An experimental and computational study of the unimolecular-decay reaction of diethyl-substituted Criegee intermediate (CH)COO.

We have performed direct kinetic measurements to determine the thermal unimolecular-decay rate coefficient of (CH)COO as a function of temperature (223-296 K) and pressure (4-100 torr) using time-resolved UV-absorption spectroscopy. The stabilised (CH)COO Criegee intermediate was produced by photolysing 3-bromo-3-iodopentane ((CH)CIBr) with 213 nm radiation in the presence of O. We performed quantum-chemistry calculations and master-equation simulations to complement the experimental work.

Direct Kinetic Measurements of a Cyclic Criegee Intermediate; Unimolecular Decomposition of (CH)COO.

We report the first direct kinetic measurements of a cyclic stabilized Criegee Intermediate. We have measured the unimolecular reaction rate coefficient of cyclohexanone oxide ((CH)COO) in the temperature 213-296 K and pressure 7-50 Torr ranges using absorption spectrometry. The (CH)COO was produced by the photolysis of (CH)CIBr at 213 nm in the presence of O.

Putative NAD(P)-Binding Rossmann Fold Protein Is Involved in Chitosan-Induced Peroxidase Activity and Lipoxygenase Expression in .

Oxidative burst, the rapid production of high levels of reactive oxygen species in response to external stimuli, is an early defense reaction against pathogens. The fungal elicitor chitosan causes an oxidative burst in the moss (formerly ), mainly due to the peroxidase enzyme Prx34. To better understand the chitosan responses in , we conducted a screen of part of a mutant collection to isolate plants with less peroxidase activity than wild-type (WT) plants after chitosan treatment.

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 (/)-pent-3-en-2-yl 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]).

Solving the discrepancy between the direct and relative-rate determinations of unimolecular reaction kinetics of dimethyl-substituted Criegee intermediate (CH)COO using a new photolytic precursor.

We have performed direct kinetic measurements of the thermal unimolecular reaction of (CH)COO in the temperature range 243-340 K and pressure range 5-350 Torr using time-resolved UV-absorption spectroscopy. We have utilized a new photolytic precursor, 2-bromo-2-iodopropane ((CH)CIBr), which photolysis at 213 nm in the presence of O produces acetone oxide, (CH)COO. The results show that the thermal unimolecular reaction is even more important main loss process of (CH)COO in the atmosphere than direct kinetic studies have suggested hitherto.

Missing Selectivity of Targeted 4β-Phorbol Prodrugs Expected to be Potential Chemotherapeutics.

Targeting cytotoxic 4β-phorbol esters toward cancer tissue was attempted by conjugating a 4β-pborbol derivative with substrates for the proteases prostate-specific antigen (PSA) and prostate-specific membrane antigen (PSMA) expressed in cancer tissue. The hydrophilic peptide moiety was hypothesized to prevent penetration of the prodrugs into cells and prevent interaction with PKC. Cleavage of the peptide in cancer tumors was envisioned to release lipophilic cytotoxins, which subsequently penetrate into cancer cells.

Tuning the stability of alkoxyisopropyl protection groups.

Five different 2-alkoxypropan-2-yl groups are introduced as acid-labile protecting groups for the 5'- and 3'-hydroxy groups of a 2'-deoxynucleoside. All studied protecting groups were readily introduced with good to excellent yields using the appropriate enol ether as a reagent and 0.5 to 1 mol % toluenesulfonic acid as a catalyst.

Distribution of female genital tract anomalies in two classifications.

Objective: This study assessed the distribution of Müllerian duct anomalies in two verified classifications of female genital tract malformations, and the presence of associated renal defects.

Study Design: 621 women with confirmed female genital tract anomalies were retrospectively grouped under the European (ESHRE/ESGE) and the American (AFS) classification. The diagnosis of uterine malformation was based on findings in hysterosalpingography, two-dimensional ultrasonography, endoscopies, laparotomy, cesarean section and magnetic resonance imaging in 97.

Long-term outcome after transvaginal mesh repair of pelvic organ prolapse.

Introduction And Hypothesis: The aim of this study was to report long-term subjective and objective outcomes after the transvaginal mesh (TVM) procedure in long-term. Possible late-onset complications were of particular interest.

Methods: This was a retrospective analysis of TVM performed using Prolift™ transvaginal mesh measuring subjective outcome using validated questionnaires.

Twin pregnancy in the congenital malformed uterus.

The frequency and outcome of twin pregnancies in women with uterine malformation were studied. The cohort comprised 13 (4.9%) women with twin pregnancy found among 263 women.

Quality of life and pelvic floor dysfunction symptoms after hysterectomy with or without pelvic organ prolapse.

Objective: To assess the effect of hysterectomy with or without pelvic organ prolapse (POP) on health-related quality of life (HRQoL) and pelvic floor disorders.

Study Design: Prospective clinical study at two central hospitals in Finland. During one year 322 women underwent elective hysterectomy for benign conditions with or without vaginal wall repair.

Stability of Criegee intermediates formed by ozonolysis of different double bonds.

