Optical properties of some new azo photoisomerizable bismaleimide derivatives

Novel polythioetherimides bearing azobenzene moieties were synthesized from azobismaleimides and bis-2-mercaptoethylether. Kinetics of trans-cis photoisomerization and of thermal conversion of cis to trans isomeric forms were investigated in both polymer solution and poly(methyl methacrylate) doped films using electronic absorption spectroscopy. Thermal recovery kinetics is well described by a two-exponential relation both in solution and polymer matrix, while that of low molecular weight azobismaleimide fit a first-order equation. The photoinduced cis-trans isomerization by visible light of azobenzene chromophores was examined in solution and in polymer films. The rate of photoinduced recovery was very high for azobismaleimides.     

Synthesis and Characterization of Novel Quaternary Ammonium Urethane-Dimethacrylate Monomers—A Pilot Study

Six novel urethane-dimethacrylate analogues (QAUDMAs) were synthesized and characterized. They consisted of the 2,4,4,-trimethylhexamethylene diisocyanate (TMDI) core and two methacrylate-terminated wings containing quaternary ammonium groups substituted with alkyl chains of 8, 10, 12, 14, 16, or 18 carbon atoms. QAUDMAs, due to the presence of quaternary ammonium groups, may have possible antibacterial effects. Since they showed satisfactory physicochemical properties, they will be subjected to further research towards the development of dental composites with a capacity to reduce secondary caries. The synthesis of QAUDMAs included three stages: (i) transesterification of methyl methacrylate (MMA) with N-methyldiethanolamine (MDEA), (ii) N-alkylation of the tertiary amino group with alkyl bromide, and (iii) addition of TMDI to the intermediate achieved in the second stage. The formation of QAUDMAs was confirmed by ¹H and ¹³C NMR. They were characterized for density (d_m), viscosity (η), refractive index (RI), glass transition temperature (T_g), polymerization shrinkage (S), and degree of conversion (DC). QAUDMAs were yellow, viscous resins (the η values ranged from 1.28 × 10³ to 1.39 × 10⁴ Pa·s, at 50 °C). Their RI ranged from 1.50 to 1.52, T_g from −31 to −15 °C, DC from 53 to 78%, and S from 1.24 to 2.99%, which is appropriate for dental applications.     

新型四唑并[1,5-a]哌嗪类螺环化合物的合成研究

以取代苄胺、1-叔丁氧羰基-4-哌啶酮、叠氮基三甲基硅烷(TMSN3)和异腈化合物为原料,经4组分“一锅煮”反应,得到新型四唑并[1,5-a]哌嗪类螺环化合物.研究了温度和溶剂对反应的影响,得到最佳反应条件:以甲醇为溶剂,65℃回流条件下反应48 h.所有产物结构经1HNMR和MS进行表征.     

新型非对称聚酰亚胺的合成与性能研究

通过对4,4’-双(N-甲基联苯酰亚胺)的单硝化反应、亲核取代反应、水解反应和闭环脱水反应,成功合成了2-邻甲基苯氧基4,4’,5,5’-联苯四甲酸二酐。将这种新型非对称酸酐与4,4’-二氨基二苯醚和对苯二胺进行高温聚合反应制得了非对称聚酰亚胺。聚酰亚胺的特性黏度分别为0.55dL/g和0.89dL/g,它们在有机溶剂中的溶解性能较好,同时具有优良的热稳定性和热氧稳定性。     

Novel Strategy for Anhydride-Functionalization of Poly(Vinyl Chloride): Synthesis and Characterization

A new strategy for anhydride-functionalization of poly(vinyl chloride) is suggested. First, some chlorine groups of poly(vinyl chloride) were converted to phenylamine-oxy groups by a nucleophilic substitution reaction in the presence of a solvent composed of 4-aminophenol, K₂CO₃, and dry N,N-dimethylformamide at room temperature, to avoid cross-linking. The phenylamine-functionalized poly(vinyl chloride) was further reacted with maleic and 1,2,4-benzenetricarboxylic acid anhydrides. The chemical structures of all samples as representatives were characterized by Fourier transform infrared and nuclear magnetic resonance spectroscopies. The chemical compositions of the synthesized anhydride-functionalized poly(vinyl chloride) were investigated by elemental analysis, and their thermal behaviors were characterized by means of differential scanning calorimetry and thermogravimetric analyzer.     

