Synthesis and Characterization of Aminoporphyrin‐End‐Functionalized Poly(N‐isopropylacrylamide) with Photodynamic and Thermoresponsive Effects

The novel aminoporphyrin‐end‐functionalized poly(N‐isopropylacrylamide) (PNIPAM) polymer H₂N‐TPP‐PNIPAM (TPP=5,10,15,20‐tetraphenyl‐21H,23H‐porphyrin) behaves as a multifunctional platform that displays a photodynamic effect, thermosensitivity, and fluorescence properties. The polymer was designed by using an asymmetrical aminoporphyrin (i.e., H₂N‐TPP‐Cl) as the initiator for the atom‐transfer radical polymerization of N‐isopropylacrylamide (NIPAM). The polydispersity index (PDI) obtained by gel‐permeation chromatography indicated that the molecular‐weight distribution was narrow (1.09<PDI<1.27). The lower critical solution temperatures of H₂N‐TPP‐PNIPAM showed a decreasing trend as the molecular weight was increased as a result of the incorporation of the porphyrin group at the end of the chain. The fluorescence spectra revealed the luminescent properties of the materials. The results of confocal laser scanning microscopy showed that the polymer could enter the cytoplasm through endocytosis. In addition, the multifunctional platform exhibited low toxicity against normal cells (L929) and cancer cells (Hela) and enhanced photodynamic activity towards HeLa cells, without significant necrocytosis towards L929 cells; as a result this material may be useful in the future for practical photodynamic therapy.     

Linear {NiII–LnIII–NiII} Complexes Containing Twisted Planar Ni(μ‐phenolate)2Ln Fragments: Synthesis,Structure, and Magnetothermal Properties

Sequential reaction of a multisite LH₄ ligand {2‐[2‐hydroxy‐3‐(hydroxymethyl)‐5‐methylbenzylideneamino]‐2‐methylpropane‐1,3‐diol} with appropriate lanthanide salts followed by the addition of Ni(NO₃)₂ ? 6 H₂O in a 4:1:2 stoichiometric ratio in the presence of triethylamine afforded four heterobimetallic trinuclear complexes [Ni₂Gd(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? H₂O ? CH₃CN ( 1 ), [Ni₂Tb(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? CH₃CN ( 2 ), [Ni₂Dy(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? H₂O ? CH₃CN ( 3 ), and [Ni₂Ho(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? H₂O ? CH₃CN ( 4 ). Complexes 1 – 4 possess linear trimetallic cores with a central lanthanide ion. Magnetic studies revealed a predominant ferromagnetic interaction between the Ni and Ln centers. Alternating current susceptibility measurements of complex 3 showed a small frequency dependence of the out‐of‐phase signal, χ′′_M , under zero direct current field, but without achieving a net maximum above 2 K. Magnetic studies on 1 revealed that it has a significant magnetocaloric effect.     

Energetic Salts Based on an Oxygen‐Containing Cation: 2,4‐Diamino‐1,3,5‐triazine‐6‐one

A family of energetic salts with high thermal stability and low impact sensitivity based on an oxygen‐containing cation, 2,4‐diamino‐1,3,5‐triazine‐6‐one, were synthesized and fully characterized by IR and multinuclear (¹H, ¹³C) NMR spectroscopy, elemental analysis, and differential scanning calorimetry. Insights into their sensitivities towards impact, friction, and electrostatics were gained by submitting the materials to standard tests. The structures of 2,4‐diamino‐1,3,5‐triazine‐6‐one nitrate, 2,4‐diamino‐1,3,5‐triazine‐6‐one sulfate, 2,4‐diamino‐1,3,5‐triazine‐6‐one perchlorate, 2,4‐diamino‐1,3,5‐triazine‐6‐one 5‐nitrotetrazolate were determined by single‐crystal X‐ray diffraction; their densities are 1.691, 1.776, 1.854, and 1.636 g cm^?3, respectively. Most of the salts decompose at temperatures over 180 °C; in particular, the salts 2,4‐diamino‐1,3,5‐triazine‐6‐one nitrate and 2,4‐diamino‐1,3,5‐triazine‐6‐one perchlorate, which decompose at 303.3 and 336.4 °C, respectively, are fairly stable. Furthermore, most of the salts exhibit excellent impact sensitivities (>40 J), friction sensitivities (>360 N), and are insensitive to electrostatics. The measured densities of these energetic salts range from 1.64 to 2.01 g cm^?3. The detonation pressure values calculated for these salts range from 14.6 to 29.2 GPa, and the detonation velocities range from 6536 to 8275 m s^?1; these values make the salts potential candidates for thermally stable and insensitive energetic materials.     

Oxidation of aliphatic alcohols by triethylammonium chlorochromate in non-aqueous medium – A kinetic and mechanistic study

The oxidation of some aliphatic alcohols by triethylammonium chlorochromate (TriEACC) in dimethyl sulfoxide leads to the formation of the corresponding carbonyl compounds. The reaction is first order with respect to TriEACC. The reaction exhibited Michaelis–Menten type kinetics with respect to alcohol. The reaction is catalyzed by hydrogen ions. The hydrogen-ion dependence has the form: k_obs = a + b[H⁺]. The oxidation of [1,1-²H₂] ethanol (MeCD₂OH) exhibits a substantial primary kinetic isotope effect. Oxidation of aliphatic alcohol was studied in 19 different organic solvents. The solvent effect has been analysed using Kamlet’s and Swain’s multi-parametric equation. A suitable mechanism has been proposed.     

