The Facile Production of p-Chloroaniline Facilitated by an Efficient and Chemoselective Metal-Free N/S Co-Doped Carbon Catalyst.

The catalytic hydrogenation of the toxic and harmful p-chloronitrobenzene to produce the value-added p-chloroaniline is an essential reaction for the sustainable chemical industry. Nevertheless, ensuring satisfactory control of its chemoselectivity is a great challenge. In this work, a N/S co-doped metal-free carbon catalyst has been fabricated by using cysteine as a source of C, N, and S. The presence of calcium citrate (porogen agent) in the mixture subjected to pyrolysis provided the carbon with porosity, which permitted us to overcome the issues associated with the loss of heteroatoms during an otherwise necessary activation thermal treatment. Full characterization was carried out and the catalytic performance of the metal-free carbon material was tested in the hydrogenation reaction of p-chloronitrobenzene to selectively produce p-chloroaniline. Full selectivity was obtained but conversion was highly dependent on the introduction of S due to the synergetic effect of S and N heteroatoms. The N/S co-doped carbon (CYSCIT) exhibits a mesoporous architecture which favors mass transfer and a higher doping level, with more exposed N and S doping atoms which act as catalytic sites for the hydrogenation of p-chloronitrobenzene, resulting in enhanced catalytic performance when compared to the N-doped carbon obtained from melamine and calcium citrate (MELCIT) used as a reference.

Surfactant-assisted synthesis of conducting polymers. Application to the removal of nitrates from water.

Three different conducting polymers, polythiophene (PT), polypirrol (PPY) and polyaniline (PANI) have been synthesized via oxidative chemical polymerization in aqueous media, in such a way that the synthesis protocol did not involve any toxic solvents. They have been tested in the abatement of nitrates from an aqueous solution without the need of any metal catalyst. The N-containing polymers (PANI and PPy) were able to remove nitrates to a level that accomplishes the European legislation requirements; however, the nature of each polymer greatly influenced the process mechanism. Whereas ion exchange between Cl- and SO42- counter-ions in the polymer and NO3- from water is the main responsible for the effective nitrate removal in PANI, as assessed by FTIR and XPS analyses, the nitrate removal mechanism on PPy is based in an electron transfer from the polymer to nitrate through N sites located in the pyrrolic ring. On the other hand, PT was not able to exchange nitrate unless it was synthesized with FeCl3 as oxidant/dopant and an anionic surfactant (sodium dodecyl sulfate -SDS-) is used. In that case, the electrostatic attraction between sulfate (OSO3-) groups from the surfactant and Fe3+ ions from FeCl3 produced the anchoring of Cl- to the oxidized PT growing chain, this favoring ion exchange with nitrate in the aqueous solution, followed by a redox process.

Reported changes in sexual behaviour and human papillomavirus knowledge in Peruvian female sex workers following participation in a human papillomavirus vaccine trial.

Limited data exist on the effect of clinical trial participation on sexual behavioural change. Two hundred female sex workers working in Lima, Peru received human papillomavirus (HPV) vaccine in either the standard (0, 2, 6 months) or modified (0, 3, 6 months) schedule. Participants received comprehensive screening and treatment for sexually transmitted infections (STIs), counselling on safe sex practices, education about HPV and the HPV vaccine, contraceptives (oral and condoms) and family planning at each visit. We assessed vaccine completion rates, change in sexual practices, and changes in HPV knowledge before and after participation in the vaccine trial. There were high rates of vaccine completion, 91% overall. The estimated number of reported new and total clients over a 30-day period decreased significantly (P < 0.001). Knowledge about HPV and HPV-related disease increased among all participants. In addition, all participants listed at least one preventive strategy during the month 7 follow-up survey.

Human papillomavirus prevalence, cervical abnormalities and risk factors among female sex workers in Lima, Peru.

Female sex workers (FSWs) are at high risk of human papillomavirus (HPV) infection. Questionnaires were administered to 200 FSWs aged 18-26 years in Lima, Peru, to gather risk behaviours, and cervical swab samples were collected for Pap smears and HPV DNA testing as part of a longitudinal study. Participants reported a median of 120 clients in the past month, and 99.2% reported using condoms with clients. The prevalence of any HPV in cervical samples was 66.8%; 34 (17.1%) participants had prevalent HPV 16 or 18, and 92 (46.2%) had one or more oncogenic types. Fifteen women had abnormal Pap smears, 13 of which were HPV DNA positive. Fewer years since first sex was associated with oncogenic HPV prevalence in a model adjusted for previous sexually transmitted infection (STI) status and condom use with partners (prevalence ratio = 0.77, 95% confidence interval [CI] = 0.60-0.97). Our data confirm the high rates of HPV transmission among FSWs in Peru, highlighting the need for early and effective strategies to prevent cervical cancer.

