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The success level of hypospadias repair in adults still needs to be established on a more extensive scaled study. Therefore, we conducted this study to document the success level of hypospadias repair in adults. This study presents the results of 620 adult distal hypospadias patients treated with TIPU operation. A retrospective study was performed for adult patients who underwent TIPU operations from February 2016 to September 2020. Patients who had distal hypospadias after the age of 16 were included in our study. The average operation time was between 35 and 65 min (50 min.). Complications developed in 79 (12.7%) patients: 37 urethral fistulas, 24 meatal stenosis, 11 anastomotic stenosis and 7 had a complete failure. In conclusion, primary adult distal hypospadias surgery is safe and easy. The complication rates are similar when compared to the paediatric group. As the surgical experience advances, the success of the operation increases in direct proportion.

We aimed to compare labial and buccal mucosa graft methods in female urethroplasty.Female urethroplasty surgeries performed between March 2016 and October 2020 were retrospectively reviewed. Labial and buccal mucosa graft surgeries were listed.Between March 2016 and October 2020, a total of 28 patients had graft urethroplasty surgery in our center. Fourteen had labial, 14 had buccal onlay graft urethroplasty. The pre-treatment Qmax values were 13 ml/s in the labia major onlay graft (LMOG) group and 12.5 ml/s in the buccal mucosa onlay graft (BMOG) group. The Qmax values after the treatment were remeasured at the 1st, 3rd, and 12th months. They were 20 ml/s, 24 ml/s, and 24 ml/s in the LMOG group and 23 ml/s, 25 ml/s, and 28 ml/s in the BMOG group. The operation times were 65 min (55-90) in the LMOG group; in the BMOG group, it was 70.35 min (65-90).In female urethral strictures, especially in long segments and recurrent strictures, graft urethroplasty is a successful and safe method. Dorsal buccal onlay mucosal graft and labia major grafts show similar results in the early period to complications and success. In the long term, buccal onlay mucosal graft gives better results.

In this work, we report the feasibility of the silver nanowire (AgNW) foils as highly-sensitive, reproducible and facile detection tools for surface-enhanced Raman spectroscopy (SERS) applications. These flexible and free-standing AgNW foils, fabricated by vacuum filtration method following a modified polyol synthesis of AgNWs, are adequately structured for both biological specimen filtering and trace amount of molecule detection simultaneously. The compatibility of AgNW foil in SERS is investigated by using a Raman active molecule of different steric volumes across the filter cross-section. We have shown that AgNW foils exhibit extremely strong SERS activity with detection limit up to 10(-9 )M of crystal violet (CV) molecule with 20% variation over similar to cm(2), revealing reliable homogeneity of the acquired signal. While naturally occurring polyvinylpyrrolidone (PVP) layer during polyol synthesis contribute to controlled aggregation, oxidation prevention, and size - shape control purposes, it also creates a major challenge for obtaining enormous enhancement factors. However, controlled thickness of aluminum oxide (Al2O3) coating on PVP@AgNW foils affords to achieve higher enhancement factors than the uncoated ones. What is interesting is that the maximum intensity is achieved from two cycles of Al2O3 deposited on AgNW foils. This is attributed to the two different origins: first, a higher adsorption affinity of CV molecules to Al2O3 layer than PVP layer; second, tunneling barrier formation against quantum tunneling effects.

Effect of thin film deposition route on the morphology and performance of molybdenum oxide (MoO3) based electrochromic devices was investigated. For the deposition of thin films, a sequential deposition method, which includes ultrasonic spray pyrolysis (USP) and thermal evaporation methods was used. Films deposited solely using either USP or thermal evaporation method were used as control samples. Following deposition, MoO3 thin films were then characterized using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy. Surface characteristics and chemical structure of the deposited thin films were found to depend extensively on the deposition route. Electrochromic performance and reversibility of the samples were evaluated using ultraviolet-visible spectrophotometer and cyclic voltammetry. Sample prepared by USP method showed low coloration efficiency (16 cm(2) C-1), but high stability. In contrast, sample prepared by thermal evaporation had high coloration efficiency (30 cm(2) C-1), but low stability. Sample prepared by sequential deposition method showed the highest coloration efficiency (33 cm(2) C-1) among other samples and maintained its stability with cycling. The sequential deposition route investigated in this work is highly promising and might be extended to other metal oxide systems. (c) 2017 The Electrochemical Society.

