Synthesis, Structure, and Bonding Analysis of Lewis Base and Lewis Acid/Base‐Stabilized Phosphanylgallanes

Phosphanylgallane with hydrogen and halogen substituents (RXGa PHR, R=organic substituent, X=halogen/hydrogen) are regarded as putative suitable precursors for accessing Ga=P doubly bonded species. Herein, we report on the synthesis, structure, and bonding analysis of a series of Lewis base- and Lewis acid/base-stabilized phosphanylgallane bearing P H and Ga Cl/H substitution. To avoid oligomerization, the treatment of IDip.GaCl3 and (IDip)GaH2Cl (IDip=1,3-bis(2,6-diisopropylphenyl) imidazole-2-ylidene) with LiPHR or LiPHR(BH3) (R=Ph, Tip, Mes, NiPr2, NCy2) affords the corresponding Lewis base and Lewis acid/base coordinated H,Cl-functionalized monomeric phosphanylgallane, respectively. The structure of these derivatives were determined by spectroscopic and X-ray crystallographic analyses. The observed Ga P bond lengths are comparable to those previously reported phosphanylgallane analogues. The nature of the CIDip-Ga coordination bond was assessed with Energy Decomposition Analysis, suggesting a relatively stable adduct. Reactions of the phosphanylgallane with Brønsted bases were investigated

OLPT CONDUCTIVITY IN WOLLASTONITE INLAID NR/SBR TYPE ELASTOMER BASED MATERIAL

The electrical properties of wollastonite inlaid NR/SBR type elastomer based material have been evaluated. Electrical properties of the samples were measured in the temperature range of 303 to 453 K and the frequency range of 100 Hz – 40 MHz. All electrically measured parameters were given anomalies at 385 K. Only one type of dielectric relaxation process have been observed for all measurements. Physical parameters characterizing the dielectric behavior have been obtained by fitting the experimental results in the modified Debye equation. The activation energy which is thermally activated by dielectric relaxation process have been calculated to be 0.58 eV. DC conductivity increasing by temperature has been explained with the help of VFT model whereas the AC one has been clarified by the OLPT model

Seismic data reveal eastern Black Sea Basin structure

Rifted continental margins are formed by progressive extension of the lithosphere. The development of these margins plays an integral role in the plate tectonic cycle, and an understanding of the extensional process underpins much hydrocarbon exploration. A key issue is whether the lithosphere extends uniformly, or whether extension varies\ud with depth. Crustal extension may be determined using seismic techniques. Lithospheric extension may be inferred from the waterloaded subsidence history, determined from\ud the pattern of sedimentation during and after rifting. Unfortunately, however, many rifted margins are sediment-starved, so the subsidence history is poorly known.\ud To test whether extension varies between the crust and the mantle, a major seismic experiment was conducted in February–March 2005 in the eastern Black Sea Basin (Figure 1), a deep basin where the subsidence history is recorded\ud by a thick, post-rift sedimentary sequence. The seismic data from the experiment indicate the presence of a thick, low-velocity zone, possibly representing overpressured sediments. They also indicate that the basement and\ud Moho in the center of the basin are both several kilometers shallower than previously inferred. These initial observations may have considerable impact on thermal models of the petroleum system in the basin. Understanding\ud the thermal history of potential source rocks is key to reducing hydrocarbon exploration risk. The experiment, which involved collaboration between university groups in the United Kingdom, Ireland, and Turkey, and BP and\ud Turkish Petroleum (TPAO), formed part of a larger project that also is using deep seismic reflection and other geophysical data held by the industry partners to determine the subsidence history and hence the strain evolution of\ud the basin