Oral sex practices, oral human papillomavirus and correlations between oral and cervical human papillomavirus prevalence among female sex workers in Lima, Peru.

Few data exist on oral human papillomavirus (HPV) prevalence in female sex workers (FSWs). Information regarding oral sex practices of 185 Peruvian FSWs, 18-26 years of age, was obtained via survey and compared with HPV testing results of oral rinse samples. Oral HPV prevalence was 14/185 (7.6%); four (28.9%) HPV genotypes were carcinogenic. One hundred and eighty-two participants reported having had oral sex; 95% reported condom use during oral sex with clients and 9.5% with partners. Women who had oral sex more than three times with their partners in the past month were more likely to have oral HPV than women who had oral sex three times or less (P = 0.06). Ten (71.4%) women with oral HPV were HPV-positive at the cervix; conversely 8.3% of women with cervical HPV were HPV-positive in the oral cavity. The prevalence of oral HPV was relatively low, considering the high rates of oral sex practiced by these women.

A theoretical approach to the photochemical activation of matrix isolated aluminum atoms and their reaction with methane.

The photochemical activation of Al atoms in cryogenic matrices to induce their reaction with methane has been experimentally studied before. Here, a theoretical study of the nonadiabatic transition probabilities for the ground ((2)P:3s(2)3p(1)) and the lowest excited states ((2)S:3s(2)4s(1) and (2)D:3s(2)3d(1)) of an aluminum atom interacting with a methane molecule (CH(4)) was carried out through ab initio Hartree-Fock self-consistent field calculations. This was followed by a multiconfigurational study of the correlation energy obtained by extensive variational and perturbational configuration interaction analyses using the CIPSI program. The (2)D state is readily inserted into a C-H bond, this being a prelude to a sequence of avoided crossings with the initially repulsive (to CH(4)) lower lying states (2)P and (2)S. We then use a direct extension of the Landau-Zener theory to obtain transition probabilities at each avoided crossing, allowing the formation of an HAlCH(3) intermediate that eventually leads to the final pair of products H+AlCH(3) and HAl+CH(3).

New CD3zeta allele showing a 9-bp deletion in the 3'-UT region of the gene.

We report here a non-previously described 9-bp deletion in the 3'-UT region of the CD3zeta gene, located in between two AREs.

Observations on the failure of stent-grafts in the aortic arch.

INTRODUCTION: The results of endovascular stent-grafts in the abdominal aorta and descending thoracic aorta have been encouraging. Expanding the use of thoracic stent-grafts in to the aortic arch has been associated with increasing numbers of complications. Recently isolated cases of stent-graft collapse have been reported. METHODS: This was a multi-centre European case series. Data was collected retrospectively on seven patients from five experienced endovascular centres with thoracic stent-graft collapse. RESULTS: Of the seven patients four were treated for traumatic aortic rupture. Six were male, median age 33 (range 17-54) years. During the ensuing 2 months all patients suffered stent-graft collapse. This was symptomatic in 3 patients and the rest were identified on CT. Endovascular management was possible in 6/7 patients using either a balloon expandable stent (n=6) or further stent-graft (n=1). Two patients had persistent type I endoleak despite treatment. Two of the 7 patients died, both of which presented with symptomatic thoracic stent-graft occlusion. Both deaths were a direct result of stent-graft collapse. CONCLUSIONS: Thoracic stent-graft collapse may be asymptomatic underscoring the importance of stent-graft surveillance. Endovascular management of collapse is possible in most cases using a large balloon expandable stent. Symptomatic collapse is associated with high morbidity and mortality.

Valores de referencia del antígeno prostático específico / Refence values of prostate specific antigen