Classical reinforcement learning techniques are often inadequate for problems with large state-space due to curse of dimensionality. If the states can be represented as a set of variables, it is possible to model the environment more compactly. Automatic detection and use of temporal abstractions during learning was proven to be effective to increase learning speed. In this paper, we propose a factored automatic temporal abstraction method based on an existing temporal abstraction strategy, namely extended sequence tree algorithm, by taking care of state differences via state variable changes. The proposed method has been shown to provide significant memory gain on selected benchmark problems.

In recent years, laparoscopy has begun to be widely used in many clinics for the diagnosis and repair of nonpalpable testes. Because the technique is noninvasive, it is also used to repair inguinal hernias via the retroperitoneal route. The technique and results of performing laparoscopic orchiectomy and herniorrhaphy simultaneously by the transperitoneal route in patients with abdominal testis and ipsilateral inguinal hernia were addressed in this clinical study. Between 1996 and 2001, laparoscopic intervention was applied in 44 patients ranging in age from 20 to 27 years (average, 23 years) who had both unilateral nonpalpable testis and ipsilateral inguinal hernia. The patients underwent laparoscopic orchiectomy and transperitoneal herniorrhaphy. They were followed for 6 to 24 months postoperatively (average, 16 months). No complications developed during the operation or early postoperative period in any of the patients. No case of recurrent hernia was encountered during the followup period. Efficient laparoscopic transperitoneal hernia repair can be achieved during laparoscopic orchiectomy performed in patients with abdominal testis and ipsilateral inguinal hernia. When this method is used, patients can be discharged on the day after the operation and are able to resume their daily activities within a very short time.

The buccal mucosa has begun to be used as a free graft in complex hypospadias repair gradually and successfully in recent years. However, there are limited experiences regarding use of the buccal mucosa in adult patients. In this study, the authors describe their experience using buccal mucosal grafts in hypospadias-crippled adult patients. Between March 1996 and February 2001, the buccal mucosa was used in 26 cases of complex hypospadias in which local penile skin was not present or it was insufficient for urethral repair. All patients were adults (age range, 17-24 y; average, 21 y). In these patients in whom penile skin was insufficient, urethral repair by buccal mucosa was planned, with the stipulation that at least 6 months had passed from the previous operation. The buccal mucosa has been applied to 23 patients alone and in combination with penile skin in three patients. After surgery, the patients were followed-up for 3 to 18 months (average, 12 mo). During the follow-up, fistula in the line of the proximal anastomosis, meatal stenosis, and the fistula together with meatal stenosis developed in nine (35%), four (15%), and two patients (7%), respectively. It is concluded that buccal mucosa is the free graft material that should be the first choice in complex hypospadias cases that are circumcised or undergo operation more than once and when the penile skin is not available.

It has been experimentally demonstrated that viscosity differentiates the extent to which inverted and retained housanes are formed in the liquid-phase denitrogenation of a substituted diazabicyclo[2,2,1]hept-2-enes (DBH)-type azoalkane, namely syn -2,3-diaza-4,7-dimethyl-1-ethyl bicyclo[2,2,1]heptene. The fact that the viscosity profiles coincide for the inversion/retention product ratio, assessed for a set of diverse solvents at constant temperature and through the temperature variation in a single solvent ( n -butanol), shows that the temperature dependence of the stereoselectivity is controlled by bulk viscosity effects. The simple free-volume model rationalizes the viscosity behavior of the inversion/retention ratio. Since the viscous medium differentiates between the inversion and retention reaction channels, we conclude that an unsymmetrical, nitrogen-containing intermediate, presumably the singlet diazenyl diradical, intervenes in the liquid-phase deazetation process.

Oxidation and ionization potentials of azoalkanes have been measured and combined with the available literature data to afford a data set of ten cyclic, bicyclic, and polycyclic derivatives with a wide structural variation. A linear correlation (r = 0.939) between the peak oxidation potentials (Ep) and the vertical ionization potentials (IPv) of the azoalkanes 1−10 applies (Ep = 0.95(IPv) − 6.4). The approximately unit slope is interpreted in terms of relatively constant differential solvation and cationic relaxation energies for the various azoalkanes. Density functional calculations (B3LYP/6-31G*) for bicyclic azoalkanes confirm that the cationic relaxation energies are relatively insensitive to molecular strain and rigidity; the latter are known to dictate their ionization potentials. The theoretical data indicate further that the preferred modes of geometry reorganization in the azoalkane radical cations are shortening of the NN, lengthening of the C−N bonds, and widening of the C−NN, but no torsion a...

