As the chip of synthetic biology, enzymes play a vital role in the bio-manufacturing industry. The development of diverse functional enzymes can provide a rich toolbox for the development of synthetic biology. This article reports the construction of an artificial enzyme with the introduction of a non-natural cofactor. By introducing the 4-dimethylaminopyridine (DMAP) cofactor into the optimal protein skeleton via covalent bonds based on a click-chemistry strategy, we successfully constructed a novel artificial enzyme with the DMAP cofactor as the catalytic center. The artificial enzyme successfully catalyzed an unnatural asymmetric Morita-Baylis- Hillman (MBH) reaction between cycloketenone and p-nitrobenzaldehyde, with a conversion rate of 90% and enantioselectivity (e.e.) of 38%. This study not only provides an effective strategy for the design of new artificial enzymes but also establishes a theoretical basis for the development of unnatural biocatalytic MBH reactions.
Biocatalysis ; 4-Aminopyridine/chemistry* ; Enzymes/metabolism* ; Coenzymes/chemistry* ; Benzaldehydes/chemistry* ; Protein Engineering/methods* ; Click Chemistry

Marine fungi are important members of the marine microbiome, which have been paid growing attention by scientists in recent years. The secondary metabolites of marine fungi have been reported to contain rich and diverse compounds with novel structures (Chen et al., 2019). Aspergillus terreus, the higher level marine fungus of the Aspergillus genus (family of Trichocomaceae, order of Eurotiales, class of Eurotiomycetes, phylum of Ascomycota), is widely distributed in both sea and land. In our previous study, the coral-derived A. terreus strain C23-3 exhibited potential in producing other biologically active (with antioxidant, acetylcholinesterase inhibition, and anti-inflammatory activity) compounds like arylbutyrolactones, territrems, and isoflavones, and high sensitivity to the chemical regulation of secondary metabolism (Yang et al., 2019, 2020; Nie et al., 2020; Ma et al., 2021). Moreover, we have isolated two different benzaldehydes, including a benzaldehyde with a novel structure, from A. terreus C23-3 which was derived from Pectinia paeonia of Xuwen, Zhanjiang City, Guangdong Province, China.
Acetylcholinesterase/metabolism* ; Animals ; Anthozoa/microbiology* ; Anti-Inflammatory Agents/pharmacology* ; Aspergillus/chemistry* ; Benzaldehydes/pharmacology* ; Mice ; RAW 264.7 Cells ; Signal Transduction

Ultra performance liquid chromatography (UPLC) was employed for simultaneous determination of three components and fingerprint analysis of Periplocae Cortex with gradient elution of mehtanol and water containing 0.1% phosphoric acid as mobile phase. Three components including chlorogenic acid, 4-methoxysalicylaldehyde and periplocoside were well separated under the analytical condition. Seventeen peaks were selected as the common peaks of 30 batches of Periplocae Cortex. The results showed that there is a significant difference in contents of periplocoside between the samples collected from Henan and Shanxi province. Based on the results of three components quantification and fingerprint analysis, hierarchical clustering analysis ( HCA) and principle component analysis (PCA) were used to further prove the differences between two group samples, and the results indicated that quality of Periplocae Cortex from Shanxi was more stable than that from Henan. The established UPLC fingerprint and quantitative analysis methods could be used efficiently in the quality control of Periplocae Cortex, and this study might contribute to the reasonable clinical application.
Benzaldehydes ; analysis ; China ; Chlorogenic Acid ; analysis ; Chromatography, High Pressure Liquid ; methods ; Drugs, Chinese Herbal ; analysis ; Ecosystem ; Periploca ; chemistry ; classification ; growth & development ; Plant Roots ; chemistry ; Quality Control

A new benzaldehyde, 3-hydroxy-4-(4-(2-hydroxyethyl) phenoxy) henzaldehyde(1), together with six known compounds, including isovanillic acid(2), pyrocatechol(3), glutinosalactone A(4), chrysoeriol(5), apigenin(6) and luteolin(7) were isolated from aerial part of Rehmannia glutinosa. The compounds were isolated by macroporous resin, silica gel, Sephadex LH-20 and HPLC chromatographies. The chemical structures of 1-7 were elucidated on the basis of spectral analysis (MS, 1D NMR and 2D NMR).
Benzaldehydes ; chemistry ; isolation & purification ; Drugs, Chinese Herbal ; chemistry ; isolation & purification ; Molecular Structure ; Plant Components, Aerial ; chemistry ; Rehmannia ; chemistry ; Spectrometry, Mass, Electrospray Ionization

