Insights on Clusters Formation Mechanism by Time of Flight Mass Spectrometry. 2. The Case of Acetone-Water Clusters.

This paper is the second of a series dealing with clusters formation mechanism. In part 1, water clusters with the addition of an electrophilic molecule such as ethanol were studied by Time Of Flight Mass Spectrometry (TOFMS). Mass distributions of molecular clusters of ethanol, water and ethanol-water mixed clusters, were obtained by means of two different ionization methods: Electron Ionization (EI) and picosecond laser Photo-Ionization (PI) at a wavelength of 355 nm. In part 2, the same experimental approach was employed to obtain mass spectra of clusters generated by acetone-water binary mixtures with a different composition. Strong dependence of the mass spectra of clusters with EI and PI on the acetone-water mixing ratio was observed. It was shown that the spectral pattern changes gradually and water-rich cluster signals become fainter while acetone-rich cluster signals become more intensive with increasing acetone concentrations from 0.3% to 40%. Owing to the hydrogen bond acceptor character of acetone, its self-association is discouraged with respect to ethanol. The autocorrelation function (AF) was used to analyze the variation of the water clusters composition with the increase of the acetone concentration in terms of fundamental periodicities. However, although acetone and ethanol present a very different hydrogen-bonding ability, similarly to ethanol-water system, in acetone-water system the formation of water-rich clusters and subsequent metastable fragmentation are the dominant process that determine the clusters distribution, irrespective of the ionization process, while the ionization process significantly affects the acetone-rich clusters distribution. Graphical Abstract ᅟ.

Accurate calibration of a molecular beam time-of-flight mass spectrometer for on-line analysis of high molecular weight species.

RATIONALE: Time-of-Flight (TOF) Mass Spectrometry is a powerful analytical technique, provided that an accurate calibration by standard molecules in the same m/z range of the analytes is performed. Calibration in a very large m/z range is a difficult task, particularly in studies focusing on the detection of high molecular weight clusters of different molecules or high molecular weight species. METHODS: External calibration is the most common procedure used for TOF mass spectrometric analysis in the gas phase and, generally, the only available standards are made up of mixtures of noble gases, covering a small mass range for calibration, up to m/z 136 (higher mass isotope of xenon). In this work, an accurate calibration of a Molecular Beam Time-of Flight Mass Spectrometer (MB-TOFMS) is presented, based on the use of water clusters up to m/z 3000. RESULTS: The advantages of calibrating a MB-TOFMS with water clusters for the detection of analytes with masses above those of the traditional calibrants such as noble gases were quantitatively shown by statistical calculations. A comparison of the water cluster and noble gases calibration procedures in attributing the masses to a test mixture extending up to m/z 800 is also reported. In the case of the analysis of combustion products, another important feature of water cluster calibration was shown, that is the possibility of using them as "internal standard" directly formed from the combustion water, under suitable experimental conditions. CONCLUSIONS: The water clusters calibration of a MB-TOFMS gives rise to a ten-fold reduction in error compared to the traditional calibration with noble gases. The consequent improvement in mass accuracy in the calibration of a MB-TOFMS has important implications in various fields where detection of high molecular mass species is required. In combustion products analysis, it is also possible to obtain a new calibration spectrum before the acquisition of each spectrum, only modifying some operative conditions. Copyright © 2016 John Wiley & Sons, Ltd.

Multiphoton ionization of large water clusters.

Water clusters are multimers of water molecules held together by hydrogen bonds. In the present work, multiphoton ionization in the UV range coupled with time of flight mass spectrometry has been applied to water clusters with up to 160 molecules in order to obtain information on the electronic states of clusters of different sizes up to dimensions that can approximate the bulk phase. The dependence of ion intensities of water clusters and their metastable fragments produced by laser ionization at 355 nm on laser power density indicates a (3+1)-photon resonance-enhanced multiphoton ionization process. It also explains the large increase of ionization efficiency at 355 nm compared to that at 266 nm. Indeed, it was found, by applying both nanosecond and picosecond laser ionization with the two different UV wavelengths, that no water cluster sequences after n = 9 could be observed at 266 nm, whereas water clusters up to m/z 2000 Th in reflectron mode and m/z 3000 Th in linear mode were detected at 355 nm. The agreement between our findings on clusters of water, especially true in the range with n > 10, and reported data for liquid water supports the hypothesis that clusters above a critical dimension can approximate the liquid phase. It should thus be possible to study clusters just above 10 water molecules, for getting information on the bulk phase structure.

