Undesirable Hydrolysis Research Articles

Controllable modulation of acid-base properties and balance for promoting methyl acrylate production over CsMg-Zr/SiO2

Synthesis of methyl acrylate (MA) through one-step aldol reaction of coal-based methyl acetate (Ma) with formaldehyde (FA) receives significant attention, due to the high atomic economy and rich source. Herein, an efficient CsMg-Zr/SiO2 catalyst with Cs-Mg dual base sites and Zr acid sites, which exhibited synergistic effects on reactant activation, was developed for MA production. The effect of loaded Mg component on the physicochemical properties of as-prepared CsMg-Zr/SiO2 catalyst was systematically analyzed using physical N2 adsorption, XRD, XPS, NH3-TPD, CO2-TPD, and Py-IR. The introduced Mg element would suppress the generation of strong base sites, contributing to the controllable modulation of acid-base properties and balance and the efficient inhibition of undesired hydrolysis of MA and Ma. The formed Si-O-Cs and Si-O-Mg structures identified as strong and weak base sites were identified to facilitate the activation and α-deprotonation of Ma. While the Si-O-Zr structure served as acid site is responsible for the excitation and protonation of FA. As a result, the space–time yield of MA could reach 1.58 mmol/gCat/h, with a relatively high selectivity of 90.4 %, under the optimal reaction condition over 15-CsMg-Zr/SiO2. In addition, the in situ DRIFTS observation confirmed the activation of Ma and FA on the corresponding active sites and the whole transformative process. Kinetic studies revealed the reaction order of Ma and FA with respect to 0.77 and 1.08, as well as the activation barrier of 69.2 kJ/mol. A deactivation behavior was noticed during the 600 h time-on-stream stability evaluation because of the carbonaceous compounds deposition, which could be easily removed by thermal treatment in air atmosphere.

Towards More Sustainable Schiff Base Carboxylate Anodes for Sodium-Ion Batteries.

Bismine sodium salt (BSNa), a Schiff base with two sodium carboxylates, has shown promising electrochemical performance as an anode material. However, its synthesis involves toxic reagents and generates impurities, requiring significant solvent use for purification. This study introduces a novel synthetic method using sodium hydroxide as the sole reagent, which acts as both a base and Na source in the ion exchange step. With this procedure, we reduce the amounts of chemicals, diminish toxicity, improve the purity of the target compound, and use less solvent while maintaining comparable electrochemical performance. Additionally, the procedure is carried out under anhydrous conditions that avoid the undesirable hydrolysis of the imine linkages. In a previous report, the processing of the composite electrode was not established. In this article, we address this issue; the electrochemical performance, specifically the rate capability, is enhanced by processing the electrodes in laminate form rather than powder. As alternative to N-methyl-2-pyrrolidone (NMP), a common but disadvantageous solvent in laminate processing, other solvents were explored by testing acetone (DMK), methylisopropylketone (MIPK), and a DMK-NMP mixture. The remarkable electrochemical performance (specific capacity of 260-280 mAh/g, and capacity retentions higher than 84% at 1C (260 mA/g) remained consistent across these solvents. Furthermore, we investigated replacing copper with aluminum as the current collector to reduce costs and increase the energy density of the battery. While aluminum performed comparably to copper at low specific currents C/10 (26 mA/g), it showed a significant shift in the redox process potentials at higher specific currents.

A High-Energy Tellurium Redox-Amphoteric Conversion Cathode Chemistry for Aqueous Zinc Batteries.

Rechargeable aqueous zinc batteries are potential candidates for sustainable energy storage systems at a grid scale, owing to their high safety and low cost. However, the existing cathode chemistries exhibit restricted energy density, which hinders their extensive applications. Here, a tellurium redox-amphoteric conversion cathode chemistry is presented for aqueous zinc batteries, which delivers a specific capacity of 1223.9 mAh gTe -1 and a high energy density of 1028.0Wh kgTe -1. A highly concentrated electrolyte (30mol kg-1 ZnCl2) is revealed crucial for initiating the Te redox-amphoteric conversion as it suppresses the H2O reactivity and inhibits undesirable hydrolysis of the Te4+ product. By carrying out multiple operando/ex situ characterizations, the reversible six-electron Te2-/Te0/Te4+ conversion with TeCl4 is identified as the fully charged product and ZnTe as the fully discharged product. This finding not only enriches the conversion-type battery chemistries but also establishes a critical step in exploring redox-amphoteric materials for aqueous zinc batteries and beyond.

