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G Carta

Publications and source records attributed to G Carta.

At least 19 recordsLinked to original sources

Protein adsorption on novel acrylamido-based polymeric ion-exchangers. I. Morphology and equilibrium adsorption.

The protein uptake equilibrium and particle morphology are determined for novel polymeric ion-exchange media based on acrylamido monomers with a high density of functional groups and a variety of morphological characteristics. The study considers two anion-exchangers and a cation-exchanger. Physical properties determined experimentally include particle density, ion-exchange capacity, particle size distribution, and equilibrium isotherms for model proteins. The pore structure was evaluated using size exclusion chromatography with neutral probe molecules and transmission electron microscopy. For the anion-exchangers, two types of structures were inferred. The first is comprised of particles that contain a low-density gel supported by denser polymer aggregates. This material had a very low size-exclusion limit for neutral probes, but exhibited an extremely high and reversible protein adsorption capacity (280-290 mg BSA/ml). The second structure is comprised of particles with large, open macropores. While the size-exclusion limit was very high, the protein adsorption capacity was low (60 mg BSA/ml). Moreover, the adsorption was nearly irreversible. The physical structure of the cation-exchanger appeared to be intermediate between those of the anion-exchangers, containing both large pores and smaller pores yielding an intermediate, but reversible, protein uptake capacity (120-130 mg alphaCHY/ml). The different behavior of these materials with regards to protein adsorption correlates well with their physical structure. For these ion-exchangers, high protein adsorption capacities are attained when a low-density polymer gel with a high concentration of functional groups is present.

Acrylamides↗

Protein adsorption on novel acrylamido-based polymeric ion exchangers. II. Adsorption rates and column behavior.

Uptake kinetics and breakthrough behavior were determined for bovine serum albumin (BSA) and alpha-chymotrypsinogen (alphaCHY) in new polymeric ion-exchange media based on acrylamido monomers. Two anion exchangers and a cation exchanger were investigated. As shown in Part I of this work, the two anion exchangers have different morphologies. The first one, BRX-Q, comprises a low-density gel with a matrix of denser polymeric aggregates. While this material has a very low size-exclusion limit for neutral probes, it exhibits an extremely high binding capacity for BSA. The second anion exchanger, BRX-QP, comprises large open pores but has a very low binding capacity. The cation exchanger, BRX-S, also comprises large open pores but exhibits an intermediate capacity; likely as a result of the presence of smaller pores. Dynamic protein uptake experiments showed that the highest mass transfer rates are obtained with BRX-Q. The apparent diffusivity is also highest for this material and increases substantially as the protein concentration is reduced. For these particles, the external film resistance is dominant at very low protein concentrations. Much lower rates and apparent diffusivities are obtained for BRX-QP. Finally intermediate rates and apparent diffusivities are found with BRX-S. The concentration dependence of the apparent pore diffusivity is much less pronounced in this case. The apparently paradoxical result that mass transfer rates are highest for the material with the smallest neutral-probe size-exclusion limit can be explained in terms of a general conceptual model where parallel pore and adsorbed-phase diffusion paths exist in these particles. In the first case, adsorbed phase diffusion in gel pores is dominant, while in the second transport is dominated by diffusion in a macroporous network. In the third case, both contributions are important. The conceptual model provides an accurate prediction of the breakthrough behavior of columns packed with these media using independently determined rate parameters. Dynamic binding capacities of 80-140 mg/ml were observed for BSA on BRX-Q in ca. 1.5 cm columns operated at 300-900 cm/h in agreement with theoretical predictions.

Acrylamides↗

Lipopolysaccharide increases arginine-vasopressin release from rat suprachiasmatic nucleus slice cultures.

