Synthesis and cytotoxicity of a ruthenium nitrosyl nitric oxide donor with isonicotinic acid and a cell penetrating peptide

The syntheses and properties of trans-[Ru(NH₃)₄(L)(NO)](BF₄)₃ (L = isonicotinic acid (inaH) (I) or ina-Tat48–60 (II)) are described. Tat48–60, a cell penetrating peptide fragment of the Tat regulatory protein of the HIV virus, was linked to the ruthenium nitrosyl through inaH. I and II release NO after reduction forming trans-[Ru(NH₃)₄(L)(H₂O)]^3 +. The IC₅₀ values against B16-F10 melanoma cells of I and II (21 μmol L^− 1 and 23 μmol L^− 1, respectively) are close to that of the commercially available cisplatin (33 μmol L^− 1) and smaller than similar complexes. The cytotoxicity is assigned to the NO released from I and II.     

Photochemical production of nitric oxide from a nitrosyl phthalocyanine ruthenium complex by irradiation with light in the phototherapeutic window

The photochemical behavior of [Ru(NO)(NO)₂pc] (pc = phthalocyanine) is reported in this paper. In addition to ligand localized absorption bands (λ < 300 nm), the electronic spectrum of this complex in dichloromethane solution was dominated by an intense absorption at 640 nm characterized as Q-bands. Irradiation of [Ru(NO)(NO)₂pc] at 366 and 660 nm led to the production of nitric oxide (NO) as detected by a NO-sensor. NO production by light irradiation at high energy involved excitation of d_π–π^* transition, while a photoinduced electron transfer occurred at long wavelength irradiation. The NO quantum yields varied from 1.4 × 10⁻³ to 2.3 × 10⁻² mol einstein⁻¹, depending on oxygen concentration.     

Mechanism of the chlorine evolution on a ruthenium oxide/titanium oxide electrode and on a ruthenium electrode

The mechanism of the chlorine evolution on titanium electrodes coated with a layer of ruthenium oxide and titanium oxide under different experimental conditions, and on a ruthenium electrode, both in acidic chloride solution, has been investigated. Potentiodynamic current density—potential curves were recorded as a function of the time anodic pre-polarisation, the composition of the solution and the temperature. Moreover, potential decay curves were determined. Theoretical potential decay curves were deduced for both the Tafel reaction (2 Cl_ad→Cl₂) and the Heyrovsky reaction (Cl^? + Cl_ad → Cl₂ + e^?) as a rate determining step in the formation of molecular chlorine. They were compared with those found experimentally. The influence of possible diffusion of atomic chlorine out of the electrode was also taken into consideration. It was found that for all the electrodes investigated, molecular chlorine is formed both at anodic polarisation and on open circuit according to the Volmer—Heyrovsky mechanism, where the Heyrovsky reaction is the rate-determining step. The transfer coefficient is 0.5 for the chlorine evolution at an “ideal” ruthenium oxide titanium oxide electrode and at a ruthenium electrode.     

钛基锡锰钌氧化物阳极的电化学性能

通过热分解法制备不同钌含量的钛基锡锰氧化物阳极。X射线衍射谱图显示所制备的电极的主要相态为金红石型β—MnO2;循环伏安曲线与稳态极化曲线测试表明随着钌含量的增加,电极上的氧化电流也快速上升,析氯的选择性提高;适量掺混钌可以增加涂层表面析氯反应活性点的数目,当钌的质量分数为2％时,反应活性点的数目达到最大;电化学阻抗谱研究表明掺杂钌明显减小电极氧化物涂层的膜电阻R和析氯反应的电荷传递电阻Rct。有效地提高电极的电催化效果。钛基锡锰钌涂层电极可用于制备次氯酸钠,NaClO的生成速率为34．8mg／（L·min）。     

Synthesis, characterization and crystal structure of a novel thiocyanate–ruthenium(II) complex

