Contemplation on the heats of combustion of isomeric hydrocarbons

Within the Hückel molecular orbital theory, the heats of combustion of isomeric hydrocarbons are related to some topological factors. The standard heats of combustion values of alternant hydrocarbons, expressed as kcal/g, seem to be related to a₄ coefficient of their secular polynomials.     

Molecular dynamics and quantum chemical studies on nitroglycerine

A constant temperature molecular dynamics study has been performed on PM3 (RHF) geometry optimized nitroglycerine molecule. The dynamics was carried out by using MM+ method at 550 K which is above the explosion point of nitroglycerine. Some molecular orbital characteristics of nitroglycerine at elevated temperatures were computed.     

AM1 treatment of some dinitro derivatives of [22](1,4)-cyclophane

Semiempirical molecular orbital treatment at the level of AM1(RHF) approach has been performed on [2₂](1,4)-cyclophanes (para-cyclophane derivatives) having two nitro substituents at different positions (the bridge positions and phane-deck(s)). All the isomeric structures presently studied are found to be stable but endothermic.     

A Possible Complex between TNT and Epinephrine – A DFT Study

The interaction between TNT and a vitally significant biological molecule, epinephrine, was investigated at the level of density functional theory. Two models are constructed; (i) an intimate pair of TNT and epinephrine and (ii) a π complex of them. The calculations (in vacuo conditions) have showed that these molecules in the intimate pair model orient themselves in an angular arrangement, whereas a π complex formation between these molecules is quite likely in the case of parallel arrangement of aromatic rings. The calculated electrostatic charges, UV and NMR spectra support the idea of a strong interaction between TNT and epinephrine whatever the type of interaction is.     

Analysis of urinary nucleosides. V. Identification of urinary pyrimidine nucleosides by liquid chromatography/electrospray mass spectrometry

Modified urinary nucleosides are potentially invaluable in cancer diagnosis, as they reflect altered RNA turnovers. High-performance liquid chromatography (HPLC) was combined with full-scan mass spectrometry, tandem mass spectrometry, MS(n) analysis and accurate mass measurements in order to identify pyrimidine nucleosides purified from urine. Potential nucleosides were assessed by their evident UV absorbance in the HPLC chromatogram and then further examined by the various mass spectrometric techniques. In this manner numerous pyrimidine nucleosides were identified in the urine samples from cancer patients including pseudouridine, cytidine, two methylcytidines and an acetylcytidine. Furthermore, a number of novel modified pyrimidine nucleosides were tentatively identified via critical interpretation of the combined mass spectrometric data.     

Ring fission of chiral cyclic acetals plus intramolecular [4 + 2] cycloaddition: a sequential access to medium-size lactones. Application to the synthesis of carbasugars

A set of alpha,beta-unsaturated cyclic acetals were reacted with t-butyllithium in THF. A conjugate elimination took place, triggering a ketal ring cleavage when two eq. of TMEDA were added to the medium. The lithium alcoholate thus obtained could be trapped in situ by 2,2,2-trifluoroethyl acrylate. The resulting acryloyl (1Z,3E)-dienyl ether was then submitted to an intramolecular Diels-Alder cycloaddition under high pressure (12 kbar, 50 degrees C). Depending on the structure of the linkage between the diene and the acrylate, the expected ("fused") lactones were obtained with total endo- or exo-selectivities and high to complete diastereoselectivities. A remarkable inversion of selectivity, from endo to exo, with respect to the stereochemical elements of the tether could be observed in these cases. A five step diastereoselective transformation of two of the resulting nine-membered ring lactones into modified carbasugars was finally achieved in 23% overall yield.     

Short capillary ion-pair high-performance liquid chromatography coupled to electrospray (tandem) mass spectrometry for the simultaneous analysis of nucleoside mono-, di- and triphosphates

A liquid chromatography/mass spectrometry (LC/MS) method for the analysis of complex mixtures of nucleoside mono-, di- and triphosphates has been developed. A short capillary column (35mm x 0.3mm i.d.) was operated under ion-pair high-performance liquid chromatography conditions and hyphenated to (negative) electrospray (tandem) mass spectrometry. As such, the separation of 12 nucleotides was performed by a binary gradient elution using CH(3)OH/H(2)O and N,N-dimethylhexylamine (N,N-DMHA) as ion-pairing agent. The influence of different N,N-DMHA concentrations on the chromatographic and mass spectrometric performance was evaluated to achieve optimal LC/MS conditions. In addition it was demonstrated that a controlled admission of ammonium dihydrogen phosphate (NH(4)H(2)PO(4)) improved both chromatographic performance and mass spectrometric detection. Because the system was hyphenated to an orthogonal designed electrospray interface (Z-spraytrade mark), long acquisition times were possible without loss of sensitivity.     

Search for tensor couplings in the weak interaction

The existence of exotic couplings in the weak interaction can be tested by a precise measurement of the β-ν angular correlation parameter a in nuclear beta decay. In the case of ⁶He, the ratio of tensor and axial-vector couplings can be determined. The goal of the LPC Trap experiment is to improve the limits on the existence of tensor currents. The LPCTrap setup is installed on the low energy beam line LIRAT of the SPIRAL/GANIL facility. The ⁶He⁺ ions are confined in a novel transparent Paul trap allowing the detection in coincidence of both the β-particle and the recoil ion. The detection setup enables to detect the position and energy of these two particles. The a parameter can then be extracted from the time of flight spectrum of the recoil ions. The first ⁶He⁺ decay events were observed in May 2005 during a commissioning run. Over 10⁵ coincidence events have been recorded during a second run in July 2006.     

High resolution NMR imaging: Gd-DTPA labeled enzyme as a probe for permeability studies in polyacrylamide gels.

The penetration of horse liver alcohol dehydrogenase (HLAD) molecules into polyacrylamide gel beads, which are used to immobilize the enzyme, was studied. HLAD was labeled with gadolinium diethylene-triamine-pentaacetic acid (Gd-DTPA), using the N-hydroxy-succinimide active ester of DTPA as a chelating agent. The HLAD-(Gd-DTPA)27 has a 3.7-fold larger longitudinal (R1) and a 14-fold larger transversal relaxivity (R2) (at 2.4 T) than the plain Gd-DTPA. A series of dry polyacrylamide gel beads, with total monomer concentration ranging from 5% to 30% were synthesized and swollen in a buffered solution of HLAD-(Gd-DTPA)27. The gel beads were examined with high resolution NMR imaging. The T1- and T2-weighted images revealed that the permeability for the labeled HLAD decreased with increasing total monomer concentration of the gel beads. These imaging results correlate fairly well with the enzymatic reactivities measured for the same range of gel beads but swollen in a solution of non labeled HLAD and NAD+ (nicotinamide adenine dinucleotide). It is concluded that Gd-labeling can be used to monitor the distribution of weakly concentrated, water soluble products in a solid matrix.     

Ammonia deposition in fullerene: (NH3)n@C60

Deposition of ammonia molecules in fullerene has been investigated theoretically by performing semi-empirical molecular orbital calculation at PM3 level within RHF formalism. C₆₀ cluster has been doped endohedrally by ammonia molecules. Structural and electronic properties of the systems considered have been studied. It has been found that C₆₀ cluster can store at most six ammonia molecules. The ammoniacal endofullerenes, (NH₃)_n@C₆₀, have been found stable but endothermic.