Development of Immunonutrient from Pumpkin (Cucurbita Moschata Duchense Ex. Lamk.) Seed

Pumpkin seeds has long been used as a source of nutrition. Based on its content, it is possible that part of this plant used as immunonutrient. The purpose of this research is to study the immunomodulatory activity of pumpkin seeds. It effects on the non-specific immune response was determined through carbon clearance test, organ indexes (liver, spleen and thymic gland) and mice peritoneal exudate activity (PEA). The effects on specific immune response were determined through total antibody titre, delayed type of hypersensitivity (DTH) reaction and number of lymphocytes. On non specific immune response test, pumpkin seed at a low dose (PLD-3.8 g/kg bw) and at a high dose (PHD-7.6 g/kg bw) showed immunostimulanting effect with phagocytic index of 1.219 and 1.347, respectively. PHD increased PEA activity (p<0.01) in lysing microbes. On specific immune response test, PLD and PHD showed immunostimulation effect indicated through 50% haemaglutination activity (HA titre) i.e., 1:512 and 1:2048, respectively compared to than that of control (1:256) for secondary antibody titre. Through cellular immunity test, 48 hours after challenged, PHD showed significant (p<0.05) increased in footpad thickness. After 7 days administration, both doses of pumpkin increased lymphocytes number significantly (p<0.05). Based on the data it can be concluded that, pumpkin seeds have immunomodulatory effects, and can therefore be used as immunonutrient     

Optofluidic droplet router

This contribution presents an optofluidic droplet router which is able to route and steer microdroplets using optically induced forces created solely by the bulk photovoltaic effect on a nonlinear substrate. The combination of microfluidic tools with the properties of a photorefractive crystal allows for the generation of dielectrophoretic forces that can be either repulsive, leading to virtual barriers, or attractive, creating virtual rails. The sign of these forces is solely determined by the electrical properties of the liquid medium under investigation. Moreover, the induced structures on the bottom of the microfluidic channel are optically reconfigurable, so that the same device can easily be adopted for different purposes. Appropriate droplet‐generating devices are fabricated by UV illumination of SU‐8 and polydimethylsiloxane replica molding of the master structures. The bottom of the channels is formed by an iron‐doped lithium niobate crystal, whose internal electric fields are induced by structured illumination patterns and exert dielectrophoretic forces on droplets in the microfluidic section.

     

Effect of agar hydrogel and magnesium ions on the biomimetic mineralization of calcium carbonate

Here, agar hydrogel was selected as diffusion medium and template to control the biomimetic mineralization of calcium carbonate (CaCO₃). Due to three dimensional network structures and abundant functional groups (such as, hydroxyl groups), Ca²⁺ ions were uniformly distributed in the network and electrostatically attracted. The diffusion speed and range of CO₃^2? ions were mediated by the concentration of hydrogel medium. Under the synergistic effect of Mg²⁺ ions, the crystal CaCO₃ was induced by gas phase diffusion method in the hydrogel system. The results showed that the concentrations of Mg²⁺ ions and agar hydrogel had no obvious effect on the calcite phase of CaCO₃, but the morphologies and sizes changed with concentrations of medium and Mg²⁺ ions. Attribute to template effect, the crystallization behavior and growth rate of CaCO₃ crystals were regulated. Since Mg²⁺ ions were easily adsorbed on the surfaces of unit cell, the unique structure of CaCO₃ was precisely controlled. This study provides a useful reference and inspiration for the understandings of the contributions of ion supply rate in bio-mineralization and hydrogel medium in biomimetic mineralization.     

Investigation of chemical activity,SCHIFF base reactions and staining effects of some amino acids by spectrophotometric and theorical methods

In this study, the staining properties of selected amino acids with Brassica oleraceae extract in alum and alum-free media were investigated. Basic, acidic and neutral amino acids (arginine, glutamic acid and glycine) were used to investigate the effect of staining. It was determined that all amino acids were stained in alum media. In the second step, the R group of amino acids found in the proteins of the cell nucleus was reacted with salicyl aldehyde. This reaction was successful only with Arginine. The staining properties of the newly formed compound were also investigated in alum and alum-free environments. Evaluation of the results was done using FT-IR and ¹H NMR methods. All compounds were optimized with the Gaussian G09 program (DFT/B3LYP/6.311 ?G(d.p) basic set. HOMO, LUMO and HOMO-LUMO gap values were determined. Chemical reaction capabilities of amino acids were discussed with the help of HOMO-LUMO gap values.     

药物化学中的大分子效应※

药物种类按照分子量来划分可以分为小分子药物(自然提取或化学合成的)和大分子药物(生物制剂). 尽管目前小分子药物仍然是市场的主流, 但其研发增速趋缓, 而大分子药物在药物研发中的地位日渐突显, 并被预期在未来药物市场中占据越来越高的份额. 除了生物制剂大分子药物, 将小分子药物与天然或合成大分子结合制备得到的化学合成大分子药物, 近年来受到药物研究者们越来越多的关注. 由于大分子具有丰富的骨架结构及空间构架, 其所特有的骨架效应、多价效应, 以及通过分子组装而产生的聚集效应和靶向效应等, 能够为药物化学的设计带来更多新的可能. 有鉴于此, 本综述将简略介绍药物化学设计中的大分子效应, 重点讨论合成大分子的骨架效应、多价效应、聚集效应和靶向效应等为药物化学设计所带来的新性能. 通过对药物化学中大分子效应所带来的优势、问题和重要研究进展的探讨, 以期能够推动化学合成大分子药物的发展, 为药物化学设计提供新的思路.