The role of tRNA identity elements in aminoacyl-tRNA editing.

The rules of the genetic code are implemented by the unique features that define the amino acid identity of each transfer RNA (tRNA). These features, known as "identity elements," mark tRNAs for recognition by aminoacyl-tRNA synthetases (ARSs), the enzymes responsible for ligating amino acids to tRNAs. While tRNA identity elements enable stringent substrate selectivity of ARSs, these enzymes are prone to errors during amino acid selection, leading to the synthesis of incorrect aminoacyl-tRNAs that jeopardize the fidelity of protein synthesis. Many error-prone ARSs have evolved specialized domains that hydrolyze incorrectly synthesized aminoacyl-tRNAs. These domains, known as editing domains, also exist as free-standing enzymes and, together with ARSs, safeguard protein synthesis fidelity. Here, we discuss how the same identity elements that define tRNA aminoacylation play an integral role in aminoacyl-tRNA editing, synergistically ensuring the correct translation of genetic information into proteins. Moreover, we review the distinct strategies of tRNA selection used by editing enzymes and ARSs to avoid undesired hydrolysis of correctly aminoacylated tRNAs.

Thermoplastic starch/polyvinyl alcohol blends modification by citric acid–glycerol polyesters

Thermoplastic starch/polyvinyl alcohol (TPS/PVA) films have limitations for being used in long–term applications due to starch retrogradation. This leads to plasticizer migration, especially when low molecular weight plasticizers such as glycerol, are used. In this work, we employed mixtures of oligomers based on glycerol citrates with higher molecular weight than glycerol as plasticizers for potato–based TPS/PVA blends obtained by melt–mixing. This constitutes an alternative to reduce plasticizer migration while keeping high swelling degree, and to provide high mechanical performance. The novelty lies in the usage of these oligomers by melt-mixing technique, aspect not deeply explored previously and that represents the first step towards industrial scalability. Prior to the blending process, oligomers mixtures were prepared with different molar ratios of citric acid (0–40 mol%) and added them. This minimizes the undesirable hydrolysis effect of free carboxylic groups on starch chains. The results demonstrated that the migration of plasticizers in TPS/PVA blends decreased by up to 70 % when the citric acid content increased. This reduction was attributed to the higher molecular weight (the majority in the range 764–2060 Da) and the 3D structure of the oligomers compared to using raw glycerol. Furthermore, the films exhibited a 150 % increase in Young's modulus and tensile strength without a reduction in elongation at break, while maintaining a high gel content, due to a moderate crosslinking.

Sustainable production of dimethyl-protected cyclic lysine over Pd/m-Al2O3-Si catalysts and its application in synthesis of antibacterial nylon‑6 copolymers

Antibacterial monomers are prerequisites for synthesizing antibacterial polymers, especially during the current COVID-19 pandemic. Dimethyl-protected cyclic lysine (DMCL) is a promising functional monomer for nylon-6 based self-cleaning antibacterial polymers. However, the production of DMCL still faces formidable challenges, such as harsh reaction conditions and low catalyst activities. In this study, we developed a Pd/m-Al2O3-Si catalyst, which exhibited high efficiency in converting α-amino-ε-caprolactam (α-ACL) to DMCL, affording a yield of as high as 97.1% at 100 °C and 1 MPa H2. The lack of Brönsted acid sites on the catalyst surface facilitated the formation of DMCL and suppressed undesirable hydrolysis or cracking by-products from the lactam-based reactant. The recycled experiments showed that Pd/m-Al2O3-Si performed excellent stability and physical strength with essentially no damage to its microspheres after the reaction. The nylon‑6 copolymers produced from the as-synthesized DMCL exhibited similar structure and thermal stability with pure nylon-6, showing great potential in synthesizing the self-cleaning antibacterial polymers. This work provides a sustainable and efficient method for producing DMCL and other lysine-based antibacterial monomers, showing a great prospect for the utilization of bio-based chemicals in synthesizing functional polymers.

