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PubMed2004

Partition-controlled progesterone release from waterborne, in situ-gelling materials.

The primary goal of this work was to evaluate the long-term constant zero-order release of progesterone from a waterborne, in situ-gelling, injectable material. The motivation for this is to develop an intrafallopian tube embolization system for contraception. Poly(ethylene glycol) diacrylate (PEGDA, 575 g/mol) or poly(propylene glycol) diacrylate (PPODA, 540 g/mol) as a Michael-type addition acceptor was combined with pentaerythritol-tetrakis (3-mercaptopropionate; a Michael-type addition donor) to create a 75 wt.% emulsion solution in 0.1M PBS (pH 7.4 for PEGDA and pH 12 for PPODA) that gels in minutes by the Michael-type reaction to form a hydrophobic solid. Samples, with approximately 5.5 or 25 wt.% progesterone, were formed in Tygon tubing. Samples (1.6 mm x 1.0 cm cylinders) showed constant, partition-controlled release of progesterone for a prolonged period (time dependent on the mass of progesterone). Cylinders with approximately 25 wt.% load of progesterone exhibited constant release (approximately 40 microg per day) for more than 50 days in both the PEGDA and PPODA systems. This type of release is normally associated with preformed hydrophobic matrix systems. In contrast, these in situ-gelling materials reported here can be used to provide zero-order, partition-controlled release of progesterone and enhance the efficiency of an intrafallopian tube embolization system through progesterone release in an injectable, in situ-forming system.

Delayed-Action Preparations↗

PubMed2004

Glass transitions and viscoelastic properties of carbopol and noveon compacts.

Glass transitions of five varieties of Carbopol (acrylic acid polymers cross-linked with allyl sucrose or allyl pentaerythritol) and two varieties of Noveon (calcium salts of acrylic acid polymer cross-linked with divinylglycol) differing in cross-linking density and nature and content in residual solvents, were analysed (as compressed probes) by differential scanning calorimetry (DSC), modulated temperature differential scanning calorimetry (MTDSC), and oscillatory rheometry. All carbopol compacts showed a main glass transition, at a temperature between 130 and 140 degrees C, Tg, independently of their cross-linking degree and molecular weight. Additionally two batches of Carbopol 971P, which had greater contents in residual solvents, also presented a secondary transition at 65-70 degrees C. Sorption of water during storage of carbopol compacts at different relative humidity environments caused the Tg to strongly decrease. Compacts stored at 97.5% relative humidity have Tg below 0 degrees C and behave, at room temperature, as flexible hydrogels. The Gordon-Taylor/Kelley-Bueche equation only fit the dependence of Tg on water content well for carbopol compacts containing less than 15% water. The plasticizing effect of water was clearly evidenced in the considerable decrease in the storage and loss moduli of the compacts. Although the energy associated to the glass transitions of carbopol polymers, 0.40-0.50 Jg(-1) degrees C(-1), is high enough to be clearly detected by DSC, in some cases the evaporation of residual solvents may make it difficult to observe the Tg. This inconvenience is overcome using MTDSC or oscillatory rheometry. The decrease in Tg of carbopol caused by water sorption when compacts were stored at 97.5% R.H. explains why their loss (G") and storage (G') moduli at room temperature decreased four orders of magnitude. In contrast, in noveon varieties, calcium ions act as ionic cross-linkers of the carboxylic groups, providing rigid networks with much higher Tg, and storage and loss moduli. This explains that despite sorbing similar amounts of water to carbopol, the changes on the mechanical properties of noveon compacts were much less important (i.e., G' and G" decreased up to one order of magnitude).

Acrylic Resins↗

PubMed2004

A novel anionic dendrimer for improved cellular delivery of antisense oligonucleotides.

