Annulation of Tetrathiafulvalene to the Bay Region of Perylenediimide: Fast Electron-Transfer Processes in Polar and Nonpolar Solvents

A tetrathiafulvalene donor has been annulated to the bay region of perylenediimide through a 1H-benzo-[d]pyrrolo[1,2-a]imidazol-1-one spacer affording an extended pi-conjugated molecular dyad (TTF-PDI). To gain insight into its ground- and excited-state electronic properties, the reference compound Ph-PDI has been prepared via a direct Schiff-base condensation of N,N'-bis(1-octylnonyl) benzoperylene-1',2':3,4:9,10-hexacarboxylic-1',2'-anhydride-3,4:9,10-bis (imide) with benzene-1,2-diamine. Both the experimental and the computational (DFT) results indicate that TTF-PDI exhibits significant intramolecular electronic interactions giving rise to an efficient photoinduced charge-separation process. Free-energy calculations verify that the process from TTF to the singlet-excited state of PDI is exothermic in both polar and nonpolar solvents. Fast adiabatic electron-transfer processes of a compactly fused, pi-conjugated TTF-PDI dyad in benzonitrile, 2-methyltetrahydrofuran, anisole and toluene were observed by femtosecond transient absorption spectral measurements. The lifetimes of radical-ion pairs slightly increase with decreasing the solvent polarities, suggesting that the charge-recombination occurs in the Marcus inverted region. By utilizing the nanosecond transient absorption technique, the intermolecular electron-transfer process in a mixture of has been observed via the triplet excited PDI for the first time.

In vitro temperature evaluation during cement augmentation of proximal humerus plate screw tips

BACKGROUND The treatment of proximal humerus fractures in patients with poor bone quality remains a challenge in trauma surgery. Augmentation with polymethylmethacrylate (PMMA) cement is a possible method to strengthen the implant anchorage in osteoporotic bone and to avoid loss of reduction and reduce the cut-out risk. The polymerisation of PMMA during cement setting leads, however, to an exothermic reaction and the development of supraphysiological temperatures may harm the bone and cartilage. This study addresses the issue of heat development during augmentation of subchondrally placed proximal humerus plate screws with PMMA and the possible risk of bone and cartilage necrosis and apoptosis. METHODS Seven fresh frozen humeri from geriatric female donors were instrumented with the proximal humerus interlocking system (PHILOS) plate and placed in a 37°C water bath. Thereafter, four proximal perforated screws were augmented with 0.5 ml PMMA each. During augmentation, the temperatures in the subchondral bone and on the articular surface were recorded with K-type thermocouples. The measured temperatures were compared to threshold values for necrosis and apoptosis of bone and cartilage reported in the literature. RESULTS The heat development was highest around the augmented tips of the perforated screws and diminished with growing distance from the cement cloud. The highest temperature recorded in the subchondral bone reached 43.5°C and the longest exposure time above 42°C was 86s. The highest temperature measured on the articular surface amounted to 38.6°C and the longest exposure time above 38°C was 5 min and 32s. CONCLUSION The study shows that augmentation of the proximal screws of the PHILOS plate with PMMA leads to a locally limited development of supraphysiological temperatures in the cement cloud and closely around it. The critical threshold values for necrosis and apoptosis of cartilage and subchondral bone reported in the literature, however, are not reached. In order to avoid cement extravasation, special care should be taken in detecting perforations or intra-articular cracks in the humeral head.