Sensitivity and Specificity of Fractal Analysis to Distinguish Between Healthy and Pathologic Rectal Mucosa Microvasculature Seen During Colonoscopy.

PURPOSE: Conventional endoscopy is limited by human capability to recognize and to differentiate pathology. Fractal analysis of blood vessels has been used in other organs, such as the retina, but never before to supplement colonoscopy. The aim of this study was to assess whether it is possible to differentiate between healthy and pathologic rectal mucosa using fractal analysis of the mucosal microvascular architecture seen during colonoscopic examination (Supplemental Digital Content 1, http://links.lww.com/SLE/A145). METHODS: A total of 300 consecutive patients, 133 females and 167 males with a mean age of 49.1 (±11.3) years, undergoing endoscopy were included in the prospective cohort study. Colonoscopy of the sigmorectal region was performed, and then analyzed with computer-assisted image fractal analysis. RESULTS: Fractal analysis of mucosal vasculature allowed for differentiation between healthy and pathologic rectal mucosa, as well as different pathologies (P<0.0001). The sensitivity of fractal analysis to diagnose rectal neoplasia was 92.8% to 96.4%, while the specificity was 91.9% to 98.5% depending on the fractal parameter. The sensitivity of fractal analysis to diagnose rectal colitis was 84.2% to 92.1%, while the specificity was 95.0% to 96.0%, depending on the fractal parameter. CONCLUSIONS: Computer-assisted fractal analysis allows for differentiation between healthy and pathologic rectal mucosa, as well as between different mucosal pathologies, seen during colonoscopy. Fractal analysis improves the sensitivity and specificity of colonoscopy to aid in the diagnosis of neoplasia or colitis, and should be included in the screening and surveillance of these pathologies.

Gastroscopy in patients with hiatal hernia with and without gastroesophageal mucosal prolapse.

There are still many doubts in the literature regarding gastroesophageal mucosal prolapse (GEMP) and its clinical course. We still do not know what determines mucosal wedging in esophagogastric junction, and what is the role of the anatomy of that site. To investigate that problem we performed 120 upper digestive tract endoscopies in which a hiatal hernia was diagnosed. Patients referred to our unit with different complaints most frequently of typical or atypical gastroesophageal (GE) reflux symptoms. The aim of that study was to assess hernia dimensions in patients with and without GEMP diagnosed during endoscopy. Additionally we analyzed the type and prevalence of gastrointestinal symptoms reported by patients to confirm the observation that GEMP symptoms differ from gastroesophageal reflux disease (GERD) symptoms. METHODS: One-hundred and twenty patients were included in this study. All of the patients were diagnosed with a hiatal hernia during routine gastroscopy. Using standardized methodology the region of the hiatal hernia was photographed, and hernia longitudinal and transverse dimensions were measured. RESULTS: The study group comprised 57 females (52.5%) and 63 males - mean age (SD) 58.5 ± 18.4. Most of the patients had standard GERD symptoms (n = 96; 80%). The average length of hiatus, in patients with GEMP (n = 24; 20%) was 3.56 ± 0.59 cm, and the average width was 2.32 ± 0.62 cm (n = 96; 80%) vs. 4.64 ± 0.74 cm and 2.98 ± 0.68 cm respectively in patients without GEMP (p <0.001). CONCLUSIONS: GEMP occurs in smaller sized hiatal hernias. We confirmed that disease symptoms of the majority of patients with GEMP differ from patient with GERD but without GEMP. However this difference was not significant enough to allow to differentiate between diagnoses based solely on the symptoms.

Vibronic spectra of the p-benzoquinone radical anion and cation: a matrix isolation and computational study.

The electronic and vibrational absorption spectra of the radical anion and cation of p-benzoquinone (PBQ) in an Ar matrix between 500 and 40,000 cm(-1) are presented and discussed in detail. Of particular interest is the radical cation, which shows very unusual spectroscopic features that can be understood in terms of vibronic coupling between the ground and a very low-lying excited state. The infrared spectrum of PBQ˙(+) exhibits a very conspicuous and complicated pattern of features above 1900 cm(-1) that is due to this electronic transition, and offers an unusually vivid demonstration of the effects of vibronic coupling in what would usually be a relatively simple region of the electromagnetic spectrum associated only with vibrational transitions. As expected, the intensities of most of the IR transitions leading to levels that couple the ground to the very low-lying first excited state of PBQ˙(+) increase by large factors upon ionization, due to "intensity borrowing" from the D0 → D1 electronic transition. A notable exception is the antisymmetric C=O stretching vibration, which contributes significantly to the vibronic coupling, but has nevertheless quite small intensity in the cation spectrum. This surprising feature is rationalized on the basis of a simple perturbation analysis.

