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1.
Hromadová M Pospísil L Fanelli N Giannarelli S 《Langmuir : the ACS journal of surfaces and colloids》2005,21(5):1923-1930
The reduction mechanism of the pesticide vinclozoline (3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione) was studied in nonaqueous solvents in the confined environment of a cyclodextrin (CD) cavity. The effect of the cavity dimensions on the mechanism of the redox process was evaluated using glucose as a reference and using three cyclodextrin molecules of different cavity sizes, namely, alphaCD, betaCD, and gammaCD. In the absence of CD the main reduction product of vinclozoline in the first reduction step is dichloroaniline. An addition of glucose leads to a quantitative change of mechanism with 10 products in total. Addition of CD, however, leads exclusively to dechlorination of the phenyl ring. The degree of dechlorination depends strongly on the choice of cyclodextrin molecule. The importance of the complex formation equilibria in the change of the mechanism is supported by a series of semiempirical AM1 quantum-mechanical calculations. Very good correlation (correlation coefficient 0.995) was obtained between the complex stabilization energy of the inclusion complex and the degree of pesticide dechlorination. Additionally, we were able to show that the complexes are stabilized by the formation of intermolecular hydrogen bonds between the host and guest species. CD molecules do not simply act as proton donors in a nonaqueous environment, but also protect parts of the molecule included within the cavity and steer the degradation process toward fewer products. 相似文献
2.
Volonterio A Bellosta S Bravin F Bellucci MC Bruché L Colombo G Malpezzi L Mazzini S Meille SV Meli M Ramírez De Arellano C Zanda M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4510-4522
Partially modified retro- (PMR) and retro-inverso (PMRI) psi[NHCH(CF(3))]Gly peptides, a conceptually new class of peptidomimetics, have been synthesized in wide structural diversity and variable length by aza-Michael reaction of enantiomerically pure alpha-amino esters and peptides with enantiomerically and geometrically pure N-4,4,4-trifluorocrotonoyl-oxazolidin-2-ones. The factors underlying the observed moderate to good diastereocontrol have been investigated. The conformations of model PMR-psi[NHCH(CF(3))]Gly tripeptides have been studied in solution by (1)H NMR spectroscopy supported by MD calculations, as well as in the solid-state by X-ray diffraction. Remarkable stability of turn-like conformations, comparable to that of parent malonyl-based retropeptides, was evidenced, as a likely consequence of two main factors: 1) severe torsional restrictions about sp(3) bonds in the [CO-CH(2)-CH(CF(3))-NH-CH(R)-CO] module, which is biased by the stereoelectronically demanding CF(3) group and the R side chain; 2) formation of nine-membered intramolecularly hydrogen-bonded rings, which have been clearly detected both in CHCl(3) solution and in some crystal structures. The former factor seems to be more important, as turn-like conformations were found in the solid-state even in the absence of intramolecular hydrogen bonding. The relative configuration of the -C*H(CF(3))NHC*H(R)- stereogenic centers has a major effect on the stability of the turn-like conformation, which seems to require a syn stereochemistry. X-ray diffraction and ab initio computational studies showed that the [-CH(CF(3))NH-] group can be seen as a sort of hybrid between a peptide bond mimic and a proteolytic transition state analogue, as it combines some of the properties of a peptidyl -CONH- group (low NH basicity, CH(CF(3))-NH-CH backbone angle close to 120 degrees, C-CF(3) bond substantially isopolar with the C=O) with some others of the tetrahedral intermediate [-C(OX)(O(-))NH-] involved in the protease-mediated hydrolysis reaction of a peptide bond (high electron density on the CF(3) group, tetrahedral backbone carbon). 相似文献
3.
Fermo P Gilardoni S Jauni Simarro T Bolzacchini E Lasagni M Gianelle V Pozzoli L Perrone G Librando V 《Annali di chimica》2003,93(4):389-396
The carbonaceous component in the Milan urban particulate matter, i.e. the two components black carbon (BC) and organic carbon (OC), has been measured by means of a thermogravimetric analyzer combined with an infrared spectrophotometer (TGA/FT-IR). While black carbon may be considered a primary pollutant, organic carbon includes both primary emissions and secondary organic aerosols. Since carbonaceous aerosol (including a small quantity of inorganic carbon, too) makes up roughly from 25% to 50% of the average annual PM 2.5 mass concentration, a deeper understanding of this component is required. The TGA/FT-IR technique, employed for the first time to our knowledge for the quantification of the particulate matter carbonaceous component, allows, thought the results here presented are preliminary, to assess the two components BC and OC in a simple way especially if compared with the methods reported in the literature. The total carbon (TC) determinations performed by TGA/FT-IR on Milan urban particulate matter are in good agreement with the results obtained by a total organic carbon (TOC) analyzer operating directly on the solid sample. 相似文献
4.