The cis-[Ru(dppb)(Me-bipy)(NCS)₂], dppb = 1,4-bis (diphenylphosphino)butane, Me-bipy = 4,4′-dimethyl-2,2′-bipyridine, and NCS = thiocyanate, was synthesized and characterized by spectroscopic and electrochemical techniques and its structure was determined by crystal X-ray analysis. The crystal structure reveals that the coordination geometry around the Ru(II) center is distorted octahedron where two molecules of thiocyanate are bonded to the ruthenium through nitrogen atom in cis orientation. The half-wave formal potential value E_1/2 = 0.8 V (versus Ag/AgCl) observed is considerable higher than that for the cis-[RuCl₂(dppb)(Me-bipy)] complex, E_1/2 = 0.6 V (versus Ag/AgCl), well illustrating the strong π-acceptor effect the NCS ligand toward the backbonding interaction with the Ru(II) metal center. The MLCT absorption bands of the thiocyanate complex present a higher molar absorptivity (about 12%) compared with the cis-[RuCl₂(dppb)(Me-bipy)] complex, in the same experimental conditions. These properties make the complex potentially promising for the photosensitization process.     

C NMR study on structure, composition and curing behavior of phenol-urea-formaldehyde resole resins

Phenol-urea-formaldehyde (PUF) resole resins were synthesized and analyzed by both liquid and solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. The liquid ¹³C NMR analysis indicated that the co-condensation reactions between the phenolic ring and the urea unit occurred during the synthesis of the resins. The addition of the urea component effectively reduced the free formaldehyde content in the resin systems. Methylene ether bridges in the resins were found to be mainly associated with the urea units. pH had significant influences on the structure and composition of the resins. Solid-state ¹³C NMR measurements of the cured resins suggested that the pH probably affected the curing mechanism. A longer time and a higher temperature can generally accelerate the curing process and increase the rigidity of the cured network.     

Ruthenium catalyzed asymmetric transfer hydrogenation based on chiral P,N,O Schiff base ligands and crystal structure of a ruthenium(II) complex bearing chiral P,N,O Schiff base ligands

A ruthenium catalyst, generated in situ by heating the chiral P,N,O Schiff base ligand L (L = (S)-Ph₂PC₆H₄CNCHPhCH₂OH) with Ru(DMSO)₄Cl₂ in 2-propanol, is active for asymmetric transfer hydrogenation with best enantioselectivity up to 81%. A ruthenium complex of formula RuL₂Cl₂ is prepared and its crystal structure revealed that the two chiral P,N,O Schiff ligands are in meridional configuration. This complex is also an active catalyst for asymmetric transfer hydrogenation. However, the ‘[Ru(DMSO)₄]Cl₂ + chiral P,N,O ligand’ protocol displays better enantioselectivity.     

固砷矿物臭葱石组成与结构及其浸出稳定性研究现状

综述了固砷矿物臭葱石的组成与结构性能,及其浸出稳定性研究现状。不同条件下制备的臭葱石样品,会因SO₄^2-夹杂和结晶水量变化,具有不同的组成。已提出双齿双核和双齿单核两种臭葱石结构模型,两者是否属实尚存在争议。臭葱石的溶度积介于10^-21.17~10^-25.83之间波动。在弱酸性（pH 2~6）、氧化条件下,臭葱石浸出稳定性较高,能较好满足长期堆存要求;而在强酸性或碱性区域,或在还原性条件下,其浸出稳定性较差。     

Solvothermal synthesis,structure and photoluminescent properties of europium complex based on fluorene derivatives

A novel coordination polymer, {[Eu₂(L)₃(CH₃OH)(H₂O)]·(CH₃OH)(H₂O)}_n (1), has been synthesized by solvothermal reaction of Eu(NO₃)₃·6H₂O and 9,9-diethylfluorene-2,7-dicarboxylic acid in a mixture solution of CH₃OH and H₂O. Single crystal X-ray structural analysis reveals that complex 1 crystallizes in an orthorhombic, space group P2(1)2(1)2(1), holding the unusual (2,3,8)-connected 3D topological network. Thermogravimetric analysis shows remarkable thermal stability of the structural framework of compound 1, the photoluminescence properties are also discussed.     

Development of the formulation for a detergent composition based on mixture of surfactants and binary complex former

Theoretical Foundations of Chemical Engineering - The mathematical planning of an experiment aimed at developing the optimal composition of a synthetic detergent containing a mixture of two anionic...     

