Kinetics and mechanism of the thermal decomposition reaction of acetone cyclic diperoxide in the gas phase

The kinetics of the thermal decomposition reaction of gaseous 3,3,6,6-tetramethyl-1,2,4,5-tetroxane (ACDP) in the presence of n-octane was studied in the 403.2–523.2 K temperature range. This reaction yields acetone as the organic product. Under optimum conditions, first-order kinetics were observed, included when the S/V ratio of the Pyrex reaction vessel was increased by a nearly six-fold factor. In the range 443.2–488.2 K the temperature dependence of the rate constants for the unimolecular reaction in conditioned vessels is given by In k₁/(s^?1) = (31.8 ± 2.5) ? [(39.0 ± 2.5)/RT]. The value of the energy of activation in kcal/mol correspond to one O? O bond homolysis of the ACDP molecule in a stepwise biradical initiated decomposition mechanism. At the lower reaction temperatures as well in preliminary experiments participation of a surface catalyzed ACDP decomposition process could be detected. © 1994 John Wiley & Sons, Inc.     

Effects of ultrasonic irradiation in flow-injection systems

The effects of ultrasonic irradiation on transport and reactions in several flow-injection manifolds are described. The influences of ultrasound on the physical dispersion of the injected plug is considered. Its effects on systems involving homogeneous (catalytic and non-catalytic) and heterogeneous (liquid/liquid extraction, precipitation) reactions are critically evaluated. In general, greater sensitivity is obtained, especially for heterogeneous systems, slow reactions and low analyte concentrations. Finally, practical considerations and potential uses of the combination of ultrasonic irradiation with flow-injection analysis are discussed.     

Individual and simultaneous enzymatic determination of ethanol and acetaldehyde in wines by flow injection analysis

The individual and simultaneous enzymatic determination of ethanol and acetaldehyde in wine by flow injection analysis is described. Individual determinations of 0.002–0.016% (v/v) ethanol or 1.0–8.0 μg ml^?1 acetaldehyde with r.s.d. 0.7% and 0.5%, respectively, are done with a single-beam spectrophotometer, based on the use of alcohol dehydrogenase and aldehyde dehydrogenase. A diode-array detector and dual reagent injections are used for the simultaneous determination of the two compounds. The errors are 〈 3.5% and 〈 2.0% for ethanol and acetaldehyde, respectively, when the method is applied to wine samples.     

Synthesis of dihydroxylated prolines and iminocyclitols from five-membered endocyclic enecarbamates. Total synthesis of the potent glycosidase inhibitor (2R,3R,4R,5R)-2,5-dihydroxymethyl-3,4-dihydroxypyrrolidine (DMDP)

cis- and trans-3,4-Dihydroxylated prolines and the iminocyclitol 1,4-dideoxy-1,4-imino ribitol were synthesized employing a strategy involving the Heck arylation of five-membered endocyclic enecarbamates with aryldiazonium salts followed by oxidative cleavage of the electron-rich aromatic ring. The total synthesis of the potent α- and β-glucosidase inhibitor (2R,3R,4R,5R)-2,5-hydroxymethyl-3,4-dihydroxypyrrolidine (DMDP) was also achieved by the same strategy in ten steps from a chiral five-membered enecarbamate in 12% overall yield.     

Luminescent PtII and PtIV Platinacycles with Anticancer Activity Against Multiplatinum-Resistant Metastatic CRC and CRPC Cell Models

