Isopropylamine Research Articles

Saccharomyces cerevisiae (Baker’s Yeast) catalyzed efficient and facile chemo-selective synthesis of aldimines

An efficient and reliable method has been developed for chemo-selective synthesis of Schiff bases (SB) (3a–n) by using Baker’s yeast (BY) as biocatalyst. The reaction is highly chemo-selective as only benzaldehydes take part in the reaction, whereas acetophenones fail to take part in this reaction. Furthermore, it was observed that amino acids (glycine, phenylalanine & tryptophan) and aliphatic amines (isopropyl amine and 1-amino butane) did not take part in the reaction. The present method is very efficient as it involves simple work up and gives the products in good to excellent yield. The reaction is totally carried out under eco- friendly and environmentally begin conditions by using ethanol (EtOH) as a green solvent. Thus it is anticipated that the present newly developed method will open a gateway for the chemist to prepare the selective SB (Aldimines) in the presence of ketones in facile and eco-friendly conditions.

Gold-Catalyzed Divergent Ring-Opening Rearrangement of Cyclopropenes Enabled by Dichotomous Gold-Carbenes.

The gold-catalyzed ring-opening rearrangement of cyclopropenes affords an efficient route to either polysubstituted naphthols or aryl-substituted furans. Owing to the unique dichotomy of gold-carbenes, this protocol provides a switchable reaction selectivity between naphthols and furans enabled by the use of TFP-Au(MeCN)SbF6 (tri(2-furyl) phosphine) or PNP(AuNTf2 )2 (bis(diphenylphosphino)(isopropyl) amine) as catalysts respectively. It is proposed that the gold-carbene intermediate might be involved in the cyclopropene→naphthol rearrangement while the gold-carbocation is more likely to be involved in the cyclopropene→furan rearrangement.

Effect of the Support on Rhenium Carbide in the Hydrodeoxygenation of Guaiacol as Lignin-Derived Model Compound

The effect of support on the formation of rhenium carbide in the hydrodeoxygenation (HDO) of guaiacol as a lignin-derived compound was evaluated. Catalysts were prepared by incipient wetness impregnation, carburized at 650 °C under a mixture 25/75 of ethylene/hydrogen, and characterized by XRD, N2-physisorption, TPR, TPD of NH3 or isopropylamine (IPA), and XPS. The results have demonstrated that the support choice affects the carburization of rhenium. Indeed, over non-acidic support (e.g., SiO2), limited carburization of the metal was observed, while over ZrO2 and Al2O3, carburization of rhenium occurred, and different carbidic species were obtained depending on the surface and chemical identity of the support. The rhenium carbide species obtained over ZrO2 was the most active and selective toward benzene (22% at 98% of conversion).

A Multi-Analyte LC-MS/MS Method for Determination and Quantification of Six Nitrosamine Impurities in Sartans like Azilsartan, Valsartan, Telmisartan, Olmesartan, Losartan and Irbesartan.

A sensitive and robust method for determination and quantification of potential genotoxic impurities in sartans has been developed. These impurities need to be controlled at trace levels during quantification in drug substances and drug products for safe consumption. Recent regulatory requirements also suggested the need to have highly sensitive analytical method for trace level quantification of nitrosamine impurities. In this paper, we have described a simple, rapid and sensitive liquid chromatography-mass spectrometry method for six potential genotoxic nitrosamine impurities: N-Nitroso dimethyl amine (NDMA), N-Nitroso diethyl amine (NDEA), N-Nitroso Ethyl Iso propylamine (NIPEA), N-Nitroso-Nmethyl-4-aminobutyric acid (NMBA) N-Nitroso diisopropylamino (NDIPA) and N-Nitroso dibutyl amine (NDBA) in Azilsartan (AZL), Valsartan (VAL), Telmisartan (TEL), Olmesartan (OLM), Losartan (LOS) and Irbesartan (IRB) with a limit of quantification of less than 0.003ppm. Chromatographic separation is achieved using Poroshell HPH- C18, 150 × 4.6mm, 2.7μm column with 0.1% formic acid in water as mobile phase A and 0.1% formic acid in methanol as mobile phase B at a flow rate of 0.5mL/min using gradient mode of elution at a total run time of 20min. Six nitrosamine impurities are ionized and quantified in positive mode of atmospheric pressure chemical ionization using multiple reaction monitoring. As per ICH guidelines, method validation is performed and evaluated the limit of quantification and detection and found to give good S/N ratios with good linearity range of 0.003-0.045ppm with regression coefficient > 0.999 for all the six nitrosamine impurities. Method recoveries are also established using three-step sample preparation and are found to be satisfactory within 80-120%. The single method can be used routinely applied for the detection of nitrosamines in AZL, VAL, TEL, OLM, LOS and IRB.

