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C Crescenzi

Publications and source records attributed to C Crescenzi.

18 recordsLinked to original sources
PubMed2006

On-line strategies for determining trace levels of nitroaromatic explosives and related compounds in water.

We report the development and tests of several systems for the simultaneous determination of 18 energetic compounds and related congeners in untreated water samples. In these systems a Restricted Access Material trap or liquid-chromatography precolumn (with a C(18) or porous graphitic carbon, PGC, stationary phase) followed by a PGC analytical column are used for sample clean-up, enrichment and separation of the trace level analytes, which are then analyzed by mass spectrometry (MS). The relative merits of two MS ionization interfaces (atmospheric pressure chemical ionization, APCI, and atmospheric pressure photoionization, APPI) were also compared for the MS identification and quantification of these analytes. APCI was found to be superior in cases where both alternatives are applicable. A major drawback when applying APPI is that no signal is obtained for the cyclic nitramines and nitrate esters. Using APCI, a wide spectrum of unstable compounds can be determined in a single analysis, and the feasibility of using large volume samples (up to 100 mL) in combination with the sensitivity of the MS detection system provide method detection limits ranging from 2.5 pg/mL (for 2,4-dinitrotoluene and 2,6-diamino-6-nitrotoluene) to 563 pg/mL (for pentaerythritol tetranitrate, PETN), with repeatability ranging from 2 to 7%. Other chemometric parameters such as robustness, selectivity, repeatability, and intermediate precision were also evaluated in the validation of the extraction methods for use in water analysis. Tests with untreated groundwater and drinking water samples, spiked with 20 ng of the analytes, yielded results similar to those obtained with high purity water samples.

Analytic Sample Preparation Methods↗
PubMed2005

Supercritical fluid extraction of energetic nitroaromatic compounds and their degradation products in soil samples.

This paper explores the use of supercritical fluid extraction (SFE), in combination with various analyte collection strategies, for extracting energetic nitroaromatic compounds and their degradation products from soil samples. The required selectivity has been achieved by a combination of an SFE program and active trapping. Several different collection strategies were tested, using a selection of liquids (methanol, toluene, methyl tert-butyl ether, acetonitrile), inert and solid-phase extraction materials (Nexus, Oasis, LiChrolut), and 1-cm liquid chromatography precolumns (porous graphitic carbon, PGC). The best results were obtained using SFE in combination with a PGC precolumn. This setup allows on-line cleanup of the extract, and comparable results were obtained using either GC-ECD or GC-chemical ionization-MS for confirmatory analysis. The time required for a complete analysis was less than 60 min, and only 1 mL of toluene was needed for a 0.5-g representative sample. In contrast, the EPA standard method 8330 required 18-h sonication and 20 mL of acetonitrile for a 4.0-g sample and further time for sample cleanup and HPLC analysis. The method presented here provides method detection limits in the low-nanogram range, with relative standard deviations lower than 7%. The optimized method has been compared and validated with EPA method 8330 in terms of efficiency parameters such as robustness, accuracy (trueness and precision), and capability of detection. The validation demonstrated that the two analytical methodologies give comparable performance for the determination of nitroaromatic compounds, but SFE is superior for analyzing amine degradation products.

Journal Article↗
PubMed2004

Iatrogenic illness on a general medical service at a university hospital. 1981.

We found that 36% of 815 consecutive patients on a general medical service of a university hospital had an iatrogenic illness. In 9% of all persons admitted, the incident was considered major in that it threatened life or produced considerable disability. In 2% of the 815 patients, the iatrogenic illness was believed to contribute to the death of the patient. Exposure to drugs was a particularly important factor in determining which patients had complications. Given the increasing number and complexity of diagnostic procedures and therapeutic agents, monitoring of untoward events is essential, and attention should be paid to educational efforts to reduce the risks of iatrogenic illness.

Adult↗
PubMed2003

Determination of nitroaromatic compounds in air samples at femtogram level using C18 membrane sampling and on-line extraction with LC-MS.

