Determination of inosine 5′-monophosphate and guanosine 5′-monophosphate in pig feed by capillary zone electrophoresis

A capillary zone clectrophoresis method was developed for the determination of IMP and GIMP, commonly used as flavor enhancers in poultry feed, in a real sample of complex composition. A baseline separation of inosine 5′-monophosphate and guanosine 5′-monophosphate was achieved within 10 min and the other components in the sample did not interfere with the separation. Quantitative results obtained from pig feed samples are presented. The separation conditions and experimental reproducibility are also discussed.     

A novel anthracenyl tagged protecting group for "phase-switching" applications in parallel synthesis

A new "phase-switching" protecting group 1 that facilitates the parallel synthesis of carboxylic acids, esters, and carboxamides is described. Its use permits chemistries to be performed in solution, which may be conveniently monitored with conventional analytical techniques, followed by subsequent immobilization onto a solid-phase support to aid compound purification. Carboxylic acids, esters, and carboxamides are then cleaved from the solid support following activation of the "safety-catch" and treatment with the desired nucleophile.     

An efficient preparation of isosteric phosphonate analogues of sphingolipids by opening of oxirane and cyclic sulfamidate intermediates with alpha-lithiated alkylphosphonic esters

D-erythro-(2S,3R,4E)-Sphingosine-1-phosphonate (1), the isosteric phosphonate analogue of naturally occurring sphingosine 1-phosphate (1a), and D-ribo-phytosphingosine 1-phosphonate (2), the isosteric phosphonate analogue of D-ribo-phytosphingosine-1-phosphate (2a), were synthesized starting with methyl 2,3-O-isopropylidene-d-glycerate (4) and D-ribo-phytosphingosine (3), respectively. Oxirane 12 was formed in eight steps from 4, and cyclic sulfamidate 22 was formed in five steps from 3. The phosphonate group was introduced via regioselective ring-opening reactions of oxirane 12 and cyclic sulfamidate 22 with lithium dialkyl methylphosphonate, affording 13 and 23, respectively. The synthesis of 1 was completed by S(N)2 displacement of chloromesylate intermediate 14b with azide ion, followed by conversion of the resulting azido group to a NHBoc group and deprotection. The synthesis of 2 was completed by cleavage of the acetal, N-benzyl, and alkyl phosphonate ester groups.     

Coriatone and corianlactone, two novel sesquiterpenes from Coriaria nepalensis

Both coriatone (1). a novel highly oxygenated picrotoxane-type sesquiterpene, and corianlactone (2). with an unprecedented sesquiterpene basic skeleton, named coriane, were isolated from Coriaria nepalensis Wall. The structures of 1 and 2 were determined by analysis of their two-dimensional NMR data, and the structure of 2 was confirmed by X-ray analysis. Compounds 1 and 2 showed no remarkable inhibitory activity toward K(562) cells. They are cytotoxic with IC(50) > 50 microg/mL (cis-platinim: IC(50) = 0.49 microg/mL).     

Migration of 99Tc in a Weak Loess Aquifer: A Field Column Experiment

The migration of ⁹⁹Tc in a weak loess aquifer was investigated in-situ with undisturbed aquifer medium columns. The columns were obtained horizontally at a depth of 3236 m in an Underground Research Facility (URF). Quartz containing ³H (HTO) and ⁹⁹Tc (in the form of ⁹⁹TcO₄ ^-) was introduced into one end of the columns and the columns were covered tightly. Aquifer water was introduced into the columns directly from an experimental shaft in the UFR. Effluents from the columns were collected and the activity of ³H and ⁹⁹Tc were determined with a liquid scintillation analyzer. The breakthrough curves of ³H and ⁹⁹Tc indicate that ⁹⁹Tc migrates a little faster than that ³H does in the aquifer.     

Structures, stabilities, and electronic and optical properties of c(58) fullerene isomers, ions, and metallofullerenes.