Strategies toward the Difunctionalizations of Enamide Derivatives for Synthesizing α,β-Substituted Amines.

Enamide and enecarbamate derivatives containing a nucleophilic center at the β-position from their nitrogen atom as well as a latent electrophilic site at their α-position are interesting motifs in organic chemistry. This dual reactivity─analogous that of the enamines─enables difunctionalization and increased structural complexity. Furthermore, an electron-withdrawing group on nitrogen drastically increases their stability. In that respect, enamides and enecarbamates are excellent partners for multicomponent transformations, and our research primarily focuses on these compounds in particular.Difunctionalization generally occurs through the nucleophilic addition of the enecarbamate on an electrophile to form iminium, which can subsequently react with a nucleophilic species. Although potent, such an approach is highly challenging due to the low stability of the intermediate iminium, leading to undesired hydrolysis or oligomerization. Epimerization, competitivity, and compatibility issues between the reaction partners are additional hindrances to developing these methodologies. To overcome these limitations, we described many complementary strategies.To control the enantioselectivity of these transformations, chiral phosphoric acids were found to be particularly well-suited to activate multiple reactants due to the formation of a hydrogen bonds network, allowing for an organized transition state in a chiral pocket. Interestingly, when deprotonated as phosphates, they can also play the role of ligands for Lewis acidic metals.To avoid iminium oligomerization, we successfully used stabilized α-arylated enamides. However, this approach was restricted to a simple nucleophilic addition at the β-position. To achieve the difunctionalizations of α-unsubstituted derivatives, we explored reversibly linked nucleophile and electrophile to address their compatibility problem. Alternatively, we devised a sequential methodology for resolving the stability issue of the N-acyl iminium based on its intermediate trapping using a temporary nucleophile (alcohol or thiol). Interestingly, the trapping agent could further be displaced by the desired final α-substituent under Lewis acidic or photocatalytic activation. This led us to design new chiral and bifunctional phosphoric acid catalysts bearing chromophores to merge asymmetric organocatalysis and photochemistry.These photocatalysis studies incited us to focus on radical processes to manage original functionalizations that would not be feasible otherwise. β-Alkylation and β-trifluoromethylation of enecarbamates via visible-light-promoted atom transfer radical additions were successfully performed. As β-allylations remained unattainable with the precedent methods, we eventually turned our attention to cerium(IV)-mediated oxidative single electron transfers. It allowed for singly occupied molecular orbital activation of these substrates to elicit their umpolung reactivity.Thus, the functionalization of enecarbamate derivatives appears as a valid synthetic strategy for obtaining important building blocks for agrochemical, pharmaceutical, and cosmetic industries, including diamines, haloamines, aminotryptamines, and less accessible trifluoromethylated or allylic compounds.

Malonic-acid-functionalized fullerene enables the interfacial stabilization of Ni-rich cathodes in lithium-ion batteries

High-capacity LiNi 1-x-y Co x Mn y O 2 (NCM) (x + y ≤ 0.2) is a potential candidate for realizing high-energy-density lithium-ion batteries (LIBs). However, successful application of this cathode requires overcoming the irreversible phase transition (layered-to-spinel/rock-salt), interfacial instability caused by residual lithium compounds, and the electrolyte oxidation promoted by highly oxidized Ni 4+ . In this study, we investigate the roles of fullerene with malonic acid moieties (MA-C 60 ) as a superoxide dismutase mimetic (SODm) electrolyte additive in LIBs to deactivate reactive radical species (O 2 •- , LiOCO 3 • , and Li(CO 3 ) 2 • ) induced by electrochemical oxidation of residual lithium compound, Li 2 CO 3 on the LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) cathode surface and to scavenge trace water to avoid undesirable hydrolysis of LiPF 6 . Further, MA-C 60 maintains the structural stability of NCM811 cathodes and mitigates the parasitic reaction of residual lithium compounds with LiPF 6 through the formation of a stable cathode–electrolyte interface. Our findings showed that MA-C 60 helps overcome the challenges associated with Li 2 CO 3 oxidation at the NCM811 cathode, which produces CO 2 gas and O 2 •- that react with the solvent molecules. • Electrochemical oxidation of Li 2 CO 3 generates superoxide radicals and CO 2 . • MA-C 60 is capable of scavenge superoxide radical and water molecule. • MA-C 60 -derived cathode interfaces ensure structural stability of NCM811 cathode.