Vascular endothelial growth factor (VEGF): can we use it as prognostic factor in endometrial cancer?

AIM: The aim of the study was to investigate if VEGF levels reflect the severity of endometrial cancer and the clinic relationship between microvasal density (MVD) and concentration of VEGF in tumor. METHODS: The study was conducted on 22 patients affected by endometrial cancer who were submitted to total abdominal radical hysterectomy plus bilateral salpingo-ophorectomy. VEGF (pg/mL) and MVD values were measured on histologic specimens of endometrial cancer obtained during the surgical treatment. The means and standard deviations of estimated values were calculated and a statistical comparison was effected by student t test for not coupled data. Pearson correlation test was used to analyze the eventual correlation among VEGF and MVD values in overall patients. RESULTS: We have documented that VEGF expression and MVD change according to FIGO stage, lympho-vascular infiltration and lymph node involvement. Pearson correlation test shows a good linear positive correlation in overall patients between VEGF and MVD values. CONCLUSIONS: Results obtained show a possible use of VEGF as prognostic factor in endometrial cancer. Confirmation of these data may permit both to identify high-risk patients, who must be treated with a more aggressive treatment, and to use an angiogenic therapy in endometrial cancer.

Double laparotomy wound recurrence of endometrial carcinoma.

INTRODUCTION: Abdominal scar recurrence of endometrial carcinoma after abdominal total hysterectomy is very rare. We report a case of a 65-year-old woman who had two recurrences in the abdominal incisional scar after total hysterectomy. CASE REPORT: A 65-year-old woman underwent total hysterectomy with bilateral salpingo-oophorectomy and pelvic lymphadenectomy because of well-differentiated endometrial adenocarcinoma (Stage IIB). Thus, the patient was treated by external beam radiotherapy. She developed two recurrences in the abdominal incisional scar two and three years after total hysterectomy, respectively. Surgery plus chemotherapy and surgery plus hormonal therapy were used for treatment of the first and second scar recurrence, respectively. CONCLUSIONS: It is a very intriguing and controversial biologic question how neoplastic cells can implant and grow in an abdominal scar without other concomitant metastases. We report a review of the literature and the possible mechanism of recurrences in laparotomy wounds.

Female adnexal tumor of probable wolffian origin: clinicopathological, immunohistochemical and cytofluorimetric analyses of a 22-year-old virgin. case report.

The term female adnexal tumor of probable Wolffian origin "FATWO" designs this tumor wich arises by the rare persisting remnants of the mesonephric duct (Wolffian duct). About 40 cases have been reported in literature. Few cases of recurrence have been reported, FATWO usually shows no signs of hormonal activity. We report a case of the youngest patient affected by FATWO in October 2002. At laparotomy the left adnexa were deformed by a well-capsulated mass, totally removed and sent to the pathologist with a specimen of peritoneal fluid and of the omentum. The histological examination showed a prevalent tubular structure with focal retiform area, without intraluminal mucines. Immunohistochemical findings of the case reported are similar to those described by other authors, except for inhibin which has not been detected by us. The cytofluorimetry showed the low presence of aneuploid cells, with a very low prolifing component (< 1%).

Comparative evaluation of standard criteria and CA-125 in ovarian cancers treated with platinum or paclitaxel.

PURPOSE: To assess CA-125 in defining tumor response in patients treated with paclitaxel. PATIENTS AND METHODS: We analyzed 150 women treated for epithelial ovarian carcinoma with platinum or paclitaxel. We compared the patients treated with two agents, using a precise definition of CA-125 response, determined by 50% and 75% reductions, like other authors have published. RESULTS: CA-125 criteria gave response rates very similar to the standard response rates, both for patients treated with platinum (75% vs 63%) and also for those treated with paclitaxel (40% vs 39%). Rates of false-positive prediction of response by CA-125 were also similar for patients treated with these two agents. CONCLUSION: Precise 50% or 75% CA-125 response criteria are as sensitive as standard criteria for assessing activity of therapy for the ovarian cancers treated with platinum or paclitaxel. We propose that they may be useful in defining response in lieu of or in addition to standard response criteria in clinical trials involving epithelial ovarian cancer.

Insulin resistance and weight gain in postmenopausal women of diverse ethnic groups.