Pyrolysis study of iso-propylamine with SVUV-photoionization molecular-beam mass spectrometry

The pyrolysis of isopropylamine (IPA) was studied in a jet-stirred reactor at 1 atm within 670–1100 K. Pyrolysis products and intermediates were identified and quantified with both synchrotron vacuum ultraviolet photoionization mass spectrometry and gas chromatography analysis. Propiolonitrile, propanenitrile, 1-methylethenylamine, 3-butenenitrile, pyridine and benzonitrile were newly identified compared with previous studies of amines. HCN and 1-methylethenylamine were found to be the dominant N-containing species in IPA pyrolysis. The peak mole fractions and temperatures of C1-C2 hydrocarbons are generally higher than C3-C4 ones. The peak temperatures tend to rise with the increase of degree of unsaturation for hydrocarbons with the same C numbers. Based on the observations, a detailed kinetic model consisting of 429 species and 2407 reactions was developed with reasonable predictions against the measured data. Rate-of-production analysis indicates that IPA is mainly consumed by the H-abstraction at the Cα atom: (CH3)2CHNH2+H = (CH3)2CNH2+H2. Sensitivity analysis shows that the unimolecular decomposition via CC bond cleavage and H-abstraction at the Cα atom play promoting roles. The H-abstraction of propene by H-atom yielding allyl radical and self-combination of methyl radicals forming ethane exhibit inhibiting effects. Compared to the pyrolysis of n-propylamine (NPA), more amine- or imine-like species were generated during NPA pyrolysis while more nitriles were detected in IPA pyrolysis. Moreover, the peak temperatures of hydrocarbons in both NPA and IPA pyrolysis shift to higher values with the increase of degree of unsaturation. The results will enrich the understanding of IPA for further combustion kinetic studies of low sooting fuels.

Synthesis and Characterization of Ag/Al2O3 Catalysts for the Hydrogenation of 1-Octyne and the Preferential Hydrogenation of 1-Octyne vs 1-Octene.

Catalysts featuring 2, 5, and 10 wt % silver supported on alumina were prepared by the deposition precipitation method and activated under hydrogen. All catalysts were characterized by Brunauer–Emmett–Teller (BET) measurements, inductively coupled plasma-optical emission spectrometry (ICP-OES), backscattered electron scanning electron microscopy (BSE-SEM), high-resolution transmission electron microscopy (HR-TEM), hydrogen-temperature-programmed reduction (H2-TPR), H2-chemisorption, thermogravimetric analysis (TGA), infrared (IR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, and isopropylamine (IPA) TPD and evaluated in a continuous plug flow fixed-bed reactor. Metal nanoparticles with average sizes of 4.5, 11.5, and 21.1 nm were identified by HR-TEM for the 2, 5, and 10 wt % Ag/Al2O3 catalysts, respectively. A conversion of 99% was observed for 1-octyne over particles between 10 and 15 nm in size, with stable operation up to 24 h (decreasing thereafter) at a temperature of 140 °C and a pressure of 30 bar in the competitive hydrogenation reaction. No conversion of 1-octene was noted in competitive reactions (mixed 1-octyne and 1-octene feed) but rather a gain of 1-octene throughout the 72 h time-on-stream. The performance of all catalysts was influenced by both the metal and support, where the latter impacted the overall acidity of the catalysts, thus affecting their long-term stability.

Novel domino synthesis of 2‐(2,3.4‐substituted phenyl) quinazolin‐4‐amine

AbstractConvenient domino protocol was developed for the synthesis of 2‐arylquinazolin‐4‐amines by the reaction of N‐(2‐cyanophenyl) substituted benzimidoyl isothiocyanates with isopropyl amine. The major advantages of this protocol are short reaction times, mild conditions, simple work up, high yields, and pure products. The efficacy of this protocol owes to the competence of synthesis, pure isolation of imidoyl isothiocyanates, and the unique structure conformation of the corresponding intermediate thiourea derivatives.