The formation of Criegee intermediates by ozonolysis of different species containing C═N and C═P bonds is studied computationally. Electronic structure calculations are carried out for the energetics of ozonolysis, and the lifetime of the Criegee intermediate formed is computed by transition state theory. All calculations are carried out for formation of CH2OO, the simplest Criegee intermediate.

Isomerization and decomposition of a Criegee intermediate in the ozonolysis of alkenes: dynamics using a multireference potential.

The isomerization and decomposition dynamics of the simplest Criegee intermediate CH2 OO have been studied by classical trajectory simulations using the multireference ab initio MR-PT2 potential on the fly. A new, accelerated algorithm for dynamics with MR-PT2 was used. For an initial temperature of 300 K, starting from the transition state from CH2 OO→CH2 O2  , the system reaches the dioxirane structure in around 50 fs, then isomerizes to formic acid (in ca.

On the factors affecting product distribution in laccase-catalyzed oxidation of a lignin model compound vanillyl alcohol: experimental and computational evaluation.

Laccases (EC 1.10.3.

Rectovesical ligament and fusion defect of the uterus with or without obstructed hemivagina and ipsilateral renal agenesis.

Objective: The rectovesical ligament is a peritoneal band in women with failure of fusion of the two Müllerian ducts. The aim was to evaluate existence of this abnormal structure in women with dysfused uterus and its possible relations to concomitant vaginal and renal anomalies.

Study Design: The study group comprised 47 women with uterine fusion defect (37 didelphic and 10 bicornuate uterus).

Objective cure rates and patient satisfaction after the transobturator tape procedure during 6.5-year follow-up.

Study Objective: To report the subjective and objective outcomes and patient satisfaction with the outside-in transobturator tape (TOT) procedure during long-term follow-up.

Design: Clinical follow-up study (Canadian Task Force classification II-2).

Setting: University hospital.

Pregnancies in women with uterine malformation, treated obstruction of hemivagina and ipsilateral renal agenesis.

Purpose: The aim of this study was to evaluate the outcome of pregnancies in women who had uterine malformation and surgically treated obstructed hemivagina with ipsilateral renal agenesis.

Methods: The study group comprised 21 women with malformed uterus (12 didelphic, 6 septate and 3 bicornuate uterus). All of them had a history of surgical excision of the longitudinal vaginal septum caused obstructed hemivagina and ipsilateral renal agenesis.

Tension-free vaginal tape procedure without preoperative urodynamic examination: long-term outcome.

Objectives: To evaluate the long-term outcome of the tension-free vaginal tape procedure.

Methods: A total of 191 patients were operated on with tension-free vaginal tape between January 1998 and May 2000. Of these, 127 (66%) had stress urinary incontinence, 64 (34%) had mixed urinary incontinence and 39 (20%) had recurrent incontinence.

Pregnancy outcomes after transvaginal myomectomy by colpotomy.

Objective: To examine long-term effects of transvaginal myomectomy by colpotomy on uterine ruptures, fertility and pregnancy outcome.

Study Design: Transvaginal myomectomy by colpotomy was performed for sixteen patients who had symptomatic uterine leiomyomas and wished to preserve their fertility. Data on possible pregnancies, infertility treatments, hysterectomies and other reoperations during a follow-up period of ten years were retrospectively collected from the hospital records.

Combined anterior vaginal wall mesh with sacrospinous ligament fixation or with posterior intravaginal slingplasty for uterovaginal or vaginal vault prolapse.

Objective: To evaluate outcomes of anterior vaginal wall mesh augmentation with concomitant sacrospinous ligament fixation (SSLF) or with concomitant posterior intravaginal slingplasty (IVS) for uterovaginal or vaginal vault prolapse.

Study Design: Women with symptomatic uterovaginal or vaginal vault prolapse were randomly allocated to SSLF or IVS. All underwent concomitant anterior repair augmented with self-tailored multifilament polypropylene and polyglactin composite mesh.

Is coproporphyrin III a copper-acquisition compound in Paracoccus denitrificans?

Paracoccus denitrificans is a soil bacterium which can respire aerobically and also denitrify if oxygen is absent. Both processes are highly dependent on copper enzymes and copper is therefore likely to be an essential trace element for the bacterium. If copper is not easily available, a copper-acquisition mechanism would be highly beneficial.

[Intrauterine adhesions--Asherman's syndrome].

Intrauterine adhesions known as Asherman's syndrome evolve after trauma to the basal layer of the endometrium usually secondary to curettage of a recently pregnant uterus. The lesions range from minor to severe cohesive adhesions that affect menstrual function and fertility. Operative hysteroscopy is the mainstay of diagnosis, classification and treatment of the intrauterine adhesions.

Outcomes after anterior vaginal wall repair with mesh: a randomized, controlled trial with a 3 year follow-up.

Objective: The objective of the study was to compare anterior colporrhaphy with and without a mesh.

Study Design: Two hundred two women with anterior prolapse were assigned to undergo colporrhaphy alone or reinforced with a tailored polypropylene mesh. Before and 2, 12, 24, and 36 months after surgery, the outcome was assessed by examination and standard questions.