The optimal design of hybridisation-competent antisense oligonucleotides (ODNs) coupled with an efficient delivery system appear to be important prerequisites for the successful use of antisense reagents for gene silencing. We selected an antisense ODN complementary to an accessible region of the epidermal growth factor receptor (EGFR) mRNA with the aid of an antisense oligonucleotide scanning array. The scanning array comprised 2684 antisense ODN sequences targeting the first 120 nts in the coding region of EGFR mRNA. The array-designed antisense ODN was covalently conjugated to a novel anionic dendrimer using a pentaerythritol-based phosphoroamidite synthon via automated DNA synthesis and the ability of this conjugate to effectively deliver and down-regulate EGFR expression in cancer cells was evaluated. Each dendrimeric structure had nine ODN molecules covalently linked to a common centre at their 3' termini. This dendrimer conjugate was markedly more stable to serum nucleases compared to the free ODNs and the cellular uptake of ODN-dendrimer conjugates was up to 100-fold greater as compared to mannitol, a marker for fluid phase endocytosis, and up to 4-fold greater than naked ODN in cancer cells. ODN-dendrimer uptake was energy-dependent and mediated, at least in part, via binding to cell surface proteins; a process that was inhibited by self-competition and by competition with free ODN, salmon sperm DNA, heparin and dextran sulphate. Fluorescent microscopy studies showed a combination of punctate and more diffuse cytosolic distribution pattern for fluorescently labelled ODN-dendrimer conjugate in A431 cells implying internalization by endocytosis followed by release and sequestration of the conjugate into the cytosol. Little or no conjugate appeared to be present in the nuclei of A431 cells. In vitro RNase H-mediated cleavage assays confirmed that covalently conjugated antisense ODNs in the dendrimer conjugate were able to hybridize and cleave the array-defined hybridisation target site within the EGFR mRNA without the need for ODN dissociation from the conjugate. In cell culture, ODN-dendrimer conjugates were effective in inhibiting cancer cell growth that correlated with a marked knockdown in EGFR protein expression. These data highlight a novel anionic dendrimer delivery system for gene silencing oligonucleotides that improved their biological stability, cellular delivery and antisense activity in cultured cancer cells.

Animals↗

PubMed2005

Prediction of heat of formation and related parameters of high energy materials.

Heat of formation is one of the most important parameters in the performance prediction of explosive and propellant formulations and their individual ingredients. This paper reports the development of user-friendly computer code for the prediction of heat of formation based on two approaches. In first methodology, the logic of Benson's Group additivity method and in the second method, the logic of Pedley method was used for predicting the heats of formation of high energy materials (HEMs). The predicted heats of formation by Benson method for various classes of high energy materials gave deviation in the range of 2-10%, whereas nearly 10-15% deviation was observed using Pedley methodology in comparison to experimental values. The linear regression coefficient values (R(2)) of 0.9947 and 0.9637 are obtained for heat of formation values predicted by this code using methodologies I and II, respectively. The newly developed code LOTUSES (version 1.3) has been validated by calculating the heats of formation of standard explosives such as TNT, pentaerythritol tetranitrate (PETN), RDX, HMX, etc., To the best of our knowledge, no such code is reported in literature which can predict heats of formation values integrated with performance parameters of HEMs belonging to all categories of organic compounds viz. aliphatic, aromatic and heterocyclic materials. The code can also be used to obtain parameters such as velocity of detonation, C-J pressure, volume of explosion products, power index, temperature of explosion and oxygen balance of HEMs. The code has been developed in Visual Basic having enhanced Windows environment. This software namely LOTUSES 1.3 is an updated version of the earlier ones namely LOTUSES 1.1 and 1.2 which do not cater for the calculation of heat of formation and temperature of explosion of HEMs. LOTUSES 1.3 is, therefore, a totally integrated software for computing most of the vital parameters of HEMs requiring mainly the molecular structural information of an explosive under consideration.

Energy-Generating Resources↗

PubMed2004

Desorption characteristics of uncoated silicon microcantilever surfaces for explosive and common nonexplosive vapors.

We measured the desorption of explosive trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), and hexahydro-1,3,5-triazine (RDX) vapors from piezoresistive silicon microcantilevers under ambient air. Depending on the amount of vapor loaded on the cantilever, TNT desorption took a few minutes to tens of minutes (for nanogram quantities). On the other hand, no significant loss of PETN or RDX was observed after many hours. We also measured desorption of common "nonexplosive" compounds (water, acetone, and ethyl alcohol) and observed that desorption was too fast to be measured. There is a good correlation between the desorption time and the melting point (or the vapor pressure) of a particular substance. In principle, this method can be used to measure desorption rates of various substances from cantilever surfaces.