Marco Vincenti Claudio Minero Stefania Lago Costanza Rovida 《Journal of separation science》1995,18(6):359-362
A rapid and effective procedure, developed for the determination of polar compounds in water, has been applied to hydroxycarbamates. In few minutes, it is possible to perform a catalyzed derivatization of such compounds directly in the aqueous medium, using n-hexyl chloroformate. Extraction with n-hexane and injection into a benchtop GC-MS system are the only two further steps to complete the analysis. Chemical ionization proved to be more effective than electron impact to produce valuable mass spectra in terms of selectivity and sensitivity. Linear quantitative responses were demonstrated over a two-order-of-magnitude range. The minimum detectable concentration was 3 ppb for acetohydroxamic acid and 10 ppb for hydroxyurethane, obtained from Po river water samples spiked with the two hydroxycarbamate standards. 相似文献
5.
Abe K Abt I Ahn CJ Akagi T Ash WW Aston D Bacchetta N Baird KG Baltay C Band HR Barakat MB Baranko G Bardon O Barklow T Bazarko AO Ben-David R Benvenuti AC Bienz T Bilei GM Bisello D Blaylock G Bogart JR Bolton T Bower GR Brau JE Breidenbach M Bugg WM Burke D Burnett TH Burrows PN Busza W Calcaterra A Caldwell DO Calloway D Camanzi B Carpinelli M Cassell R Castaldi R Castro A Cavalli-Sforza M Church E Cohn HO Coller JA Cook V Cotton R Cowan RF Coyne DG D'Oliveira A Damerell CJ Dasu S 《Physical review letters》1995,74(9):1512-1516
6.
Abe K Abt I Ahn CJ Akagi T Allen NJ Ash WW Aston D Baird KG Baltay C Band HR Barakat MB Baranko G Bardon O Barklow T Bazarko AO Ben-David R Benvenuti AC Bienz T Bilei GM Bisello D Blaylock G Bogart JR Bolton T Bower GR Brau JE Breidenbach M Bugg WM Burke D Burnett TH Burrows PN Busza W Calcaterra A Caldwell DO Calloway D Camanzi B Carpinelli M Cassell R Castaldi R Castro A Cavalli-Sforza M Church E Cohn HO Coller JA Cook V Cotton R Cowan RF Coyne DG D'Oliveira A Damerell CJ Daoudi M 《Physical review D: Particles and fields》1995,52(7):4240-4244
7.
Antonio Cipiciani Stefania Primieri Antonio Arcelli 《Journal of inclusion phenomena and macrocyclic chemistry》1994,15(3):207-214
The hydrolysis reaction of 2-nitro-4-carboxyphenyl acetate was studied in dichloromethane in the presence of an added electrolyte (NaOH) and cationic surfactants systems with varying quantities of added water at 25°C. The kinetic and conductivity data were correlated. 相似文献
8.
Abe K Abt I Ash WW Aston D Bacchetta N Baird KG Baltay C Band HR Barakat MB Baranko G Bardon O Barklow T Bazarko AO Ben-David R Benvenuti AC Bienz T Bilei GM Bisello D Blaylock G Bogart JR Bolton T Bower GR Brau JE Breidenbach M Bugg WM Burke D Burnett TH Burrows PN Busza W Calcaterra A Caldwell DO Calloway D Camanzi B Carpinelli M Cassell R Castaldi R Castro A Cavalli-Sforza M Church E Cohn HO Coller JA Cook V Cotton R Cowan RF Coyne DG D'Oliveira A Damerell CJ Dasu S De Sangro R De Simone P 《Physical review D: Particles and fields》1994,50(9):5580-5590
9.
Abe K Abt I Acton PD Agnew G Ash WW Aston D Bacchetta N Baird KG Baltay C Band HR Baranko G Bardon O Battiston R Bazarko AO Bean A Belcinski RJ Ben-David R Benvenuti AC Biasini M Bienz T Bilei GM Bisello D Blaylock G Bogart JR Bolton T Bower GR Brau JE Breidenbach M Bugg WM Burke D Burnett TH Burrows PN Busza W Calcaterra A Caldwell DO Calloway D Camanzi B Carpinelli M Carr J Cassell R Castaldi R Castro A Cavalli-Sforza M Chadwick GB Chen L Church E Claus R Cohn HO Coller JA Cook V Cotton R 《Physical review letters》1993,71(16):2528-2532
10.
Starting from trifluoromethyl β-dicarbonyl compounds, a rare loss of CF3CO was observed in the amination reactions performed under heterogeneous conditions using NsONHCO2Et as the aminating agent and CaO or NaH as the base, while corresponding nonfluorinated β-dicarbonyl compounds under analogous conditions give non deacylated aminated compounds. This reaction can facilitate a direct synthesis of N-substituted α-amino esters or α-amino ketones. 相似文献