Robot-assisted laparoscopic surgery for treatment of urinary tract stones in children: report of a multicenter international experience

This study aimed to report a multi-institutional experience with robot-assisted laparoscopic surgery (RALS) for treatment of urinary tract stones in children. The medical records of 15 patients (12 boys), who underwent RALS for urolithiasis in 4 international centers of pediatric urology over a 5-year period, were retrospectively collected. The median patient age was 8.5 years (range 4–15). Eleven/fifteen patients (73.3%) had concurrent uretero–pelvic junction obstruction (UPJO) and 2/15 patients (13.3%) had neurogenic bladder. Stones were in the renal pelvis in 8/15 (53.3%), in the lower pole in 3/15 (20%), in the bladder in 2/15 (13.3%), and in multiple locations in 2/15 (13.3%). One patient (6.6%) had bilateral multiple kidney stones. The median stone size was 10.8 mm (range 2–30) in upper tract location and 27 mm (range 21–33) into the bladder. Eleven patients with concomitant UPJO underwent simultaneous robot-assisted pyelolithotomy and pyeloplasty in 12 kidney units. Two patients with isolated staghorn stones received robot-assisted pyelolithotomy. Robot-assisted cystolithotomy was performed in two patients with bladder stones. The median operative time was 131.8 min (range 60–240). The stone-free rate was 80% following initial surgery and 100% after secondary treatment. Clavien 2 complications (hematuria, infections) were recorded in 5/15 patients (33.3%). Three/fifteen patients (20%) with residual renal stones were successfully treated using ureterorenoscopy (Clavien 3b). RALS was a feasible, safe and effective treatment option for pediatric urolithiasis in selected cases such as large bladder stones, bilateral kidney stones, staghorn stones or concomitant anomalies such as UPJO requiring simultaneous pyeloplasty

Kinetics and thermochemistry of the reaction of 3-methylpropargyl radical with molecular oxygen

We have measured the kinetics and thermochemistry of the reaction of 3-methylpropargyl radical (but-2-yn-1-yl) with molecular oxygen over temperature (223-681 K) and bath gas density (1.2 - 15.0 x 10(16)cm(-3)) ranges employing photoionization mass-spectrometry. At low temperatures (223-304 K), the reaction proceeds overwhelmingly by a simple addition reaction to the -CH2 end of the radical, and the measured CH3CCCH2 center dot+O-2 reaction rate coefficient shows negative temperature dependence and depends on bath gas density. At intermediate temperatures (340-395 K), the addition reaction equilibrates and the equilibrium constant was determined at different temperatures. At high temperatures (465-681 K), the kinetics is governed by O-2 addition to the third carbon atom of the radical, and rate coefficient measurements were again possible. The high temperature CH3CCCH2 center dot +O(2 )rate coefficient is much smaller than at low T, shows positive temperature dependence, and is independent of bath gas density. In the intermediate and high temperature ranges, we observe a formation signal for ketene (ethenone). The reaction was further investigated by combining the experimental results with quantum chemical calculations and master equation modeling. By making small adjustments (2 - 3 kJ mol(-1)) to the energies of two key transition states, the model reproduces the experimental results within uncertainties. The experimentally constrained master equation model was used to simulate the CH3CCCH2 center dot+ O-2 reaction system at temperatures and pressures relevant to combustion. (C) 2018 The Combustion Institute. Published by Elsevier Inc. All rights reserved.Peer reviewe

Temperature and Pressure Dependence of the Reaction between Ethyl Radical and Molecular Oxygen : Experiments and Master Equation Simulations

