Synthesis,characterization, DNA binding,cytotoxicity and molecular docking properties of three novel butterfly-like complexes with nitrogen-containing heterocyclic ligands

Three novel complexes, namely [Nd·L₁·HCOO·(H₂O)₄] ( 1 ), [Pr·L₁·HCOO·(H₂O)₄] ( 2 ) and [In·L₂·Cl·(H₂O)₂] ( 3 ) (L₁ = 1,1-bis(5-(pyrazin-2-yl)-1,2,4-triazol-3-yl)methane, L₂ = 1,1-bis(5-(pyrazin-2-yl)-1,2,4-triazol-3-yl)ketone), were synthesized and characterized. The molecular structures of 1 – 3 were confirmed using single-crystal X-ray diffraction. All three obtained complexes are zero-dimensional and connected to each other by hydrogen bonds. In 1 and 2 the metal is surrounded by nine donors and 3 has seven coordination sites. The interaction of 1 – 3 with calf thymus DNA (CT-DNA) was explored using UV absorption spectra and fluorescence spectra. The intrinsic binding constants of 1 – 3 with CT-DNA are about 1.9 × 10⁴, 1.4 × 10⁴ and 1.1 × 10⁴, respectively. Stern–Volmer quenching plots of 1 – 3 have slopes of 0.1508, 0.134 and 0.1205, respectively. The ability of these complexes to cleave pBR322 plasmid DNA was demonstrated using gel electrophoresis assay. Apoptosis studies of the three novel complexes showed a significant inhibitory effect on HeLa cells. Furthermore, MTT assays were used to evaluate the anticancer activity of the three complexes. The cytotoxicity study indicated that complex 1 possesses a higher inhibitory rate of HeLa cells than the other complexes. Especially, the efficacy of 1 was shown to be the highest for cisplatin at 24 h. A further molecular docking technique was introduced to understand the binding of the complexes toward the target DNA.     

Multipolar Porphyrin-Triazatruxene Arrays for Two-Photon Fluorescence Cell Imaging

Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP) _n (n=1–3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40–0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT-ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δ_TPA values of TAT-(ZnP)₂ and TAT-(ZnP)₃ further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π-conjugated quadrapole/octupole molecules and the extension of D -π-A-D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin-based TPEF materials by the construction and extension of D -π-A-D multipolar array.     

Synthesis,characterization, and thermal properties of novel silicon 1,1,3,3-tetramethylguanidinate derivatives and use as single-source chemical vapor deposition precursors

A series of chemical vapor deposition (CVD) precursors have been synthesized by a single-step reaction of 1,1,3,3-tetramethylguanidine and a variety of silicon chlorides. The structures of the 1,1,3,3-tetramethylguanidinate-based compounds were verified by ¹H NMR, ¹³C NMR, XPS, EI-MS, and elemental analysis. The thermal stability, transport behavior, and vapor pressures of these compounds were evaluated by simultaneous thermal analyses (STA). These compounds are highly stable and those in liquid form are very volatile. Silicon carbonitride (SiCN) thin films were prepared by using bis (tetramethylguanidine)-dimethyl-silane as the precursor in helicon wave plasma chemical vapor deposition (HWP-CVD). The properties of the films were investigated by SEM, AFM, and XPS. The results showed that the films have good uniformities, low friction coefficient, and high hardness, enabling the films for fabrication of semiconductor devices.     

Cascaded DNA circuits-programmed self-assembly of spherical nucleic acids for high signal amplification

Signal amplification is an important issue in DNA nanotechnology and molecular diagnostics. In this work, we report a strategy for the catalytic self-assembly of spherical nucleic acids(SNAs) programmed by two-layer cascaded DNA circuits through integrating an entropy-driven catalytic network, a catalytic hairpin assembly circuit, and a facile SNA assembly-based reporter system. This integrated system could implement ～100,000-fold signal amplification in the presence of 1 p M of input target.Possessing powerful amplification ability of nucleic acid signal, our strategy should be of great potential in fabricating more robust dynamic networks to be applied for signal transduction, DNA computing, and nucleic acid-based diagnostics.     

Alkaloid and Glycoside Compounds from the Fruits of Berberis atrocarpa and Their Anticomplementary Activities

Chemistry of Natural Compounds -     

Enhanced antifungal activities of four Zn(II) complexes based on uniconazole

Four Zn(II) complexes, [Zn L ₂(SO₄)]_n ( 1 ), [Zn L ₄(H₂O)₂]?2(NO₃)?4EtOH ( 2 ), [Zn L ₂Cl₂]? L ( 3 ), and [Zn L ₂Br₂]? L ( 4 ) ( L  = uniconazole), were synthesized using a hydrothermal method and characterized by elemental analysis, FT‐IR spectroscopy, and single‐crystal XRD. Complex 1 formed a one‐dimensional polymer chain. However, complexes 2 ‐ 4 were obtained as zero‐dimensional mononuclear coordination compounds. The antifungal activities of these complexes were then evaluated against four selected fungi using the mycelial growth rate method. The resulting data indicate that all complexes show better antifungal activities than their ligands and mixtures. In addition, the interactions between the metal salts of complexes 1 ‐ 4 and uniconazole seem to be synergistic. Furthermore, the polymer chain structure of complex 1 significantly enhanced the bioactivity, especially against Botryosphaeria ribis ( I ). Density functional theory (DFT) calculations were carried out to help explain the enhanced bioactivity after the formation of Zn(II) complexes. The resulting data show that the HOMO–LUMO energy gaps of complexes 1 ‐ 4 (0.0578, 0.0946, 0.1053, and 0.1245 eV) are smaller than that of the free ligand (0.1247 eV) and correlate with the antifungal activity of the zinc complexes.