新型催化材料氮化钼的批量制备与结构表征

环境法规关于硫、氮含量的严格规定要求对燃料进行深度脱硫脱氮,氮化钼作为一种催化材料具有良好的脱硫脱氮活性和较高的选择性。但其制备条件苛刻,为加快其应用进程,采用溶胶—凝胶法制备了负载型氮化钼的前驱体,采用流化床反应器、三级脱水、循环未反应氮化剂的流化氮化新工艺实现了氮化钼的批量合成。采用正交实验的方法确定了最优氮化条件:空速7 000 h-1、H2/N2为4、升温速率为1.2℃/min、氮化终温为650℃,活性组分含量为10%。并采用BET、XRD、SEM等对制备的氮化钼及其前驱体进行了结构表征。     

Oxo-Titanium(IV) Complex/Polymer Composites—Synthesis,Spectroscopic Characterization and Antimicrobial Activity Test

The emergence of a large number of bacterial strains resistant to many drugs or disinfectants currently used contributed to the search of new, more effective antimicrobial agents. In the presented paper, we assessed the microbiocidal activity of tri- and tetranuclear oxo-titanium(IV) complexes (TOCs), which were dispersed in the poly(methyl methacrylate) (PMMA) matrix. The TOCs were synthesized in reaction to Ti(OR)₄ (R = ⁱPr, ⁱBu) and HO₂CR’ (R’ = 4-PhNH₂ and 4-PhOH) in a 4:1 molar ratio at room temperature and in Ar atmosphere. The structure of isolated oxo-complexes was confirmed by IR and Raman spectroscopy and mass spectrometry. The antimicrobial activity of the produced composites (PMMA + TOCs) was estimated against Gram-positive (Staphylococcus aureus ATCC 6538 and S. aureus ATCC 25923) and Gram-negative (Escherichia coli ATCC 8739 and E. coli ATCC 25922) bacteria and yeasts of Candida albicans ATCC 10231. All produced composites showed biocidal activity against the bacteria. Composites containing {Ti₄O₂} cores and the {Ti₃O} core stabilized by the 4-hydroxybenzoic ligand showed also high activity against yeasts. The results of investigations carried out suggest that produced (PMMA + TOCs) composites, due to their microbiocidal activity, could find an application in the elimination of microbial contaminations in various fields of our lives.     

Synthesis,Characterization and Material Application of Novel Polyimide

Novel polyimide-II containing 8-hydroxyquinoline as pendent groups was prepared by reacting N,N′-(1,1′-biphenyl)-4,4′-diyl bismaleimide--diamine polyimide-I (BPBMDDM) with 5-chloromethyl-8-hydroxyquinoline hydrochloride (CMHQ) in the presence of base catalyst. N,N′-(1,1′-biphenyl)-4,4′-diyl bismaleimide--diamine polyimide-I (BPBMDDM) was prepared by Michael addition reaction of N,N′-(1,1′-biphenyl)-4,4′-diyl bismaleimide (BPBM) with 4,4′-diaminodiphenyl methane (DDM). The resulting polyimide-II (BPBMDDMCMHQ) was characterized by spectral techniques. Polymeric metal chelates of polyimide-II were prepared using the transition metal ions Zn(II), Cu(II), Ni(II), Co(II), and Mn(II), and were characterized. Ion-exchange properties of polyimide-II (BPBMDDMCMHQ) for Fe(III), Zn(II), Ni(II) and Cu(II) metal ions were also studied by batch-equilibration method. The polyimide-II (BPBMDDMCMHQ) has good metal uptake capacity at varying pH range and can be recycled. It has thermal stability up to 240°C.     

Synthesis and Characterization of Novel Polyurethane Composites Based on Hybrid Inorganic/Organic Phosphazene‐Containing Microspheres

Novel polyurethane (PU) composites were prepared, based on hybrid inorganic/organic phosphazene‐containing microspheres. The FT‐IR spectra have shown that the microspheres have been linked with PU matrix. The microstructure of the composites is investigated by SEM. In comparison with PU, the glass transition temperatures and thermal stability of the composites are increased. The results from tensile testing of the composites have indicated that tensile strength is improved and elongation at break is almost invariable. The investigation on the surface properties of the composites showed that the water contact angles are obviously increased by adding 2 and 4 wt.‐% microspheres to the matrix.

     

Synthesis and Characterization of Novel Polymeric-Schiff Bases and Their Complexes

An investigation of the solid state conductivity of polymeric-Schiff bases derived from the condensation reaction of polyacrylamide and an aldehyde (4-methoxybenzaldehyde and 4-chlorbenzaldehyde) has been carried out and Co(II) and Ni(II) complexes have been prepared. Polymeric-Schiff bases and their metal complexes were characterized by molar conductance, magnetic susceptibility, and electronic and IR spectral studies. Conductivity measurements were carried out at 20 °C in dimethylformamide to determine the electrolytic behavior. The ¹H-NMR and ¹³C-NMR spectra, elemental analysis, and viscosity average molecular mass (M _v) of the polymeric-Schiff bases and their complexes were determined. All of the polymer–metal complexes showed high thermally stability. The DC conductivities of the solid samples were measured using a four-probe technique.     

Novel Cationic RAFT‐Mediated Polystyrene/Clay Nanocomposites: Synthesis,Characterization, and Thermal Stability

Two novel cationic RAFT agents, PCDBAB and DCTBAB, were anchored onto MMT clay to yield RAFT‐MMT clays. The RAFT‐MMT clays were then dispersed in styrene where thermal self‐initiation polymerization of styrene to give rise to exfoliated PS/clay nanocomposites occurred. The RAFT agents anchored onto the clay layers successfully controlled the polymerization process resulting in controlled molecular masses and narrow polydispersity indices. The nanocomposites prepared showed enhanced thermal stability, which was a function of the clay loading, clay morphology, and slightly on molecular mass.

