotripsy of uric acid calculi was done using various optical fiber diameters (272-940 microm) and pulse energies (0.5-1.5 J) for constant irradiation (0.25 kJ). Fragmentation and cyanide were quantified. Cyanide values were divided by fragmentation values, and fragment sizes were characterized. To test the second hypothesis, uric acid calculi were irradiated with Ho:YAG, pulsed-dye, and alexandrite lasers. Fragmentation and cyanide were measured, and cyanide per fragmentation was calculated. Fragment sizes were characterized. Finally, Ho:YAG lithotripsy (0.25 kJ) of purine and nonpurine calculi was done, and cyanide production was measured. RESULTS: Fragmentation increased as pulse energy increased for the 550- and 940-microm optical fibers (P < 0.05). Cyanide increased as pulse energy increased for all optical fibers (P < 0.002). Cyanide per fragmentation increased as pulse energy increased for the 272-microm optical fiber (P = 0.03). Fragment size increased as pulse energy increased for the 272-microm, 550-microm, and 940-microm optical fibers (P < 0.001). The mean cyanide production from 0.25 kJ of optical energy was Ho:YAG laser 106 microg, pulsed-dye 55 microm, and alexandrite 1 microg (P < 0.001). The mean cyanide normalized for fragmentation (microg/mg) was 1.18, 0.85, and 0.02, respectively (P < 0.001). The mean fragment size was 0.6, 1.1, and 1.9 mm, respectively (P < 0.001). After 0.25 kJ, the mean amount of cyanide produced was monosodium urate stones 85 microg, uric acid 78 microg, xanthine 17 microg, ammonium acid urate 16 microg, calcium phosphate 8 microg, cystine 7 microg, and struvite 4 microg (P < 0.001). CONCLUSIONS: Cyanide production varies with Ho:YAG pulse energy. To minimize cyanide and fragment size, Ho:YAG lasertripsy is best done at a pulse energy < or = 1.0 J. Cyanide production from laser lithotripsy of uric acid calculi varies among Ho:YAG, pulsed-dye, and alexandrite lasers and is related to pulse duration. Cyanide is produced by Ho:YAG lasertripsy of all purine calculi.

Holmium: YAG lithotripsy: optimal power settings.

PURPOSE: We tested the hypothesis that holmium:YAG laser lithotripsy speed is best maximized by using low pulse energy at high pulse frequency. MATERIALS AND METHODS: To demonstrate that optical fiber damage increases with pulse energy and irradiation, the 365-microm optical fiber irradiated calcium hydrogen phosphate dihydrate (CHPD), calcium oxalate monohydrate (COM), cystine, magnesium ammonium phosphate hexahydrate (MAPH), and uric acid calculi at pulse energies of 0.5 to 2.0 J. Optical energy output was measured with an energy detector after 10 J to 200 J of total energy. To demonstrate that lithotripsy efficiency varies with power, fragmentation was measured at constant power settings at total energies of 200 J and 1 kJ with the 365-microm optical fiber. Fragmentation was measured for the 272-microm optical fiber at pulse energies of 0.5 J to 1.5 J at 10 Hz. To demonstrate that low pulse energy produces smaller fragments than high pulse energy, fragment size was characterized for COM and uric acid calculi after 0.25 kJ of irradiation using the 272-microm to 940-microm optical fibers at 0.5 J to 1.5 J. RESULTS: Damage to the 365-microm optical fiber was greatest for irradiation of CHPD, followed by MAPH, and COM (P<0.001). There was no significant optical fiber damage after cystine and uric acid lithotripsy. For the 365-microm optical fiber and CHPD, fragmentation after 200 J was greatest for pulse energies < or =1.0 J (P< 0.001). For other compositions, fragmentation was not statistically different among the power settings for constant irradiation. No significant difference was noted in fragmentation for any composition at different pulse energies (1.0 v. 2.0 J) for 1-kJ irradiation. However, for all compositions, the calculated lithotripsy speed was greatest at high power settings (P<0.001). For the 272-microm optical fiber, CHPD fragmentation was greatest for the 1.0-J pulse energy. The mean fragment size and relative quantity of fragments > or =2 mm both increased as pulse energy increased. CONCLUSIONS: Optical fiber degradation varies with stone composition, irradiation, and pulse energy. Holmium:YAG lithotripsy speed is maximized with higher power (either increased pulse energy or higher pulse frequency). Because low pulse energy may be safer and yields smaller fragments than high pulse energy, holmium:YAG lithotripsy speed is best increased by using pulse energies < or =1.0 J at a high repetition rate.

Evaluation of fibrocartilage regeneration and bone response at full-thickness cartilage defects in articulation with pyrolytic carbon or cobalt-chromium alloy hemiarthroplasties.

Hemiarthroplasty is one method used to treat osteoarthritic joints. Often, however, an adverse response of the articular cartilage to the metal implants occurs. The purpose of this study was to evaluate and compare the response of a surgically created defect to pyrolytic carbon and cobalt-based alloy hemiarthroplasties. The cartilage on the lateral side of the tibial plateau of a canine knee joint was abraded to create a full-thickness defect. Two small holes were drilled into the exposed subchondral bone. Next, either a carbon or metal implant was placed in the lateral femoral condyle. The implantation period was 1 year. Histologic examination of the tibial defects revealed a smooth bony surface for both implant groups. In addition, there was no evidence of a residual adverse inflammatory response nor of a significant increase in subchondral bone formation for either group. Surface cracks resulting from the presence of the implant were seen in 14% of the carbon implant specimens and in 100% of the metal implants. Fibrocartilage regeneration was seen in 86% of the carbon implants and in 25% of the metal implants. Thus the carbon appears to be better tolerated mechanically compared to wrought cobalt-chromium alloy. Pyrolytic carbon shows promise for use in hemiarthroplasty.

A selected ion monitoring GC/MS assay for 3,4,4'-trichlorocarbanilide and its metabolites in biological fluids.

A selected ion monitoring gas chromatography/mass spectrometric method for the quantitative determination of 3,4,4'-trichlorocarbanilide (TCC) and its major metabolites (the 2'-hydroxy sulfate and the N- and N'-glucuronides) in human plasma and urine was developed using the deuterium-labelled compounds as internal standards. Limits of detection of 3 ng/mL in urine for the N-glucuronides and of 1.5 ng/mL in plasma for the 2'-hydroxy sulfate were attained. Use of the method was illustrated in a study in human subjects employing TCC-containing bar soaps.