Structural basis for substrate specificity of the peroxisomal acyl-CoA hydrolase MpaH' involved in mycophenolic acid biosynthesis.

Mycophenolic acid (MPA) is a fungal natural product and first-line immunosuppressive drug for organ transplantations and autoimmune diseases. In the compartmentalized biosynthesis of MPA, the acyl-coenzyme A (CoA) hydrolase MpaH' located in peroxisomes catalyzes the highly specific hydrolysis of MPA-CoA to produce the final product MPA. The strict substrate specificity of MpaH' not only averts undesired hydrolysis of various cellular acyl-CoAs, but also prevents MPA-CoA from further peroxisomal β-oxidation catabolism. To elucidate the structural basis for this important property, in this study, we solve the crystal structures of the substrate-free form of MpaH' and the MpaH'S139A mutant in complex with the product MPA. The MpaH' structure reveals a canonical α/β-hydrolase fold with an unusually large cap domain and a rare location of the acidic residue D163 of catalytic triad after strand β6. MpaH' also forms an atypical dimer with the unique C-terminal helices α13 and α14 arming the cap domain of the other protomer and indirectly participating in the substrate binding. With these characteristics, we propose that MpaH' and its homologs form a new subfamily of α/β hydrolase fold protein. The crystal structure of MpaH'S139A /MPA complex and the modeled structure of MpaH'/MPA-CoA, together with the structure-guided mutagenesis analysis and isothermal titration calorimetry (ITC) measurements, provide important mechanistic insights into the high substrate specificity of MpaH'.

Free fatty acid formation in oil palm fruits during storage

Free fatty acids (FFAs) are derived from the undesired hydrolysis reaction of glycerides with the presence of lipase, and quantified as acid value for crude palm oil (CPO) grading. Since FFA content is directly proportional to time, duration from harvest to sterilization of fruits is not more than a day. This paper reports peculiar trend of FFA formation over time when the analysis of FFA was carried out differently. Analysis results of FFA and glyceride contents by timely picking the fruitlets (R-fruit) from fresh fruit bunch (FFB) were compared with the fruitlets from spikelet (S-fruit) that were initially removed all for 7 days. The results showed that the increment of FFA content of the latter was 10 hour faster. This implies that the fruitlets from spikelet resemble the detached fruits which having higher rate of FFA formation compared to the fruitlets that attached to FFB. By using SigmaPlot, the graphs of R-fruit and S-fruit were best fitted into damped sine, 5 parameter with linear and rational with 4 parameters respectively. Nevertheless, lower R2 value was obtained for the fruitlets from readily-removed spikelet compared to the fruitlets from FFB, indicating that other factors might have also affected the formation of FFA.

An α2,3-Sialyltransferase from Photobacterium phosphoreum with Broad Substrate Scope: Controlling Hydrolytic Activity by Directed Evolution.

Defined sialoglycoconjugates are important molecular probes for studying the role of sialylated glycans in biological systems. We show that the α2,3‐sialyltransferase from Photobacterium phosphoreum JT‐ISH‐467 (2,3SiaTpph) tolerates a very broad substrate scope for modifications in the sialic acid part, including bulky amide variation, C5/C9 substitution, and C5 stereoinversion. To reduce the enzyme's hydrolytic activity, which erodes the product yield, an extensive structure‐guided mutagenesis study identified three variants that show up to five times higher catalytic efficiency for sialyltransfer, up to ten times lower efficiency for substrate hydrolysis, and drastically reduced product hydrolysis. Variant 2,3SiaTpph (A151D) displayed the best performance overall in the synthesis of the GM3 trisaccharide (α2,3‐Neu5Ac‐Lac) from lactose in a one‐pot, two‐enzyme cascade. Our study demonstrates that several complementary solutions can be found to suppress the common problem of undesired hydrolysis activity of microbial GT80 sialyltransferases. The new enzymes are powerful catalysts for the synthesis of a wide variety of complex natural and new‐to‐nature sialoconjugates for biological studies.