Biomass pyrolysis: thermal decomposition mechanisms of furfural and benzaldehyde.

The thermal decompositions of furfural and benzaldehyde have been studied in a heated microtubular flow reactor. The pyrolysis experiments were carried out by passing a dilute mixture of the aromatic aldehydes (roughly 0.1%-1%) entrained in a stream of buffer gas (either He or Ar) through a pulsed, heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 75-150 Torr with the SiC tube wall temperature in the range of 1200-1800 K. Characteristic residence times in the reactor are 100-200 µsec after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 µTorr. Products were detected using matrix infrared absorption spectroscopy, 118.2 nm (10.487 eV) photoionization mass spectroscopy and resonance enhanced multiphoton ionization. The initial steps in the thermal decomposition of furfural and benzaldehyde have been identified. Furfural undergoes unimolecular decomposition to furan + CO: C4H3O-CHO (+ M) → CO + C4H4O. Sequential decomposition of furan leads to the production of HC≡CH, CH2CO, CH3C≡CH, CO, HCCCH2, and H atoms. In contrast, benzaldehyde resists decomposition until higher temperatures when it fragments to phenyl radical plus H atoms and CO: C6H5CHO (+ M) → C6H5CO + H → C6H5 + CO + H. The H atoms trigger a chain reaction by attacking C6H5CHO: H + C6H5CHO → [C6H6CHO]* → C6H6 + CO + H. The net result is the decomposition of benzaldehyde to produce benzene and CO.

Endobronchial metastasis from hepatocellular carcinoma - a case description with literature review.

Endobronchial metastases from hepatocellular carcinoma are very rare. Up to date, no more than 7 cases were reported. The authors present a case of 20-year old female with metastatic hepatocellular carcinoma to superior lobar bronchus. Examination of cytological and small biopsy specimens obtained from bronchoscopy revealed characteristic microscopic features and immunohistochemical profile of hepatocellular carcinoma.

Carbocations generated under stable conditions by ionization of matrix-isolated radicals: the allyl and benzyl cations.

Carbocations are crucial intermediates in many chemical reactions; hence, considerable effort has gone into investigating their structures and properties, for example, in superacids, in salts, or in the gas phase. However, studies of the vibrational structure of carbocations are not abundant, because their infrared spectra are difficult to obtain in superacids or salts (where furthermore the cations may be perturbed by counterions), and the generation of gas-phase carbocations in discharges usually produces several species. We have applied the technique of ionizing neutral compounds by X-irradiation of cryogenic Ar matrices to radicals embedded in such matrices, thus producing closed-shell cations that can be investigated leisurely, and in the absence of counterions or other perturbing effects, by various forms of spectroscopy. This Article describes the first set of results that were obtained by this approach, the IR spectra of the allyl and the benzyl cation. We use the information obtained in this way, together with previously obtained data, to assess the changes in chemical bonding between the allyl and benzyl radicals and cations, respectively.

The bisketene radical cation and its formation by oxidative ring-opening of cyclobutenedione.

Parent cyclobutenedione 1 was photolyzed and ionized in an Ar matrix at 10K. The bisketene 2 that results in both cases (in the form of its radical cation after ionization) was characterized by its IR spectrum and by high-level quantum chemical calculations. Experiment and theory show that the neutral bisketene has only a single conformation where the two ketene moieties are nearly perpendicular, whereas the radical cation is present in two stable planar conformations. The mechanism of the ring-opening reaction, both in the neutral and in the radical cation, is discussed on the basis of calculations. In the latter case it is a nonsynchronous process that involves an avoided crossing of states.

Ossification of the ligamentum flavum of the lumbosacral spine in the Polish hospitalized population - a prospective cohort study.

