Using three rounds of structure-guided directed evolution, the catalytic activity of the (S)-selective arylmalonate decarboxylase variant G74C/C188S could be increased up to 920-fold. The best variant had a 220-fold improved activity in the production of (S)-naproxen with excellent enantioselectivity (>99% ee).
Variant G74C of arylmalonate decarboxylase (AMDase) from Bordatella bronchoseptica has a unique racemising activity towards profens. By protein engineering, variant G74C/V43A with a 20-fold shift towards promiscuous racemisation was obtained, based on a reduced activity in the decarboxylation reaction and a two-fold increase in the racemisation activity. The mutant showed an extended substrate range, with a 30-fold increase in the reaction rate towards ketoprofen. Molecular dynamics simulations and the substrate profile of the racemase indicate that the steric and polar effects of the substrate structure play a more dominant role on catalysis than mere kinetic α-proton acidity. The observation that the conversion of β,γ-unsaturated carboxylic acids does not lead to a rearrangement to form their α,β isomers indicates a concerted rather than a stepwise mechanism. Interestingly, a substrate bearing a nitro group instead of the carboxylic acid group on the α-carbon atom was also converted by the racemase.
Water-soluble components in the outermost layer of human skin are called natural moisturizing factor (NMF). NMF is one of the most important factors of skin moisturizing mechanisms. It is known that individuals with psoriasis, atopic dermatitis, and ichthyosis possess skin with lower-than-normal NMF content. Therefore, a noninvasive method for NMF content measurement of the human skin would be very useful to both dermatologists and cosmetic chemists. We attempted to measure the NMF content by focusing on the infrared wavelengths that are commonly absorbed by most NMF components. In order to estimate the intensity of absorption that is common to NMF components, we simulated the attenuated total reflection (ATR)-infrared (IR) spectrum of human skin by the combination of multiple Gaussian peaks. The spectroscopic signal of NMF linearly correlated with the actual NMF content measured by chromatographic methods. Therefore, we concluded that we can determine the skin surface NMF content from the ATR-IR spectrum of skin. This noninvasive and simple method is useful for studying NMF in a wide variety of skin regions and under various skin conditions.
A series of MnOx-decorated CeO2 (MnCeO) catalysts with different morphologies have been prepared by the shape-controlled synthesis of single-crystalline CeO2, such as nanorod, nanoparticle, and nanocube, by a hydrothermal method followed by the deposition of MnOx phase by a simple impregnation method. Their shape-dependent physicochemical properties were investigated by means of XRD, BET, UV–vis, HRTEM, XPS, TPR and oxygen storage/release properties measurements. The MnOx/CeO2 nanorod (MnCeO-NR) showed prominent carbon soot combustion activity at lower temperature under tight contact mode with a T50 temperature of 317 °C, which is attributed to larger surface area and higher oxygen release rate, as compared with particle and cubic catalysts. MnCeO-NR also exhibited higher catalytic activity (a shift of T50 by 127 °C) in NO-assisted soot combustion under a loose contact mode. Not only the higher surface area but also the superior NO conversion ability at low temperature as well as greater NO absorption contributes to the improved catalytic activities. The MnCeO-NR further displayed high stability and satisfactory recyclability without significant loss of catalytic activity. The use of cheaper combinations without noble metals makes the MnOx/CeO2 catalyst a promising candidate to satisfy future requirements in industry.
In a 32-year-old pregnant woman, routine ultrasonography revealed right hydronephrosis and a huge retroperitoneal mass (20 × 7 cm) containing a fluid collection. Percutaneous drainage of the mass was performed and 2 L of clear, yellowish fluid was collected. Four months following the delivery, a recurrent retroperitoneal lymphocele was identified. Six months after the delivery, laparoscopic marsupialization was performed through a 10-mm umbilical camera port and two 5-mm ports on the right side of the abdomen. A posterior peritoneal window was established by creating a wide opening in the anterior wall of the lymphocele. Subsequent ultrasonography did not indicate a recurrence of the lymphocele or right hydronephrosis over a followup period of 8 months.
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