The Properties of Polymethyl Methacrylate (PMMA) Bone Cement Filled with Titania and Hydroxyapatite Fillers

Commercial acrylic bone cement was modified by incorporating different filler loadings of bioactive hydroxyapatite and titania nanopowders. The effects of nanofiller loading on the mechanical and thermal properties were evaluated. The peak temperature during the polymerization of bone cement was observed to decrease with increasing filler loading. In addition, the flexural strength decreased and morphological studies of the fracture surfaces revealed an increase in porosity with the increase in filler loading. Silanation was conducted on the optimum filler loading, and the influence of silanation on the mechanical properties of bone cement was assessed.     

Effects of a Hindered Amine Stabilizer (HAS) on radiolytic and thermal stability of poly(methyl methacrylate)

Commercial Poly(methyl methacrylate) (PMMA) containing Tinuvin 622, a Hindered Amine Stabilizer (HAS), in 0.3% (wt/wt) concentration was investigated. The samples were irradiated with gamma radiation (⁶⁰Co) at room temperature in air. The viscosity‐average molecular weight (M_v) was analyzed by viscosity technique. Both control PMMA (without HAS) and PMMA + 622 (with HAS) showed a decrease in molecular weight with the increase in dose, reflecting the random scissions that occurred in the main chain. The G value (scissions/100 eV of energy transferred to the system) was also obtained by viscosity analysis. G value results showed that the addition of Tinuvin 622 into the PMMA matrix significantly decreased the number of scissions/100 eV at dose range of 0–60 kGy. Analysis of infrared spectra showed a decrease in the carbonyl index (CI) in irradiated samples. However the CI decrease was found lower for PMMA + 622 than for control PMMA sample. Thermogravimetric analysis (TGA) revealed that maximum decomposition temperature of additive PMMA is 42°C higher than control PMMA for unirradiated system. On the other hand this difference is not significant in irradiated systems at 60‐kGy irradiation dose. The activation energy of the thermal degradation of PMMA was 165 kJ/mol, this activation energy increased 60 kJ/mol when Tinuvin 622 was added to PMMA matrix. Therefore Tinuvin 622 is a suitable radiostabilizing agent for commercial PMMA in a 0–60 kGy dose interval. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

钴掺杂NaP分子筛合成及其吸附Pb(II)性能

以硅酸钠和偏铝酸钠为原料,通过水热合成法制备钴掺杂NaP分子筛,通过X射线衍射光谱(XRD)、扫描电子显微镜(SEM)、N₂吸附-脱附等表征手段对样品的晶相、形貌和孔结构进行表征分析,并对其Pb(II)吸附性能进行评价。结果表明:与未掺杂钴的NaP分子筛相比,掺杂量为n(Al₂O₃)∶n(Co(NO₃)₂)=8∶1的Co-NaP分子筛的比表面积增大了约5倍(从26.767 m²/g增大到162.490 m²/g);其孔容约增大了约2.5倍(从0.029 cm³/g增大到0.104 cm³/g)。吸附时间为120 min,吸附温度为25 ℃,Pb(II)初始浓度为100 mg/L时,Co-NaP分子筛对Pb(II)的去除率可达98.8%,以乙二胺四乙酸二钠为再生助剂,在30 ℃下再生30 min,可使吸附后时Co-NaP分子筛完全再生,再生后的吸附剂经过3次吸附-再生循环后,Pb(II)去除率仍可达97%。     

Analytical Applications of Mixed Ligand Complexes. II. Separation-Gravimetric Determination of Cu(II) as Its Mixed Ligand Complex with 1,10-Phenanthroline and p-Cresotic Acid

Abstract

A method is presented for the gravimetric determination of Cu(II) followed by its separation from Ni(II), Co(II), Mn(II), and other anions and cations by precipitating it as its mixed ligand complex with 1,10-phenanthroline and p-cresotic acid (5-methylsalicylic acid). The precipitate is equivalent to 0.184 times its weight of copper. The method has potential for use in the large-scale separation of copper.     