Platinum-based chemotherapy persists to be the only effective therapeutic option against a wide variety of tumours. Nevertheless, the acquisition of platinum resistance is utterly common, ultimately cornering conventional platinum drugs to only palliative in many patients. Thus, encountering alternatives that are both effective and non-cross-resistant is urgent. In this work, we report the synthesis, reduction studies, and luminescent properties of a series of cyclometallated (C,N,N′)Pt^IV compounds derived from amine–imine ligands, and their remarkable efficacy at the high nanomolar range and complete lack of cross-resistance, as an intrinsic property of the platinacycle, against multiplatinum-resistant colorectal cancer (CRC) and castration-resistant prostate cancer (CRPC) metastatic cell lines generated for this work. We have also determined that the compounds are effective and selective for a broader cancer panel, including breast and lung cancer. Additionally, selected compounds have been further evaluated, finding a shift in their antiproliferative mechanism towards more cytotoxic and less cytostatic than cisplatin against cancer cells, being also able to oxidize cysteine residues and inhibit topoisomerase II, thereby holding great promise as future improved alternatives to conventional platinum drugs.     

Distance-Dependent Electron Transfer Kinetics in Axially Connected Silicon Phthalocyanine-Fullerene Conjugates

The effect of donor-acceptor distance in controlling the rate of electron transfer in axially linked silicon phthalocyanine-C₆₀ dyads has been investigated. For this, two C₆₀-SiPc-C₆₀ dyads, 1 and 2 , varying in their donor-acceptor distance, have been newly synthesized and characterized. In the case of C₆₀-SiPc-C₆₀ 1 where the SiPc and C₆₀ are separated by a phenyl spacer, faster electron transfer was observed with k_cs equal to 2.7×10⁹ s⁻¹ in benzonitrile. However, in the case of C₆₀-SiPc-C₆₀ 2 , where SiPc and C₆₀ are separated by a biphenyl spacer, a slower electron transfer rate constant, k_cs=9.1×10⁸ s⁻¹, was recorded. The addition of an extra phenyl spacer in 2 increased the donor-acceptor distance by ∼4.3 Å, and consequently, slowed down the electron transfer rate constant by a factor of ∼3.7. The charge separated state lasted over 3 ns, monitoring time window of our femtosecond transient spectrometer. Complimentary nanosecond transient absorption studies revealed formation of ³SiPc* as the end product and suggested the final lifetime of the charge separated state to be in the 3–20 ns range. Energy level diagrams established to comprehend these mechanistic details indicated that the comparatively high-energy SiPc^.+-C₆₀^.− charge separated states (1.57 eV) populated the low-lying ³SiPc* (1.26 eV) prior returning to the ground state.     

On the controversial magnetic properties of the schiff-base metal-organic polymer {[Fe(C13H17N3)2]SO4·6H2O}n

Within the search for magnetic ordering in organic and metal-organic compounds, the polymeric material of formula {[Fe(C₁₃H₁₇N₃)₂]SO₄·6H₂O}_n has been extensively studied by magnetic measurements. Our results show a basic agreement with the previous ones. Nevertheless, our study, including more data, leads to an interpretation in terms of superparamagnetism rather than metamagnetism as was previously reported.     

A more sensitive MS detector does not obviously lead to a more sensitive assay: experiences with ES-285

In this paper the transfer of an existing method for the quantitative determination of the anticancer agent ES-285 in human plasma using liquid chromatography tandem mass spectrometry on an API 365 to an API 3000 mass spectrometer is described. The transfer appeared not to be straightforward. Problems arose resulting from carry-over and interferences. In addition, due to the expansion of the calibration range, data ought to be weighted with a different factor to increase the accuracy of the lower concentrations. After finding appropriate solutions for these problems, the lower limit of quantitation could be lowered from 10 to 1 ng/mL for ES-285 in human plasma. The usefulness and necessity of the modified assay was demonstrated by analysis of plasma samples from a patient receiving a low dosage of the drug.     

Hypersurfaces of the Euclidean sphere with nonnegative Ricci curvature

In this paper we prove that a compact oriented hypersurface of a Euclidean sphere with nonnegative Ricci curvature and infinite fundamental group is isometric to an H(r)-torus with constant mean curvature. Furthermore, we generalize, whithout any hypothesis about the mean curvature, a characterization of Clifford torus due to Hasanis and Vlachos. Received: 19 March 2002