The aim of this study was to determine whether Escherichia coli lipopolysaccharide at the doses of 25, 50 and 100 microM influences arginine-vasopressin (AVP) secretion in young rat suprachiasmatic nucleus (SCN) neurons. Lipopolysaccharide administered in the medium for 3 h increased significantly the arginine-vasopressin release lasting up to 6 h after treatment. These results provide the first evidence that lipopolysaccharide influences AVP secretion in SCN neurons. Moreover, these findings may explain some central effects observed in vivo after lipopolysaccharide administration.

Animals↗

Permissive role of dopamine D(2) receptors in the hypothermia induced by delta(9)-tetrahydrocannabinol in rats.

Cannabinoids produce analgesia, hypomotility, catalepsy, cognitive deficits and positive reinforcement. Moreover, Delta(9)-tetrahydrocannabinol (9-THC) and synthetic cannabinoids stimulate dopaminergic neurons and increase dopamine release in different brain areas. In order to clarify the role of endogenously released dopamine in the hypothermic response to cannabinoids, the effect of D(1) and D(2) dopamine receptor agonists and antagonists on Delta(9)-THC-induced hypothermia was studied in rats. Delta(9)-THC (2.5 and 5 mg/kg intraperitoneally [IP]) decreased body temperature in a dose-related manner. This effect was antagonized not only as expected by the CB(1) cannabinoid receptor antagonist SR 141716A (0.5 mg/kg, IP) but also, unexpectedly, by the dopaminergic D(2) receptor antagonists S(-)-sulpiride (5 and 10 mg/kg, IP) and S(-)-raclopride (1 and 3 mg/kg, IP). Conversely, the hypothermic effect of Delta(9)-tetrahydrocannabinol was potentiated by the D(2) dopamine receptor agonists (-)-quinpirole (0.025 and 0.500 mg/kg, SC) and (+)-bromocriptine (0.5 and 1 mg/kg, IP). In contrast, the Delta(9)-THC-induced hypothermic effect was not modified by either by the D(1) dopamine agonist SKF 38393 (10 mg/kg SC) or by the D(1) dopamine antagonist SCH 23390 (0.5 mg/kg SC). These results suggest that the D(2) dopamine receptors have a permissive role in the hypothermic action of cannabinoids.

Animals↗

Repeated lipopolysaccharide administration produces tolerance to anorexia and fever but not to inhibition of thirst in rat.

In 24 h water and food deprived rats, a single lipopolysaccharide treatment (0.25, 0.50 and 1 mg/kg, i.p.) induced inhibition of thirst and hunger as well as fever. Moreover, the same treatment increased serum cytokines, plasma nitrite/nitrate and corticosterone and urinary prostaglandin levels. In another group of 24 h water and food deprived rats, a repeated lipopolysaccharide treatment (0.25, 0. 50 and 1 mg/kg, i.p.), given at 0, 2, 6, 12 and 24 h, induced tolerance to inhibition of food intake and fever, but not to antidipsogenic effect. Moreover, the same repeated treatment stopped the increase in serum cytokines, plasma corticosterone and urinary prostaglandin concentrations and failed to reduce plasma nitrite/nitrate levels. This data, together with the evidence that a pretreatment with N(G)-nitro-L-arginine methyl ester hydrochloride (L-NAME) (5 and 10 microg per rat) reverses the antidipsogenic effects in lipopolysaccharide tolerant rats, suggests that the persistent reduction of water intake after a repeated lipopolysaccharide treatment is due to the antidipsogenic action of nitric oxide in the brain.

Animals↗

D(2) dopamine receptors enable delta(9)-tetrahydrocannabinol induced memory impairment and reduction of hippocampal extracellular acetylcholine concentration.