小分子化合物对神华煤结构组成和热行为的影响

小分子化合物是通过二硫化碳、四氢呋喃、甲醇三种溶剂对神华煤进行逐级索氏抽提获得的。利用红外光谱和热重分析分别对原煤和抽掉小分子化合物后的残煤进行测试,可知小分子化合物被抽出后,煤的结构组成及热行为均发生了变化,残煤的脂肪烃和环烷烃基团明显减少,热失重速率降低,最大失重温度向高温段移动。     

Barrier,rheological, and antimicrobial properties of sustainable nanocomposites based on gellan gum/polyacrylamide/zinc oxide

In this study, we used a solution casting method to prepare gellan gum (G)-based ternary nanocomposite films containing polyacrylamide (P) and zinc oxide (ZnO) nanoparticles. All composites were prepared using the chemical cross-linker N,N-methylenebisacrylamide. The nanocomposites were characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction, and scanning electron microscopy. Attenuated total reflectance FTIR revealed strong hydrogen bonding interactions among gellan gum, polyacrylamide, and ZnO, which enhanced the physiochemical, thermal, and mechanical properties of the GPZnO nanocomposites. The addition of ZnO nanoparticles increased the glass transition temperature (T_g: 181.8–196.3°C), thermal stability (T_5%: 87.8–96.5°C), and char yield (23.9–29.1%) of the GP composite films, as well as their the tensile strength (from 33.5 to 43.8 MPa) and ultraviolet (UV) blocking properties (~99.2% protection against UVB [280–320 nm]). ZnO significantly influenced the rheological properties of the GP composite. The prepared GP and GPZnO nanocomposites exhibited shear thinning behavior and their viscosities decreased when there is an increase in shear rate. Storage and loss modulus increased with frequency with the addition of ZnO nanoparticles. The GPZnO films exhibited reduced hydrophilicity, moisture content, and water barrier properties compared with the GP film. The GPZnO nanocomposites exhibited effective antimicrobial activity against six different pathogens. The prepared GPZnO films could be useful in biodegradable packaging applications.     

Synthesis,structure and magnetic properties of a tetranuclear Mn(II) complex with carbohydrazone based ligand

A new tetranuclear complex of Mn(II), [Mn₄(L)₂(CH₃OH)₂(μ-N₃)₄(N₃)₂] ∙ 2(CH₃OH) (1), was synthesized and characterized by spectroscopic methods, single-crystal X-ray diffraction analysis and TGA analysis where HL is bis-[(E)-N′-(phenyl(pyridin-2-yl)methylene)]carbohydrazide. Single crystal X-ray analysis reveals that 1 has a Mn₄ core in which Mn(II) ions are connected by azide and enolate oxygen atoms. IR spectroscopy and X-ray analysis indicate that the carbohydrazone is coordinated to the metal cores as a mononegative ligand in the enol form. The magnetic behavior of 1 was investigated between 2 and 295 K and indicated that the magnetic coupling mediated via azide bridge is ferromagnetic whereas the enolate oxygen mediates antiferromagnetic coupling that leads to overall antiferromagnetic behavior.     

High performance waterborne coatings based on dispersions of a solid epoxy resin and an amine-functional curing agent

A novel, waterborne epoxy system comprised of non-ionic stabilized dispersions of a solid epoxy resin and an amine curing agent has been designed for ambient-cure coatings. The performance characteristics of coatings formulated from the new system have been compared to a standard system. The new system produced formulated coatings with robust performance over a wide range of amine-to-epoxy stoichiometries (65 to 130%). At 100% stoichiometry, the new system was found to have lower VOC, faster hardness development, better gloss, and higher impact resistance than the standard system. The new formulations also exhibited superior water and salt spray resistance, and a definitive viscosity rise at the end of potlife. Unlike the standard system, coating morphology of the new waterborne system was found to be similar to a solvent-based coating. For the new system, good coalescing solvents, as judged by gloss and gloss potlife, were found to have low solubility parameters and high boiling points. Presented at the 76th Annual Meeting of the Federation of Societies for Coatings Technology, on October 15, 1998, in New Orleans, LA. P.O. Box 1380, Houston, TX 77251-1380.     

