The irreversibly bound interfacial layer deposited by the γ-aminopropysilanetriol adhesion promoter onto a crystalline silicon substrate, which remains even after profuse washing, was found by XPS to have resulted from the fragmentation and rearrangement of the original γ-aminopropylsilanetriol molecule. A mechanism is proposed, involving the homolytic scission of the terminal N-C bond. One of the subsequent reactions is believed to involve hydrogen loss by abstraction and the formation of a terminal vinyl group, which bonds to the substrate. Support for this mechanism is found in IR spectroscopy of this layer. 相似文献
The acidity of H-MTW-type zeolite has been investigated using infrared spectroscopy of adsorbed pyridine. Pore volume has been measured by nitrogen andn-hexane adsorption. The zeolite exhibits infrared signals at 3612 and 3580 cm–1 tentatively attributed to bridging hydroxyl groups vibrating in the main channel and in the six-membered rings of the structure, respectively. Both hydroxyl groups possess high acid strength and are readily accessible to pyridine. H-MTW shows an-hexane cracking activity at 350°C comparable to that obtained with MFI and BEA-type materials with a product selectivity between medium and large pore structural types. 相似文献
During the last few years, morphological, immunohistochemical, and genetic findings have placed anaplastic large cell lymphoma (ALCL) as a distinct clinicopathologic entity, and several reports have focused on the existence of different subtypes of the tumor. Particular attention has been paid to the ALCL-Hodgkin's-like (HL) subtype, which seems to be on the border between Hodgkin's disease (HD) and high-grade non-Hodgkin's lymphoma (HG-NHL). From September 1994 to July 1997, during the course of an Italian multicentric trial, 40 ALCL-HLs were randomized to receive as front-line chemotherapy MACOP-B (methotrexate with leucovorin, doxorubicin, cyclophosphamide, vincristine, prednisone, and bleomycin-a third-generation HG-NHL regimen) or ABVD (doxorubicin, bleomycin, vinblastine, and dacarbazine-a scheme specific for HD). All patients with bulky disease in the mediastinum at diagnosis underwent local radiotherapy after the chemotherapeutic program. Complete response (CR) was achieved in 17 of the 19 (90%) patients who were treated with MACOP-B, and in 19 of the 21 (91%) patients who were administered ABVD. The probability of relapse-free survival, projected at 32 months, was 94% for the MACOP-B subset and 91% for the ABVD subset. The majority of patients with mediastinal bulky disease obtained CR (evaluated with 67Ga single photon emission computed tomography [SPECT]) after their radiotherapy. The present study suggests that ALCL-HL, in line with its borderline status, responds in an equivalent way to third-generation chemotherapy for HG-NHL and to conventional HD treatment in terms of both CR and relapse-free survival rates. However, as to the latter, a longer follow-up period may be needed before stating the absolute equivalence of the two regimens used. 相似文献
In recent years, environmental and economic reasons have motivated the development of transition metal‐free carbon‐carbon bond forming reactions and some excellent reviews have covered this research area of particular interest for the pharmaceutical industry. However, none of these reviews has been specifically dedicated to summarize and discuss the results achieved in the rapidly growing field of the transition metal‐free direct (hetero)arylation reactions of heteroarenes. This review, which covers the literature from 2008 to 2014, aims to provide a thorough insight into the synthetic and mechanistic aspects of these atom economic and environmentally benign reactions also highlighting their advantages and possible disadvantages compared to conventional methods for the synthesis of arylheteroarenes and biheteroaryls via transition metal‐catalyzed reactions.
The structure and properties of polymer‐derived Si–(B–)O–C glasses have been shown to be significantly influenced by the boron content and pyrolysis temperature. This work determined the impact of these two parameters on the thermodynamic stability of these glasses. High‐temperature oxide melt solution calorimetry was performed on a series of amorphous samples, with varying boron contents (0–7.7 at.%), obtained by pyrolysis of precursors made by a sol–gel technique. Thermodynamic analysis of the calorimetric results demonstrated that at a constant pyrolysis temperature, adding boron makes the materials energetically less stable. While the B‐containing glasses pyrolyzed at 1000°C were energetically less stable than the competitive crystalline components, increasing the pyrolysis temperature to 1200°C led to their enthalpic stability. 29Si and 11B MAS nuclear magnetic resonance (NMR) spectroscopy measurements on selected samples confirmed a decrease in the concentrations of mixed Si‐centered SOiC4?i and B‐centered BOjC3?j bonds at the expense of formation of SiO4 and B(OSi)3 species (indicating a tendency toward phase separation) when the boron content and pyrolysis temperature increased. In light of the findings from calorimetry and NMR spectroscopy, we propose a structure–energetic relationship in Si–(B–)O–C glasses. 相似文献
This work is a companion to a previous article, Part I, published in The Canadian Journal of Chemical Engineering, dealing with CO2 absorption in aqueous solutions containing a single aminic reagent (specifically methyldiethanolamine (MDEA) or piperazine (PZ)). In this second part, different PZ/MDEA mixtures are experimentally studied and their performances are compared with that of the single reagents. It is indeed well known that small quantities of PZ added to MDEA aqueous solutions are sufficient to obtain a significant improvement in the kinetics of the process. PZ is considered an activator or promoter for MDEA, but the mechanism of this synergy has still not been clearly demonstrated. The aim of this study is an attempt to understand how PZ and MDEA can interact by experimentally analyzing this beneficial mutual effect and by explaining it with the help of a suitable yet not complex model. We believe that the involved chemistry is not more complex than that reported in Part I for the single reagents. According to our findings, it is MDEA that enhances the action of PZ, as opposed to what many authors claim. Moreover, our results seem to rule out the existence of any PZ shuttle effect. 相似文献