1. The systemic administration of Delta(9)-tetrahydrocannabinol (2.5 - 7.5 mg kg(-1)) reduced hippocampal extracellular acetylcholine concentration and impaired working memory in rats. 2. Both effects were antagonized not only by the CB(1) cannabinoid receptor antagonist SR141716A (0.5 mg kg(-1), i.p.) but also unexpectedly by the D(2) dopamine receptor antagonist S(-)-sulpiride (5, 10 and 25 mg kg(-1), i.p.). Conversely, Delta(9)-tetrahydrocannabinol-induced memory impairment and inhibition of hippocampal extracellular acetylcholine concentration were potentiated by the subcutaneous administration of the D(2) dopamine receptor agonist (-)-quinpirole (25 and 500 microg kg(-1)). The inhibition of hippocampal extracellular acetylcholine concentration and working memory produced by the combination of (-)-quinpirole and Delta(9)-tetrahydrocannabinol was suppressed by either SR141716A or S(-)-sulpiride. 3. Our findings suggest that impairment of working memory and inhibition of hippocampal extracellular acetylcholine concentration are mediated by the concomitant activation of D(2) dopamine and CB(1) cannabinoid receptors, and that D(2) dopamine receptor antagonists may be useful in the treatment of the cognitive deficits induced by marijuana.

Acetylcholine↗

Changes in conjugated linoleic acid and its metabolites in patients with chronic renal failure.

BACKGROUND: Conjugated linoleic acid (CLA) is a mixture of isomers of linoleic acid with conjugated double bonds that constitutes the most abundant fatty acid with conjugated dienes (CDs) in humans. CLA, erroneously considered in the past as a product of lipoperoxidation, has a dietary origin and has shown to possess anticarcinogenic and anti-atherogenic activity, mainly in animal studies. CLA can be metabolized to conjugated linolenic acid (CD18:3) and to conjugated eicosatrienoic acid (CD20:3) and these metabolites may be implicated in CLA activity. Because of the presence of dyslipidemia and the high incidence of cardiovascular and neoplastic diseases in uremic patients, we evaluated CLA and its metabolites in these patients in order to evaluate their metabolism and site distribution. METHODS: We measured CLA, CD18:3, CD20:3, CD fatty acid hydroperoxides (lipoperoxidation products), and linoleic acid in the plasma, adipose tissue, and red blood cell (RBC) membranes by using high-pressure liquid chromatography in the following groups: (1) 23 chronic renal failure (CRF) patients with creatine clearance (CCr)> 10 mL/min (26.2 +/- 16.7); (2) 21 end-stage CRF patients in conservative treatment with CCr <10 mL/min (6.8 +/- 1.8); (3) 30 hemodialysis (HD) patients; and (4) 30 healthy controls. RESULTS: The incorporation of CLA, CD18:3, and CD20:3 in RBC membranes was significantly reduced in group 1 and was even more reduced in groups 2 and 3. CLA significantly increased both in the plasma and adipose tissue of end-stage CRF patients only. CD18:3 and CD20:3 did not change in the plasma and adipose tissue of any group. No significant changes in linoleic acid and CD fatty acid hydroperoxides were found. CONCLUSIONS: The alterations of CD in CRF patients are not due to lipoperoxidation. The increased levels of CLA in plasma and adipose tissue of end-stage CRF patients may be due either to a reduced metabolization of CLA to CD18:3 and CD20:3, or to an altered site distribution with reduced incorporation in cellular membranes and accumulation in the plasma and adipose tissue. The clinical significance of these changes remains to be investigated.

Adipose Tissue↗

Surgical treatment of invasive carcinoma of the vulva. Our experience.