Insights into the mechanism of inhibition of phospholipase A2 by resveratrol: An extensive molecular dynamics simulation and binding free energy calculation

Phospholipase A2 (PLA2) is one of the enzymes involved in the development of cardiovascular diseases, vascular inflammation, risk of heart attacks, and strokes. This enzyme is responsible for catalyzing the hydrolytic cleavage of ester bonds of phospholipids in the biological pathway of inflammation. To prevent the undesired hydrolysis of phospholipids, the catalytic activity of PLA2 needs to be blocked. Resveratrol is a plant-derived polyphenol inhibitor, proven to have anti-inflammatory properties. However, there is still substantial ambiguity about its inhibitory function. The present study uncovers a detailed molecular mechanism behind the resveratrol action in inhibition of PLA2, by applying and comparing two 200-ns molecular dynamics simulations. The results of structural analyses revealed that the binding of resveratrol to PLA2 reduces the content of β-sheets and increases a 5-helix to PLA2 structure, producing more folding and stability in protein. In the active site, the resveratrol is placed between the N-terminal α-helix and the newly formed 5-helix through the hydrophobic interactions with ILE19 and LEU3 residues, as well as the hydrogen bond interactions. These interactions play the role of a network at the entrance of the enzyme active site and prevent the penetration of water molecules into the PLA2 cavity. A high occupancy hydrogen bonding has been identified between SER23 of the protein and hydroxyl group of resveratrol. Furthermore, the estimation of binding free energy verified the binding affinity of resveratrol is thermodynamically sufficient to be stably bounded to PLA2. It also proved that the van der Waals interactions, particularly hydrophobic interactions, have the most significant role in PLA2-resveratrol binding and stability. Overall, our results provide useful information on the stepwise mechanism of the inhibition of PLA2 enzyme by resveratrol, as a target for improving the pharmacological applications.

Correlation between partial inhibition of hydrogen evolution using thiourea and catalytic activity of AB5-type hydrogen storage alloy towards borohydride electrooxidation

Direct borohydride fuel cells (DBFCs) are devices which directly convert the chemical energy stored in the borohydride ion and oxidant into electrical energy as a result of redox reactions. Unfortunately, a significant amount of fuel is lost as a result of the undesirable hydrolysis reaction. The selection of an efficient borohydride hydrolysis inhibitor requires detailed knowledge regarding the interaction mechanism between the inhibitor molecule and electrode surface. In this study, various amounts of thiourea additives (0.011–1.600 mM) were tested to select the best fuel composition for DBFC application. When AB5-type anode was used, only partial inhibition of sodium borohydride hydrolysis was a desirable phenomenon. Partially released hydrogen results in the improvement of catalytic properties of the alloy. The addition of 0.016 mM thiourea does not inhibit the oxidation of borohydride, on the contrary, it increases the practical capacity from 27% to 41% of the theoretical value. Moreover, we indicate that the addition of thiourea prevents corrosion as well as degradation of the electrode surface. Pressure measurements confirmed the effectiveness of thiourea in relation to hydrogen evolution, while X-ray photoelectron spectroscopy and Raman spectroscopy revealed that the electrode surface was not poisoned.

A Polymer with "Locked" Degradability: Superior Backbone Stability and Accessible Degradability Enabled by Mechanophore Installation.

Though numerous applications require degradable polymers, there are surprisingly few polymer systems that combine superior stability and controllable degradability. Particularly, the degradability of a conventional degradable polymer is typically enabled by cleavable groups on the backbone, which can be attacked by stimuli in ambient conditions, causing undesirable material deterioration. Here we report a general strategy to overcome this issue: "locking" the degradability during handling and use of the polymers and "unlocking" it when degradation is needed. This strategy is demonstrated with a cyclobutane-fused lactone (CBL) polymer. The cyclobutane keeps polymer backbone intact under conditions that hydrolyze the lactone and allows the ester group to be recovered when undesirable hydrolysis occurs. When backbone degradation is needed, the degradability can be unlocked by mechanochemical activation that converts the polyCBL into a linear polyester. The rare combination of two intrinsically conflicting properties, i.e., backbone stability and accessible degradability, can make this polymer a potential option for new sustainable materials.