Computer Modeling Explains the Structural Reasons for the Difference in Reactivity of Amine Transaminases Regarding Prochiral Methylketones.

Amine transaminases (ATAs) are pyridoxal-5′-phosphate (PLP)-dependent enzymes that catalyze the transfer of an amino group from an amino donor to an aldehyde and/or ketone. In the past decade, the enzymatic reductive amination of prochiral ketones catalyzed by ATAs has attracted the attention of researchers, and more traditional chemical routes were replaced by enzymatic ones in industrial manufacturing. In the present work, the influence of the presence of an α,β-unsaturated system in a methylketone model substrate was investigated, using a set of five wild-type ATAs, the (R)-selective from Aspergillus terreus (Atr-TA) and Mycobacterium vanbaalenii (Mva-TA), the (S)-selective from Chromobacterium violaceum (Cvi-TA), Ruegeria pomeroyi (Rpo-TA), V. fluvialis (Vfl-TA) and an engineered variant of V. fluvialis (ATA-256 from Codexis). The high conversion rate (80 to 99%) and optical purity (78 to 99% ee) of both (R)- and (S)-ATAs for the substrate 1-phenyl-3-butanone, using isopropylamine (IPA) as an amino donor, were observed. However, the double bond in the α,β-position of 4-phenylbut-3-en-2-one dramatically reduced wild-type ATA reactivity, leading to conversions of <10% (without affecting the enantioselectivity). In contrast, the commercially engineered V. fluvialis variant, ATA-256, still enabled an 87% conversion, yielding a corresponding amine with >99% ee. Computational docking simulations showed the differences in orientation and intermolecular interactions in the active sites, providing insights to rationalize the observed experimental results.

The Prognosis of Glyphosate herbicide intoxicated patients according to their salt types

Purpose: Glyphosate herbicide (GH) is a widely used herbicide and has been associated with significant mortality as poisoned cases increases. One of the reasons for high toxicity is thought to be toxic effect of its ingredient with glyphosate. This study was designed to determine differences in the clinical course with the salt-type contained in GH. Methods: This was a retrospective study conducted at a single hospital between January 2013 and December 2017. We enrolled GH-poisoned patients visited the emergency department. According to salt-type, patients were divided into 4 groups: isopropylamine (IPA), ammonium (Am), potassium (Po), and mixed salts (Mi) groups. The demographics, laboratory variables, complications, and their mortality were analyzed to determine clinical differences associated with each salt-type. Addtionally, we subdivided patients into survivor and non-survivor groups for investigating predictive factors for the mortality. Results: Total of 348 GH-poisoned patients were divided as follows: IPA 248, Am 41, Po 10, and Mi 49 patients. There was no difference in demographic or underlying disease history, but systolic blood pressure (SBP) was low in Po group. The ratio of intentional ingestion was higher in Po and Mi groups. Metabolic acidosis and relatively high lactate level were presented in Po group. As the primary outcome, the mortality rates were as follows: IPA, 26 (10.5%); Am, 2 (4.9%); Po, 1 (10%); and Mi, 1 (2%). There was no statistically significant difference in the mortality and the incidence of complications. Additionally, age, low SBP, low pH, corrected QT (QTc) prolongation, and respiratory failure requiring mechanical ventilation were analyzed as independent predictors for mortality in a regression analysis. Conclusion: There was no statistical difference in their complications and the mortality across the GH-salt groups in this study.

Transaminase Catalysis for Enantiopure Saturated Heterocycles as Potential Drug Scaffolds

