Novel dammarane-type saponins from Gynostemma pentaphyllum and their neuroprotective effect

Abstract

Three novel dammarane-type saponins, 2α,3β,12β,20(S),24(S)-pentahydroxydammar-25-ene-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-20-O-β-D-glucopyranoside (1, namely gypenoside J1), 2α,3β,12β,20(S),25-pentahydroxydammar-23-ene-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-20-O-β-D-glucopyranoside (2, namely gypenoside J2) and 2α,3β,12β,20(S)-tetrahydroxydammar-25-en-24-one-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-20-O-β-D-xylopyranosyl-(1→6)-β-D-glucopyranoside (3, namely gypenoside J3) along with one known gypenoside (gypenoside LVII) were isolated from the aerial parts of G. pentaphyllum using various chromatographic methods. Their structures were elucidated on the basis of IR, 1D- (¹H and ¹³C), 2D-NMR spectroscopy (HSQC, HMBC and COSY), and mass spectrometry (ESI-MS/MS). Their activity was tested using CCK-8 assay. These four compounds showed little anti-cancer activity with IC₅₀ values more than 100?μM against four types of human cancer lines. The effects of them against H₂O₂-induced oxidative stress in human neuroblastoma SH-SY5Y cells were evaluated and they all showed potential neuroprotective effects with 3.64–18.16% higher cell viability than the H₂O₂-induced model group.     

Evaluation of hydrophobic‐interaction chromatography resins for purification of antibody‐drug conjugates using a mimetic model with adjustable hydrophobicity

Antibody drug conjugates are cytotoxic pharmaceuticals, designed to destroy malignant cells. A cytotoxic molecule is attached to an antibody that binds specific to a cancer‐cell surface. Given the high toxicity of the drugs, strict safety standards have to be kept. For this reason, an antibody drug conjugates model was developed with fluorescein 5‐isothiocyanate as the nontoxic payload surrogate. Due to the similar hydrophobicity, this model is used to establish a suitable purification process and characterization method for antibody drug conjugates. Because of the pH dependent solubility of fluorescein, the hydrophobicity of conjugates can be modulated by the pH value. Based on the complex heterogeneity and hydrophobicity of the conjugates a chromatographic purification is challenging. Hydrophobic interaction chromatography is used for analytical as well as for preparative separation. Because of the increased hydrophobicity of the conjugates compared to native antibody, hydrophobic interaction chromatography often suffer from resolution and recovery problems. Conjugates were separated differing on the number of payloads attached to the antibody. For this matter, the drug–antibody ratio is determined and used as a quantitative term. The conjugates are purified at high recoveries and resolution by step gradients using suitable resins, allowing the separation of the target drug–antibody ratio.     

Purification and antioxidant capacity analysis of anthocyanin glucoside cinnamic ester isomers from Solanum nigrum fruits

In a recent study, anthocyanins, which have a strong free radical‐scavenging activity, were examined for their potential to effectively prevent cancer. However, clinical trials are limited by the purity of the anthocyanin. Multiple methods are used to extract and purify anthocyanins. Based on previous work on Solanum nigrum, which is a widely distributed plant, in this study, DM130 macroporous resin, Sephadex LH20, and a C18 column were used to separate cis–trans anthocyanin isomers. These anthocyanins constitute the majority of total S. nigrum anthocyanins. The results showed that this “DM130‐LH20‐C18 system” can be used to obtain a cinnamic acid‐derived cis–trans anthocyanin, petunidin‐3‐(p‐coumaroyl)‐rutinoside‐5‐glucoside, with a purity of 98.5%, for effective quantitation. In order to determine the antioxidant ability of the petunidin‐3‐(p‐coumaroyl)‐rutinoside‐5‐glucoside cis–trans isomers, three ordinary methods were adopted. The maximum antioxidant ability of the cis–trans anthocyanin was dozens of times higher than that of vitamin C.     

An efficient synthesis of highly functionalized dinucleotide cap analogs

An efficient synthesis of new cap analogs containing aminoallyl linkers such as m⁷G[5′]pppp[5′]U-aminoallyl and m₂^7,3′OG[5′]pppp[5′]U-aminoallyl is reported. The final cap analog has been isolated with high purity (>99.8%) after ion-exchange column purification.     

