S-0 and S-1 State Structure, Methyl Torsional Barrier Heights, and Fast Intersystem Crossing Dynamics of 5-Methyl-2-hydroxypyrimidine

We report the analysis of the SI So rotational band contours of jet-cooled 5-methyl-2-hydroxypyrimidine (5M2HP), the enol form of deoxythymine. Unlike thymine, which exhibits a structureless spectrum, the vibronic spectrum of 5M2HP is well structured, allowing us to determine the rotational constants and the methyl group torsional barriers in the S-0 and S-1 states. The 0(0)(0), 6a(0)(1), 6b(0)(1), and 14(0)(1) band contours were measured at 900 MHz (0.03 cm(-1)) resolution using mass-specific two-color resonant two-photon ionization (2C-R2PI) spectroscopy. All four bands are polarized perpendicular to the pyrimidine plane (>90% c type), identifying the S-1 <- S-0 excitation of 5M2HP as a 1n pi* transition. All contours exhibit two methyl rotor subbands that arise from the lowest 5-methyl torsional states 0A '' and 1E ''. The S-0 and S-1 state torsional barriers were extracted from fits to the torsional subbands. The 3-fold barriers are V-3 '' = 13 cm(-1) and V3' = SI cm(-1); the 6-fold barrier contributions V-6 '' and V-6' are in the range of 2-3 cm(-1) and are positive in both states. The changes of A, B, and C rotational constants upon S-1 <- S-0 excitation were extracted from the contours and reflect an "anti-quinoidal" distortion. The 0(0)(0) contour can only be simulated if a 3 GHz Lorentzian line shape is included, which implies that the S-1(1n pi*) lifetime is similar to 55 ps. For the 6a(0)(1) and 6b(0)(1) bands, the Lorentzian component increases to 5.5 GHz, reflecting a lifetime decrease to similar to 30 ps. The short lifetimes are consistent with the absence of fluorescence from the 1n pi* state. Combining these measurements with the previous observation of efficient intersystem crossing (ISC) from the Si state to a long-lived T-1((3)n pi*) state that lies similar to 2200 cm(-1) below [S. Lobsiger, S. et al. Phys. Chem. Chem. Phys. 2010, 12, 5032] implies that the broadening arises from fast intersystem crossing with k(ISC) approximate to 2 x 10(10) s(-1). In comparison to 5-methylpyrimidine, the ISC rate is enhanced by at least 10 000 by the additional hydroxy group in position 2.

The \bar{B} \to X_s γγdecay: NLL QCD contribution of the Electromagnetic Dipole operator O_7

We calculate the set of O(\alpha_s) corrections to the double differential decay width d\Gamma_{77}/(ds_1 \, ds_2) for the process \bar{B} \to X_s \gamma \gamma originating from diagrams involving the electromagnetic dipole operator O_7. The kinematical variables s_1 and s_2 are defined as s_i=(p_b - q_i)^2/m_b^2, where p_b, q_1, q_2 are the momenta of b-quark and two photons. While the (renormalized) virtual corrections are worked out exactly for a certain range of s_1 and s_2, we retain in the gluon bremsstrahlung process only the leading power w.r.t. the (normalized) hadronic mass s_3=(p_b-q_1-q_2)^2/m_b^2 in the underlying triple differential decay width d\Gamma_{77}/(ds_1 ds_2 ds_3). The double differential decay width, based on this approximation, is free of infrared- and collinear singularities when combining virtual- and bremsstrahlung corrections. The corresponding results are obtained analytically. When retaining all powers in s_3, the sum of virtual- and bremstrahlung corrections contains uncanceled 1/\epsilon singularities (which are due to collinear photon emission from the s-quark) and other concepts, which go beyond perturbation theory, like parton fragmentation functions of a quark or a gluon into a photon, are needed which is beyond the scope of our paper.

Within-subject comparison of two rigid bar designs connecting two interforaminal implants: patients' satisfaction and prosthetic results

BACKGROUND: There is evidence for the superiority of two-implant overdentures over complete dentures in the mandible. Various anchorage devices were used to provide stability to overdentures. The aim of the present study was to compare two designs of a rigid bar connecting two mandibular implants. MATERIALS AND METHODS: Completely edentulous patients received a new denture in the maxilla and an implant-supported overdenture in the mandible. They were randomly allocated to two groups (A or B) with regard to the bar design. A standard U-shaped bar (Dolder bar) was used connecting the two implants in a straight line. For comparison, precision attachments were soldered distal to the bar copings. Group A started the study with the standard bar (S-bar), while group B started with the attachment-bar (A-bar). After 3 months, they had to answer a questionnaire (visual analogue scale [VAS]); then the bar design was changed in both groups. After a period of another 3 months, the patients had to answer the same questions; then they had the choice to keep their preferred bar. Now the study period was extended to another year of observation, and the patients answered again the same questionnaire. In vivo force measurements were carried out with both bar types at the end of the test periods. The prosthetic maintenance service carried out during the 6-month period was recorded for both bar types in both groups. Statistical analysis as performed with the SPSS statistical package (SPSS Inc., Chicago, IL, USA). RESULTS: Satisfaction was high in both groups. Group B, who had entered the study with the attachment bar, gave slightly better ratings to this type for four items, while in group A, no differences were found. At the end of the 6-month comparison period, all but one patient wished to continue to wear the attachment bar. Prosthetic service was equal in groups A and B, but the total number of interventions is significantly higher in the attachment bar. Force patterns of maximum biting were similar in both bar designs, but exhibited significantly higher axial forces in the attachment bar. CONCLUSIONS: Both bar designs provide good retention and functional comfort. High stability appears to be an important factor for the patients' satisfaction and oral comfort. Rigid retention results in a higher force impact and appears to evoke the need for the retightening of occlusal screws, resulting in more maintenance service.

[Management of a failing implant supporting a bar-retained maxillary overdenture by means of alveolar ridge augmentation. Implant loss and reimplantation]

This case report presents the treatment sequence of a 56 years old patient after he developed periimplantitis at the implant in position of tooth 22. This implant was integrated in an overdenture reconstruction connected to a soldered screw retained gold bar. The entire 2-stage procedure of implant explantation, simultaneous bone augmentation and new implant placement is documented. The onlay-graft was performed by means of the Transfer-Ring-Control System (Meisinger). The existing gold bar could be resoldered and adapted to the new implant. Accordingly the overdenture was relined and the female retainer mounted. The treatment period covered almost one year.