As efforts in rational drug design are driving the pharmaceutical industry towards more complex molecules, the synthesis and production of these new drugs can benefit from new reaction routes. In addition to the introduction of new centers of asymmetry, complexity can be also increased by ring saturation, which also provides improved developability measures. Therefore, in this report, our aim was to develop transaminase (TA)-catalyzed asymmetric synthesis of a new group of potential chiral drug scaffolds comprising a saturated amine heterocycle backbone and an asymmetric primary amine sidechain (55a–g). We screened the Codex® Amine Transaminase Kit of 24 transaminases with the morpholine containing ketone 57a, resulting in one (R)-selective TA and three (S)-selective TAs operating at 100 mM substrate concentration and 25 v/v% isopropylamine (IPA) content. The optimized reaction conditions were than applied for asymmetric transamination of further six ketones (57b–g) containing various amine heterocycles, in which a strong effect of the substitution pattern of the γ-position relative to the substituted N-atom could be observed. Mediated by the most enantiotope selective (S)-TAs in scaled-up process, the (S)-amines [(S)-55a–g] were isolated with moderate-to-excellent yields (47–94%) in enantiopure form (&gt;99% ee).

Promising integrated technique for the treatment of highly saline nanofiltration rejected stream of steel industry

This work presents a novel concept for the integration of closed-circuit reverse osmosis (CCRO) technology and solvent-based precipitation as a means of producing an exceptional quality of water by separating the salts especially chlorides and sulphates from highly saline nanofiltration (NF) rejected stream of the steel industry. The NF rejected stream was extremely concentrated with salts like chloride (1560 mg/L), sulphate (4212 mg/L), manganese (28 mg/L), sodium (418 mg/L) and total dissolved solids (TDS), as high as 8100 mg/L, which are well above the permissible limit for surface discharge. The outcome of this work showed that reverse osmosis (RO) with continuous brine recycling achieved excellent desalination performance. Miscible organic solvents such as diisopropylamine (DIIPA), isopropylamine (IPA), and ethylamine (EA) were found to be effective in precipitating chloride and sulphate ions from highly concentrated RO brine. The overall removal efficiency of sulphate and chloride was found to be 99.88% and 91%, respectively. Preliminary treatment cost was estimated and found to be around 7.35 $/m3. The treated water can either be recycled in the system or safely released into the environment. The readers of this research article will be benefitted by gaining a thorough understanding of the treatment of concentrated brine from nanofiltration using an integrated RO-precipitation technique.

2-(Pyridin-2-yl)isopropyl (PIP) Amine: An Enabling Directing Group for Divergent and Asymmetric Functionalization of Unactivated Methylene C(sp3)–H Bonds

ConspectusDirecting group (DG) assistance provides a good solution to the problems of reactivity and selectivity, two of the fundamental challenges in C(sp3)-H activation. However, the activation of unbiased methylene C(sp3)-H bonds remains challenging due to the high heterolytic bond dissociation energy and substantial steric hindrance. Two main strategies have been developed thus far, that is, use of a strongly coordinating bidentate DG pioneered by Daugulis and use of a weakly coordinating monodentate DG accelerated by pyridine-type ligands, as disclosed by Yu. The seminal work by Daugulis sparked significant interest in the application of the monoanionic bidentate auxiliary in aliphatic C-H activation reactions. Our research has focused on enabling the divergent functionalization and enantiotopic differentiation of unactivated methylene C-H bonds. Inspired by the structure of bidentate 8-aminoquinoline and the accelerating effect of the gem-dimethyl moiety in cyclometalations, we developed a strongly coordinating bidentate 2-(pyridine-yl)isopropyl (PIP) amine DG consisting of a pyridyl group, a gem-dimethyl moiety, and an amino group, which enabled the divergent functionalization of unactivated β-methylene C(sp3)-H bonds to forge C-O, C-N, C-C, and C-F bonds with palladium catalysts. The exclusive β-selectivity was ascribed to the preferential formation of kinetically favored [5,5]-bicyclic palladacycle intermediates. DFT calculations revealed that the well-designed gem-dimethyl group was responsible for the lowered energy and compressed bite angle of the key transition state related to C-H cleavage.More recently, the combination of PIP amine with axially chiral ligands was found to promote asymmetric functionalization of unbiased methylene C(sp3)-H bonds, a challenging research topic in the area of C-H activation that remains to be addressed. Two different types of axially chiral ligands, namely, non-C2-symmetric chiral phosphoric acids (CPAs) and 3,3'-disubstituted BINOLs, have been developed. The former enabled Pd(II)-catalyzed inter- and intramolecular arylation of unbiased methylene C(sp3)-H bonds with high enantioselectivity, whereas the latter promoted a series of asymmetric functionalization reactions, such as alkynylation, arylation, alkenylation/aza-Wacker cyclization, and intramolecular amidation. The unexpectedly high stereocontrol compared with other bidentate DGs might be attributable to steric communication between the ligand and gem-dimethyl moiety of PIP amine. Thus far, the combination of PIP amine DG with 3,3'-disubstituted BINOL ligands is arguably the most general strategy for asymmetric functionalization of unbiased methylene C(sp3)-H bonds. Finally, the ease of installation and removal of PIP under mild conditions and synthetic applications are described.