The 1205 classical isomers of fullerene C58, as well as one quasi-fullerene C58 isomer with a heptagonal ring (labeled as Cs:hept) have been investigated by the quantum chemical methods PM3, HCTH/3-21G, and B3LYP/6-31G(d). Isomer C3v:0001, which has the lowest number of adjacent pentagons, is predicted to be the most stable isomer, but the quasi-fullerene isomer Cs:hept is only 2.50 kcal mol-1 higher in energy. Systematic investigations of the electronic properties of C3v:0001 and Cs:hept find that the C3v:0001 isomer has high vertical electron affinity (3.19 eV). The nucleus-independent chemical shifts (NICS) value at the center of Cs:hept (-5.1 ppm) is more negative than that of C60 (-2.8 ppm). The NICS value at the center of the heptagonal ring in Cs:hept (-2.5 ppm) indicates weakly aromatic character. In contrast, the C58(6-) and C58(8-) ions of the C3v:0001 and Cs:hept geometries possess large aromatic character, with NICS values between -14.0 and -26.2 ppm. To clarify the thermodynamic stabilities of C58 isomers at different temperatures, the entropy contributions are taken into account on the basis of the Gibbs energy at the B3LYP/6-31G(d) level. The C3v:0001 isomer prevails in a wide range of temperatures, and the Cs:hept isomer is also an important component around 2800 K. The IR spectra of C58 isomers are simulated to facilitate experimental identification of different isomers. In addition, the electronic spectra and the second-order hyperpolarizabilities are predicted by ZINDO and the sum-over-states model. The static second-order hyperpolarizability of the C3v:0001 isomer is 96.5 % larger than that of C60, and its second-order hyperpolarizabilities at external field frequencies are at least nine times larger than those of C60.     

Direct determination of cadmium at parts-per-billion level in waters by derivative atomic absorption spectrometry using atom trapping technique

A method has been described for the direct determinations of trace cadmium using derivative atom trapping flame atomic absorption spectrometry with an improved water-cooled stainless steel trapping equipment. The characteristic concentration (gave a derivative absorbance of 0.0044) and detection limit (3sigma) of cadmium were 0.028 and 0.02 ng ml(-1) when collecting for a 1 min, respectively, which were 992 and 145-fold better than those of the conventional flame atomic absorption spectrometry. The detection limit and sensitivity of the proposed method for a 2 min collection time were 1 and 2 orders of magnitude higher than those of conventional flame atomic absorption spectrometry. The present method was applied to the determinations of cadmium in water samples with a recovery range of 91 approximately 111% and a relative standard deviation of 4.7 approximately 5.6%.     

Direct determination of brucine by square wave voltammetry on 4-amino-2-mercaptopyrimidine self-assembled monolayer gold electrode

4-Amino-2-mercaptopyrimidine self-assembled monolayer (AMP SAMs/Au) was prepared on a gold electrode. The AMP SAMs/Au was characterized by using attenuated total reflection-fourier transform infrared (ATR-FTIR) and A.C. Impedance. The electrochemical behavior of brucine on AMP SAMs/Au was studied by cyclic voltammetry (CV) and square wave adsorptive stripping voltammetry (SWASV). The modified electrode showed an excellent electrocatalytic activity for the redox of brucine. The catalytic current increased linearly with the concentration of brucine in the range of 4.0 x 10(-7) to 2.0 x 10(-4) mol l(-1) by square wave voltammetry response. The detection limit was 6.0 x 10(-8) mol l(-1).     

Determination of gentamycin by synchronous derivative fluorimetry

Use of synchronous first-derivative fluorimetry for determination of gentamycin is described. Gentamycin reacts with acetylacetone and formaldehyde in pH 5.6 HOAc/NaOAc buffer solution to form N-gentamyl-2,6-dimethyl-3,5-diacethyl-1,4-dihydropyridine[I] which is a fluorescent substance. Spectra of [I] and the reagent blank can be separated with synchronous derivative fluorimetry, and gentamycin can be determined directly. The synchronous spectral peaks of [I] and the reagent blank are at 434 and 411 nm, respectively. The first-derivative peak of [I] is at 425 nm. Effects of pH, foreign ions, buffer system, and heating time on the determination of gentamycin have been examined. The linear regression equation of the calibration graph is C=0.0513H-0.0416, with a correlation coefficient of linear regression of 0.9978. C means total potency of gentamycin: U ml(-1); H means peak height in the linear regression equation calibration graph. The linear range for the determination of gentamycin is from 0.00 to 3.00 U ml(-1). Recovery is from 95.06 to 112.0%, R.S.D. of 3.8%. The results determined by the fluorimetric method agreed roughly with those by the microbiological method. The method is simple and has low detection limit.