Aldehyde Reductase Activity of Carboxylic Acid Reductases.

Carboxylic acid reductase enzymes (CARs) are well known for the reduction of a wide range of carboxylic acids to the respective aldehydes. One of the essential CAR domains - the reductase domain (R-domain) - was recently shown to catalyze the standalone reduction of carbonyls, including aldehydes, which are typically considered to be the final product of carboxylic acid reduction by CAR. We discovered that the respective full-length CARs were equally able to reduce aldehydes. Herein we aimed to shed light on the impact of this activity on aldehyde production and acid reduction in general. Our data explains previously inexplicable results and a new CAR from Mycolicibacterium wolinskyi is presented.

Cardiac output calculation using the Liljestrand and Zander formula: is this method applicable during immediate transition after birth? - A post hoc analysis.

The transition from intrauterine to extrauterine life is a critical period for neonates. Assessing the cardiovascular transition during this period immediately after birth is crucial but challenging. The present study compares adjusted estimated cardiac output values calculated by the Liljestrand and Zander formula (COest/adj LaZ) with non-invasively measured cardiac output values (CO-bioimpedance) during immediate transition after birth. We performed a secondary outcome analysis of a prospective observational study in preterm and term neonates. Ten and 15 min after birth, arterial blood pressure and heart rate were assessed, and CO-bioimpedance was measured using electrical bioimpedance method (Aesculon monitor, Osypka, Germany). We calculated COest/adj LaZ and compared it to CO-bioimpedance. Further, we performed a correlation analysis. Thirty-two neonates with a median (IQR) gestational age of 37.0 (32.0-39.4) weeks were included. Mean ± SD CO-bioimpedance was 0.62 ± 0.15 l/min, and COest/adj LaZ was calculated to be 0.64 ± 0.10 l/min, whereby both correlated significantly (p = 0.025, r = 0.359) with each other.  Conclusion: The present study demonstrates high comparability of COest/adj LaZ and CO-bioimpedance in neonates during immediate transition after birth, suggesting that cardiac output can be derived in a cost-effective and feasible manner if other methods are not available. What is Known: • Echocardiography is considered the gold standard for non-invasive CO evaluation, but its feasibility during the immediate transition period is limited. What is New: • Non-invasive methods such as CO-bioimpedance for cardiac output (CO) measurement and the Liljestrand and Zander (LaZ) formula for estimating CO offer promising alternatives during the immediate transition period.

Thiols Act as Methyl Traps in the Biocatalytic Demethylation of Guaiacol Derivatives.

Demethylating methyl phenyl ethers is challenging, especially when the products are catechol derivatives prone to follow-up reactions. For biocatalytic demethylation, monooxygenases have previously been described requiring molecular oxygen which may cause oxidative side reactions. Here we show that such compounds can be demethylated anaerobically by using cobalamin-dependent methyltransferases exploiting thiols like ethyl 3-mercaptopropionate as a methyl trap. Using just two equivalents of this reagent, a broad spectrum of substituted guaiacol derivatives were demethylated, with conversions mostly above 90 %. This strategy was used to prepare the highly valuable antioxidant hydroxytyrosol on a one-gram scale in 97 % isolated yield.

Effect of Particle Wettability and Particle Concentration on the Enzymatic Dehydration of n-Octanaloxime in Pickering Emulsions.

Pickering emulsion systems have emerged as platforms for the synthesis of organic molecules in biphasic biocatalysis. Herein, the catalytic performance was evaluated for biotransformation using whole cells exemplified for the dehydration of n-octanaloxime to n-octanenitrile catalysed by an aldoxime dehydratase (OxdB) overexpressed in E. coli. This study was carried out in Pickering emulsions stabilised solely with silica particles of different hydrophobicity. We correlate, for the first time, the properties of the emulsions with the conversion of the reaction, thus gaining an insight into the impact of the particle wettability and particle concentration. When comparing two emulsions of different type with similar stability and droplet diameter, the oil-in-water (o/w) system displayed a higher conversion than the water-in-oil (w/o) system, despite the conversion in both cases being higher than that in a "classic" two-phase system. Furthermore, an increase in particle concentration prior to emulsification resulted in an increase of the interfacial area and hence a higher conversion.