AIM: The aim of this study was to assess the prevalence, clinical features and distribution of lumbosacral ossifications of the ligamentum flavum (OLF), using MRI, CT and microCT, in hospitalized Polish patients. METHODS: Patients were recruited prospectively between January 2011 and January 2013. Patients were further qualified to the study group only if CT or MRI of the lumbosacral region detected OLF. Level of OLF excision was determined by the localization of spinal stenosis. After excision the LF fragments containing OLF were stored in a 4% solution of formaldehyde until microCT assessment. RESULTS: A total of 184 agreed to take part in the study. In 50 patients (27.2%) OLF were found. Thus, the study group consisted of 17 women (34%) and 33 men, with a mean age of 55.4 ± 17.2 years. OLF occurred more often in men (66%) than in women (34%) (p = 0.0014). The most common site for the localization of OLF in women, as well as in men was the L5/S1 level (60% and 53.3% respectively). The mean volume of OLF was 3.87 ± 5.27 mm3 (4.66 ± 5.71 mm3 vs. 1.27 ± 2.19 mm3, in men and women respectively; p = 0.023). The LF were thickened in 21 (42%) patients. The mean volume of OLF in patients with normal LF was 4.78 ± 5.95 mm3 and in patients with thickened LF 5.33 ± 6.10 mm3 (p = 0.75). CONCLUSIONS: The prevalence of lumbosacral OLF in the Polish hospitalized population is very high. The most common site of their localization is the L5/S1 level. LF thickening is not associated with OLF formation.

Thermal decomposition of CH3CHO studied by matrix infrared spectroscopy and photoionization mass spectroscopy.

A heated SiC microtubular reactor has been used to decompose acetaldehyde and its isotopomers (CH(3)CDO, CD(3)CHO, and CD(3)CDO). The pyrolysis experiments are carried out by passing a dilute mixture of acetaldehyde (roughly 0.1%-1%) entrained in a stream of a buffer gas (either He or Ar) through a heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 50-200 Torr with the SiC tube wall temperature in the range 1200-1900 K. Characteristic residence times in the reactor are 50-200 µs after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 µTorr. The reactor has been modified so that both pulsed and continuous modes can be studied, and results from both flow regimes are presented. Using various detection methods (Fourier transform infrared spectroscopy and both fixed wavelength and tunable synchrotron radiation photoionization mass spectrometry), a number of products formed at early pyrolysis times (roughly 100-200 µs) are identified: H, H(2), CH(3), CO, CH(2)=CHOH, HC≡CH, H(2)O, and CH(2)=C=O; trace quantities of other species are also observed in some of the experiments. Pyrolysis of rare isotopomers of acetaldehyde produces characteristic isotopic signatures in the reaction products, which offers insight into reaction mechanisms that occur in the reactor. In particular, while the principal unimolecular processes appear to be radical decomposition CH(3)CHO (+M) → CH(3) + H + CO and isomerization of acetaldehyde to vinyl alcohol, it appears that the CH(2)CO and HCCH are formed (perhaps exclusively) by bimolecular reactions, especially those involving hydrogen atom attacks.

In-spray supercharging of peptides and proteins in electrospray ionization mass spectrometry.

Enhanced charging, or supercharging, of analytes in electrospray ionization mass spectrometry (ESI MS) facilitates high resolution MS by reducing an ion mass-to-charge (m/z) ratio, increasing tandem mass spectrometry (MS/MS) efficiency. ESI MS supercharging is usually achieved by adding a supercharging reagent to the electrospray solution. Addition of these supercharging reagents to the mobile phase in liquid chromatography (LC)-MS/MS increases the average charge of enzymatically derived peptides and improves peptide and protein identification in large-scale bottom-up proteomics applications but disrupts chromatographic separation. Here, we demonstrate the average charge state of selected peptides and proteins increases by introducing the supercharging reagents directly into the ESI Taylor cone (in-spray supercharging) using a dual-sprayer ESI microchip. The results are comparable to those obtained by the addition of supercharging reagents directly into the analyte solution or LC mobile phase. Therefore, supercharging reaction can be accomplished on a time-scale of ion liberation from a droplet in the ESI ion source.

The products of the thermal decomposition of CH3CHO.

We have used a heated 2 cm × 1 mm SiC microtubular (µtubular) reactor to decompose acetaldehyde: CH(3)CHO + Δ â†’ products. Thermal decomposition is followed at pressures of 75-150 Torr and at temperatures up to 1675 K, conditions that correspond to residence times of roughly 50-100 µs in the µtubular reactor. The acetaldehyde decomposition products are identified by two independent techniques: vacuum ultraviolet photoionization mass spectroscopy (PIMS) and infrared (IR) absorption spectroscopy after isolation in a cryogenic matrix. Besides CH(3)CHO, we have studied three isotopologues, CH(3)CDO, CD(3)CHO, and CD(3)CDO. We have identified the thermal decomposition products CH(3) (PIMS), CO (IR, PIMS), H (PIMS), H(2) (PIMS), CH(2)CO (IR, PIMS), CH(2)=CHOH (IR, PIMS), H(2)O (IR, PIMS), and HC≡CH (IR, PIMS). Plausible evidence has been found to support the idea that there are at least three different thermal decomposition pathways for CH(3)CHO; namely, radical decomposition: CH(3)CHO + Δ â†’ CH(3) + [HCO] → CH(3) + H + CO; elimination: CH(3)CHO + Δ â†’ H(2) + CH(2)=C=O; isomerization∕elimination: CH(3)CHO + Δ â†’ [CH(2)=CH-OH] → HC≡CH + H(2)O. An interesting result is that both PIMS and IR spectroscopy show compelling evidence for the participation of vinylidene, CH(2)=C:, as an intermediate in the decomposition of vinyl alcohol: CH(2)=CH-OH + Δ â†’ [CH(2)=C:] + H(2)O → HC≡CH + H(2)O.