OBJECTIVE: The purpose of this study was to investigate the clinical findings, treatment and outcome of patients with vulvar carcinoma in the L'Aquila area. METHODS: Fifteen cases of vulvar carcinoma seen between September 1991 and December 1999 at the Department of Obstetrics and Gynecology of the University of L'Aquila were reviewed. Clinical, pathologic, surgical and follow-up data were collected from patient records. Mean age at diagnosis was 66.4 years. All patients were evaluated through a careful medical history and physical examination, vulvoscopy, abdomino-pelvic CT or MR, urethrocystoscopy, rectocolonscopy and SCC, and CEA determination. Radical surgery included six patients treated by the Taussig-Way operation. Modified radical surgery accounted for nine patients treated by the Byron three-incision approach. RESULTS: The major early complication was groin wound breakdown which occurred in four cases. The major late complication was chronic leg edema which was reported in six patients. The average number of nodes removed per patient was 19.5. Seven patients (46.7%) had a T2N0M0 pathologic stage, four (26.7%) were T2N1M0, four (26.7%) T1N0M0. Five patients died of local and distant recurrences within 37 months after surgical treatment; ten patients are alive, nine are apparently free from disease whereas one presented local and systemic recurrence within 18 months after surgery. CONCLUSIONS: Vulvar carcinoma predominantly affects older women. Most patients in our series (11/15) had tumors more than 2 cm in diameter. Although the vulva is an external organ and early detection should be achieved, many patients presented with extensive primary lesions due to both patient and physician delay. Stage of disease, tumor size, and nodal metastases are potential prognostic factors useful in selecting patients for a more conservative surgical approach.

Aged↗

[Pregnancy in adolescence. Consequences and considerations].

Many authors have pointed out that sexual activity is starting at an increasingly early age in young adolescents. In 1990 pregnancies in under 15-year-olds in the United States accounted for 3% of the total, a figure that has increased by 13% over the past decade. Moreover, pregnancy in adolescence may result in a number of complications, including pre-term birth, PIH, sexually transmitted diseases. The aim of this study was to evaluate the incidence of adolescent pregnancy in our user basin and to analyse the clinical evolution of these cases. The sample included 61 girls aged between 15.4 and 17.9 years old, mean age 16.7. Of these, 65.6% were students. The majority opted for voluntary abortion (85.2%). Those who chose to continue the pregnancy came from small towns with less than 1000 inhabitants (77.7%). They subsequently married their partners and continued to live with their parents. From an obstetric point of view, only one case of pre-term birth was recorded at week 26, and two cases of IUGR. The fact that the percentage of pregnancies in adolescence has remained unchanged over the years in spite of the numerous health and contraception campaigns represents a strong stimulus to investigate the countless facets of this problem.

Adolescent↗

Protein diffusion in charged polyacrylamide gels. Visualization and analysis.

Protein diffusion in anionic, cross-linked polyacrylamide-based gels supported in fused-silica capillaries was characterized by a direct visualization method. Microphotography was used to obtain transient protein concentration profiles in these gels using cytochrome c as a probe molecule. Gels based on acrylamido-methylpropane sulfonic acid with 2.5-10% N,N'-methylene-bisacrylamide as a cross-linker and with a total polymer concentration of 0.21 g/cm3 yielded diffuse protein concentration profiles which were quantitatively consistent with a Fickian diffusion model. An analytical method was developed to calculate the diffusivity as a function of protein concentration in the gel from the experimental profiles. The diffusivity was found to assume values in the range 2.5-5.5x10(-8) cm2/s and varied somewhat with the protein concentration in the gel. The effects of some of the polymer properties, such as cross-link density, polymer concentration and charge, were also investigated for a limited range of conditions to derive qualitative trends. Results showed that the transport rates increased with a decrease in the cross-link density, were extremely reduced when the polymer concentration was doubled, and were slightly increased when the charge density was decreased by half by polymerizing a 1:1 mixture of acrylamide and acrylamido-methylpropane sulfonic acid monomers.

Acrylic Resins↗

Dopamine D(2) receptor antagonists prevent delta(9)-tetrahydrocannabinol-induced antinociception in rats.