This paper explores the use of C18 solid-phase extraction membranes for sampling very low concentrations of nitroaromatic compounds in the atmosphere. After sampling, analytes trapped in the membrane are desorbed on-line directly by a chromatographic mobile phase. The analytes are then separated onto a porous graphitic carbon (PGC) HPLC column. Finally, they are analyzed by an LC-MS/MS detector equipped with an atmospheric pressure chemical ionization (APCI) interface. The method was validated by controlled exposure of the membranes to standard gaseous mixtures of 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (2,4-DNT). The developed method was fully characterized, and no breakthrough was observed when sampling volumes up to 9.2 m3. Analyses of membranes following medium- and long-term storage demonstrated that samples could be stored on the C18 membranes without degradation or losses. In addition, the results obtained with this technique were compared with those obtained by a gas chromatographic method in which analytes were collected on Tenax TA and thermally desorbed. The developed method allows sampling at flow rates of 15 L/min and has method detection limits in the femtogram/liter range, with a relative standard deviation lower than 10%. An additional advantage of this method is that it separates most of the TNT and DNT isomers, as demonstrated by applying the method to the analysis of headspace over military-grade TNT explosives.

Journal Article↗
PubMed2001

Synthesis and evaluation of molecularly imprinted polymers for extracting hydrolysis products of organophosphate flame retardants.

A molecularly imprinted polymer (MIP) that selectively retains diphenyl phosphate was prepared using a structural analogue, ditolyl phosphate, as a template. Diphenyl phosphate is a degradation product of the flame retardant additive, triphenyl phosphate. The latter has been shown to be a common airborne contaminant in indoor environments and to be emitted from various goods such as video display units. Triphenyl phosphate induces several documented biological responses, including allergenic effects. Two different polymers, one prepared from methacrylic acid and the other from 2-vinylpyridine (2-Vpy), were investigated for their ability to recognise diphenyl phosphate. The polymers were used in solid-phase extraction cartridges (MISPE) and evaluated by comparing their recovery and breakthrough parameters with those of corresponding non-imprinted polymers (NIPs). The polymer made from the basic monomer showed the most selective recognition to the acidic analyte. Diphenyl phosphate was adsorbed to the basic MIP (2-Vpy-MIP) when methanol was used as mobile phase, and approximately 80% of the analyte was recovered when eluted from this polymer using a mixture of methanol and trifluoroacetic acid. There was a clear difference in the retention strengths of 2-Vpy-MIP and the corresponding 2-Vpy-NIP. The selectivity of the investigated 2-Vpy-MIP polymer towards a structural analogue of diphenyl phosphate, di(2-ethylhexyl) phosphate was also assessed. This compound was less strongly retained using the same experimental conditions. The results indicate that the prepared 2Vpy-MIP strongly recognises diphenyl phosphate due to the imprinting effect. This interaction probably arises mostly from an ionic interaction between the basic monomers and the acidic analyte. An LC-electrospray ionisation multiple MS method, using negative ion detection and ion-pair chromatography, was developed for separation and quantification of the strongly acidic dialkylated phosphate esters. The instrumental limit of detection was below 50 pg for all investigated compounds and the MS method was shown to be linear in the investigated range of 0.05-85 ng.

Chromatography, Liquid↗
PubMed2001

Method development for trace determination of poly(naphthalenesulfonate)-type pollutants in water by liquid chromatography-electrospray mass spectrometry.

A very sensitive analytical procedure based on LC-MS for determining trace amounts of the more relevant poly(naphthalenesulfonate) (PNS) contaminants present in environmental waters is presented. Extraction was performed on a styrene-divinylbenzene copolymer resin solid-phase extraction cartridge after addition of ammonium acetate to the sample. Small amounts of ammonium acetate in the mobile phase allowed the determination and characterisation of the four shorter oligomers by liquid chromatography-electrospray mass spectrometry. Under such conditions the electrospray process generates fully ionised molecules which greatly simplifies interpretation of spectra and quantitation. Additionally, confirmatory ions can be generated by the in-source collision-induced decomposition process. The effectiveness of the method was assessed in recovery experiments from drinking and river water samples spiked with commercial mixtures of PNS concrete plasticizers also referred as naphthalenesulfonate-formaldehyde condensates. Moreover, the performance of this method was compared to methods using ion-pair chromatography coupled with fluorimetric and mass spectrometric detection. Method detection limits were in the low picomolar range (1 ng/l for the monomer) for each isomer. In order to evaluate the environmental relevance of PNS type compounds waste, river and ground water grab samples were analysed. Concentrations of PNS oligomers detected in these samples ranged between 53 ng/l and 32 microg/l.