En el presente estudio se determinaron los valores de referencia del PAS (antígeno prostático específico) en individuos en estado de salud para patologías prostáticas, teniendo en cuenta la falta de información en individuos en estas condiciones. Se incluyeron en el estudio, 618 individuos del sexo masculino, con edades comprendidas entre 40 y 69 años, que concurrieron al laboratorio “Medical Center” entre 1999 y 2001, procedentes de consultorios urológicos, con solicitudes de estudios laboratoriales. Para la selección de los individuos se siguieron las recomendaciones del Panel de Expertos en Teoría de los Valores de Referencia de la IFCC (Federación Internacional de Química Clínica). Individuos sin patología prostática, clínicamente sin dificultad en la micción y examen dígito rectal normal, con resultados negativos a los auxiliares de diagnóstico citoscopía y ecografía. Se realizó la medición con el método inmunoensayo de partículas (MEIA), IMX Abbott, USA. En primer término se analizó el tipo de distribución de los valores de concentración de PAS de todos los individuos, empleando el test de Kolmogorov ­ Smirnov. Los valores de referencia de PAS obtenidos, entre los percentiles 2,5% y 97,5% mostraron diferencias de valores por grupo etário, con aumento progresivo (Kruskall­Wallis, p<0,0001). Los valores de referencia del PAS en ng/mL, fueron: de 40 a 49 años de 0,25 a 2; de 50 a 59 años de 0,64 a 3,24; de 60 a 69 años de 0,54 a 3,7. Los valores obtenidos servirán de guía para aplicar criterios de medicina preventiva que ayudaran al profesional de la salud en el diagnóstico precoz de patología prostática.

Development of prostate hyperplasia is an almost universal phenomenon in aging men. The PSA levels in serum are useful in the clinical evaluation in men over the age of 45. The objective of this study was to establish the reference values of prostate specific antigen (PSA) in serum in a selected Paraguayan population by microparticle enzimoimmunoassay MEIA. Six hundred eighteen people were evaluated with ages ranging from 40 to 69 years old who attended to “Laboratory Medical Center” in Asunción, Paraguay during 1999­2001. All were subjected to digital rectal examination, biopsy and echograph to assure the prostate disease free state. The International Federation of Chemical Chemistry (IFCC) reference value guidelines were used for individual selection. PSA concentrations were determined by microparticle enzimoimmunoassay (Autoanalyzer IMXABBOT/USA). The PSA concentration was presented as percentiles since neither the values nor the logarithms fitted into a normal distribution (Kolmogorov­Smirnov Test). Therefore, a nonparametric test (Kruskal­Wallis) was used for the estimation of differences between datum groups. According to age, our data showed statistical differences (p<0,0001). At increasing levels of PSA: 40 ­ 49 years old the serum value ranged from 0.25 ­ 2.0 ng/mL, 50 ­ 59 years old from 0.64 to 3.24 ng/mL and 60 ­ 69 from 0.54 to 3.7 ng/mL. These data represented the percentiles 2.5% and 97.5%. These PSA reference values will serve in screening programs as tools to detect prostate diseases in our population.

Higher proliferative capacity of T lymphocytes from patients with Crohn disease than from ulcerative colitis is disclosed by use of Herpesvirus saimiri-transformed T-cell lines.

BACKGROUND: T lymphocytes play a crucial role in the pathogenesis of inflammatory bowel disease. Achieving stable T-cell lines, rather than continuous bleeding of patients, is desirable in order to dissect their implication in the disease. METHODS: Long-lasting T-cell lines from patients with Crohn disease and ulcerative colitis and from healthy volunteers have been obtained by transformation of T lymphocytes using the lymphotropic Herpesvirus saimiri. Lines were subjected to phenotypic and functional analyses, and the results compared with freshly isolated peripheral blood mononuclear cells. RESULTS: Fresh cells revealed only minor differences between patients and controls, with regard to phenotype and proliferative capacity. In contrast, the use of T-cell lines showed that cells from Crohn disease patients, but not ulcerative colitis patients, over-responded to several membrane or cytoplasmic stimuli when compared to control T-cell lines. Thus, higher responses were found when stimulated with alphaCD3 and IL2, alphaCD3 and alphaCD28, IL2 alone, phorbol esters (PMA) and alphaCD3 and, finally, PMA and alphaCD2 (P < 0.05 in all instances). Further, lines from patients with Crohn disease responded more vigorously to alphaCD3 and alphaCD28 or alphaCD3 and PMA when compared to ulcerative colitis (P < 0.05 in both instances). CONCLUSIONS: The data obtained with these lines suggest that T cells from patients with Crohn disease differ in vivo in their proliferative capacity, as compared with those from ulcerative colitis patients, a finding that may reflect the clear Th-1 phenotype found in the former and absent in the latter.

Intrinsic defects explain altered proliferative responses of T lymphocytes and HVS-derived T-cell lines in gastric adenocarcinoma.