Journal Article↗

PubMed2003

Recombinant (2-->3)-alpha-sialyltransferase immobilized on nickel-agarose for preparative synthesis of sialyl Lewis(x) and Lewis(a) precursor oligosaccharides.

The specificity of recombinant (2-->3)-alpha-sialyltransferase (ST3Gal-III), expressed in baculovirus-infected insect cells, has been determined with various oligosaccharide acceptors and sugar-nucleotide donors using a fluorescence based assay. Recombinant ST3Gal-III tagged with a polyhistidine tail was immobilized on Ni(2+)-NTA-Agarose as an active enzyme for use in the synthesis of three sialylated oligosaccharides: (i) the divalent molecule [alpha-Neu5Ac-(2-->3)-D-Galp-(1-->4)-beta-D-GlcpNAc-O-CH(2)](2)-C-(CH(2)OBn)(2) (12); (ii) the dansylated derivative, alpha-Neu5Ac-(2-->3)-D-Galp-(1-->3)-beta-D-GlcpNAc-O-(CH(2))(6)-NH-dansyl and; (iii) the tetrasacharide alpha-Neu5Ac-(2-->3)-beta-D-Galp-(1-->4)-beta-D-GlcpNAc-(1-->2)-alpha-D-Manp-O-CH(3). Compound 12 was itself prepared from the divalent N-acetyllactosamine molecule built on pentaerythritol by a chemo-enzymatic route.

Animals↗

PubMed2002

Identification of nitrate ester explosives by liquid chromatography-electrospray ionization and atmospheric pressure chemical ionization mass spectrometry.

Liquid chromatography-mass spectrometry (LC-MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), in the negative-ion mode, was investigated for the analyses of three widely used nitrate ester explosives, pentaerythritol tetranitrate, nitroglycerin and ethylene glycol dinitrate, as well as six additional nitrate esters, using post-column additives. In ESI, ammonium nitrate, sodium nitrite, propionic acid and ammonium chloride promoted formation of characteristic adduct ions of the respective nitrate esters. In APCI, chlorinated agents, dichloromethane, chloroform, carbon tetrachloride and ammonium chloride, were employed, fanning chloride attachment adduct ions. Three forensic samples, Booster DYNO, Semtex and Smokeless Powder, were analyzed to demonstrate the validity of the developed LC-MS methods.

Atmospheric Pressure↗

PubMed2003

Extending the range of compounds amenable for gas chromatography-mass spectrometric analysis.

Gas chromatography-mass spectrometry (GC-MS) suffers from a major limitation in that an expanding number of thermally labile or low volatility compounds of interest are not amenable for analysis. We found that the elution temperatures of compounds from GC can be significantly lowered by reducing the column length, increasing the carrier gas flow rate, reducing the capillary column film thickness and lowering the temperature programming rate. Pyrene is eluted at 287 degrees C in standard GC-MS with a 30 m x 0.25 mm I.D. column with 1-microm DB5ms film and 1-ml/min He column flow rate. In contrast, pyrene is eluted at 79 degrees C in our "Supersonic GC-MS" system using a 1 m x 0.25 mm I.D. column with 0.1-microm DB5ms film and 100-ml/min He column flow rate. A simple model has been invoked to explain the significantly (up to 208 degrees C) lower elution temperatures observed. According to this model, every halving of the temperature programming rate, or number of separation plates (either through increased flow rate or due to reduced column length), results in approximately 20 degrees C lower elution temperature. These considerably lower elution temperatures enable the analysis of an extended range of thermally labile and low volatility compounds, that otherwise could not be analyzed by standard GC-MS. We demonstrate the analysis of large polycyclic aromatic hydrocarbons (PAHs) such as decacyclene with ten fused rings, well above the current GC limit of PAHs with six rings. Even a metalloporphirin such as magnesiumoctaethylporphin was easily analyzed with elution temperatures below 300 degrees C. Furthermore, a range of thermally labile compounds were analyzed including carbamates such as methomyl, aldicarb, aldicarbsulfone and oxamyl, explosives such as pentaerythritol tetranitrate, Tetryl and HMX, and drugs such as reserpine (608 a.m.u.). Supersonic GC-MS was used, based on the coupling of a supersonic molecular beam (SMB) inlet and ion sources with a bench-top Agilent 6890 GC plus 5972 MSD. The Supersonic GC-MS provides enhanced molecular ion without any ion source related peak tailing. Thus, the lower GC separation power involved in the analysis of thermally labile and low volatility compounds is compensated by increased separation power of the MS gained from the enhanced molecular ion. Several implications of these findings are discussed, including our conclusion that slower chromatography leads to better analysis of thermally labile compounds.