OBJECTIVE: This study was conducted to examine the influence of insulin resistance on weight change in postmenopausal women of various ethnic groups. SUBJECTS: Data were obtained from 3389 women (60% White, 20% Black, 12% Hispanic, and 8% Asian/Pacific Islander), ages 50-79, enrolled in either the Women's Health Initiative Clinical trial or Observational Study, whose blood samples were selected randomly from the full cohort of 161 809 women for analyses. MEASUREMENTS: Glucose, insulin, and lipids were measured on fasting serum samples drawn at baseline and after 3 y of follow-up. Weight, height, waist circumference, and blood pressure were measured. Physical activity and energy intake were assessed via questionnaire. Insulin resistance was estimated using the HOMA (homeostasis model) calculation. RESULTS: Average age was 62 y, average BMI (body mass index) was 27.4 kg/m2, and average weight change was a gain of 0.4 kg in 3 y. In a multivariate analysis, insulin resistance and insulin concentrations were independent predictors of increases in weight in White women (P=0.002 and 0.004, respectively) and in the combined group (P=0.027 and 0.039). For the whole group, after adjustment for other covariates, those in the highest quartile of insulin resistance gained 0.4 kg in 3 y, whereas those in the lowest quartile lost 0.06 kg. Similar trends were found for insulin resistance and weight gain in Hispanic and Asian/Pacific Islander women, but they did not reach statistical significance. In Black women, no relation was seen between either insulin or insulin resistance and weight change. A significant interaction between obesity and insulin resistance was observed (P=0.002 for White women and 0.032 for the whole group), so that there is weight gain with increasing insulin resistance in the leaner women, but weight loss with increasing insulin resistance in the most obese. CONCLUSION: Insulin resistance appears to be a predictor of weight gain in postmenopausal women, except for the most obese women. The effect is more pronounced in women who have a lower BMI, and the effect was not seen in the Black women who as a group had a higher BMI.

[Role of intestinal resection in primary cytoreduction of ovarian cancer]. / Il ruolo della resezione intestinale nella citoriduzione primaria del cancro dell'ovaio.

BACKGROUND: The aim of this study is to define the role of the intestinal removal for the therapy of ovarian cancer in advanced stadium. METHODS: We have examined 247 females with epithelial ovarian cancer in advanced stadium, that had intestinal removal. RESULTS: The survival in the females that had a very good intestinal removal is greatest than in the females that hadn't a very good intestinal removal.

[Cytoreductive surgery in patients with stage IV ovarian carcinoma]. / La chirurgia citoriduttiva nelle pazienti con carcinoma dell'ovaio allo stadio IV.

BACKGROUND: The aim of this study is to evaluate the efficacy of cytoriductive surgical in females with ovarian carcinoma in advanced stadium, and to define the role of this surgical for the survival of females with hepatic metastases. METHODS: This is a retrospective study. 164 females with ovarian cancer in IV stadium was examined. 64 females had hepatic metastasis. All patients had cytoriductive surgical. RESULTS: The survival in the patients without hepatic metastasis was 38 months if the cytoreduction was very good; it was 18.3 months if there is residual disease. The survival in the patients with hepatic metastasis was 50.1 months if the cytoreduction was very good; it was 27 months if there is residual disease. CONCLUSIONS: A very good surgical is very important for the survival of patients with ovarian cancer in advanced stadium. This is true also in the patients with hepatic metastases.

[HPV infection. Clinical features and treatment]. / Infezione da HPV. Aspetti clinici e trattamento.

The aspecific and exiguous symptoms and the lacking information are among the reasons of the diffusion of the vulvo-vaginal papillomatosis. We carried out the present study between 1995 and 1999 in the outpatient clinic of cervico-vaginal pathology of the Second University of Naples. 680 patients (aged between 18 and 56 years) underwent vulvoscopic and colposcopic examination. The did not show any relevant symptoms specific for HPV infection. Among the viral strains, HPV-16 and HPV 18 are able to induce a cervical cancer. To eliminate the pathology the primary prevention is necessary: it consist of both an adequate information about the micro-condilomatosis, the role of the activator agent, the modality of the infection, and the annual screening examinations such as pap-test and colposcopy. As first line treatment during secondary prevention, we utilize Roferon A, and perform diathermocoagulation according with the local diffusion and the degree of the disease (mild, moderate, severe). At the end of the therapy with Roferon A we observed that the infective focus was eliminated in about 60% of the cases and, only for moderate and severe micro-condilomatosis a diathermocoagulation was necessary.