We have taken advantage of a recently described technique of transformation and immortalization of T lymphocytes using the lymphotropic Herpesvirus saimiri, to achieve long-lasting T-cell lines from gastric cancer patients and healthy volunteers. Blood samples were drawn and T lymphocytes were transformed. Once sustained growth was observed, lines were subjected to phenotypic and functional analyses, and the results compared with freshly isolated peripheral blood mononuclear cells. Cytofluorometric analysis revealed that CD3 and CD45 were found at lower proportion in primary cells from patients than from control individuals (54% vs 75%, p<0.001, 90% vs 96%, p<0.05, respectively), and in HVS-derived T-cell lines (90% vs 98%, p<0.05, 97% vs 100%, p<0.05, respectively). Proliferative analyses showed that primary isolated cells were unable to respond adequately to CD3-, CD2-, and PHA-mediated stimulation, as compared to controls. Similarly, T-cell lines from patients proliferated to a lesser extent when CD3- and CD2-mediated stimuli were considered, especially when simultaneous stimulation via CD3 and CD2 molecules was carried out (47,824 counts per minute [cpm] vs 121,478 cpm, p<0.05). Altogether these results show that the defects reported in T cells from patients with cancer are not exclusively due to tumour-derived factors, since the alterations persist in long-lasting, HVS-transformed, T-cell lines, suggesting that this model seems a suitable one to disclose them.

Significance of protein p53 overexpression in the clinical course of high-risk superficial bladder cancer.

OBJECTIVES: This is a retrospective study in which the long-term biological behavior of 67 "high-risk" superficial bladder tumors and the prognostic relevance (prediction of disease recurrence and progression) of the determination of the p53 phenotype in these cases were studied. MATERIAL AND METHODS: 67 tumors with a "high-risk" of progression were selected from the 1,103 transurethral resections for bladder cancer carried out in 640 patients in this center between 1987 and 1992. These included 39 T1G3, 14 Tis (isolated or associated with Ta-T1, non-G3 tumors), and 14 Ta-T1, non-G3 tumors with submucosal lymphatic affection (L+). The median follow-up of these cases was 69.7 months. An immunohistochemical technique with monoclonal antibodies (DO-7) was used to detect the p53 phenotype in paraffin-fixed material. RESULTS: Tumor recurrence occurred in 31 patients (46.3%) and local or distant progression in 14 (20.9%). Radical cystectomy was carried out in 16 (23.9%) cases. p53 overexpression of > or =20% ("p53+") was detected in 40 tumors (59.7%). The rate of recurrence and progression, the disease and progression-free intervals, cancer-specific survival, disease-free survival and progression-free survival were similar in the 3 tumor groups (in all cases, p > 0.05). There were no significant differences in the overexpression of protein p53, using the standard cutoff point of 20% stained nuclei, on comparing the same variables in the whole group of 67 patients (in all cases, p > 0.05). CONCLUSION: The detection of protein p53 was not found to be of use in the retrospective prediction of disease progression or survival in "high-risk" superficial bladder cancer.

Villous adenoma of the appendix. Diagnostic and therapeutic approach.

UNLABELLED: Appendix villous adenoma is a rare pathological entity that shows a particular form of clinical presentation that is different from villous adenomas in other places along the gastrointestinal tract. PATIENTS AND METHODS: We reviewed cases of appendix villous adenoma diagnosed in our hospital during the last five years; we studied age, distribution, sex, clinical presentation, diagnostic methods used, treatment and follow-up of patients. RESULTS: We diagnosed 6 cases of villous adenoma of the appendix, acute appendicitis being the most common form of clinical presentation. Treatment was appendectomy in two cases, right hemicolectomy in two patients, subtotal colectomy in one case, and Hartmann's technique with appendectomy in one more case. CONCLUSIONS: We consider appendectomy the treatment of choice when no malignant degeneration is present in the adenoma and invasion of surgical resection borders is absent.

Inhibition of phosphodiesterase type III before aortic cross-clamping preserves intramyocardial cyclic adenosine monophosphate during cardiopulmonary bypass.