Chiral Dinuclear Vanadium Complex-Mediated Oxidative Coupling of Resorcinols.

A method for the highly regio- and enantioselective oxidative coupling of resorcinols has been established by using dibrominated dinuclear vanadium(V) catalyst 1c under air. When resorcinols bearing an aryl substituent were applied as substrates to the coupling, axially chiral biresorcinols were obtained as single regioisomers in high yield with up to 98% ee.

Harnessing nature's catalysts: Advances in enzymatic alkene cleavage.

Double bonds are prevalent in various substrates and renewable feedstocks, and their cleavage typically necessitates harsh reaction conditions involving high temperatures, organic solvents, and hazardous catalysts such as heavy metals or ozone. This review explores the sustainable enzymatic alternatives developed by nature for alkene cleavage. It provides a comprehensive overview of alkene-cleaving enzymes, detailing their mechanisms, substrate specificities, and applications. The enzymes discussed include those acting on aliphatic, cyclic, and activated aromatic systems. Emphasizing the significance of these biocatalysts in green chemistry and biocatalysis, this review highlights their potential to replace traditional chemical oxidants with safer, cost-effective, and environmentally friendly options. Future research directions include expanding enzyme substrate scopes, enhancing their operational stability and activity, and integrating them into scalable processes for broader application in the pharmaceutical, flavor, and fragrance industries.

Enzymatic reactions towards aldehydes: An overview.

Many aldehydes are volatile compounds with distinct and characteristic olfactory properties. The aldehydic functional group is reactive and, as such, an invaluable chemical multi-tool to make all sorts of products. Owing to the reactivity, the selective synthesis of aldehydic is a challenging task. Nature has evolved a number of enzymatic reactions to produce aldehydes, and this review provides an overview of aldehyde-forming reactions in biological systems and beyond. Whereas some of these biotransformations are still in their infancy in terms of synthetic applicability, others are developed to an extent that allows their implementation as industrial biocatalysts.

Antiarrhythmic Drug Dosing in Children-Review of the Literature.

Antiarrhythmic drugs represent a mainstay of pediatric arrhythmia treatment. However, official guidelines and consensus documents on this topic remain scarce. There are rather uniform recommendations for some medications (including adenosine, amiodarone, and esmolol), while there are only very broad dosage recommendations for others (such as sotalol or digoxin). To prevent potential uncertainties and even mistakes with regard to dosing, we summarized the published dosage recommendations for antiarrhythmic drugs in children. Because of the wide variations in availability, regulatory approval, and experience, we encourage centers to develop their own specific protocols for pediatric antiarrhythmic drug therapy.

Thiols Act as Methyl Traps in the Biocatalytic Demethylation of Guaiacol Derivatives.

Demethylating methyl phenyl ethers is challenging, especially when the products are catechol derivatives prone to follow-up reactions. For biocatalytic demethylation, monooxygenases have previously been described requiring molecular oxygen which may cause oxidative side reactions. Here we show that such compounds can be demethylated anaerobically by using cobalamin-dependent methyltransferases exploiting thiols like ethyl 3-mercaptopropionate as a methyl trap. Using just two equivalents of this reagent, a broad spectrum of substituted guaiacol derivatives were demethylated, with conversions mostly above 90 %. This strategy was used to prepare the highly valuable antioxidant hydroxytyrosol on a one-gram scale in 97 % isolated yield.

Precision of time-resolved near-infrared spectroscopy-based measurements of cerebral oxygenation in preterm infants.