Studies on the Mechanical Properties of Gelatin and Its Blends with Vinyltrimethoxysilane: Effect of Gamma Radiation

Gelatin films were prepared by casting. Tensile strength (TS), elongation at break (Eb) and tensile modulus (TM) of the gelatin films were found to be 56 MPa, 6.1% and 1.14 GPa, respectively. Effect of gamma radiation (Co-60) on the mechanical properties of the gelatin films was studied. Vinyltrimethoxysilane (VTMS) was added to the gelatin during casting varying 1–7% by weight and found to increase the TS and TM significantly. Then the films were irradiated and found further increase of TS and TM. Water uptake of the gelatin films and 5% VTMS containing gelatin films were also evaluated.     

Catalytic Behavior of Cobalt (II) Phthalocyanine Immobilized on Bentonite Clay in Bulk Polymerization of Methyl Methacrylate

The catalytic behavior of cobalt (II) phthalocyanine (CoPc) immobilized on bentonite clay, with different complex loadings ranging between 0.2 and 2.2 wt%, in the presence of n-butyl amine solvent, was investigated in bulk polymerization of methyl methacrylate without using an activator or cocatalyst. The interaction of CoPc molecules with a bentonite surface, encouraged by the amine, involved the inclined stacking model, i.e., interaction between N-atoms of the macro-ring system and OH's of the support. Two different mechanistic pathway regions could be suggested, depending on complex loadings. The first was in the range, 0.2?1.0 wt% CoPc, behaving in ionic fashion as the bare bentonite. Isolated oriented molecules probably activated bentonite through the exposure of new internal acid sites during intercalation. The second, in the range of 1.4?2.2 wt% CoPc, proceeded via combined mechanisms, ionic functioned by bentonite support and free radical functioned by complex packed oriented stacks, staggered in clay galleries to cover a fraction of internal active acid sites. The number of polymer chains formed per one CoPc center (reaction turnovers) was >2–～10 with diluted catalyst samples. With higher loadings, one chain was formed per active site. Such behaviors, without a detectable effect on polymer characteristics or enchainment sequence, were studied in light of intercalation, orientation and accessibility models.     

一种平面Pd(Ⅱ)配合物的合成结构以及光催化性质的研究

配合物[Pd(dmphen)CO3]·H2O(dmphen是2,9-二甲基-1,10-菲咯啉)已合成和表征。钯配合物是采用水热合成法制备的,利用X射线单晶衍射法、元素分析、红外等方法对其进行表征。本文以亚甲基蓝(MB)为探针进行了光催化反应对其进行降解,测评了[Pd(dmphen)CO3]·H2O配合物的光催化降解活性。结果表明,在300 W氙灯光源照射下,该配合物对亚甲基蓝光的催化降解有一定效果,亚甲基蓝(MB)的光催化降解率由时间和Pd配合物的参与共同决定。     

Gamma radiation synthesis and swelling properties of hydrogels based on poly(ethylene glycol)/methacrylic acid (MAc) mixtures

In this work, gamma radiation was used to prepare hydrophilic hydrogels based on different mass ratios of poly(ethylene glycol) (PEG) and methacrylic acid (MAc) monomer. The thermal stability of hydrogels was characterized thermogravimetric analysis (TGA). The effect of temperature and pH, as external environments, on the equilibrium swelling of PEG/MAc hydrogels was also studied. The results showed that the gel fraction of PEG/MAc hydrogels is lower than that of PMAc hydrogel, in which the gel fraction of PMAc hydrogel was decreased greatly with increasing the mass ratio of PEG polymer in the initial solutions. The results showed that PEG/MAc hydrogels reached the equilibrium swelling state in water after 6 hours. It was found that the equilibrium swelling of PEG/MAc hydrogels displayed a transition change within the temperature range 30–40°C. This change in equilibrium swelling was illustrated by differential scanning calorimetry (DSC). However, it was observed that the equilibrium swelling of PEG/MAc hydrogels increases progressively with increasing the pH value from 4 up to 8. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