To develop a LC-MS/MS method for the determination of protocatechuic acid, protocatechuic aldehyde, salvianolic acid A, salvianolic acid B, cryptotanshinone and tanshinone II(A) in rat plasma and brain. The plasma and brain samples were precipitated with ethyl acetate, then were separated on an Agilent eclipse plus-C18 column (2.1 mm x 50 mm, 3.5 microm) using acetonitrile (consisting of 0.1% formic acid) and water (consisting of 0.1% formic acid) as mobile phase in gradient elution mode. The mass spectrometer was operated under both positive and negative ion mode with the ESI source, and the detection was performed by MRM. The transition of 154.3/153.1 m/z for protocatechuic acid, 137.3/108 m/z for protocatechuic aldehyde, 493.0/295.2 m/z for Salvianolic acid A, 718.0/520.0 m/z for salvianolic acid B, 321.4/152.3 m/z for chloramphenicol, 297.4/254.3 m/z for cryptotanshinone, 295.5/249.3 m/z for tanshinone II(A) and 285.2/154.0 m/z for Diazepam. The calibration curves in the range of 0.625-1 000 microg x L(-1) for protocatechuic acid and protocatechuic aldehyde, 1.25-1 000 microg x L(-1) for salvianolic acid A, 2.5-1 000 microg x L(-1) for salvianolic acid B, 0.15-1 000 microg x L(-1) for cryptotanshinone, 0.625-1 000 microg x L(-1) for tanshinone II(A) are with good linearityin rat plasma and brain. The analysis method is sensitive, simple, and suitable enough to be applied in the pharmacokinetic study of the 6 main components. Animal testing gives the lgBB of the drugs and further studies of the 6 components cross the blood-brain barrier can be carried out.
Animals ; Benzaldehydes ; administration & dosage ; blood ; pharmacokinetics ; Benzofurans ; administration & dosage ; blood ; pharmacokinetics ; Blood-Brain Barrier ; metabolism ; Brain ; metabolism ; Caffeic Acids ; administration & dosage ; blood ; pharmacokinetics ; Catechols ; administration & dosage ; blood ; pharmacokinetics ; Chromatography, Liquid ; methods ; Diterpenes, Abietane ; administration & dosage ; blood ; pharmacokinetics ; Hydroxybenzoates ; administration & dosage ; blood ; pharmacokinetics ; Injections, Intravenous ; Lactates ; administration & dosage ; blood ; pharmacokinetics ; Phenanthrenes ; administration & dosage ; blood ; pharmacokinetics ; Plant Preparations ; administration & dosage ; blood ; pharmacokinetics ; Rats ; Reproducibility of Results ; Salvia miltiorrhiza ; chemistry ; Tandem Mass Spectrometry ; methods

Sixteen compounds were isolated from Conioselinum vaginatum by silica column chromatography over silica gel and Sephadex LH-20, as well as recrystallization. On the basis of their physical and chemical properties and spectral data, their structures were identified as ligustilide (1), 1,3-dilinolein (2), coniferaldehyde (3), myristicin (4), stigmasterol (5), beta-sitosterol (6), vanillin (7), pregnenolone (8), bergapten (9), xanthotoxin (10), methyl indole-3-carboxylate (11), ferulic acid (12), (E)-3-methoxy-4,5-methylenedioxy-cinnamic alcohol (13), p-hydroxybenzaldehyde (14), 3-methoxy-4,5-methylenedioxy-acetophenone (15), and alpha-(ethoxymethyl)-4-hydroxy- benzenemethanol (16). Among them, compound 15 was a new natural product, and compounds 2, 3, 10, 11, 14, and 16 were obtained from this genus for the first time.
Apiaceae ; chemistry ; Benzaldehydes ; chemistry ; Dextrans ; chemistry ; Drugs, Chinese Herbal ; chemistry ; Mass Spectrometry ; Molecular Structure ; Sitosterols ; chemistry

Eighteen compounds were isolated by a combination of various chromatographic techniques including column chromatography over macroporous resin, MCI gel, silica gel, and sephadex LH-20 and reversed-phase HPLC. Their structures were elucidated by spectroscopic data analysis as adinoside A (1), stryspinoside (2), benzyl alcohol beta-glucopyranoside (3), benzyl 2-o-beta-D-glucopyranosyl-2,6-dihydroxybenzoate (4) , gentisic acid 2-O-beta-D-glucopyranoside (5), eugenyl beta-D-glucopyranoside (6) , eugenyl-P-xylopyranosyl-(1-->6)-beta-glucopyranoside (7), (-)-lyoniresinol 9-O-fP-D-glucopyranoside (8) , (+)-lyoniresinol 9-O-beta-D-glucopyranoside (9) , apigenin-7-O-L-rhamnopyranoside (10), luteolin-3 '-O-L-rhamnoside (11) , ursolic acid (12) , beta-sitosteryl-3beta-glucopyranoside-6'-O-palmitate (13), abscisic acid (14), guanosine (15), 5-methyluracil (16), trans-cinnamic acid (17), and 4-hydroxybenzaldehyde(18). These compounds were obtained from this plant for the first time.
Benzaldehydes ; analysis ; Flowers ; chemistry ; Gentisates ; analysis ; Glucosides ; analysis ; Hydroxybenzoates ; analysis ; Lonicera ; chemistry ; Luteolin ; analysis ; Thymine ; analysis ; Triterpenes ; analysis

OBJECTIVE1H-NMR technology was carried out to investigate the chemical difference between 30 batches of Cibotium baronetz decoction pieces and look for new method for quality control of C. baronetz decoction pieces.