Chromatography, High Pressure Liquid↗
PubMed2001

Fibers coated with molecularly imprinted polymers for solid-phase microextraction.

The simplicity and flexibility of solid-phase microextraction have been combined with the selectivity of molecularly imprinted polymers (MIPs). Silica fibers were coated reproducible with a 75-microm layer of methacrylate polymer either nonimprinted or imprinted with clenbuterol to compare their extraction characteristics under various conditions. Although the template molecule could be removed effectively from the imprinted polymer, structural analogues of clenbuterol were used for evaluation. The influence of pH on the extractability of brombuterol was investigated. Extraction yields up to approximately 80% were obtained when both types of fibers were used to extract brombuterol from phosphate buffer (pH 7.0). In contrast, yields of about 75 and <5% were obtained when extraction was performed from acetonitrile with imprinted and nonimprinted polymers, respectively, which demonstrates the selectivity of the MIP-coated fiber. Time sorption profiles were measured for the extraction of brombuterol from buffer and acetonitrile at the 10 and 100 ng/mL level with both types of fibers in order to compare extraction characteristics. Equilibrium times of about 30 and 90 min were found for the extraction of brombuterol from acetonitrile and buffer, respectively. The MIP-coated fibers were capable of extracting five structural analogues of clenbuterol from both buffer and acetonitrile, which suggests that the amine alcohol part of these molecules is responsible for interaction with the imprinted polymer. To achieve selective extraction of brombuterol from human urine, MIP-coated fibers were washed with acetonitrile after the extraction. Clean extracts and yields of approximately 45% were obtained, demonstrating the suitability of MIP-coated fibers for the analysis of biological samples.

Journal Article↗
PubMed2001

Determination of clenbuterol in bovine liver by combining matrix solid-phase dispersion and molecular imprinted solid-phase extraction followed by liquid chromatography/electrospray ion trap multiple-stage mass spectrometry.

Matrix solid-phase dispersion (MSPD) is a new sample pretreatment for solid samples. This technique greatly simplifies sample pretreatment but, nonetheless, the extracts often still require an extra cleanup step that is both laborious and time-consuming. The potential of combining MSPD with molecularly imprinted solid-phase extraction (MISPE) was investigated in this study. Liver samples were ground in a mortar with C18 sorbent and the homogenized mixture packed into an SPE cartridge and placed on top of a MISPE cartridge. Subsequently, clenbuterol was eluted from the MSPD cartridge onto the MISPE cartridge using acetonitrile containing 1% acetic acid. The ability of the molecularly imprinted polymer to selectively adsorb analyte in acetonitrile was exploited for re-extracting clenbuterol directly from this acetonitrile extract via the double cartridge tandem system. The analyte was eluted from the MISPE cartridge using acidified methanol. A clear eluate was obtained, which was subsequently evaporated, redissolved, and analyzed by HPLC electrochemical detection (ECD) or ion trap mass spectrometry (LC/IT-MS). The MISPE cartridge used in this study was imprinted using bromoclenbuterol, a structural analogue of clenbuterol, as the template. These MISPE cartridges showed excellent stability. The complete extraction procedure was rapid, and recoveries exceeded 90% for the target analyte. The method detection limit for the LC/IT-MS procedure was < 0.1 microg/kg. This method, therefore, satisfies the stringent requirements of European Union regulation EEC 2377/90.

Adrenergic beta-Agonists↗
PubMed2001

Green fluorescent protein variants fold differentially in prokaryotic and eukaryotic cells.

