Organic chloramine analysis and free chlorine quantification by electrospray and atmospheric pressure chemical ionization tandem mass spectrometry.

Atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI), together with tandem mass spectrometry (MSn), are used to study the mechanism of chlorination of amines and to develop a method for qualitative and quantitative determination of organic chloramines. Cyclohexylamine and 1,4-butanediamine (putrescine) are used as model compounds to investigate the mechanisms of the reactions between primary aliphatic amines and hypochlorous acid (aqueous Cl2). The chlorination products are identified and characterized by collision-induced dissociation (CID) and H/D exchange. Chlorination occurs by electrophilic addition of Cl+ and may be followed by HCl elimination, hydrolysis, or, in the case of diamines, amine elimination by intramolecular nucleophilic substitution. The relative rates of chlorination at amine and chloramine nitrogens are a function of pH and depend on the basicity of the amine. A novel method for active chlorine quantification using ESI or APCI mass spectrometry is suggested on the basis of the extent of chlorination of a sacrifical amine standard. This measurement has a limit of detection for N-chlorocyclohexylamine in the range of 0.1-10 microM, a linear dynamic range of 10(2)-10(3), and an accuracy of +/-10%, as determined for wastewater samples.

Chiroselective self-directed octamerization of serine: implications for homochirogenesis.

Serine undergoes chiroselective self-directed oligomerization to form a singly protonated octamer under positive ion electrospray conditions, as identified by ion trap tandem mass spectrometry. The experiments also show a series of higher-order clusters (metaclusters) corresponding to [(Ser8H)n]n+, n = 1, 2, 3. There is a magic number effect favoring formation of the protonated octamer over its homologues and also a strong preference for octamer formation from homochiral serine molecules. Collision-induced dissociation suggests that the protonated octamer is composed of four hydrogen-bonded dimers, stabilized by further extensive hydrogen bonding. Density functional calculations support this model and show that the protonated homochiral octamer is energetically stabilized relative to its possible fragments (dimer plus protonated hexamer, etc). The calculations also show that heterochiral octamers are less stable than homochiral octamers (e.g., the protonated 7:1 cluster is 2.1 kcal/mol less stable than the 8:0 analogue). The implications of these results for the origin of homochirality are discussed.

Serine octamer metaclusters: formation, structure elucidation and implications for homochiral polymerization.

Multiply charged serine metaclusters (composed of two or more homochiral octameric units) are generated by electrospray ionization, and their unique fused structures (hydrogen-bonded through the sticky ends of the drum-shaped octameric units) have been elucidated using tandem mass spectrometry experiments and molecular mechanics calculations.

Surface modification using a commercial triple quadrupole mass spectrometer.

We report instrumental modifications to a commercial mass spectrometer that allow surface modification experiments to be performed using low-energy (electronvolt range) mass-selected ion beams. The design of the detector housing allows placement of the surface on the ion optical axis and some distance beyond the off-axis detector. Manipulation of the potentials applied to the final lens, detector housing, conversion dynode, and electron multiplier allow the ions to pass through the detector housing and impinge upon the surface without loss of the normal mode of detector operation. Ex situ analysis of the modified surface is performed using a home-built multisector mass spectrometer. The ability to modify organic thin films is demonstrated by a number of soft landing and surface modification experiments including (i) soft landing of (CH3)2SiNCS+ ions formed from trimethylsilyl isothiocyanate upon a fluorinated self-assembled monolayer (F-SAM) surface, (ii) soft landing and dissociative soft landing of the pseudomolecular cation of triphenylpyrylium tetrafluoroborate, viz. the triphenylpyrylium cation, upon an F-SAM surface, (iii) dissociative soft landing of 35ClCH2(CH3)2SiOSi(CH3)2+ formed from 1,3-bis(chloromethyl)disiloxane upon an F-SAM surface, (iv) surface passivation by reaction of the trimethylsilyl cation, Si(CH3)3+, with a hydroxyl-terminated self-assembled monolayer (OH-SAM), and (v) transhalogenation by reaction of CCl3+ (m/z 119) with an F-SAM surface.

Gadolinium-DTPA enhanced MR imaging of septic dural sinus thrombosis.

We present a case of septic transverse/sigmoid sinus thrombosis imaged with gadopentetate dimeglumine enhanced magnetic resonance (MR). The appearance of the septic thrombus was atypical and did not conform to the usual blood degradation products probably because of the septic nature of the process. Enhanced T1-weighted images demonstrate both the "delta" sign and the tentorial enhancement as previously seen with contrast enhanced CT. Surgical correlation was obtained and helps to account for the appearance of the clot on MR.

Localization of technetium-99m pertechnetate in peripheral nerve tumors.

Technetium-99m pertechnetate scintigraphy in three patients with pathologically proven peripheral nerve tumors (six in total) demonstrated its ability to assess accurately the size, location, and the extent of all lesions. Pertechnetate localized only in areas of abnormal nerve involvement and all lesions were better seen in delayed images than the earlier ones. Pertechnetate imaging appears to be a promising method of noninvasive evaluation of clinically evident and occult tumors of peripheral nerve origin.

Simultaneous renal vein thrombosis and bilateral adrenal hemorrhage: MR demonstration.

A case of simultaneous renal vein thrombosis and bilateral adrenal hemorrhage is presented, demonstrating the ability of magnetic resonance (MR) imaging to identify these abnormalities without the use of intravenous contrast agents or radiopharmaceuticals. Adrenal hemorrhage appeared as markedly enlarged adrenal glands with homogeneous high signal intensity on both T1 and T2 weighted spin echo MR images. The kidney involved with renal vein thrombosis was enlarged and demonstrated increased signal from the renal parenchyma on T2 weighted images.