METHODSix hundreds MHz H-NMR spectroscopy and principle component analysis (PCA) were used to discriminate between 30 batches of commercially available cibotium samples based on multi-component metabolite profiles.

RESULTSaccharide is the principle component of C. baronetz decoction pieces, and steroid and triterpene were the discriminately chemical component. Protocatechuic acid, protocatechuic aldehyde, cibotiumbaroside A, cibotiumbaroside B and 4-O-caffeoyl-D-glucoside could be used as the marker for controlling the quality of commercial C. baronetz decoction pieces.

CONCLUSIONPattern-recognition techniques applied to proton nuclear magnetic resonance (1H-NMR) spectra of 80% methanol extraction of C. baronetz could correctly discriminate not only the quality, but also the chemical component for batches of commercial C. baronetz decoction pieces.

Benzaldehydes ; chemistry ; Caffeic Acids ; chemistry ; Catechols ; chemistry ; Drugs, Chinese Herbal ; chemistry ; standards ; Ferns ; chemistry ; Furans ; chemistry ; Glucose ; chemistry ; Glucosides ; chemistry ; Glycosides ; chemistry ; Hydroxybenzoates ; chemistry ; Magnetic Resonance Spectroscopy ; methods ; Maltose ; chemistry ; Quality Control ; Steroids ; chemistry ; Sucrose ; chemistry ; Triterpenes ; chemistry

ATP-binding cassette transporter A1 (ABCA1) promotes cholesterol and phospholipid efflux from cells to lipid-poor apolipoprotein A-I (apoA-I), and plays a key role in the initial steps of the whole process of reverse cholesterol transport (RCT). Upregulation of ABCA1 is beneficial for atherosclerosis (AS) prevention and/or therapy, which indicated that ABCA1 was a target for anti-AS drug development. In the previous study, a high-throughput screening method was established using ABCA1p-LUC HepG2 cell line to find the upregulators of ABCA1. In the present study, compound 2030421B was found using this method, with EC50 of 0.50 microg x mL(-1). The compound was further identified as an upregulator of ABCA1 expression by real-time quantitative reverse transcription-polymerase chain reaction (RT-PCR) and Western blotting analysis. Studies also showed that the 2030421B could induce apoA-I-mediated cholesterol efflux and inhibit lipids uptake into mouse peritoneal macrophages RAW264.7.
ATP Binding Cassette Transporter 1 ; ATP-Binding Cassette Transporters ; genetics ; metabolism ; Animals ; Anticholesteremic Agents ; administration & dosage ; chemistry ; pharmacology ; Apolipoprotein A-I ; metabolism ; Benzaldehydes ; administration & dosage ; chemistry ; pharmacology ; Biological Transport ; Cells, Cultured ; Cholesterol ; secretion ; Dose-Response Relationship, Drug ; Hep G2 Cells ; High-Throughput Screening Assays ; Humans ; Lipid Metabolism ; Lipids ; analysis ; Macrophages, Peritoneal ; cytology ; metabolism ; Mice ; Molecular Structure ; RNA, Messenger ; Up-Regulation ; drug effects

A simple and sensitive capillary electrophoresis method with field-enhanced stacking concentration for the analysis of protocatechuic aldehyde, protocatechuic acid, danshensu, rosmarinic acid and salvianolic acid B in Salvia miltiorrhiza var. miltiorrhiza f. alba was developed. The separation was achieved with a fused-silica capillary (75 microm x 50.2 cm, effective length was 40 cm) and a running buffer 15 mmol x L(-1) borax (pH 10.0) containing 20% CH3 OH. The UV detection wavelength was 210 nm. The applied voltage was 28 kV, and the cartridge temperature was 25 degrees C. Water plug was introduced from the anode by 0.5 psi x 4 s before injection. Sample was injected by electrokinetic injection - 8 kV x 3 s. The linear range of protocatechuic aldehyde is 3.0-60.00 mg x L(-1) (R2 = 0.999 8); that of protocatechuic acid, danshensu, rosmarinic acid and salvianolic acid B are 1.0-20.00 mg x L(-1) (R2 are 0.999 1, 0.999 4, 0.998 9 and 0.999 8, respectively), and the limits of detection of five analyts are 0.55, 0.40, 0.25, 0.32, 0.38 microg x L(-1), respectively, Stacking factor is higher and precision is satisfactory. The recoveries ranges were from 97.3% to 99.8%. The proposed method was used to determine the protocatechuic aldehyde, protocatechuic acid, danshensu, rosmarinic acid and salvianolic acid B in S. miltiorrhiza var. miltiorrhiza f. alba. The proposed method is simple, rapid, accurate and high sensitivity, and can be used to control of the quality of S. miltiorrhiza var. miltiorrhiza f. alba.
Benzaldehydes ; analysis ; Benzofurans ; analysis ; Catechols ; analysis ; Cinnamates ; analysis ; Depsides ; analysis ; Electrophoresis, Capillary ; methods ; Hydroxybenzoates ; analysis ; Lactates ; analysis ; Plant Extracts ; analysis ; Quality Control ; Salvia miltiorrhiza ; chemistry ; Sensitivity and Specificity ; Solubility ; Water