Delta(9)-Tetrahydrocannabinol (1 and 5 mg/kg, i.p.) produced, dose-dependently, antinociceptive effects using hot plate and tail flick tests in rats. These effects were suppressed not only by the cannabinoid CB(1) receptor antagonist SR 141716A (0.5 mg/kg; i.p.) but also by the dopamine D(2) receptor antagonists S(-)-sulpiride (5 and 10 mg/kg; i.p.) and S(-)-raclopride (1.5 and 3 mg/kg; i.p.). Conversely, Delta(9)-tetrahydrocannabinol antinociceptive effects were potentiated by the dopamine D(2) receptor agonists (-)-quinpirole (0.025 mg/kg, s.c.) and (+)-bromocriptine (0.5 and 1 mg/kg; i.p.). Our results indicate that the antinociceptive effects of Delta(9)-tetrahydrocannabinol are mediated by the concomitant activation of cannabinoid CB(1) and dopamine D(2) receptors and that dopamine D(2) receptor agonists may be useful in improving the analgesic effects of cannabinoids.

Analgesics, Non-Narcotic↗

Peroxidase-catalyzed pro- versus antioxidant effects of 4-hydroxytamoxifen: enzyme specificity and biochemical sequelae.

Some studies have shown the potential relevance of the oxidation products of 4-hydroxytamoxifen (4OHTAM) in carcinogenesis. Other studies show 4OHTAM has antioxidant properties. We characterized the one-electron oxidative activation reactions of 4OHTAM and three other phenolics, 3-hydroxytamoxifen (3OHTAM), 1-(4-hydroxyphenyl)-1, 2-diphenylethene, and phenol (PhOH), catalyzed by myeloperoxidase (MPx), horseradish peroxidase (HRP), lactoperoxidase, mushroom tyrosinase, and nonenzymatic initiators in vitro under a variety of conditions and in cells. Differences in activation of the phenolics by the enzymes were directly compared using cis-parinaric acid (PnA)-loaded human serum albumin. All phenolics were substrates for the enzymes, but MPx only weakly activated 4OHTAM to its phenoxyl radical. In HL60 cells loaded metabolically with PnA so that effects on phospholipids could be monitored by HPLC with fluorescence detection, PhOH plus H2O2 caused massive oxidation across all phospholipid classes. 4OHTAM dose-dependently protected phosphatidylethanolamine, phosphatidylserine, and phosphatidylcholine against both H2O2-induced and normal metabolic oxidation. This suggested 4OHTAM is a poor substrate for intracellular MPx. In rat aorta smooth muscle cells loaded with PnA, 4OHTAM also protected against AMVN-induced peroxidation of those three phospholipids and sphingomyelin, whereas 3OHTAM did not. Spin trapping of glutathionyl radicals (GS*) with DMPO and quantifying the ESR-silent nitrone form of the GS-DMPO adduct by HPLC showed that neither 3OHTAM plus H2O2 nor 4OHTAM plus H2O2 caused a significant level of GSH oxidation with isolated MPx, nor did the latter in HL60 cells, whereas PhOH plus H2O2 was a potent source of GS* in both systems. Both 4OHTAM and 3OHTAM formed the nitrone adduct under cell-free conditions when activated with HRP. The data show that the substrate specificity of a given (myelo)peroxidase determines if a phenolic exerts pro- (through generation of reactive phenoxyl radicals) or antioxidant (through radical scavenging) properties in intracellular environments.

Animals↗

An increase in vitamin A status by the feeding of conjugated linoleic acid.

Previous research indicated that conjugated linoleic acid (CLA) is a potent inhibitor of mammary carcinogenesis. The present study showed a progressive increase in retinol (vitamin A alcohol) in the liver in proportion to CLA intake in rats that were fed different levels of CLA (in increments of 0.5%) for 1 month. The escalation reached a magnitude of about fivefold over the control at 2% dietary CLA. In contrast, the increase in liver retinyl esters peaked at about twofold between 0.5% and 1% CLA. Only retinol was detected in mammary tissue; a maximal twofold increase was attained at 0.5% CLA, and no dose-response effect was evident. The above findings are discussed in relation to two important questions: 1) How does CLA raise vitamin A status in the animal? 2) Is the increase in vitamin A associated with the anticarcinogenic effect of CLA?