UNLABELLED: Inotropes are often used to treat myocardial dysfunction shortly after cardiopulmonary bypass (CPB). beta-Adrenergic agonists improve contractility, in part by increasing cyclic adenosine monophosphate (cAMP) production, whereas phosphodiesterase type III inhibitors prevent its breakdown. CPB is associated with abnormalities at the beta-receptor level and diminished adenyl cyclase activity, both of which tend to decrease cAMP. These effects may be increased in the presence of preexisting myocardial dysfunction. We tested the hypothesis that inhibition of phosphodiesterase type III before global myocardial ischemia and pharmacologic arrest results in the preservation of intramyocardial cAMP concentration during CPB. Twenty adult patients undergoing coronary artery bypass grafting with CPB were studied. After CPB was instituted, a myocardial biopsy was obtained from the apex of the left ventricle. Patients were randomized to receive either placebo or milrinone (50 micro/kg) through the bypass pump 10 min before aortic cross-clamping. Another myocardial biopsy was performed adjacent to the left ventricular apex just before weaning from CPB. Myocardial cAMP concentration was determined by radioimmunoassay. Myocyte protein content was determined by the Bradford method by using a commercial kit. There were no significant demographic differences between the groups; however, patients in the Milrinone group had a lower left ventricular ejection fraction than placebo (41% +/- 13% vs 53% +/- 7%; P < 0.05). Patients who received milrinone had larger cAMP concentrations at the end of CPB compared with placebo (21 +/- 12.5 pmol/mg protein versus 12.8 +/- 2.2 pmol/mg protein; P < 0.05). The administration of milrinone before aortic cross-clamping is associated with increased intramyocardial cAMP concentration at the end of CPB. IMPLICATIONS: The administration of a single dose of milrinone before aortic cross-clamping resulted in significantly larger intramyocardial cyclic adenosine monophosphate concentration in myocardial biopsy specimens compared with controls.

Cell surface phenotype and cytokine secretion in Caco-2 cell cultures: increased RANTES production and IL-2 transcription upon stimulation with IL-1beta.

Caco-2 is a colonic tumour cell line which, when cultured, spontaneously exhibits enterocyte-like characteristics. Given the difficulties in maintaining long-lasting cultures of enterocytes, this cell line may be a suitable in vitro model to carry out experiments trying to delineate the involvement of enterocytes in local immune responses, and their role in pathology. It seems then reasonable to obtain a detailed immune analysis of Caco-2, and compare it with available data on enterocytes. Cytofluorometry revealed several leukocyte markers on Caco-2, present also on human enterocytes. These markers include surface proteases (CD10, CD13 and CD26), antigen-presenting cell markers (CD13, CD14, CD35 and CD63), integrins (CD18 and CD61), epithelial/endothelial markers (CD21, CD31, CD47 and CD59) and finally, CD25 and CD28. In contrast to enterocytes, HLA-class 11 molecules are not found on Caco-2, whether resting or gamma-IFN-stimulated. Moreover, culture experiments with allogeneic lymphocytes revealed that Caco-2 cells were unable to induce their proliferation. Cytokine analysis showed an increased RANTES synthesis and IL-2 transcription upon stimulation with IL-1beta. Finally, amongst RANTES receptors, CCR1 is found on Caco-2 cells, whereas CCR3 and CCR5 are not.

Bacitracin irrigation: a cause of anaphylaxis in the operating room.

IMPLICATIONS: We report a unique case of acute anaphylaxis after mediastinal irrigation with a dilute bacitracin solution.

Lens culinaris, Phaseolus vulgaris and vicia faba lectins specifically trigger IL-8 production by the human colon carcinoma cell line CACO-2.

Cultured Caco-2 cells were stimulated with Lens culinaris, Phaseolus vulgarisandVicia fabalectins. The production of IL-1, IL-6, IL-8 and MCP-1 was measured by ELISA and RT-PCR. IL-8 production appeared to be specifically triggered upon stimulation with all three lectins used, since none of the other cytokines tested were produced. The IL-8 secreted may induce the extravasation of activated neutrophils and generate tissue damage. A similar mechanism may be implicated in the lesions observed after infection by some enteric pathogens, with lectin-like domains on their membrane. Finally, this model may be suitable one to study the regulation of IL-8 production.

Endovascular repair of abdominal aortic aneurysm in a renal transplant patient.

A 65-year-old man presented with an asymptomatic infrarenal abdominal aortic aneurysm of 6 cm in transverse diameter. Five years before he received a cadaveric renal transplant. The patient also had the following risk factors and associated diseases: arterial hypertension, coronary artery disease, previous myocardial infarction, coronary angioplasty and stent, ileal resection secondary to Chron disease, hepatopathy, hyperlipidemia and hepato-renal cystic disease. The ASA classification was III, IV. Considering previous abdominal operations and risk factors, we decided to repair the aneurysm with a minimal aggression. The aneurysm was successfully approached by an endovascular route implanting a 22x10 bifurcated aorto-iliac endovascular prosthesis. The patient died 13 months later after being diagnosed of enterocolitis by cytomegalovirus complicated with sepsis and lung infection. We consider this less invasive modality of treatment a valid and useful alternative in this high-risk group of patients.