Synthesis of SAPO-56 using N,N,N’,N’-tetramethyl-1,6-hexanediamine and co-templates based on primary, secondary, and tertiary amines

Biomethane is a renewable fuel with a small environmental footprint. In its production, the removal of CO2 from the fermentation gas is critical. Pressure and vacuum swing adsorption (PSA and VSA) processes have certain advantages over other processes for the removal. Silicoaluminophosphate-56 (SAPO-56) has promising properties as an adsorbent for PSA- or VSA-based upgrading of raw biogas. It is typically synthesized by using N,N,N’,N’-tetramethyl-1,6-hexanediamine (TMHD) as a structure directing agent (SDA). In this study, TMHD was partly replaced with three different low-cost templates: isopropylamine (IPA), dibutylamine, and tripropylamine. SAPO-56 was co-crystallized with mixtures of templating amines with up to a ratio of 30%:70% of TMHD:IPA. With using TMHD and IPA, small and defined crystals of SAPO-56 plus SAPO-47 formed instead of the large aggregates of SAPO-56 that formed when only TMHD was used. Solid-state 13C NMR spectroscopy was used to show that the IPA and TMHD had not been decomposed and that both molecules were included within the as-synthesized crystals of SAPO-56. Synthetic composition diagrams were drawn with respect to the P2O5, SiO2, and Al2O3 compositions of the reaction mixtures and the formed crystalline SAPOs. In relation to these diagrams, the domains for stability of SAPO-56 were contrasted with those of SAPO-11, -17, -20, and -47. In particular, it was observed that SAPO-47 co-crystallized with SAPO-56 when a very large fraction of IPA was used under otherwise optimized conditions. As consistent with other studies, the SAPO-56 synthesized with dual SDAs had a very high uptake of CO2 at conditions relevant for PSA- or VSA-driven upgrading of raw biogas into methane.

Exploring the Structural Chemistry of Pyrophosphoramides: N,N′,N″,N‴-Tetraisopropylpyrophosphoramide

N,N′,N″,N‴-Tetraisopropylpyrophosphoramide 1 is a pyrophosphoramide with documented butyrylcholinesterase inhibition, a property shared with the more widely studied octamethylphosphoramide (Schradan). Unlike Schradan, 1 is a solid at room temperature making it one of a few known pyrophosphoramide solids. The crystal structure of 1 was determined by single-crystal X-ray diffraction and compared with that of other previously described solid pyrophosphoramides. The pyrophosphoramide discussed in this study was synthesised by reacting iso-propyl amine with pyrophosphoryl tetrachloride under anhydrous conditions. A unique supramolecular motif was observed when compared with previously published pyrophosphoramide structures having two different intermolecular hydrogen bonding synthons. Furthermore, the potential of a wider variety of supramolecular structures in which similar pyrophosphoramides can crystallise was recognised. Proton (1H) and Phosphorus 31 (31P) Nuclear Magnetic Resonance (NMR) spectroscopy, infrared (IR) spectroscopy, mass spectrometry (MS) were carried out to complete the analysis of the compound.

Ultra-Sensitive LC-MS/MS Method for the Trace Level Quantification of Six Potential Genotoxic Nitrosamine Impurities in Telmisartan