[Gestational HSV in the work setting]. / HSV gestazionale in ambiente di lavoro.

OBJECTIVE: The purpose of our studies has been that to individualize the in partnership factors of risk to infection Herpes Simplex Virus-Type 2 in pregnant women and to appraise the role of the job in such context. METHODS: A champion of 79 pregnant women with infection from HSV-2 has responded to a questionnaire regarding the appearance of the infection, her own job and the degree of stress, if they used services hygienic public. RESULTS: In this champion of pregnant women 63% they are workers. Of these the 85% they introduced signs of a reinfection. For the housewives in 67% there was a reinfection. 84% of the housewives it uses services hygienic privacies. The infection from HSV has appeared in 28.5% of the been born by women with first infection from HSV genitalis, and in 12.5% of the been born by women with reinfection from HSV. CONCLUSIONS: The women that work are mostly to risk of reinfection, they have more evident troubles. This is consequence of a style of life that contemplates a state of superior stress and a great tiredness from the same and of the appearance of vulvo-vaginal infections sustained by microorganisms transmitted through the hygienic services.

Combination oral agent and insulin therapy for type 2 diabetes mellitus.

Type 2 diabetes is a chronic metabolic disorder that results from defects in both insulin secretion and insulin action. Over time, there is progressive beta-cell failure. Combination oral and insulin therapy aims at treating both the defects in underlying pathophysiology and replacing insulin once beta-cell failure has occurred. Combination therapy is routinely used in the management of diabetes to reduce hemoglobin A1c, weight gain, and the number of insulin injections a patient requires. This article examines the effects of combining various oral agents with insulin on glycemic control, hypoglycemia, weight gain, and nonglycemic benefits of these combinations.

Effect of physician specialty on outcomes in diabetic ketoacidosis.

OBJECTIVE: More than 100,000 people are hospitalized annually in the U.S. with diabetic ketoacidosis (DKA). Outcome differences have not been examined for these patients based on whether their primary care provider is a generalist or a diabetes specialist. The objective of this study was to investigate hospital charges and hospital length of stay (LOS) for patients with DKA according to the specialty of their primary care provider. RESEARCH DESIGN AND METHODS: We investigated all patients with a primary diagnosis of DKA during a 3.5-year period (n = 260) in a large urban teaching hospital. Hospital charges and LOS were studied regarding the specialty of the primary care provider. Demographic factors, severity of illness, laboratory data, and readmission rates were compared. RESULTS: Patients cared for by generalists and endocrinologists had a similar case mix and severity of DKA. The age-adjusted mean LOS for patients of generalists was 4.9 days (95% CI 4.5-5.4), and the mean LOS for patients of endocrinologists was 3.3 days (2.6-4.2) (P < 0.0043). Mean hospital charges differed (P < 0.0001) with an age- and sex-adjusted mean for patients of endocrinologists of $5,463 ($4,179-7,141) and a mean for patients of generalists of $10,109 ($9,151-11,166). The additional charges incurred by generalists were due in part to patients undergoing more procedures. No differences in diabetes-related complications occurred during admission, but the endocrinologist-treated group had a lower readmission rate for DKA during the study period than the generalist-treated group (2 vs. 6%, respectively) (P = 0.03). CONCLUSIONS: Endocrinologists provide more cost-effective care than generalists do when serving as primary care providers for patients hospitalized with DKA.

Time length of negativization of hCG serum values after either surgical or medical treatment of ectopic pregnancy.

OBJECTIVE: The aim of this study was to compare the time length until the human chorionic gonadotropin titer became negative after medical or surgical treatment of ectopic pregnancy. EXPERIMENTAL DESIGN: Prospective, randomized study. PARTECIPANTS AND INTERVENTIONS: We compared time to resolution in 30 cases of tubal pregnancies successfully treated, 15 underwent laparoscopic linear salpingostomy (group 1) and 15 medical treatment with single-ose methotrexate (group 2). The patients of both groups had no meaningful differences of age, gestational age and human chorionic gonadotropin mean values. MEASURES: During the follow-up human chorionic gonadotropin serum values were obtained every two days until the titer was negative. RESULTS: The time to resolution was 33.6 +/- 6.6 days in group 1, 31.5 +/- 7.8 in group 2 with no statistically meaningful differences. CONCLUSION: The data, comparable with results obtained by laparoscopic treatment, suggest that human chorionic gonadotropin value becomes negative independently of type of treatment and residual trophoblast.

