Synthesis, electrochemistry, and interactions with beta-cyclodextrin of dendrimers containing a single ferrocene subunit located "off-center".

Two series of dendrimers containing a single ferrocene unit located in the focal point of these macromolecules have been synthesized and characterized. The first series of dendrimers has considerable lipophilic character, with tert-butyl ester groups located in their peripheral regions. In contrast, the second series of dendrimers was obtained by the hydrolysis of these peripheral ester groups, yielding water-soluble dendrimers with carboxylic acid groups in their surfaces. The electrochemical properties of these macromolecules were strongly affected by the dendritic groups attached to the ferrocene subunits. Host-guest interactions between the water-soluble dendrimers and the well-known receptor beta-cyclodextrin were also investigated. The dendritic groups were found to hamper markedly the formation of inclusion complexes between the cyclodextrin receptor and the dendrimer's ferrocene unit.

Mobile Outreach Crisis Services (MOCS): an innovative model for taking psychiatric care into the community.

Mobile outreach psychiatric services have become a popular model of providing care to the mentally ill. A mobile program has been instituted in Tulsa, Oklahoma, to provide care to homeless mentally ill in Tulsa County and to assist with emergency crisis intervention. The SPMI (Severely and Persistently Mentally III) have been a challenge for both medical and psychiatric providers, and MOCS (Mobile Outreach Crisis Services) was developed to address these problems. This article describes MOCS, briefly reviews recent literature, and discusses ways this program can benefit primary care physicians.

On-line capillary electrophoresis-electrospray ionization mass spectrometry using a polymerized anionic surfactant.

On-line capillary electrophoresis-electrospray ionization-mass spectrometry (CE-ESI-MS) has been used to determine the tricyclic antidepressant drugs (imipramine, doxepin, and amitriptyline) as well as the beta-adrenergic blocker drugs (propranolol and alprenolol). A CE-ESI-MS interface linking a manually operated CE system and a Finnigan MAT-900 sector mass spectrometer (with an Analytica electrospray ionization source) has been constructed in-house and employed for this study. Although a water/methanol based capillary zone electrophoresis (CZE) buffer was initially used to determine these analytes, enhanced resolution was obtained by addition of a polymerized surfactant, i.e., poly-sodium undecylenic sulfate (poly-SUS), into the electrokinetic chromatography (EKC) buffer. When a low concentration of this poly-SUS surfactant was added to a volatile EKC buffer, these structurally similar cationic drugs were EKC separated and on-line detected by ESI-MS.

Structurally diagnostic ion-molecule reactions and collisionally activated dissociation of 1,4-benzodiazepines in a quadrupole ion trap mass spectrometer.

The ion-molecule reactions of various 1,4-benzodiazepines and dimethyl ether ions were studied with a quadrupole ion trap mass spectrometer. The methoxymethylene ions of dimethyl ether selectively react with 3-hydroxy-1,4-benzodiazepines (temazepam, oxazepam) to form (M+13)+ adducts by methylene substitution, and they react with 1,4-benzodiazepines that do not have hydroxyl substituents (diazepam, nordiazepam, nitrazepam) to form (M+15)+ adduct by a simple methyl cation transfer. These adducts are formed by elimination of methanol or formaldehyde, respectively, from (M+CH2OCH3)+ precursor ions. Ion-molecule reactions of model compounds with dimethyl ether ions suggest that the reactive site in the formation of (M+15)+ adducts is the imine functional group of the 1,4-benzodiazepines, while the reactive site for formation of (M+13)+ adducts involves a functional group interaction between the hydroxyl and carbonyl functional groups. Fragmentation induced by chemical ionization and collisionally activated dissociation provides further structural information for the differentiation of 1,4-benzodiazepines. Also, the gas-phase basicities of diazepam and temazepam have been estimated by bracketing techniques to be between 220.7 and 222.2 kcal/mol.

Selective ion-molecule reactions of lactams with dimethyl ether ions.

The ion-molecule reactions of dimethyl ether ions CH3OCH3 (+) and (CH3OCH3)H(+), and four- to seven-membered ring lactams with methyl substituents in various positions were characterized by using a quadrupole ion trap mass spectrometer and a triple-quadrupole mass spectrometer. In both instruments, the lactams were protonated by dimethyl ether ions and formed various combinations of [M + 13] (+), [M + 15] (+), and [M + 45] (+) adduct ions, as well as unusual [M + 3] (+) and [M + 16] (+) adduct ions. An additional [M + 47] (+) adduct ion was formed in the conventional chemical ionization source of the triple-quadrupole mass spectrometer. The product ions were isolated and collisionally activated in the quadrupole ion trap to understand formation pathways, structures, and characteristic dissociation pathways. Sequential activation experiments were performed to elucidate fragment ion structures and stepwise dissociation sequences. Protonated lactams dissociate by loss of water, ammonia, or methylamine; ammonia and carbon monoxide; and water and ammonia or methylamine. The [M + 16] (+) products, which are identified as protonated lactone structures, are only formed by those lactams that do not have an N-methyl substituent. The ion-molecule reactions of dimethyl ether ions with lactams were compared with those of analogous amides and lactones.