Gas Chromatography-Mass Spectrometry↗

PubMed2003

Capillary electrochromatography with monolithic stationary phases. II. Preparation of cationic stearyl-acrylate monoliths and their electrochromatographic characterization.

A novel cationic monolithic stationary phase based on the co-polymerization of pentaerythritol diacrylate monostearate (PEDAS) with a selected quaternary amine acrylic monomer was designed for performing capillary electrochromatography at high flow velocity. While PEDAS functioned as both the ligand provider and the cross-linker, the quaternary amine acrylic monomer was introduced to control the magnitude of the electroosmotic flow (EOF). The fabrication of the cationic stearyl-acrylate monolith (designated as cationic C17 monolith) with controlled porosity was achieved by free radical polymerization using the initiator 2,2'-azobisisobutyronitrile in the presence of a ternary porogenic solvent composed of cyclohexanol, ethylene glycol and water. Four different quaternary amine acrylic monomers were investigated in order to find the optimum monomer for achieving maximum electroosmotic flow (EOF) velocity. Both photo- and thermally-initiated polymerization proved effective in producing the cationic C17 monolith, and the best monolith was achieved when [2-(acryloyloxy)ethyl]trimethyl ammonium methyl sulfate (AETA) was used as the quaternary amine acrylic monomer. Although the zeta potential of the resulting cationic C17 monolith is positive with respect to water, the magnitude and direction of the EOF was markedly affected by the nature of the electrolyte in the mobile phase. Consequently, anodal, zero or cathodal EOF was observed depending on the nature of the electrolyte, and this was attributed to the adsorption of the ionic components of the electrolyte on to the solid stationary phase, which is characterized by its amphiphilic nature consisting of C17 chains, ester functions, hydroxyl groups and quaternary amine moieties. Optimized PEDAS-AETA monoliths yielded columns with high separation efficiency and allowed rapid separations on the time scale of seconds to be achieved with short capillaries.

Acrylates↗

PubMed1998

Alterations of the vascular and the myocardial guanylate cyclase/cGMP-system induced by long-term hypertension in rats.

NO as produced by NO-synthases (NOS) contributes to the regulation of cardiovascular functions. In hypertension, there is a reduced production and/or activity of endogenous NO in the vasculature. We investigated if hypertension alters the NO-sensitivity of soluble guanylate cyclase (sGC) in blood vessels and heart muscle isolated from 15 month old spontaneously hypertensive rats (SHR15) and normal Wistar rats (WIS). Inhibition of NOS by 1 mM N omega-nitro-L-arginine decreased dP/dtmax in WIS (-27.6 +/- 3.4%) and SHR15 (-26.0 +/- 4.4%), while stimulation of NOS with 1 mM L-arginine increased dP/dtmax in WIS (9.9 +/- 0.7%) and SHR15 (8.9 +/- 2.3%). The positive inotropic response to 0.1 microM glyceryl trinitrate (GTN) was comparable in WIS (dP/dtmax: 4.5 +/- 1.7%) and SHR15 (dP/dtmax: 3.75 +/- 0.7%) as was the positive inotropic response to the NO-donor sodium (Z)-1-(N,N-diethylamino)diazen-1-ium-1,2-diolat (DEA/NO, 1 microM) in WIS (dP/dtmax: 10.7 +/- 2.9%) and SHR15 (dP/dtmax: 5.1 +/- 1.5%, P = 0.1873). In aortas of SHR15 we found an increased superoxide production of 19.4 +/- 1.7 nM/mg/min (WIS: 6.1 +/- 0.6 nM/mg/min) in the smooth muscle and the endothelial layer. Endothelium-dependent relaxation by acetylcholine was markedly impaired in SHR15 as was the vasorelaxant activity of S-nitroso-N-acetyl-D,L-penicillamine (SNAP), pentaerythritol tetranitrate and GTN. Maximal cGMP-production by sGC isolated from the lung and stimulated with SNAP (0.5 mM) was much lower in SHR15 (115 +/- 14 pmol/mg/min) than in WIS (348 +/- 36 pmol/mg/min). We suggest that hypertension is associated with a reduced activity of the sGC/cGMP-system in the vasculature but not in the heart muscle. Our results provide the first evidence that excess superoxide production in hypertension may trigger a desensitization of vascular sGC.