Nitrosamine impurities are potentially genotoxic which are considered under cohort of concern as per ICH M7 guidelines and need to be controlled at trace levels during quantification in drug substances and drug products for safe human consumption. Recent regulatory requirements also suggest the need to have highly sensitive analytical methods for the accurate quantification of Nitrosamine impurities. In this paper we have presented simple, rapid and ultra-sensitive LC-MS/MS method for six potential genotoxic nitrosamine impurities: N-Nitroso dimethyl amine (NDMA), N-Nitroso diethyl amine (NDEA), N-Nitroso Ethyl Iso propylamine (NEIPA), N-Nitroso-N-methyl-4-aminobutyric acid (NMBA) N-Nitroso diisopropylamino (NDIPA) and N-Nitroso dibutyl amine (NDBA) with a LOQ of 0.004 ppm. Chromatographic separation is achieved using Zorbax SB C18 150 × 3.0 mm, 3.5 μ column with 0.1% formic acid in water as mobile phase A and 0.1% formic acid in methanol as mobile phase B at a flow rate of 0.3 ml/min using gradient mode of elution at a total run time of 18 minutes. Six nitrosamine impurities are successfully ionized and quantified in positive mode of atmospheric pressure chemical ionization (APCI) using multiple reaction monitoring (MRM). Method validation is performed as per ICH guidelines evaluating the limit of quantification and detection and found to give good S/N ratios with good linearity range of 0.002 - 2 ppm with regression coefficient >0.99 for all the six nitrosamine impurities. Method recoveries are established using three-step sample preparation protocol and are found to be satisfactory within 80% - 120%. The method can be used routinely applied for the detection of Nitrosamines in Telmisartan at a concentration of 1.5 ng/ml (0.03 ppm with respect to telmisartan concentration of 50 mg/ml).

Simultaneous enantioseparation and simulation studies of atenolol, metoprolol and propranolol on Chiralpak® IG column using supercritical fluid chromatography

Enantioseparation of three β-blockers, i.e., atenolol, metoprolol and propranolol, was studied on amylose tris(3-chloro-5-methylphenylcarbamate) immobilized chiral stationary phase using supercritical fluid chromatography (SFC). The effect of organic modifiers (methanol, isopropanol and their mixture), column temperature and back pressure on chiral separation of β-blockers was evaluated. Optimum chromatographic separation with respect to resolution, retention, and analysis time was achieved using a mixture of CO2 and 0.1% isopropyl amine in isopropanol: methanol (50:50, V/V), in 75:25 (V/V) ratio. Under the optimized conditions, the resolution factors (Rs) and separation factors (α) were greater than 3.0 and 1.5, respectively. Further, with increase in temperature (25–45 °C) and pressure (100–150 bars) there was corresponding decrease in retention factors (k), α and Rs. However, a reverse trend (α and Rs) was observed for atenolol with increase in temperature. The thermodynamic data from van't Hoff plots revealed that the enantioseparation was enthalpy driven for metoprolol and propranolol while entropy driven for atenolol. To understand the mechanism of chiral recognition and the elution behavior of the enantiomers, molecular docking studies were performed. The binding energies obtained from simulation studies were in good agreement with the elution order found experimentally and also with the free energy values. The method was validated in the concentration range of 0.5–10 μg/mL for all the enantiomers. The limit of detection and limit of quantitation ranged from 0.126 to 0.137 μg/mL and 0.376–0.414 μg/mL, respectively. The method was used successfully to analyze these drugs in pharmaceutical preparations.

Exploration of synthesis, structural aspects, DFT studies and bio-efficacy of some new DHA-benzohydrazide based copper(II) complexes

A copper (II) complex with ligand obtained by the dehydrative condensation of 3-acetyl-6-methyl-2H-pyran-2,4(3H)‑dione (DHA) and benzohydrazide has been synthesized (4). This species was additionally coordinated by various solvent molecules, namely ethanolamine, methanol, DMF, dimethyl amine, isopropyl amine, diisobutylamine, and ethylenediamine to synthesize complexes 5a-5g. All the complexes were characterized by single crystal X-ray diffraction analysis and other analytical techniques. In each case, the copper atom is tetra-coordinated by chelating carbohydrazide ligand through O, N, O donor atoms and the N/O heteroatom from the coordinated solvent (except for ethylenediamine, where Cu is pentacoordinated). The intermolecular interactions present in each complex have been quantified using Hirshfeld surface analysis, and the electrostatic properties associated with these complexes were calculated using DFT studies. Considering the expected bioactivity of carbohydrazide derivatives, the antibacterial activity of ligand and copper complexes was tested against pathogenic Gram-positive and Gram-negative bacteria using ciprofloxacin as positive control. Compounds 4 and 5f show potent antibacterial activity against B. subtilis with MIC and MBC value of 32 μM.