NMR Parameters and Vibrational Investigation of 2-Dicyanovinyl-5-（4-ethoxyphenyl） thiophene by ab initio HF and DFT Calculations

Optimized geometry and harmonic vibrational frequency of 2-dicyanovinyl-5-(4- ethoxyphenyl)thiophene (C16H12N2OS) are calculated at the HF/6-31++G(d,p) and B3LYP/6- 311++G(d,p) levels. Mulliken charges in the ground state are also calculated. The research shows the presence of intermolecular interaction in the title compound. The scaled harmonic vibrational frequencies have been compared with experimental FT-IR spectra. A detailed interpretation of the infrared spectra of the title compound is reported. The theoretical spectrograms for IR spectra of the title compound have been constructed. The isotropic chemical shift computed by 13C and 1H NMR analyses also shows good agreement with the experimental observations.     

5-(Perfluorooctylthio)acetamidofluorescein (5-FOAF) as a convenient tag for inspecting the surface coverage of fluorinated coatings

Fluorinated compounds are commonly used for anti-stick coating but it is difficult to inspect the coverage of the coating without expensive instruments. Herein, we demonstrated that the 5-(perfluorooctylthio)acetamidofluorescein (5-FOAF) probe can be synthesized in one step and used as a testing reagent to inspect the fluorinated coating on silica- or metal-based surfaces. 5-FOAF is composed of a perfluoroalkyl domain, which has high specific affinity towards fluorinated compounds, and a fluorophore domain, which exhibits fluorescence emission visible by naked eyes. Thus, 5-FOAF will retain on the surface coated with fluorinated compounds but not on the un-coated surface and the emitted fluorescence from the retained tags serves as a semi-quantitative measure of the fluorine coverage across the surface. For this study, silica-based or metal-based surfaces were activated by silane chemistry and then coated with fluorinated compounds. The coating procedure was judiciously optimized to achieve a homogeneous coating. 5-FOAF probe was synthesized in-house and shown to retain on the fluorinated surface 2-5 times stronger than the bare surface. Moreover, by studying the retention on a non-fluoro hydrophobic substrate made of polydimethylsiloxane, the affinity of 5-FOAF with the fluorinated coating was confirmed to be specific and distinguishable from nonspecific hydrophobic interaction. In conclusion, we synthesized a novel chemical, 5-FOAF, and demonstrated its usefulness as a simple testing reagent for fluorinated coatings.     

A two-dimensional Zn(II) coordination polymer with a three-dimensional supramolecular architecture comprising 5-dimethylamino-isophthalic acid and 1,3-bis(4-pyridyl)propane

A new zinc coordination polymer, [Zn(L)(bpp)·H₂O]_n, was synthesized using 5-dimethylamino-isophthalic acid (H₂L) and 1,3-bis(4-pyridyl)propane (bpp) as organic linkers. In the complex, adjacent Zn²⁺ ions are linked by L^2? anions to form a one-dimensional (1D) [ZnL]_n chain. Then bpp ligands expand the 1D chains into a corrugated two-dimensional (2D) layer network by linking neighboring Zn²⁺ ions. These adjacent layers are further stacked together by direct C?H···π supramolecular interactions, generating a three-dimensional (3D) supramolecular structure. From the viewpoint of topology, the 2D network can be rationalized to a uninodal four-connected non-interpenetrated sql/Shubnikov tetragonal plane net with {4⁴.6²} topology. Moreover, the solid state properties such as thermogravimetric analysis and luminescence were also investigated.     

Diisobutylaluminum hydride-promoted cyclization of silylated 1,3-dien-5-ynes: Application to total synthesis of a 20-norabietane derivative

The diisobutylaluminum hydride (DIBAL-H)-promoted benzocyclization, recently developed by this group, was adopted for the synthesis of a natural product containing a 9,10-dihydrophenanthrene skeleton to demonstrate its synthetic utility. One of the extracts from the roots of Salvia hydrangea DC. ex Bentham (Lamiaceae), a 20-norabietane derivative, was selected as the target molecule. The key step forming the 9,10-dihydrophenanthrene skeleton was achieved by the DIBAL-H-promoted cyclization of a silylated 1,3-dien-5-yne easily accessible from a substituted α-tetralone.     

Controllable synthesis of composites of ZSM-5 and KIT-1 using an ionic liquid as template

ZSM-5/KIT-1 composites were synthesized using an ionic liquid as a template. The structures and morphologies of as-obtained products were characterized using an infrared spectroscopy, X-ray diffractometer, N₂ adsorption/desorption, scanning electron microscopy and transmission electron microscopy. The resultant zeolites show a fully crystalline microporous MFI zeolite framework and a three-dimensional network of short worm-like channels. Mesopores and microspores of 4.2 and 0.8 nm in diameter coexist in the zeolite composites. Moreover, the ratio of ZSM-5 and KIT-1 could be simply adjusted by controlling the pre-crystalline time. We believe that the strategy for fabricating ZSM-5/KIT-1 through a simple method could potentially promote the large-scale production of zeolite composites.