Animals↗

PubMed2002

A method for treating wastewater containing formaldehyde.

Many industrial activities utilise formaldehyde as a key chemical in organic synthesis including: synthesis of special chemicals such as pentaerythritol and ethylene glycol, synthetic resins, paper products, medicinal products and drugs and others, too numerous to mention. Therefore, effluents arising from these applications may contain significant amounts of formaldehyde. In a biodegradation experiments of a wastewater sample containing formaldehyde ranging from 31.5 to 125 mg/l, residual formalin (a solution of formaldehyde gas in water) ranging from 40% to 85%, respectively, was found at the end of the run (16 d) showing the inhibition effect of formalin which increased with the increase in formalin concentration. The biodegradation of formalin decreased significantly at concentrations higher than 300 mg/l. A method to convert formaldehyde to an easily biodegradable substance is herein described. In the commercial manufacture of resins from phenol and formalin the reaction is never completely quantitative. As a result during the dehydration stage phenol and formalin are distilled from the wastewater. Phenol is toxic to several biochemical reactions. However, biological transformation of phenol to a non-toxic entity is possible through specialized microbes. Transformation of phenol is inhibited by the presence of formaldehyde. Biotransformation of phenol in a wastewater containing high concentrations of formaldehyde started shortly after treating the wastewater with calculated amounts of sodium sulphite. Sodium sulphite is believed to react with formaldehyde forming sodium formaldehyde bisulphite, which is not only non-toxic to microorganisms but also a biodegradable substance. From the DO measurements before and after the addition of sodium sulphite, the authors noticed that the dissolved oxygen in a wastewater containing formaldehyde is not affected by the addition of the calculated amount of sodium sulphite, which is just enough to consume the measured amount of formaldehyde in that wastewater.

Biodegradation, Environmental↗

PubMed2001

Release of protein from highly cross-linked hydrogels of poly(ethylene glycol) diacrylate fabricated by UV polymerization.

Highly crosslinked hydrogel spheres were fabricated using UV photopolymerization of poly(ethylene glycol) diacrylate (PEG-DA) and pentaerythritol triacrylate (PETA) with 2,2'-dimethoxy-2-phenyl-acetophenone (DMPA) as the photoinitiator. Spheres were fabricated both with and without one of three comonomers: acrylic acid, acrylamide or allylamine. Photopolymerization rates and polymer morphology were determined using attenuated total reflectance/Fourier transform infrared spectroscopy and electron microscopy, respectively. These gels were further characterized for volume change, equilibrium water content, diffusivity of the expanding gel, molecular weight between crosslinks and polymer mesh size. Hydrogels with comonomers generally demonstrated an increase in equilibrium water content, average molecular weight between crosslinks and mesh size. Bovine serum albumin was incorporated into the hydrogel to simulate delivery of a model protein drug. The protein diffusion coefficients, based a Fickian release model, were calculated to be between 10(-10) and 10(-12) cm2/s with slight variance due to PETA concentration and the type of comonomer used.

Diffusion↗

PubMed2000

A particulate pulse-release system and mathematical description with the Maxwell-Stefan theory.