Funding Information: We thank Stephen Klippenstein for providing us with the geometries, harmonic frequencies, and relative energies of the stationary points from his recent CH + O publication as well as the state sum for the loose recombination transition state. T.T.P. acknowledges support from the Doctoral Programme in Chemistry and Molecular Sciences of the University of Helsinki and the Magnus Ehrnrooth Foundation for funding. Project K129140 for G.L. was implemented with the support provided by the Ministry of Innovation and Technology of Hungary from the National Research, Development and Innovation Fund, financed under the OTKA funding scheme. T.T.P., E.A.R., and A.J.E. acknowledge support from the Academy of Finland (Grants 325250 and 346374). The authors also acknowledge CSC IT Center for Science in Finland for computational resources. 2 5 • 2 Publisher Copyright: © 2023 The Authors.We have used laser-photolysis - photoionization mass-spectrometry to measure the rate coefficient for the reaction between ethyl radical and molecular oxygen as a function of temperature (190-801 K) and pressure (0.2-6 Torr) under pseudo first-order conditions ([He] >> [O2] >> [C2H5 center dot]). Multiple ethyl precursor, photolysis wavelength, reactor material, and coating combinations were used. We reinvestigated the temperature dependence of the title reaction's rate coefficient to resolve inconsistencies in existing data. The current results indicate that some literature values for the rate coefficient may indeed be slightly too large. The experimental work was complemented with master equation simulations. We used the current and some previous rate coefficient measurements to optimize the values of key parameters in the master equation model. After optimization, the model was able to reproduce experimental falloff curves and C2H4 + HO2 center dot yields. We then used the model to perform simulations over wide temperature (200-1500 K) and pressure (10-4-102 bar) ranges and provide the results in PLOG format to facilitate their use in atmospheric and combustion models.Peer reviewe

Kinetics and thermochemistry of the reaction of 1-methylpropargyl radicals with oxygen molecules : Experiments and computations

We have used laser-photolysis/photoionization mass spectrometry to measure the kinetics of the reaction of 1-methylpropargyl (but-3-yn-2-yl, CH C=CH-CH3) radicals with oxygen molecules as a function of temperature (T = 200 - 685 K) and bath gas density (1.2 - 15 x 10(16) cm(-3)). The low temperature (TPeer reviewe

An experimental and computational study of the reaction between pent-3-en-2-yl radicals and oxygen molecules : switching from pure stabilisation to pure decomposition with increasing temperature

We have used laser-photolysis-photoionization mass spectrometry, quantum chemical calculations, and master equation simulations to investigate the kinetics of the reaction between (E/Z)-pent-3-en-2-yl (CH3-CH - CH - CH-CH3), a resonance-stabilised hydrocarbon radical, and molecular oxygen. The time-resolved experiments were performed over a wide temperature range (240-750 K) at relatively low pressures (0.4-7 Torr) under pseudo-first-order conditions (excess [O-2]). Helium bath gas was used in most experiments, but nitrogen was employed in a few measurements to investigate the effect of a heavier collider on the kinetics of the studied reaction. The experimental traces were directly used to optimise parameters in the master equation model using the recently implemented trace fitting feature in the MESMER program. At low temperatures (T < 300 K), the reaction proceeds by barrierless recombination reactions to form peroxyl adducts, and the radical traces are single-exponential. Between 326 K and 376 K, equilibration between the reactants and the peroxyl adducts is observed, and the radical traces are multi-exponential. Interestingly, at temperatures above 500 K, single-exponential decays were again observed, although the reaction is much slower than at low temperatures. The master equation simulations revealed that at both low and high temperatures, the radical decay rate is governed by a single eigenvalue. At low temperatures, this eigenvalue corresponds to recombination reactions, and at high temperatures to the phenomenological formation of bimolecular products. Between low and high temperatures (the exact temperature thresholds depend on [O-2]), there is a region of avoided crossing in which the rate coefficient "jumps" from one eigencurve to the other. Although chemically significant eigenvalues are not well separated from internal energy relaxation eigenvalues at elevated temperatures (600 K at 0.01 bar, 850 K at 100 bar), we observed that many of the Bartis-Widom rate coefficients produced by the master equation model were valid up to 1500 K. Our simulations predict that the most important reaction channel at high temperatures is the formation of (E/Z)-penta-1,3-diene and hydroperoxyl. The experimentally constrained master equation model was used to simulate the title reaction over a wide range of conditions. To facilitate the use of our results in autoignition and combustion models, modified Arrhenius representations are given for the most important reaction channels.Peer reviewe

Geophysical Characterization, Redox Zonation, and Contaminant Distribution at a Groundwater/Surface Water Interface

