Crystal structures and in vitro anticancer studies on new unsymmetrical copper(II) Schiff base complexes derived from meso-1,2-diphenyl-1,2-ethylenediamine: a comparison with related symmetrical ones

Two new unsymmetrical copper(II) Schiff base complexes, [CuLⁿ(py)]ClO₄ (n = 1, 2) in which Lⁿ represents a tridentate N₂O type Schiff base ligand, were synthesized. Lⁿs were derived from monocondensation of meso-1,2-diphenyl-1,2-ethylenediamine with salicylaldehyde or 3-methoxysalicylaldehyde. The reaction between [CuLⁿ(py)]ClO₄ and other salicylaldehyde derivatives resulted in new N₂O₂ unsymmetrical tetradentate Cu^II complexes, CuL^3–6. Crystal structures of [CuL¹(py)]ClO₄, CuL⁴, and CuL⁵ were obtained. These new complexes as well as a series of related symmetrical ones (i.e. CuL^7–12) were tested for their in vitro anticancer activity against human liver cancer cell line (Hep-G2) by MTT and apoptosis assay. All of the complexes showed considerable cytotoxic activity against tumor cell lines (IC₅₀ = 5.13–16.24 μg mL^?1). The symmetrical CuL⁷ was the most potent anticancer derivative (IC₅₀ = 5.13 μg mL^?1) compared to the control drug 5-FU (IC₅₀ = 5.4 μg mL^-1, p < 0.05). Flow cytometry experiments showed that the copper derivatives especially [CuL²(py)]ClO₄ and CuL⁷ induced more apoptosis on Hep-G2 tumor cell lines compared to 5-FU.     

A Green Protocol for Solvent-Free Conversion of Epoxides to Thiiranes with Dowex-50WX8–Supported Thiourea

Structurally different epoxides were efficiently converted to the corresponding thiiranes by Dowex-50WX8–supported thiourea under solvent-free conditions. The reactions were carried out either in an oil bath or under microwave irradiation to give the thiiranes in 75–98% yields within 30 sec–120 min.     

NaHSO4·H2O as a Heterogeneous Acidic Reagent for Mild and Convenient Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones and Their Sulfur Derivatives

One-pot cyclocondensation reaction of aromatic aldehydes, 1,3-dicarbonyl compounds and urea/thiourea in the presence of NaHSO₄·H₂O produced 4-aryl substituted 3,4-dihydropyrimidin-2(1H)-ones and their sulfur analogs in high to excellent yields. The reactions were carried out in refluxing n-hexane and were completed within 2.5–11 h.     

Electro-optical properties of zigzag and armchair boron nitride nanotubes under a transverse electric field: Tight binding calculations

The electro-optical properties of zigzag and armchair BNNTs in a uniform transverse electric field are investigated within tight binding approximation. It is found that the electric field modifies the band structure and splits band degeneracy where these effects reflect in the DOS and JDOS spectra. A decrease in the band gap, as a function of the electric field, is observed. This gap reduction increases with the diameter and it is independent of chirality. An analytic function to estimate the electric field needed for band gap closing is proposed which is in good agreement with DFT results. In additional, we show that the larger diameter tubes are more sensitive than small ones. Number and position of peaks in DOS and JDOS spectra for armchair and zigzag tubes with similar radius are dependent on electric field strength.     

Flow-injection determination of ascorbic acid and cysteine simultaneously with spectrofluorometric detection.

A simple and sensitive spectrofluorometric method was developed for the simultaneous determination of ascorbic acid and cysteine by a flow-injection system. This method is based on the reduction of Tl(III) with ascorbic acid or cysteine in acidic media, producing fluorescence reagent, TlCl3(2-) (lambdaex = 227 nm, lambdaem = 419 nm). The injected sample solution was divided into two separate streams. The first stream was treated with Tl(III) at pH 3.0 and then passed through a 270 cm reaction coil to the flow cell of the spectrofluorometer, where the fluorescence intensity was measured. This signal is related to ascorbic acid and cysteine concentration. The second part of the injected sample solution was treated with Tl(III) in HCl solution and then passed through a 50 cm reaction coil to the flow cell and the fluorescence intensity was measured. This signal is related only to cysteine. Thus, the ascorbic acid content was determined directly by the difference according to the calibration curve. Ascorbic acid and cysteine can be determined in the range of 1 x 10(-6) to 5.0 x 10(-5) M, at a rate of 16 samples per hour. The limits of detection (S/N = 3) were 8 x 10(-7) M for ascorbic acid and 7 x 10(-7) M for cysteine. The influence of potential interfering substances was studied. The proposed method was successfully applied to the simultaneous determination of both analytes in real samples.     

