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排序方式: 共有249条查询结果,搜索用时 15 毫秒
1.
2.
A study of the conditions of applicability to weak complexes of the relation log x = v log V + log (βv,cCc) = f(logV), where V and C are variable and constant total concentrations of the constituants of the complexe, shows that for conditions other than C ? V, another function φ(log V) accounts better for the formation equilibrium of the complexe. From f(log V) and φ (log V) a relation t(log V) is derived whose simple analysis permits the determination of the composition and the stability constant of weak complexes. Applications are given to 1:1, 1:2, 2:2 composition. 相似文献
3.
Peter Schiess Charles Monnier Peter Ringele Ebrahim Sendi 《Helvetica chimica acta》1974,57(6):1676-1691
Addition of phenyl-, alkyl-, alkenyl- and alkinyl-Grignard reagents to pyridine-N-oxide in THF leads to 5-substituted (2Z, 4E)-pentadien-aldoximes 6 having (E) (syn)-configuration of the C, N-double bond. The unsaturated oximes are shown to arise through an electrocyclic ring opening reaction from the primary Grignard adducts 5 . These can be trapped by protonation at low temperature. 相似文献
4.
Le Paih J Monnier F Dérien S Dixneuf PH Clot E Eisenstein O 《Journal of the American Chemical Society》2003,125(39):11964-11975
The reaction of a variety of alkynes RCtbd1;CH with a variety of carboxylic acids R(1)CO(2)H, in the presence of 5% of RuCl(COD)C(5)Me(5), selectively leads to the dienylesters (1E,3E)-RCH(1)=CH(2)-CH(3)=C(R)(O(2)CR(1)). The reaction also applies to amino acid and dicarboxylic acid derivatives. It is shown that the first step of the reaction consists of the head-to-head alkyne coupling and of the formation of the metallacyclic biscarbene-ruthenium complex isolated for R = Ph and catalyzing the formation of dienylester. D-labeled reactions show that the alkyne protons remain at the alkyne terminal carbon atoms and carboxylic acid protonates the C(1) carbon atom. QM/MM (ONIOM) calculations, supporting a mixed Fischer-Schrock-type biscarbene complex, show that protonation occurs preferentially at the carbene carbon C(1) adjacent to Ru, in the relative cis position with respect to the Ru-Cl bond, to give a mixed C(1)alkyl-C(4)carbene complex in which the C(4) carbene is conjugated with the noncoordinated C(2)=C(3) double bond. This 16-electron intermediate has a weak stabilizing alpha agostic C-H bond. This most stable isomer appears to have a C(4) center more accessible to the nucleophilic addition which accounts for the experimentally observed product. 相似文献
5.
Danielle Giron S. Monnier M. Mutz P. Piechon T. Buser F. Stowasser K. Schulze M. Bellus 《Journal of Thermal Analysis and Calorimetry》2007,89(3):729-743
Adequate very sensitive quantification methods are needed for the development and are also now required for the monitoring
of undesirable solid form(s) as routine tests. The pre-requisite for quantitation are selectivity, sensitivity and most important
the purity of standards and their proper storage, what is a challenge for metastable forms.
Several analytical techniques are available such as X-ray diffraction, spectroscopy, thermal analysis and microcalorimetry.
The different steps of the validation of the analytical methods and problems to be solved are discussed. Examples illustrate
the different techniques and compare their possible advantages and limits. The relative standard deviation of measurements
should allow for checking the homogenization procedure of mixtures for calibration. The validation should be carried out following
ICH guidelines for validation of analytical methods. Comparison of different techniques in adequate concentration range add
confidence in the analytical results. 相似文献
6.
The exchange of mercury ions and of certain organic mercury complexes with a drop of mercury was studied systematically by means of radioactive isotopes. Under defined conditions, the exchange is quantitative, very rapid and sèlective; most other ions remain in solution so that traces of mercury can be determined by neutron activation. Only ions with higher oxidation potentials than mercury interfere. 相似文献
7.
Andrejevic Blant S Grosjean P Ballini JP Wagnières G van den Bergh H Fontolliet C Monnier P 《Journal of photochemistry and photobiology. B, Biology》2001,61(1-2):1-9
To date, little is known about precise time-dependent distribution and histological localization of tetra(m-hydroxyphenyl)chlorin (mTHPC) in human healthy tissues and squamous cell malignancies in the upper aero-digestive tract. A fluorescence microscopy study was performed on 50 healthy tissue biopsies and on 13 tumors (graded from Tis to T1 SCC) from 30 patients. Tissue samples were taken between 4 h and 11 days following injection of 0.15 mg/kg mTHPC. A fairly comparable distribution pattern in various tissues was observed over time in different patients. Vascular localization of mTHPC fluorescence predominates at a short delay, whereas the dye is essentially located in the tumoral and healthy mucosa after longer delays. A much lower uptake and retention of mTHPC fluorescence was noted in striated muscle and cartilage as compared to neoplastic lesions. No significant selectivity was found between healthy and tumoral mucosa. The obtained data are important to confirm drug-light interval that have been selected for effective PDT for early SCC malignancies while minimizing the risks of over- or under-treatment. The low fluorescence level in striated muscle provides the opportunity to develop interstitial PDT as a treatment modality for invasive SCC of unfavorable locations in the oral cavity or pharynx, such as the base of the tongue. 相似文献
8.
9.
M. Lavagnini F. Pfuner R. Monnier L. Degiorgi H.-M. Eiter L. Tassini B. Muschler R. Hackl J.-H. Chu N. Ru K.Y. Shin I.R. Fisher 《Physica B: Condensed Matter》2012,407(11):1864-1867
We summarize our recent efforts in investigating the charge–density-wave (CDW) state of the rare-earth tri-tellurides RTe3 by means of infrared and Raman techniques. We identify the CDW gap, as order parameter of the broken-symmetry ground state, as well as the collective mode of the CDW condensate. 相似文献
10.
Hang Yin Qian Cheng Roselyne Rosas Prof. Stéphane Viel Dr. Valérie Monnier Prof. Laurence Charles Prof. Didier Siri Dr. Didier Gigmes Dr. Olivier Ouari Prof. Ruibing Wang Dr. Anthony Kermagoret Dr. David Bardelang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(54):12552-12559
A viologen derivative carrying a benzimidazole group ( V-P-I 2+; viologen–phenylene–imidazole V-P-I ) can be dimerized in water using cucurbit[8]uril (CB[8]) in the form of a 2:2 complex resulting in a negative shift of the guest pKa, by more than 1 pH unit, contrasting with the positive pKa shift usually observed for CB-based complexes. Whereas 2:2 complex protonation is unclear by NMR, silver cations have been used for probing the accessibility of the imidazole groups of the 2:2 complexes. The protonation capacity of the buried imidazole groups is reduced, suggesting that CB[8] could trigger proton release upon 2:2 complex formation. The addition of CB[8] to a solution containing V-P- I 3+ indeed released protons as monitored by pH-metry and visualized by a coloured indicator. This property was used to induce a host/guest swapping, accompanied by a proton transfer, between V-P-I 3+ ⋅ CB[7] and a CB[8] complex of 1-methyl-4-(4-pyridyl)pyridinium. The origin of this negative pKa shift is proposed to stand in an ideal charge state, and in the position of the two pH-responsive fragments inside the two CB[8] which, alike residues engulfed in proteins, favour the deprotonated form of the guest molecules. Such proton release triggered by a recognition event is reminiscent of several biological processes and may open new avenues toward bioinspired enzyme mimics catalyzing proton transfer or chemical reactions. 相似文献