Mechanistic aspects of the oxidative and reductive fragmentation of N-nitrosoamines: a new method for generating nitrenium cations, amide anions, and aminyl radicals.

A new method for investigating the mechanisms of nitric oxide release from NO donors under oxidative and reductive conditions is presented. Based on the fragmentation of N-nitrosoamines, it allows generation and spectroscopic characterization of nitrenium cations, amide anions, and aminyl radicals. X-irradiation of N-nitroso-N,N-diphenylamine 1 in Ar matrices at 10 K is found to yield the corresponding radical ions, which apparently undergo spontaneous loss of NO* under the conditions of this experiment (1*+ seems to survive partially intact, but not 1*-). One-electron reduction or oxidation of 1 is observed upon doping of the Ar matrix with DABCO, an efficient hole scavenger, or CH2Cl2, an electron scavenger, respectively. The resulting diphenylnitrenium cation, 2+, and the diphenylamide anion, 2-, were characterized by their full UV-vis and mid-IR spectra. The best spectra of 2+ and 2- were obtained if 1 was homolytically photodissociated to diphenylaminyl radical 2* and NO* prior to ionization. 2+ and 2- are bleached on irradiation at <340 nm to form 2* or, in part, 1. DFT and CCSD quantum chemical calculations predict that the dissociation of 1*+ and 1*- is slightly endothermic, a tendency which is partially reversed if one allows for complexation of the resulting 2+ (and, presumably, 2-) with NO*. The method described in this work should prove generally applicable to the generation and study of nitrenium cations and amide anions R2N+/- under matrix and ambient conditions (i.e., in solution).

Anthralin: primary products of its redox reactions.

One-electron reduction significantly enhances the ability of anthralin, 1, to act as a hydrogen atom donor. On annealing of an MTHF glass in which the radical anion of anthralin, 1*-, is generated radiolytically, this species decays mainly by loss of H* to give the anthralyl anion, 2- . On the other hand, radicals formed on radiolysis of matrices that are suitable for the generation of radical anions or cations are capable to abstract H* from anthralin to give the anthralyl radical, 2* . Both 2- and 2* are obtained simultaneously by mesolytic cleavage of the radical anion of the anthralin dimer. Contrary to general assumptions, the anthralyl radical is found to be much more reactive toward oxygen than the anion. All intermediates are characterized spectroscopically and by reference to quantum chemical calculations. Attempts to generate the radical cation of anthralin by X-irradiation of an Ar matrix containing anthralin led also to significant formation of its radical anion, i.e., anthralin acts apparently as an efficient electron trap in such experiments.

Oxidative rearrangements of tricyclic vinylcyclobutane derivatives.

Three tricyclic vinylcyclobutanes (3-methylenetricyclo[5.3.0.0(2,6)]decanes 1-3) have been subjected to ionization by photoinduced electron transfer in solution and by X-irradiation in Ar matrices. All three compounds undergo oxidative cycloreversion; the cleavage of the four-membered ring, however, occurs in a different direction depending on the presence of a methyl group in position 6 of the tricyclic framework. In those derivatives, cycloreversion is found to lead to 1-methyl-8-methylene-1,6-cyclodecadiene radical cations (5.+ from 1, 8.+) from 2) which upon back electron transfer yield two different hydrocarbons (6 from 5.+, 9 from 8.+), depending on the configuration around the endocyclic double bonds of the respective cyclodecadiene derivative. In the absence of a methyl group on C6, the cycloreversion leads to a radical cation complex between 1-methylenecyclopent-2-ene and cyclopentene (12.+) which appears to revert to 3 on back electron transfer. The intermediate radical cations 5.+, 8.+, and 12.+ have been identified and characterized by UV/Vis and IR spectra in Ar matrices. The mechanism of their formation is elucidated by quantum chemical calculations.