四环素-铜（Ⅱ）配合物与DNA相互作用的吸收光谱研究

用紫外光谱方法研究了四环素(TC)-Cu(Ⅱ)配合物与DNA的相互作用．吸收光谱研究表明，DNA能与四环素(TC)及Cu(Ⅱ)形成的配合物发生反应，配合物与DNA的作用方式随着配合物类型及DNA浓度的不同而不尽相同：当四环素与铜形成1：1型配合物时，较低浓度的DNA能与配合物以嵌插方式相互作用，而较高浓度的DNA与该配合物除了发生嵌插作用外，还存在另外的作用方式；当四环素与铜形成1：2型配合物时，DNA与该配合物则主要以嵌插方式相互作用，并且这两种配合物与DNA的嵌插作用均是通过四环素配体插入的．     

叔胺萃取分离钴(II)、铁(II)

研究了不必预先氧化二价铁,直接用叔胺从氯化物溶液中萃取分离钴(II)、铁(II)的新方法. 考察了不同改性剂对叔胺萃取钴(II)、铁(II)的影响以及各种因素对钴(II)、铁(II)萃取、洗涤及反萃的影响. 提出了用叔胺萃取分离钴(II)、铁(II)的最佳工艺参数.     

Studies on Some Biologically Cobalt(II), Copper(II) and Zinc(II) Complexes With ONO, NNO and SNO Donor Pyrazinoylhydrazine-Derived Ligands

Biologically active complexes of Co(II), Ni(II), Cu(II) and Zn(II) with novel ONO, NNO and SNO donor pyrazinoylhydrazine-derived compounds have been prepared and characterized on the basis of analytical data and various physicochemical studies. Distorted octahedral structures for all the complexes have been proposed. The synthesized ligands and their complexes have been screened for their antibacterial activity against bacterial species Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Klebsiella pneumonae. The activity data show the metal complexes to be more active than the parent free ligands against one or more bacterial species.     

以L-谷氨酰胺-锌(II)配合物为供体酶法制备茶氨酸及其反应机理

针对酶法合成茶氨酸中存在的自转肽副反应,合成了L-谷氨酰胺-锌(II)配合物Zn(Gln)2,以其为供体、乙胺为受体、枯草芽孢杆菌B. subtilis GGT为催化剂,酶法制备茶氨酸. 结果表明,Zn(Gln)2在反应主体相稳定性良好,以Zn(Gln)2为供体可有效抑制自转肽副反应;B. subtilis GGT对Zn(Gln)2和Gln的亲和力常数分别为0.53 mmol/L和1.01 mmol/L. 在Zn(Gln)2 6.0 mmol/L、乙胺200 mmol/L及GGT 0.5 U/mL条件下,经37℃反应2 h,茶氨酸浓度最高可达7.38 mmol/L,较以Gln为供体时提高了14.42%.     

The Interaction of Sheep Genomic DNA with a Cobalt(II) Complex Containing p-Nitrobenzoate and N,N′-Diethylnicotinamide Ligands

The synthesized cobalt(II) complex, CoPNBDENA and the binding of this complex with sheep genomic DNA were investigated by UV–Visible absorption and viscosity techniques. Also the interaction of sheep genomic DNA with the complex was studied using the agarose gel electrophoresis method. The results indicated that the complex interacted with DNA. The nature of the binding seemed to be mainly an electrostatic interaction between DNA and the cobalt(II) complex. Other binding modes such as hydrogen bonds may also exist in this system. In this study, after the interaction of DNA–CoPNBDENA, it was observed that the migration of the DNA band became slow as the amount of cobalt(II) complex was increased. This clearly demonstrates that the CoPNBDENA complex neutralizes the negative charges of DNA.     

Mixed‐Ligand Mononuclear Copper(II) Complex: Crystal Structure and Anticancer Activity

A novel copper(II) complex with mixed ligands including β‐[(3‐formyl‐5‐methyl‐2‐hydroxy‐benzylidene)amino]propionic acid anion and 1,10′‐phenanthroline was synthesized, and its crystal structure was thoroughly characterized. It exerted excellent inducing apoptosis, anti‐angiogenesis and antiproliferative properties in vitro. The complex can bind human serum albumin (HSA) at physiological pH conditions. Remarkably, it can induce formation of the mixed parallel/antiparallel G‐quadruplex structures in the G‐rich sequence of the proximal vascular endothelial growth factor (VEGF) promoter, and stabilize these G‐quadruplex structures, which provide an opportunity for anti‐angiogenesis chemotherapeutics. Furthermore, the complex showed a strong uptake, and exhibited multiple anticancer functions by inhibiting the expression of p‐Akt and p‐Erk1/2 proteins and by upregulating the levels of reactive oxygen species (ROS). Because of the reported results, this new copper(II) complex qualifies itself as a potential anticancer drug candidate.     