Understanding structure and composition of thermally rearranged polymers based on small‐molecule chemistry: a perspective

We provide a critical perspective of the burgeoning literature on microporous polymers prepared using thermal rearrangement (TR) processes based on the learning derived from analogous chemistry involving small‐molecular‐weight compounds. TR polymers have shown interesting permeability–selectivity relationships in gas separation and, thus, have generated wide interest as potential membrane materials for industrial applications. The intractable nature of the products obtained by TR processes has precluded rigorous structural elucidation of the polymers. Based on small‐molecule chemistry, we conclude that structures are likely to be more complex than generally depicted in the published literature. Interestingly, a simpler chemistry, namely thermal dehydrocyclization (TCD), leads to products identical to those derived from TR, but at significantly lower temperatures. However, TCD chemistry does not involve a skeletal rearrangement of the kind purported in TR during the conversion of imide to oxazole ring resulting in spatially confined heterocyclic ring polymers. Yet, they show similar fractional free‐volume elements as exhibited by TR polymers. This is intriguing and points to a need for more careful examination of the factors responsible for microporosity in such materials. TR chemistry as currently practiced appears limited to only benzoxazole‐type structures. The ability to precisely control and reproducibly produce materials with well‐defined structure and properties will be a key to large‐scale manufacture and industrial applications of such materials. Seen from this perspective, TR processes leave much to be desired and further improvements are clearly warranted. © 2019 Society of Chemical Industry     

Thermal shock effects on the impact resistance,tolerance and flexural strength of alumina based oxide/oxide ceramic matrix composites

In this study the effects of thermal shock on the impact damage resistance, damage tolerance and flexural strength of Nextel 610/alumina silicate ceramic matrix composites were experimentally evaluated. Composite laminates with balanced and symmetric layup were gradually heated to 1200°C in an air-based furnace and held for at least 30 min before being removed and immersed in water at room temperature. The laminates were then subjected to low velocity impacts via a hemispherical steel impactor. The resultant damage was characterized non-destructively, following which the laminates were subjected to compression tests. Three-point bend tests were also performed to evaluate the effect of thermal shock on the flexural strength and related failure modes of the laminates. Thermally shocked laminates showed smaller internal damage and larger external damage areas in comparison to their pristine counterparts. For the impact energy and resultant damage size considered, the residual compressive strengths for the thermally shocked and pristine laminates were similar.     

Ionic mobility and structure of glasses based on indium and bismuth fluorides from data of IR and19F NMR spectroscopy

The InF₃-BaF₂-BiF₃ glass-forming system is investigated by the IR and¹⁹F NMR spectroscopic techniques. The influence of bismuth trifluoride on the dynamic behavior of fluorine ions and the structure of glasses in this system is demonstrated.     

Enhancement of thermal,morphological, and mechanical properties of compatibilized based on PA6-enriched graphene oxide/EPDM-g-MA/CR: Graphene oxide and EPDM-g-MA compatibilizer role

In this study, a series of elastomeric nanocomposites based on specific amounts of polyamide6 (PA6)/chloroprene rubber (CR) blends which are compatibilized with ethylene propylene diene monomer-grafted-maleic anhydride (EPDM-g-MA) and different amounts of graphene oxide (GO) were prepared with melt mixing method. The effect of compatibilizer and reinforcement concentration in the PA6/CR blend matrix was investigated using theoretical and experimental analysis. Dispersion of nanoplatelets within rubber blend matrix was proven with transmission electron microscopy and field emission-scanning electron microscopy. The modified microstructure of samples showed the significant effect of EPDM-g-MA and GO on the size reduction of CR droplets in the PA6 continuous phase. The results from differential scanning calorimetry and dynamic mechanical thermal analysis revealed the effect of EPDM-g-MA and GO as an effective nucleating agent in PA6-enriched GO/CR (PA6EGO/CR). The findings obtained from thermogravimetric analysis displayed that the GO in the presence of an EPDM-g-MA as a compatibilizer can cause a higher thermal stability in PA6EGO/CR. From mechanical properties, by adding a compatibilizer to the PA6/CR blend, the tensile strength changed from 39.0 to 45.1, the Young's modulus altered from 522.2 to 716.0 and the elongation at break changed from 246.8 to 222.2. While incorporation of 5 phr of GO to the compatibilized blend, the tensile strength increased by 25.2%, the Young's modulus increased by 36.6% and the elongation at break decreased by 20%. The Christensen–Lo model used for analyzing the stiffness of PA6EGO/EPDM-g-MA/CR with emphasis on the influence of the interphase region to predict the effect of various loadings of GO and EPDM-g-MA of Young's modulus. The rheology and creep tests showed a significant effect of EPDM-g-MA and GO content on the rheology behavior of nanocomposites.