Radical anions of 2,3-diazabicyclo[2.2.1]hept-2-ene 1 and its 18 substituted and tricyclic derivatives (2a–11c) have been characterized by their hyperfine data with the use of EPR and ENDOR spectroscopy. The structural modifications of 1, yielding 2a–11c, are methyl and/or phenyl substitutions in the 1,4-positions, introduction of methyl groups or a spirocyclopentane ring in the 7,7-positions and annelation by a cyclopropane, cyclobutane, cyclobutene, cyclopentane or cyclopentene ring in the 5,6-endo-positions. Although these modifications do not markedly alter the π-spin and charge distribution in 1˙-, they have a strong effect on the long-range coupling constant of the γ-protons in the 5,6-exo-positions: the pertinent aH(γ) value varies from +0.26 to +0.64 mT. The effect is particularly impressive for the 5,6-endo-annelation by a cycloalkane or a cycloalkene ring and it goes along with only slight changes in the geometry of the carbon framework in 1˙-. Thus, owing to the through-bond mechanism of π,σ-spin transfer (homohyperconjugation), the coupling constant, aH(γ), of the 5,6-exo-protons responds sensitively to such changes in the geometry.

Photochemical electron transfer (PET) and chemical electron transfer (CET) studies have been conducted in solution and within zeolite cavities for the bicyclo[2.1.0]pentanes (2a−j), prepared by direct photolysis of the corresponding azoalkanes 1. The advantage of the CET oxidations is that they proceed catalytically in a clean manner to afford the rearranged cyclopentenes 3 in excellent yields. A complete reversal in the regioselectivity of the 1,2 migration has been observed for the unsymmetrical derivatives of bicyclo[2.1.0]pentane, namely 2b (methyl substitution) versus 2c,i (phenyl substitution). Both in solution and in the zeolite cavities, the less substituted cyclopentene 3b‘ is obtained for the methyl derivative 2b and the more substituted cyclopentenes 3c,i for the phenyl cases 2c,i. This unexpected fact is rationalized in terms of delocalization of the positive charge into the aromatic ring for the phenyl-substituted radical cation, as corroborated by AM1 calculations. Furthermore, the electron ...

The chemical behavior of the radical cations derived from 2,3-diazabicyclo[2.2.1]hept-2-enes 1 and bicyclo[2.1.0]pentanes 2 by oxidation with tris (aryl)aminium hexachloroantimonates has been examined.

Cyclopentane-1,3-diyl radical cations were generated from the 1-methyl- and 1,4-dimethyl substituted bicyclo-[2.1.0]pentanes 1b,c through photoinduced electron transfer (PET) and radiolytic oxidation. The unsymmetrical bridgehead-substituted bicyclopentane 1b rearranged spontaneously and exclusively to the 3-methylcyclopentene 3b under PET conditions. ESR studies showed similarly that 3b[sup [sm bullet]+] was the only final oxidation product of 1b; the initial radical cation 1b[sup [sm bullet]+] was not detected because it rearranges rapidly and stereoselectively by a 1,2-hydrogen shift to 3b[sup [sm bullet]+], even at 80 K, and no trace of the more stable 1-methylcyclopentene radical cation 3a[sup [sm bullet]+] was observed. This contra-thermodynamic regioselectivity is rationalized in terms of essential localization of positive charge at the tertiary center as the reaction proceeds in the 1,3-diyl radical cation 1b[sup [sm bullet]+]. The symmetrical dimethyl derivative 1c rearranged much more reluctantly than 1b despite its lower oxidation potential, and this is attributed to the greater persistence of radical cation 1c[sup [sm bullet]+] through its reluctance to undergo a 1,2-H shift. The oxidation of these azoalkanes generates highly reactive transients, presumably diazenyl radical cations, which readily denitrogenate and undergo 1,2-H shifts in either a consecutive or concerted manner to form olefin radical cations. 25 refs., 6 figs., 2more » tabs.« less