A Near-Infrared-Controllable Artificial Metalloprotease Used for Degrading Amyloid-β Monomers and Aggregates.

Proteolysis of amyloid-β (Aβ) is a promising approach against Alzheimer's disease. However, it is not feasible to employ natural hydrolases directly because of their cumbersome preparation and purification, poor stability, and hazardous immunogenicity. Therefore, artificial enzymes have been developed as potential alternatives to natural hydrolases. Since specific cleavage sites of Aβ are usually embedded inside the β-sheet structures that restrict access by artificial enzymes, this strongly hinders their efficiency for practical applications. Herein, we construct a NIR (near-IR) controllable artificial metalloprotease (MoS2 -Co) using a molybdenum disulfide nanosheet (MoS2 ) and a cobalt complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (Codota). Evidenced by detailed experimental and theoretical studies, the NIR-enhanced MoS2 -Co can circumvent the restriction by simultaneously inhibition of β-sheet formation and destroying β-sheet structures of the preformed Aβ aggregates in living cell. Furthermore, our designed MoS2 -Co is an easy to graft Aβ-target agent that prevents misdirected or undesirable hydrolysis reactions, and has been demonstrated to cross the blood brain barrier. This method can be adapted for hydrolysis of other kinds of amyloids.

Trimetallic Carbon-Supported Catalysts for Borohydride Oxidation and Oxygen Reduction in Alkaline Solutions

Borohydrides present a particularly attractive option for alkaline liquid fuel systems, having high energy densities, a low standard potential for its oxidation, and good stability in alkaline conditions. A key area in the success of a fuel cell utilizing borohydride is the development of an anode, which can make use of the full 8-electron oxidation, directly oxidising the borohydride with as little of the undesired hydrolysis reaction occurring as possible. This is in addition to the common requirements of high activity, high stability, good electronic conductivity and effective transport of reactants and products. Here we present new studies on the oxidation of borohydride and reduction of oxygen in alkaline media under various conditions for a selection of trimetallic carbon-supported catalysts based on Pd, prepared by quick and straightforward synthetic routes. The prepared catalysts were characterised by cyclic voltammetry, chronoamperometry, and RDE based procedures. Notably, PdAuNi/C prepared via a NaBH4-2-propanol complex presents highly dispersed trimetallic alloy particles, as determined by XRD, XPS and TEM. The best performing electrodes under characterisation conditions were tested in a direct borohydride fuel cell under several different conditions. The influence of experimental parameters (temperature, borohydride concentration, as well as NaOH concentration) on the electrical behaviour of the fuel cell were studied and optimized. These results show that Pd-based trimetallic catalysts supported on carbon provide a ready route to successfully operate borohydride based fuel cells. Acknowledgements: A. Elsheikh acknowledges a Newton-Mosharafa Scholarship (Reference no. NMJ8/15) for funding. The Portuguese Foundation for Science and Technology (FCT, Portugal) is acknowledged for PhD grant no. SFRH/BD/137470/2018 (R.C.P. Oliveira), contract no. IST-ID/156/2018 (B. Šljukić) and contract no. IF/01084/2014/CP1214/CT0003 under IF2014 Programme (D.M.F. Santos). Keywords: Palladium, trimetallic catalysts, nanomaterials, borohydride oxidation, oxygen reduction, fuel cell, kinetic parameters.