One-Dimensional Hydrogen-Bonded Infinite Chain from Nickel(II) Tetraaza Macrocyclic Complex and 1,2-Cyclopentanedicarboxylate Ligand

The reaction of [Ni(L)]Cl₂·2H₂O (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,0^1.18,0^7.12]docosane) with trans-1,2-cyclopentanedicarboxylic acid (H₂-cpdc) yields a 1D hydrogen-bonded infinite chain with formula [Ni(L)(H-cpdc⁻)₂] (1). This complex has been characterized by X-ray crystallography, spectroscopy and cyclic voltammetry. The crystal structure of 1 exhibits a distorted octahedral geometry about Ni atom with four nitrogen atoms of the macrocycle and two oxygen atoms of the H-cpdc⁻ ligand at the axial position. Compound 1 crystallizes in the monoclinic system P2₁/c with a = 8.7429(17), b = 10.488(2), c = 18.929(4) Å, β = 91.82(2), V = 1734.8(6) ų, Z = 2. Electronic spectrum of 1 reveals a high-spin octahedral environment. Cyclic voltammetry of 1 undergoes two waves of a one-electron transfer corresponding to Ni^II/Ni^III and Ni^II/Ni^I processes.     

Polarographic Studies of Ni(II) Complex with Tyrosine in aqueous and aqueous-alcoholic media

The complexation behaviour of various metal ions with tyrosine and threonine has been recently investigated in our laboratories [1–2]. However, there is hardly any reference regarding polarographic studies on complex forming ability of tyrosine and hence the present studies were undertaken. This communication deals with detailed investigations on the polarographic behaviour of Ni(II)-tyrosine system in aqueous and mixed solvent media.     

2-Hydroxy-4-Benzamidothiosemicarbazide as a Chelating Reagent. Part I-Studies on its Cobalt(II) and Cobalt(III) Complexes

Three distinct cobalt complexes of 2-hydroxy-4-benzamidothiosemicarbazide, [Co(C₈H₉N₄O₂S) (H₂O)₃] Cl (I), [Co(C₃H₉N₄O₂S) (OH) (H₂ O)₂] (II) and Na [Co(C₈H₉N₄ O₂ S) (OH)₃] H₂ O (III) have been prepared at pH 3.0, 9.0 and 12.5, respectively. Magnetic measurements show subnormal values of the magnetic moment for high-spin octahedral cobaltous complexes. A possible correlation has been sought in nephelauxetic ratio, calculated from electronic spectral data. The values of 10 Dq, L.F.S.E. and Racah's interelectronic repulsion parameters have also been evaluated. The complex (III) is diamagnetic in nature.     

Apparent Polyploidization after Gamma Irradiation: Pitfalls in the Use of Quantitative Polymerase Chain Reaction (qPCR) for the Estimation of Mitochondrial and Nuclear DNA Gene Copy Numbers

Quantitative polymerase chain reaction (qPCR) has been widely used to quantify changes in gene copy numbers after radiation exposure. Here, we show that gamma irradiation ranging from 10 to 100 Gy of cells and cell-free DNA samples significantly affects the measured qPCR yield, due to radiation-induced fragmentation of the DNA template and, therefore, introduces errors into the estimation of gene copy numbers. The radiation-induced DNA fragmentation and, thus, measured qPCR yield varies with temperature not only in living cells, but also in isolated DNA irradiated under cell-free conditions. In summary, the variability in measured qPCR yield from irradiated samples introduces a significant error into the estimation of both mitochondrial and nuclear gene copy numbers and may give spurious evidence for polyploidization.