Animals↗

Decrease in linoleic acid metabolites as a potential mechanism in cancer risk reduction by conjugated linoleic acid.

Previous research suggested that conjugated linoleic acid (CLA) feeding during the period of pubescent mammary gland development in the rat resulted in diminished mammary epithelial branching which might account for the reduction in mammary cancer risk. Terminal end buds (TEB) are the primary sites for the chemical induction of mammary carcinomas in rodents. One of the objectives of the present study was to investigate the modulation of TEB density by increasing levels of dietary CLA and to determine how this might affect the risk of methylnitrosourea-induced mammary carcinogenesis. The data show a graded and parallel reduction in TEB density and mammary tumor yield produced by 0.5 and 1% CLA. No further decrease in either parameter was observed when CLA in the diet was raised to 1.5 or 2%. Thus, optimal CLA nutrition during pubescence could conceivably control the population of cancer-sensitive target sites in the mammary gland. Since both CLA and linoleic acid are likely to share the same enzyme system for chain desaturation and elongation, it is possible that increased CLA intake may interfere with the further metabolism of linoleic acid. Fatty acid analysis of total lipid showed that CLA and CLA metabolites continued to accumulate in mammary tissue in a dose-dependent manner over the range 0.5-2% CLA. There was no perturbation in tissue linoleic acid, however, linoleic acid metabolites (including 18:3, 20:3 and 20:4) were consistently depressed by up to 1% CLA. Of particular interest was the significant drop in 20:4 (arachidonic acid), which is the substrate for the cyclooxygenase and lipoxygenase pathways of eicosanoid biosynthesis. Thus the CLA dose-response effect on arachidonic acid suppression corresponded closely with the CLA dose-response effect on cancer protection in the mammary gland. This information is critical in providing new insights regarding the biochemical action of CLA.

Animals↗

Conjugated linoleic acid-enriched butter fat alters mammary gland morphogenesis and reduces cancer risk in rats.

Conjugated linoleic acid (CLA) is a potent cancer preventive agent in animal models. To date, all of the in vivo work with CLA has been done with a commercial free fatty acid preparation containing a mixture of c9,t11-, t10,c12- and c11,t13-isomers, although CLA in food is predominantly (80-90%) the c9,t11-isomer present in triacylglycerols. The objective of this study was to determine whether a high CLA butter fat has biological activities similar to those of the mixture of free fatty acid CLA isomers. The following four different endpoints were evaluated in rat mammary gland: 1) digitized image analysis of epithelial mass in mammary whole mount; 2) terminal end bud (TEB) density; 3) proliferative activity of TEB cells as determined by proliferating cell nuclear antigen immunohistochemistry; and 4) mammary cancer prevention bioassay in the methylnitrosourea model. It should be noted that TEB cells are the target cells for mammary chemical carcinogenesis. Feeding butter fat CLA to rats during the time of pubescent mammary gland development reduced mammary epithelial mass by 22%, decreased the size of the TEB population by 30%, suppressed the proliferation of TEB cells by 30% and inhibited mammary tumor yield by 53% (P < 0.05). Furthermore, all of the above variables responded with the same magnitude of change to both butter fat CLA and the mixture of CLA isomers at the level of CLA (0.8%) present in the diet. Interestingly, there appeared to be some selectivity in the uptake or incorporation of c9,t11-CLA over t10,c12-CLA in the tissues of rats given the mixture of CLA isomers. Rats consuming the CLA-enriched butter fat also consistently accumulated more total CLA in the mammary gland and other tissues (four- to sixfold increases) compared with those consuming free fatty acid CLA (threefold increases) at the same dietary level of intake. We hypothesize that the availability of vaccenic acid (t11-18:1) in butter fat may serve as the precursor for the endogenous synthesis of CLA via the Delta9-desaturase reaction. Further studies will be conducted to investigate other attributes of this novel dairy product.