Better-folding Green Fluorescent Protein (GFP) mutants selected from bacterial screenings are commonly used in widely different cellular environments. However, it is unclear if the folding efficiency of GFPs is invariant in different cell types. In this work, we have analysed the folding properties of GFP variants in bacteria versus mammalian cells. Remarkably, S65T was found to fold at comparable levels with the wild type GFP in bacteria, but at 10-fold lower levels in mammalian cells. On the other hand, Bex1 folded 3-4 times better than the wtGFP or S65T in E. coli, and 10-20-fold or more than 95-fold better, respectively, in mammalian cells. The Vex1 mutant demonstrated similar properties to Bex1. No evidence of differential GFP unfolding in vivo or of preferential degradation of unfolded GFP molecules was found. Moreover, no relationship between GFP folding efficiency and expression levels, or protein stability was detected. Trivial Aconfounding factors, like GFP unfolding caused by different pH or fluorescence quenching due to molecular crowding, were also excluded. In summary, our results demonstrate that specific GFP variants follow different folding trajectories in mammalian versus bacterial cells. The specificity of this differential folding supports a role of chaperones in guiding the folding of GFP in vivo. J. Cell. Biochem. Suppl. 36: 117-128, 2001.

Animals↗
PubMed2001

5-lipoxygenase regulates malignant mesothelial cell survival: involvement of vascular endothelial growth factor.

Evidence indicates that lipoxygenases (LO) may play a role in cancer cell survival. We show that human malignant pleural mesothelial (MM) cells, but not normal mesothelial (NM) cells, express a catalytically active 5-LO. Pharmacological or genetic inhibition of MM cell 5-LO determined nucleosome formation and induced a DNA fragmentation pattern typical of apoptosis. This was completely reversed by exogenously added 5(S)-HETE but not by 12(S)-, 15(S)-HETE, or leukotriene (LT)B4. A 5-LO antisense oligonucleotide potently and time-dependently reduced vascular endothelial growth factor (VEGF) mRNA and constitutive VEGF accumulation in the conditioned media of MM cells. When NM cells were transfected with a 5-LO cDNA, basal and arachidonic acid-induced VEGF formation increased consistently by 6- and 12-fold, respectively. This was associated with a significant increase in DNA synthesis that was counteracted by a specific anti-VEGF antibody. Arachidonic acid and 5(S)-HETE also potently stimulated the activity of a VEGF promoter construct. Thus, 5-LO is a key regulator of MM cell proliferation and survival via a VEGF-related circuit.

Apoptosis↗
PubMed2000

Hot phosphate-buffered water extraction coupled on-line with liquid chromatography/mass spectrometry for analyzing contaminants in soil.

We evaluated the feasibility of analyzing rapidly traces of polar and medium polar contaminants in soil by coupling on-line a hot phosphate-buffered water extraction apparatus to a liquid chromatography/mass spectrometer system. Coupling was accomplished by using a small C-18 sorbent trap for collecting analytes and two six-port valves. The efficiency of this device was evaluated by extracting 13 selected pesticides from 200 mg of laboratory-aged soils by varying the extraction temperature, the extractant volume, and the flow rate at which the extractant passed through the extraction cell and the sorbent trap. In terms of extraction efficiency, robustness of the method, and extraction time, the best compromise was that of using 8 mL of extractant at 90 degrees C and 0.5 mL/min flow rate. Under these conditions, recoveries of 11 out of 13 analytes ranged between 82 and 103%, while those of the least hydrophilic pesticides, i.e., neburon and prochloraz, were 73 and 63%, respectively. By increasing the extractant volume to 60 mL, additional amounts of the two latter compounds could be recovered. Under this condition, however, the most hydrophilic analytes were in part no more retained by the C-18 sorbent trap. From a naturally 1.5-year aged soil, hot phosphate-buffered water removed larger amounts of three herbicides and hydroxyterbuthylazine (a terbuthylazine degradation product) than pure water and Soxhlet extraction. This result seems to confirm that hot phosphate buffer is also able to remove from soil those fractions of contaminants that, on aging, are sequestered into the humic acid framework.