Synthesis of three-dimensional hydrogels based on poly(glycidyl methacrylate-alt-maleic anhydride): Characterization and study of furosemide drug release

In the present work, three-dimensional drug carriers were synthesized via chemical modification of poly (glycidyl methacrylate-alt-maleic anhydride) P(GMA-alt-MA) by isopropylamine (IPA) and ethylenediamine (EDA) with different molar ratios. Then furosemide drug (FR) was loaded on the hydrogels and studied for its slow release in phosphate-buffered saline (PBS) solution (pH = 7.41) at 37 °C. According to the obtained results, the sample with the lowest amount of crosslinking agent (Sample A) showed the highest swelling ratio in comparison to the others. By increasing the rigidity of carrier in the result of increasing the crosslinker density, the amount of the released drug was decreased. However, the release rate for all of samples (slope of the profiles) were rather similar. All the synthesized carriers have shown pH dependent properties and the maximum release rate was shown in basic pH. Also, the drug release experiments in different temperatures showed almost thermal sensitivity properties for synthesized carriers and release rate become faster by increasing the medium temperature. The FT-IR, TGA, and FE-SEM analyses were carried out for characterization of prepared samples and the swelling behavior of prepared hydrogels were measured too. Investigation of the release data with different mathematical models showed the highest adaption with the Higuchi model for all samples.

Industrial adaptability selection for a novel ω-transaminase

ω-transaminase (ω-TA) is the most promising biocatalyst for chiral amine synthesis. However, most wild-type ω-TAs cannot be applied in industry directly due to their low stability and unfavorable reaction equilibrium. In order to discover a novel ω-TA for industrial application, we designed a procedure of adaptive selection, including the screening of substrates, protein sequences and clones, enzyme activity, and product conversion and characterization, as well as trouble-shooting of each step. Through this procedure, we screened a novel ω-TA, ATA-W12 of Caulobacter sp. from a soil metagenome. The strain could convert 20 mmol/L 1-Boc-3-pyrrolidinone and 20 mmol/L 1-Boc-3-piperidone with 85.84% and 67.42% conversion rate, respectively, in a 1-mL scale with isopropylamine (IPA) as amine donor. ATA-W12 maintained 100% activity at 40 °C for 168 h, and its optimal reaction condition is at pH 8.5 and 40 °C. These excellent properties benefit the application of IPA as an ideal amino donor in industry. We scaled up the production of (S)-(+)-1-boc-3-aminopiperidine up to 50 mL (100 g/L) scale with this novel biocatalyst for its further industrial application.

In situ growth of TiO2 nanoparticles on nitrogen-doped Ti3C2 with isopropyl amine toward enhanced photocatalytic activity

Construction of heterojunction and nitrogen doping is an effective approach for synthesizing photocatalysts with high quantum yield and efficient electron-hole separation. 2D MXene Ti3C2 has been considered a good carbonaceous nanomaterial for designing heterojunction, while the original surface groups and stacked structure limit the electron-hole separation. Herein, a hybrid of nitrogen-doped Ti3C2 nanosheets and TiO2 nanoparticles (NPs) composed of TiO2 NPs in situ growing on isopropyl amine (iPA) modified Ti3C2 (iN-Ti3C2) was developed for the first time. The novel iN-Ti3C2/TiO2 hybrid exhibited an excellent ultraviolet-light photodegradation of methylene blue (MB), with a degradation rate (0.02642 min−1) significantly higher than that of pure TiO2 NPs, bulk-Ti3C2/TiO2, dimethyl sulfoxide modified Ti3C2/TiO2 hybrid, and hydrazine monohydrate modified Ti3C2/TiO2 hybrid. The formation of heterojunction between iN-Ti3C2 and TiO2 and its role in the photocatalysis were systematically analyzed using various characterization techniques and density functional theory calculation. The iPA modification exfoliated Ti3C2 and doped N on Ti3C2 nanosheets; the in situ grown TiO2 NPs formed efficient heterojunctions with the nanosheets; the N-doping facilitated electron migration in Ti3C2 and inhibited the recombination of photogenerated electron-hole pairs; •OH dominated the photodegradation of MB. This work provides a new approach of constructing efficient photocatalysts for the treatment of organics-polluted water.