The line analog of Ramsey numbers

For positive integersr ands, f′(r, s) is defined as the smallest positive integerp such that every connected (ordinary) graph of orderp contains eitherr mutually adjacent lines ors mutually disjoint lines. It is found thatf’(r,s) =(r−1) (s−1)+2 unlessr=2 and s ≠ 1, in which casef′(2,s)=3. Definitions not given here can be found in [7, 8].     

Numerical solution of functional integral equations by the variational iteration method

In the present article, we apply the variational iteration method to obtain the numerical solution of the functional integral equations. This method does not need to be dependent on linearization, weak nonlinearity assumptions or perturbation theory. Application of this method in finding the approximate solution of some examples confirms its validity. The results seem to show that the method is very effective and convenient for solving such equations.     

An inorganic–organic hybrid material based on ZnO nanoparticles anchored to a composite made from polythiophene and hexagonally ordered silica for use in solid-phase fiber microextraction of PAHs

We report on an inorganic–organic hybrid nanocomposite that represents a novel kind of fiber coating for solid-phase microextraction (SPME) of polycyclic aromatic hydrocarbons (PAHs). The material is composed of ZnO nanoparticles, polythiophene and hexagonally ordered silica, and displays good extraction capability due to its nanostructure. The nanocomposite was synthesized by an in-situ polymerization technique, and the ZnO nanoparticles were anchored to the pores in the walls. The ZnO/polythiophene/hexagonally ordered silica (ZnO/PT/SBA-15) nanocomposite was then deposited on a stainless steel wire to obtain the fiber for SPME of PAHs. Optimum conditions include an extraction temperature of 85 °C (for 30 min only), a desorption temperature of 260 °C (for 2 min), and a salt concentration (NaCl) of 20 % (w/v). The detection limits are between 8.2 and 20 pg mL^?1, and the linear responses extend from 0.1 to 10 ng mL^?1. The repeatability for one fiber (for n?=?5), expressed as relative standard deviation, is between 4.3 and 9.1 %. The method offers the advantage of being simple to use, rapid, and low-cost (in terms of equipment). The thermal stability of the fiber and high relative recovery (compared to conventional methods) represent additional attractive features.

On the Use of Amperometry for Real Time Assessment of Drug‐Release Profile from Therapeutic Nanoparticles

A simple electrochemical method was used to directly assess the drug‐release profile. The method is based on the multiple pulse amperometric measurement of the oxidation and reduction of doxorubicin released from liposome at a MWCNTs‐modified glassy carbon electrode (MWCNT‐GCE). The released doxorubicin was detected at +0.60 and ?0.60 V by two different oxidation and reduction processes, respectively. The third potential pulse (?1.00 V) was applied for the regeneration of MWCNT‐GCE. The main advantage of this method is that there is no need for any operation for the quantitative analysis during the release of the drug from nanoparticles.     

Targeted Therapy of B7 Family Checkpoints as an Innovative Approach to Overcome Cancer Therapy Resistance: A Review from Chemotherapy to Immunotherapy

It is estimated that there were 18.1 million cancer cases worldwide in 2018, with about 9 million deaths. Proper diagnosis of cancer is essential for its effective treatment because each type of cancer requires a specific treatment procedure. Cancer therapy includes one or more approaches such as surgery, radiotherapy, chemotherapy, and immunotherapy. In recent years, immunotherapy has received much attention and immune checkpoint molecules have been used to treat several cancers. These molecules are involved in regulating the activity of T lymphocytes. Accumulated evidence shows that targeting immune checkpoint regulators like PD-1/PD-L1 and CTLA-4 are significantly useful in treating cancers. According to studies, these molecules also have pivotal roles in the chemoresistance of cancer cells. Considering these findings, the combination of immunotherapy and chemotherapy can help to treat cancer with a more efficient approach. Among immune checkpoint molecules, the B7 family checkpoints have been studied in various cancer types such as breast cancer, myeloma, and lymphoma. In these cancers, they cause the cells to become resistant to the chemotherapeutic agents. Discovering the exact signaling pathways and selective targeting of these checkpoint molecules may provide a promising avenue to overcome cancer development and therapy resistance. Highlights: (1) The development of resistance to cancer chemotherapy or immunotherapy is the main obstacle to improving the outcome of these anti-cancer therapies. (2) Recent investigations have described the involvement of immune checkpoint molecules in the development of cancer therapy resistance. (3) In the present study, the molecular participation of the B7 immune checkpoint family in anticancer therapies has been highlighted. (4) Targeting these immune checkpoint molecules may be considered an efficient approach to overcoming this obstacle.