Dynamic Modelling and Optimisation of the Batch Enzymatic Synthesis of Amoxicillin

Amoxicillin belongs to the β-lactam family of antibiotics, a class of highly consumed pharmaceutical products used for the treatment of respiratory and urinary tract infections, and is listed as a World Health Organisation (WHO) “Essential Medicine”. The demonstrated batch enzymatic synthesis of amoxicillin is composed of a desired synthesis and two undesired hydrolysis reactions of the main substrate (6-aminopenicillanic acid (6-APA)) and amoxicillin. Dynamic simulation and optimisation can be used to establish optimal control policies to attain target product specification objectives for bioprocesses. This work performed dynamic modelling, simulation and optimisation of the batch enzymatic synthesis of amoxicillin. First, kinetic parameter regression at different operating temperatures was performed, followed by Arrhenius parameter estimation to allow for non-isothermal modelling of the reaction network. Dynamic simulations were implemented to understand the behaviour of the design space, followed by the formulation and solution of a dynamic non-isothermal optimisation problem subject to various product specification constraints. Optimal reactor temperature (control) and species concentration (state) trajectories are presented for batch enzymatic amoxicillin synthesis.

Analysis of steroids in urine by gas chromatography-capillary photoionization-tandem mass spectrometry

A new heated capillary photoionization (CPI) ion source design was developed to photoionize analytes inside a transfer capillary between a gas chromatograph (GC) and a mass spectrometer (MS). The CPI setup included a wide, oval-shaped vacuum-ultraviolet (VUV) transparent magnesium fluoride (MgF2) window to maximize photoionization efficiency and thus sensitivity. The source contained a nitrogen housing around the ionization chamber inlet to avoid undesirable hydrolysis and oxidation reactions with ambient air and to maximize the proportion of formed molecular radical cations of analytes. The feasibility of the ion source was studied by analyzing 18 endogenous steroids in urine as their trimethylsilyl (TMS) derivatives with gas chromatography-tandem mass spectrometry (GC–MS/MS). The method was validated and applied to human urine samples. To our best knowledge, this is the first time that a capillary photoionization ion source has been applied for quantitative analysis of biological samples. The GC-CPI-MS/MS method showed good chromatographic resolution (peak half-widths between 3.1 to 5.3 s), acceptable linearity (coefficient of determination between 0.981 to 0.996), and repeatability (relative standard deviation (RSD%) between 5 to 18%). Limits of detection (LOD) were between 2 to 100 pg mL−1 and limits of quantitation (LOQ) were between 0.05 to 2 ng mL−1. In total, 15 steroids were quantified either as a free steroid or glucuronide conjugate from the urine of volunteers. The new CPI source design showed excellent sensitivity for analysis of steroids in complex biological samples.

Ester Synthesis in Water: Mycobacterium smegmatis Acyl Transferase for Kinetic Resolutions

AbstractThe acyl transferase from Mycobacterium smegmatis (MsAcT) catalyses transesterification reactions in aqueous media because of its hydrophobic active site. Aliphatic cyanohydrin and alkyne esters can be synthesised in water with excellent and strikingly opposite enantioselectivity [(R);E>37 and (S);E>100, respectively]. When using this enzyme, the undesired hydrolysis of the acyl donor is an important factor to take into account. Finally, the choice of acyl donor can significantly influence the obtained enantiomeric excesses.magnified image

General Acid-Type Catalysis in the Dehydrative Aromatization of Furans to Aromatics in H-[Al]-BEA, H-[Fe]-BEA, H-[Ga]-BEA, and H-[B]-BEA Zeolites

Al, Ga, Fe, and B metal substituents have been examined for their ability to change the Bronsted acid strength of BEA zeolite and inhibit undesired hydrolysis in the production of aromatics from furan, 2-methylfuran, and 2,5-dimethylfuran. We employed electronic structure calculations to examine this series of furans in H-[Al]-, H-[Fe]-, H-[Ga]-, and H-[B]-BEA zeolites. These calculations were used to parametrize a microkinetic model to make direct comparisons to experiments run with furan and DMF in the weakest and strongest acid zeolites, H-[B]-BEA and H-[Al]-BEA, respectively. Electronic structure calculations revealed that the Diels–Alder reaction remains unaffected by changes to the Bronsted acid strength of the zeolite, whereas the dehydration and hydrolysis reactions are affected in a fashion reminiscent of general acid catalysis. Interestingly, despite its significantly lower acid strength, H-[B]-BEA was experimentally shown to have an activity similar to that of H-[Al]-BEA for the production of b...