Bone density in women with endometriosis.

OBJECTIVE: To evaluate the impact of endometriosis on bone metabolism. MATERIALS AND METHODS: We compared bone mineral density and biochemical markers (plasma osteocalcin, bone alkaline phosphatase, fasting urinary hydroxyproline, urinary excretion of cross-linked N-telopeptide of type I collagen) of bone turnover in forty-nine perimenopausal women undergoing laparotomy because of benign gynecologic pathology: in twenty-four of them (group A) endometriosis was diagnosed, the remaining twenty-five represented the control group (group B). Statistical analysis was performed by means of Student "t"-test; significance was set at p < 0.05. RESULTS: Bone density of the lumbar spine (0.898 +/- 0.325 vs 0.940 +/- 0.350) and bone markers failed to show statistically significant differences between the two groups. No significant correlation was observed between any bone density measurement and severity of endometriosis. CONCLUSION: Endometriosis does not seem to induce even in advanced stages, a reduction of bone density.

Effects of hormone replacement therapy on glucose metabolism.

OBJECTIVE: To evaluate the relationship between hormone replacement therapy and glucose metabolism, and the possible role played by the administration route. DESIGN: Prospective randomized study. MATERIALS AND METHODS: Eighty-four patients in either surgical or spontaneous menopause were randomly allocated into four groups: 15 patients in surgical menopause were treated with estrogens alone administered transdermically (17 beta-estradiol, 50 micrograms/day); 15 patients in surgical menopause were treated with oral conjugated equine estrogens (0.625 mg/day); 18 patients in spontaneous menopause were treated with transdermic estrogens plus oral progestagen (17 beta-estradiol 50 micrograms/day, acetate medroxyprogestogen 10 mg/day for 12 days per month); 16 patients in spontaneous menopause were treated with oral conjugated equine estrogens (0.625 mg/day) plus oral progestagen (10 mg/day for 12 days per month). Twenty patients not given any medication represented the control group. Before starting the trial and after six months of therapy, glucose and insulin levels before and after an oral glucose loading test were evaluated. Data analysis was performed by means of Student's "t"-test, ANOVA was used to compare mean levels between the groups. Significance was set at p < 0.005. RESULTS: Dosages made after 6 months of therapy showed comparable basal glucose levels in all the studied group, while basal insuline levels in patients taking estrogen alone were lower (76.88 +/- 23.66 vs 95.91 +/- 24.57 in group 1, 80 +/- 13.34 vs 96.91 +/- 18.97 in group 2) than pretreatment values. No significant difference in glucose levels was found after glucose load in the four groups. CONCLUSION. Women treated with estrogen alone have a tendency to a lower insulin response, which could indicate a greater insulin sensitivity. This effect seems to be more evident in transdermic administration than with oral administration. The addition of progestagen seems to wane the increase in insulin sensitivity induced by estrogens.

Unrecognized diabetes among hospitalized patients.

OBJECTIVE: To evaluate the hospital care rendered to hyperglycemic individuals who did not have a diagnosis of diabetes before admission. RESEARCH DESIGN AND METHODS: A total of 1,034 consecutively hospitalized adult patients at a 750-bed inner-city teaching hospital were evaluated. Patients with one or more plasma glucose values > 200 mg/dl were identified by the laboratory data system on a daily basis. Patients without a diagnosis of diabetes at the time of admission were evaluated to determine if and how physicians addressed the hyperglycemia, whether a new diagnosis of diabetes was made during admission, and whether follow-up was planned to address the hyperglycemia. RESULTS: After excluding patients who were admitted for a primary diagnosis of diabetes, 37.5% of all hyperglycemic medical patients and 33% of hyperglycemic surgical patients were without a diagnosis of diabetes at the time of admission. These patients had a mean peak glucose of 299 mg/dl, and 66% had two or more elevated values during their hospitalization. Fifty-four percent received insulin therapy, and 59% received bedside glucose monitoring, yet 66% of daily patient progress notes failed to comment on the presence of hyperglycemia or diabetes. Diabetes was documented in only three patients (7.3%) as a possible diagnosis in the daily progress notes. CONCLUSIONS: Despite marked hyperglycemia, most medical records made no reference to the possibility of unrecognized diabetes. Given the average delay of a decade between the onset and diagnosis of type 2 diabetes, further evaluation of hyperglycemic hospitalized patients may present an important opportunity for earlier detection and the initiation of therapy.