Hematopoetic stem cell transplantation for solid tumors in Europe

Background: Hematopoetic stem cell transplants (HSCT) are discussed as treatment options for patients with solid tumors. Transplant numbers have changed substantially over the last decade, few controlled studies are available and different opinions prevail. Objective information on current practice is needed. Patients and methods: Data from 27 902 HSCT for solid tumors (2% allogeneic, 98% autologous), collected by the European Group for Blood and Marrow Transplantation (EBMT) activity survey from 1991 to 2002 were used to assess trends, transplant rates and coefficient of variation of transplant rates in Europe. Results: Transplant numbers increased from 536 in 1991 to 4154 in 1997 and decreased to 1913 in 2002. Indications were neuroblastoma (2504 HSCT; 9%), glioma (662 HSCT; 2%), soft tissue sarcoma (1253 HSCT; 4%), germ cell cancer (3291 HSCT; 12%), breast cancer (13 524 HSCT; 48%), Ewing's sarcoma (1896 HSCT; 7%), lung cancer (387 HSCT; 1%), ovarian cancer (845 HSCT; 3%) and other solid tumors (3540 HSCT; 14%). Allogeneic cells were used in <20 cases up to 1997; since then allogeneic HSCT increased to 159 in 2002, mainly for renal cell carcinoma. Low coefficients of variation in transplant rates (<60%) are observed for Ewing's sarcoma (<56.5%), suggesting consensus for this indication. Conclusions: These data give an overview on current practice of HSCT for solid tumors in Europe. They provide objective information for health-care providers and patient counsellin

Second-line high-dose chemotherapy in patients with mediastinal and retroperitoneal primary non-seminomatous germ cell tumors: the EBMT experience

Background: Results of second-line chemotherapy in patients with extragonadal non-seminomatous germ cell tumor (NSGCT) appear inferior to results in testicular NSGCT. Patients with retroperitoneal NSGCT achieve a comparable long-term survival rate of 30%, but the salvage rates of patients with mediastinal primary are less than 10%. We conducted a retrospective analysis on patients with mediastinal and retroperitoneal NSGCT treated with second-line high-dose chemotherapy (HDCT) registered with the European Group for Blood and Marrow Transplantation (EBMT). Patients and methods: Between 1987 and 1999, 59 registered patients with retroperitoneal (n=37) and mediastinal (n=22) primary NSGCT, median age 28 years (range 18-60), were treated with second-line HDCT. All had received cisplatin-containing chemotherapy as first-line treatment. Results: Toxic death occurred in three cases (5%). With a median follow-up of 58 months (range 14-114), 18/59 patients (30%) continue to be disease-free. Of three patients who had a disease recurrence after HDCT, one patient achieved a disease-free status with further chemotherapy and surgery. In total, 19 patients (32%) are currently disease-free. Sixteen of 37 patients (43%) with retroperitoneal NSGCT, and three of 22 patients (14%) with mediastinal NSGCT are currently alive and disease-free. Conclusions: Second-line HDCT might represent a possible option for patients with retroperitoneal primary NSGCT. New salvage strategies are needed for patients with mediastinal NSGC

Secondary acute leukemia following mitoxantrone-based high-dose chemotherapy for primary breast cancer patients

n/

Evidence of AlII Radical Addition to Benzene

Electrophilic AlIII species have long dominated the aluminum reactivity towards arenes. Recently, nucleophilic low-valent AlI aluminyl anions have showcased oxidative additions towards arenes C C and/or C H bonds. Herein, we communicate compelling evidence of an AlII radical addition reaction to the benzene ring. The electron reduction of a ligand stabilized precursor with KC8 in benzene furnishes a double addition to the benzene ring instead of a C H bond activation, producing the corresponding cyclohexa-1,3 (orl,4)-dienes as Birch-type reduction product. X-ray crystallographic analysis, EPR spectroscopy, and DFT results suggest this reactivity proceeds through a stable AlII radical intermediate, whose stability is a consequence of a rigid scaffold in combination with strong steric protection

Evidence of AlII Radical Addition to Benzene

Electrophilic AlIII species have long dominated the aluminum reactivity towards arenes. Recently, nucleophilic low-valent AlI aluminyl anions have showcased oxidative additions towards arenes C-C and/or C-H bonds. Herein, we communicate compelling evidence of an AlII radical addition reaction to the benzene ring. The electron reduction of a ligand stabilized precursor with KC8 in benzene furnishes a double addition to the benzene ring instead of a C-H bond activation, producing the corresponding cyclohexa-1,3(orl,4)-dienes as Birch-type reduction product. X-ray crystallographic analysis, EPR spectroscopy, and DFT results suggest this reactivity proceeds through a stable AlII radical intermediate, whose stability is a consequence of a rigid scaffold in combination with strong steric protection