Animals↗

[Apropos of a case of Dandy-Walker syndrome associated with chromosome abnormalities].

A case of Dandy-Walker syndrome associated with chromosome abnormalities (46,XX,-21, +der(13)t(13;21)(q22;q11), diagnosed during pregnancy is reported. This is a pathology characterized by malformations of the central nervous system, mainly of the cerebellum. Due to several aspects and different prognosis between classic Dandy-Walker and its variants, many clinical and therapeutic problems may raise.

Abortion, Induced↗

Colposcopy, cytology and histology in the diagnosis of squamous intraepithelial lesions of the cervix.

OBJECTIVE: To compare colposcopic findings to cytologic and histological diagnoses in women with colposcopic reports of ANTZ and/or HPV infection. METHODS: Among 791 hospitalized women referred for colposcopic examination, colposcopy showed ANTZ grade 0-2 and/or HPV infection in 271 patients (34.26%). Only 153 were fully investigated by colposcopy, cytology (under colposcopic observation) and histology (target punch biopsy: 109 patients; surgical specimens of hysterectomy: 42 patients; conization: 2 patients). Cytological and histological diagnoses were reported according to the Bethesda System. RESULTS: 132/153 Pap smears were estimable for sampling adequacy; 44/63 resulted as normal and were histologically positive for LSIL [1]. Five LSIL-positive Pap tests were negative on histology (false negative and false positive rate of 33.33% and 3.78%). The pap test was diagnostic for intraepithelial neoplasia in 34/65 cases (53.3%) and for invasive cancer in 6/11 cases (54.5%). In 67/132 cases (50.8%) adequate-for-sampling Pap smears could not predict the exact diagnosis. On the other hand, 108/141 patients with colposcopic evidence of ANTZ/cancer showed histological SIL or invasive neoplasm (76.59%): ANTZ 1 was associated to LSIL and HSIL in 74.1% and 2.4%; ANTZ 2 to LSIL, HSIL and invasive cancer in 41%, 30.76% and 10.3%. Colposcopic suspicion of invasive cancer in 8 patients was histologically demonstrated in 7 (87.5%); colposcopic diagnosis of HPV infection was confirmed in 10/12 (83.4%). CONCLUSION: A better correspondance was shown between colposcopy and histology than between cytology and histology in the diagnosis of SIL. We suggest a routine colposcopy investigation for all patients admitted to a gynecological clinic and we believe it is very important to take Pap smears under colposcopic observation if colposcopy and cervical smears are performed in the same sitting.

Adult↗

Adsorptive control of water in esterification with immobilized enzymes. Continuous operation in a periodic counter-current reactor.

A periodic counter-current adsorptive-reactor system is developed to carry out continuous esterifications in organic solvents with immobilized enzymes. The system comprises a number of fixed-beds distributed between a reaction-adsorption zone and a regeneration zone and operated in a "merry-go-round" sequence. Water formed in the reaction is adsorbed preventing the formation of a free-water phase and deactivation of the biocatalyst. The adsorbed water is, in turn, recovered by desorption in the regeneration zone. The concept is tested experimentally on a laboratory-scale using, as a model, the esterification of isoamyl alcohol and propionic acid in hexane catalyzed by an immobilized lipase. Pure isoamyl alcohol is used as a regenerant to remove excess water from the biocatalyst. In the periodic steady-state, improvements in ester productivity greater than 50% over that achievable with a conventional fixed-bed reactor are demonstrated experimentally with just two beds in a series arrangement. Use of a water-selective adsorbent in conjunction with the biocatalyst provides further improvements by reducing accumulation of water on the enzyme. A mathematical model is also developed to predict the thermodynamic activity of water along the reactor and describe the dynamic behavior of the system. The model, based on independently developed rate and equilibrium parameters, successfully predicts the experimental behavior and provides an effective tool for scale-up and optimization.

Adsorption↗