Significance: Time-resolved near-infrared spectroscopy (t-NIRS) is a new technology; at the moment, data on its precision in preterm infants are rare. Aim: Therefore, the aim of this study was to analyze the precision of t-NIRS-based measurements of the cerebral oxygenation in preterm infants. Approach: In 70 neonates [age: 4.7 ± 2.0 days, sex (f/m): 33/37], cerebral oxygenation ( t - rSO 2 ) was measured with an optode placed over the left frontotemporal lobe on the head, measurement duration was 1 min, and a reapplication was done for four further times (five applications). Results: Overall mean for t - rSO 2 values was 62.2 % ± 4.1 % . We found a within-patient variation for t - rSO 2 of 2.6%. Furthermore, 95% of all observed values were within a range of ± 5 % from the mean when looking on several reapplications and ± 2 % when looking within one application. Most of the variation in t - rSO 2 (60.4%) contributed to differences between patients. The remaining 39.6% of the variation was due to measurement errors and real changes of the measured signal within the neonates. Conclusions: Since within-patient variation of t - rSO 2 measures were below a clinical meaningful threshold of 5%, the measurement can be denoted as precise.

Catalytic and enantioselective oxa-Piancatelli reaction using a chiral vanadium complex.

An enantioselective oxa-Piancatelli reaction was established for the first time using a chiral vanadium(v) catalyst. The dual Brønsted and Lewis acid properties of the vanadium catalyst afforded 4-hydroxycyclopent-2-enone derivatives in up to 90% yields and with 93 : 7 enantiomeric ratios, as well as >20 : 1 diastereomeric ratios.

Regioselectivity of Cobalamin-Dependent Methyltransferase Can Be Tuned by Reaction Conditions and Substrate.

Regioselective reactions represent a significant challenge for organic chemistry. Here the regioselective methylation of a single hydroxy group of 4-substituted catechols was investigated employing the cobalamin-dependent methyltransferase from Desulfitobacterium hafniense. Catechols substituted in position four were methylated either in meta- or para-position to the substituent depending whether the substituent was polar or apolar. While the biocatalytic cobalamin dependent methylation was meta-selective with 4-substituted catechols bearing hydrophilic groups, it was para-selective for hydrophobic substituents. Furthermore, the presence of water miscible co-solvents had a clear improving influence, whereby THF turned out to enable the formation of a single regioisomer in selected cases. Finally, it was found that also the pH led to an enhancement of regioselectivity for the cases investigated.

Cerebral Oxygenation in Neonates Immediately after Cesarean Section and Mode of Maternal Anesthesia.

BACKGROUND: Cerebral regional oxygen saturation (crSO2) during immediate transition and resuscitation immediately after birth is of increasing interest. OBJECTIVES: The aim of the present study was to assess whether the type of maternal anesthesia during cesarean section (CS; general anesthesia vs. spinal anesthesia) has an influence on cerebral oxygenation during immediate neonatal transition after birth. METHODS: Secondary outcome parameters of prospective observational studies were analyzed. Neonates born by CS from November 2009 to September 2016 at the Medical University of Graz (Austria) were eligible. Term and preterm neonates were included, provided that: (1) crSO2 was measured by near-infrared spectroscopy, and (2) peripheral arterial oxygen saturation (SpO2) and heart rate (HR) were measured by pulse oximetry during the first 15 min after birth. Administration of supplemental oxygen was recorded and cerebral fractional tissue oxygen extraction (cFTOE) was calculated out of crSO2 and SpO2. For comparison, term and preterm neonates with maternal general anesthesia were matched to neonates with maternal spinal anesthesia during CS. RESULTS: Out of 760 eligible neonates, 64 term (38.8 ± 0.9 weeks of gestation; 32 neonates in each group) and 54 preterm neonates (32.0 ± 2.9 weeks of gestation; 27 neonates in each group) were included. In term neonates, maternal general anesthesia was associated with lower initial SpO2, HR values, and Apgar scores. The fraction of inspired oxygen (FiO2) was statistically significantly higher in the general anesthesia group. Nevertheless, crSO2 and cFTOE did not differ statistically significantly between the groups. In preterm neonates there were no statistically significant differences in SpO2, HR, crSO2, and cFTOE between the general and spinal anesthesia groups. Apgar scores at 1 min were statistically significantly lower and FiO2 was statistically significantly higher in the general anesthesia group. CONCLUSION: Cerebral tissue oxygenation in neonates during immediate transition after birth was similar after maternal general and spinal anesthesia during CS, despite differences in SpO2, HR, and supplemental oxygen in term neonates and differences in supplemental oxygen in preterm neonates.