In this contribution both the development of a multi-particulate delayed release system with release properties dependent on the swelling of an UV crosslinked coating and a mathematical model to describe its release properties are presented. The formulation consists of a water-soluble core coated with a copolymer of methacrylic acid and ethyl acrylate. Incorporating a network of crosslinked pentaerythritol triacrylate decreases the water-solubility of the coating. After immersing the formulation in water the coating will take up water and subsequently swell in such a degree that the diffusion coefficient of water in the coating will increase. This makes the coating permeable to the dissolved components present in the core. The swelling kinetics of the coating are such that the formulation has a pulse-release profile, i.e. a fast release of the contents is obtained after a pre-determined lag-time. Both the coating thickness and the duration of the UV crosslinking time can be used to adjust the lag-time. The experimental results are used to estimate the Maxwell-Stefan diffusion coefficients of water in the coating. The relation between the Maxwell-Stefan diffusion coefficient and the mole fraction of water in the coating differs from results found in the literature. However, the prediction of the release time based on the presented model is in good agreement with the experimental findings.

Acrylates↗

PubMed2002

HPLC simultaneous determination of glycerol and mannitol in human tissues for forensic analysis.

A method for simultaneous determination of glycerol and mannitol in various human tissues was devised and for this we used high-performance liquid chromatography (HPLC). Specimens were homogenized in a mixture of chloroform and methanol, phosphate buffer (pH 7.0) and pentaerythritol (IS) solution. After centrifugation, an aliquot of the aqueous layer was evaporated to dryness and derivatized with p-nitrobenzoyl chloride at 50 degrees C for 1h, then applied to HPLC with analytical conditions of: column, CAPCELL PAK C18 MG (250 mm x 3.0 mm i.d., 5 microm, Shiseido Co. Ltd., Tokyo, Japan); column temperature, 1-2 degrees C; mobile phase, 75% acetonitrile-distilled water containing 0.05% trifluoroacetic acid, 0.05% heptafluoro-n-butyric acid and 0.1% triethylamine; flow rate, 0.5 ml/min; wavelength, 260 nm. Calibration curves for both substances were linear in concentration ranges from 1 to 500 microg/0.1g and correlation coefficients exceeded 0.99. The relative standard deviation (R.S.D.) of the method was evaluated at concentrations of 10 and 100 microg/0.1g, and ranged from 0.84 to 10.6%. Using this method, we determined the regional distribution levels of glycerol and mannitol in various tissues from an autopsied brain dead man.

Brain Death↗

PubMed2003

Study of the biodegradation and in vivo biocompatibility of novel biomaterials.

The degradation of two rosin-based biomaterials, the glycerol ester of maleic rosin (GMR) and the pentaerythritol ester of maleic rosin (PMR), was examined in vitro in phosphate-buffered saline at pH 7.4 and in vivo in a subcutaneous rat model. Free films of the two biomaterials with mean thickness 0.4+/-0.02 mm were used for the study. The initial biocompatibility was followed by microscopic examination of the inflammatory tissue response to the implanted films. Sample weight loss and molecular weight decline of the free films was used to monitor the degradation quantitatively, while surface morphological changes were analysed for qualitative estimation. Biocompatibility response was followed on post-operative days 7, 14, 21 and 28 and compared with those of poly(DL-lactic-co-glycolic acid) (PLGA) (50:50) films. Both biomaterials showed slow in vitro degradation when compared with the in vivo rate. The mechanism followed was, however, bulk degradation of the films. The penta-esterified form of maleic rosin was observed to degrade more rapidly than glycerol esterified maleic rosin. The acute and subacute inflammatory reactions were characterized by fibrosis at the end of 28 days. The biomaterials showed reasonable tissue tolerance to the extent evaluated. There was a total absence of tissue necrosis or abscess formation for all implanted films. The response, although not identical to that of PLGA, is reasonable, promising new drug delivery applications for rosin biomaterials.

Animals↗

PubMed2000

Electrocatalysis at a conducting composite electrode doped with a ruthenium(II) metallodendrimer.