Buffers↗
PubMed1999

Quantification of phenylurea herbicides and their free and humic acid-associated metabolites in natural waters.

There is increasing interest in and demand for simultaneously monitoring pesticides as well as related degradation products (DPs) in natural waters, as the latter compounds can be even more toxic than the former ones. A method for determining parts per trillion levels of phenylurea herbicides and their DPs, that is their dealkylated forms and aromatic amines, is described. This method is based on solid-phase extraction with a Carbograph 4 cartridge followed by liquid chromatography (LC) with electrospray (ES) mass spectrometric detection. A study aimed at optimizing the response of the ES-MS detector for very weakly basic chloroanilines was conducted. Results showed that ion signal intensities of the above species were dependent on the composition of the LC mobile phase to an astonishing degree. At concentration levels of a few hundred ng/l, laboratory experiments showed that the aromatic amines considered here were mostly associated to dissolved humic acids (HAs) by both reversible and irreversible bindings. The addition of a reducing agent, i.e., NaBH4, succeeded in liberating that fraction of aromatic amines, which being reversibly bound to quinoidal structures of HAs are bioavailable. Analyte recoveries were better than 85% on extraction from 4 l of drinking water (spike level, 25 ng/l), 2 l of ground water (spike level, 50 ng/l) and 0.5 l of river water (spike level, 200 ng/l). Relative standard deviations ranged between 4.6 and 20% for drinking water, 4.3 and 15% for ground water, 5.9 and 13% for river water. Method detection limits calculated for drinking water, groundwater and surface water were between 3 and 11, 6 and 21, 36 and 75 ng/l, respectively.

Chromatography, Liquid↗
PubMed1984

Hospital use by the extremely elderly (nonagenarians): a two-year study.

Eighty-seven community-dwelling nonagenarians provided with extensive medical and social services as needed were followed for two years. Fifty-one subjects were admitted to an acute care hospital at least once. Total durations of hospitalization for those who required it averaged 44 days per individual over the two years. This represents about 13 hospital days per year per nonagenarian . Since it is likely that few, if any, hospitalizations would have been preventable by additional services, these data suggest that at a minimum one hospital bed would be continuously occupied for every 28 persons of this age and of this degree of infirmity . In these times of fiscal restraint it is especially important that the government and third-party payers determine the level of funding for expensive services such as acute hospitalization by assessing the needs of those who use them.

Aged↗
PubMed1982

An analysis of types and costs of health care services provided to an elderly inner-city population.

The challenge facing national policymakers is to provide health care that is comprehensive and cost-effective to our nation's growing population of elderly people. A solution worthy of consideration is the use of health maintenance organizations (HMOs) in this capacity. An analysis of the services provided by a multidisciplinary health care system to 150 inner-city elderly, many of whom were "homebound," reversal 1) this population is not homogeneous with respect to severity of disease and service utilization, and 2) a total mean cost per individual per year of $2,021.34 covers: physician, nursing, and social service home visits; visiting nurse, homemakers, home health aide, occupational therapy and physical therapy services; outpatient, laboratory and medication costs. These findings suggest that while costs for those over 65 are many times the per capita costs of younger enrollees, these costs may be significantly less than the costs of institutional care. Further investigation of the costs of maintaining low-income inner-city old, as well as other elderly populations, at home is vital to planning for future long-term care.

Aged↗
PubMed1981

Iatrogenic illness on a general medical service at a university hospital.

We found that 36% of 815 consecutive patients on a general medical service of a university hospital had an iatrogenic illness. In 9% of all persons admitted, the incident was considered major in that it threatened life or produced considerable disability. In 2% of the 815 patients, the iatrogenic illness was believed to contribute to the death of the patient. Exposure to drugs was a particularly important factor in determining which patients had complications. Given the increasing number and complexity of diagnostic procedures and therapeutic agents, monitoring of untoward events is essential, and attention should be paid to educational efforts to reduce the risks of iatrogenic illness.

Adult↗