Three transects along a groundwater/surface water interface were characterized for spatial distributions of chlorinated aliphatic hydrocarbons and geochemical conditions to evaluate the natural bioremediation potential of this environmental system. Partly on the basis of ground penetrating radar measurements, a conductive sediment layer was detected from the shore out to at least 300 m offshore which exhibited gradients in redox pairs and contaminant profiles. The cis-Dichloroethene and 1-chloroethene were predominant in the presence of elevated methane and ferrous iron concentrations and depressed sulfate and aquifer solids-bound iron concentrations. The shallow monitoring points were generally hypoxic to aerobic and exhibited values of specific conductance reflective of near-shore lake water, indicating reoxygenation of the contaminant plume due to wave infiltration. The barge transect yielded trace contaminant concentrations and showed evidence of sulfate reduction. These analyses contributed to the understanding of processes affecting contaminant fate and transport at near-shore mixing zones

Kinetics of the Methyl-Vinyl Radical + O-2 Reactions Associated with Propene Oxidation

The bimolecular rate coefficients of reactions CH3CCH2 + O-2 (1) and cis/trans-CH3CHCH + O-2 (2a/3a) have been measured using a tubular laminar flow reactor coupled with a photoionization mass spectrometer (PIMS). These reactions are relevant in the combustion of propene. Pulsed excimer laser photolysis of a ketone or a bromide precursor molecule at 193 or 248 nm wavelength was used to produce radicals of interest homogeneously along the reactor. Time-resolved experiments were performed under pseudo-first-order conditions at low pressure (0.3-1.5 Torr) over the temperature range 220-660 K. The measured bimolecular rate coefficients were found to be independent of bath gas concentration. The bimolecular rate coefficients possess negative temperature dependence at low temperatures (T 420 K). Observed products of the reaction CH3CCH2 + O-2 were CH3 and H2CO, while for the reaction cis/trans-CH3CHCH + O-2, observed products were CH3CHO and HCO. Current results indicate that the reaction mechanism of both reactions is analogous to that of C2H3 + O-2. Methyl substitution of the vinyl radical changes its reactivity toward O-2 upward by ca. 50% if it involves the alpha-position and downward by ca. 30% if the methyl group takes either of the beta-positions, respectively.Peer reviewe

What is new in surgical treatment of vesicoureteric reflux?

In addition to conventional open surgery and endoscopic techniques, laparoscopic correction of vesicoureteric reflux, sometimes even robot-assisted, is becoming an alternative surgical treatment modality for this condition in a number of centres around the world. At least for a subgroup of patients laparoscopists are trying to develop new techniques in an effort to combine the best of both worlds: the minimal invasiveness of the STING and the same lasting effectiveness as in open surgery. The efficacy and potential advantages or disadvantages of these techniques are still under investigation. The different laparoscopic techniques and available data are presented

Endogenous ribosomal frameshift signals operate as mRNA destabilizing elements through at least two molecular pathways in yeast

Although first discovered in viruses, previous studies have identified operational −1 ribosomal frameshifting (−1 RF) signals in eukaryotic genomic sequences, and suggested a role in mRNA stability. Here, four yeast −1 RF signals are shown to promote significant mRNA destabilization through the nonsense mediated mRNA decay pathway (NMD), and genetic evidence is presented suggesting that they may also operate through the no-go decay pathway (NGD) as well. Yeast EST2 mRNA is highly unstable and contains up to five −1 RF signals. Ablation of the −1 RF signals or of NMD stabilizes this mRNA, and changes in −1 RF efficiency have opposing effects on the steady-state abundance of the EST2 mRNA. These results demonstrate that endogenous −1 RF signals function as mRNA destabilizing elements through at least two molecular pathways in yeast. Consistent with current evolutionary theory, phylogenetic analyses suggest that −1 RF signals are rapidly evolving cis-acting regulatory elements. Identification of high confidence −1 RF signals in ∼10% of genes in all eukaryotic genomes surveyed suggests that −1 RF is a broadly used post-transcriptional regulator of gene expression