A pentaerythritol-based metallodendrimer with RuIIterpyridine units was synthesized and tested as a mediator for the electrochemical oxidation of methionine (L-Met), cystine (L-Cys), and AsIII. A reversible oxidation of RuII was observed with the metallodendrimer as a solute in mixed acetonitrile-water solvents and as a component of carbon-based conducting composite electrodes. Mediated oxidation of the test species was observed. In aqueous solution, the composite electrode yielded a cyclic voltammetric peak current for the oxidation of L-Met in a 0.1 M phosphate buffer (pH 7.0) at 1.1 V vs Ag/AgCl. This anodic process was employed for amperometric detection in a flow system. Linear calibration curves were obtained over the range 1.0-10 microM Met and Cys. Using the criterion of the concentration yielding a signal 3 times the uncertainty of a blank, detection limits of 0.6 and 0.5 microM were calculated for Met and Cys, respectively. The slopes with three nominally identical electrodes varied by 10%.

2,2'-Dipyridyl↗

PubMed2001

Carbon electrodes modified with ruthenium metallodendrimer multilayers for the mediated oxidation of methionine and insulin at physiological pH.

A pentaerythritol-based metallodendrimer with ruthenium(II) terpyridine units, Ru(II)Den, catalyzed the oxidation of L-methionine and insulin at pH 7.0. The Ru(II)Den was immobilized on a carbon surface through layer-by-layer electrostatic deposition; the negatively charged polymer, poly(styrene sulfonate), was its counterpart. These bilayers were assembled on a glassy carbon electrode that was first modified by deposition of a layer of the conjugate base of sulfanilic acid and then with quaternized poly(4-vinylpyridine). Reversible voltammetry for the Ru(II/III) redox couple was observed, the current for which increased linearly with layer number, n, of Ru(II)Den up to n = 12. Cyclic voltammetry was used to demonstrate the mediation of L-methionine oxidation by a Ru(II)Den-containing multilayer assembly. Flow injection amperometric determination of insulin at pH 7.0 at this modified electrode yielded a calibration curve with the following characteristics: linear dynamic range, 6 nM-0.4 microM; sensitivity, 225 nA microM(-1); detection limit (k = 3 criterion), 2 nM. Of particular importance was that the sensitivity was proportional to the number of Ru(II)Den layers.

Animals↗

PubMed2005

Desorption electrospray ionization of explosives on surfaces: sensitivity and selectivity enhancement by reactive desorption electrospray ionization.

Desorption electrospray ionization (DESI), an ambient mass spectrometry technique, is used for trace detection of the explosives trinitrohexahydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 2,4,6-trinitrotoluene (TNT), Pentaerythritol tetranitrate (PETN), and their plastic compositions (Composition C-4, Semtex-H, Detasheet) directly from a wide variety of surfaces (metal, plastic, paper, polymer) without sample preparation or pretreatment. Analysis of the explosives is performed under ambient conditions from virtually any surface in very short times (<5 s) including confirmatory tandem mass spectrometry (MS/MS) experiments, while retaining the sensitivity and specificity that mass spectrometry offers. Increased selectivity is obtained both by MS/MS and by performing additional experiments in which additives are included in the spray solvent. These reactive DESI experiments (reactions accompanying desorption) produce such ions as the chloride and trifluoroacetate adducts of RDX and HMX or the Meisenheimer complex of TNT. Desorption atmospheric pressure chemical ionization, a variant of DESI that uses gas-phase ions generated by atmospheric pressure corona discharges of toluene or other organic compounds, provides evidence for a heterogeneous-phase (gaseous ion/absorbed analyte) charge-transfer mechanism of DESI ionization in the case of explosives. Plastic explosives on surfaces were analyzed directly as fingerprints, without sample preparation, to test DESI as a possible method for in situ detection of explosives-contaminated surfaces. DESI also allowed detection of explosives in complex matrixes, including lubricants, household cleaners, vinegar, and diesel fuel. Absolute limits of detection for the neat explosives were subnanogram in all cases and subpicogram in the case of TNT. The DESI response was linear over 3 orders of magnitude for TNT. Quantification of RDX on paper gave a precision (RSD) of 2.3%. Pure water could be used as the spray solution for DESI, and it showed ionization efficiencies for RDX in the negative ion mode similar to that given by methanol/water. DESI represents a simple and rapid way to detect explosives in situ with high sensitivity and specificity and is especially useful when they are present in complex mixtures or in trace amounts on ordinary environmental surfaces.

Journal Article↗