     

New anthracene‐containing phenylene‐ or thienylene‐vinylene copolymers: Synthesis,characterization, photophysics,and photovoltaics

Four new conjugated alternating vinylene‐copolymers, PAP6 , PAT , PA , and TAT , incorporating anthracene rings along the backbone were synthesized by Heck coupling. They were very soluble in common organic solvents and absorbed at the range of 300–500 nm with optical band gaps of 2.38–2.47 eV. They behaved in solution as green emitters, with maximum photoluminescence at 455–518 nm. Finally, these soluble copolymers were used as donor material to realize bulk heterojunction solar cell with (6,6)‐C₆₁‐butyric acid methyl ester as the acceptor. More efficient photovoltaic cells were obtained from the copolymer that carried hexyloxy than dodecyloxy side groups. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Cancer Stem Cells in Ovarian Cancer—A Source of Tumor Success and a Challenging Target for Novel Therapies

Ovarian cancer is the most lethal neoplasm of the female genital organs. Despite indisputable progress in the treatment of ovarian cancer, the problems of chemo-resistance and recurrent disease are the main obstacles for successful therapy. One of the main reasons for this is the presence of a specific cell population of cancer stem cells. The aim of this review is to show the most contemporary knowledge concerning the biology of ovarian cancer stem cells (OCSCs) and their impact on chemo-resistance and prognosis in ovarian cancer patients, as well as to present the treatment options targeted exclusively on the OCSCs. The review presents data concerning the role of cancer stem cells in general and then concentrates on OCSCs. The surface and intracellular OCSCs markers and their meaning both for cancer biology and clinical prognosis, signaling pathways specifically activated in OCSCs, the genetic and epigenetic regulation of OCSCs function including the recent studies on the non-coding RNA regulation, cooperation between OCSCs and the tumor microenvironment (ovarian cancer niche) including very specific environment such as ascites fluid, the role of shear stress, autophagy and metabolic changes for the function of OCSCs, and finally mechanisms of OCSCs escape from immune surveillance, are described and discussed extensively. The possibilities of anti-OCSCs therapy both in experimental settings and in clinical trials are presented, including the recent II phase clinical trials and immunotherapy. OCSCs are a unique population of cancer cells showing a great plasticity, self-renewal potential and resistance against anti-cancer treatment. They are responsible for the progression and recurrence of the tumor. Several completed and ongoing clinical trials have tested different anti-OCSCs drugs which, however, have shown unsatisfactory efficacy in most cases. We propose a novel approach to ovarian cancer diagnosis and therapy.     

Ag Nanoparticles for Biomedical Applications—Synthesis and Characterization—A Review

Silver nanoparticles have been intensively studied over a long period of time because they exhibit antibacterial properties in infection treatments, wound healing, or drug delivery systems. The advantages that silver nanoparticles offer regarding the functionalization confer prolonged stability and make them suitable for biomedical applications. Apart from functionalization, silver nanoparticles exhibit various shapes and sizes depending on the conditions used through their fabrications and depending on their final purpose. This paper presents a review of silver nanoparticles with respect to synthesis procedures, including the polluting green synthesis. Currently, the most commonly used characterization techniques required for nanoparticles investigation in antibacterial treatments are described briefly, since silver nanoparticles possess differences in their structure or morphology.     

Novel porphyrin‐grafted poly(phenylene vinylene) derivatives: Synthesis and photovoltaic properties

A series of novel porphyrin‐grafted poly (phenylene vinylene) derivatives, Porp‐RO‐PPV, were synthesized by a simple two‐step method. These copolymers contain conjugated poly(phenylene vinylene) derivatives as polymer backbone and covalently linked porphyrin units as side chain, which were confirmed by FTIR and ¹H NMR, and used for photovoltaic devices. The thermal, optical properties and sensitizing effect, and photovoltaic properties have been investigated. The emission spectra of Porp‐RO‐PPV copolymers revealed the existence of strong energy transfer from PPV backbone to porphyrin units. The energy conversion efficiency (η_e) of photovoltaic devices based on Porp‐RO‐PPV+PCBM reached 0.33% (78.2 mW/cm², AM1.5) and porphyrin units in the copolymers showed good sensitizing effect at low concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and Characterization of Novel Colored Polyurethanes

ABSTRACT

Azo disperse dyes containing N, N-diethylol group have been prepared and each dye was polycondensed with 4,4′ -Diphenyl methane diisocyanate. The resultant colored polyurethanes were characterized by nitrogen content, IR spectral studies, number average molecular weight ([Mbar]n), estimated by conductometric titration, and thermogravimetry. The electrical conductivity of all the polyurethanes was measured at room temperature.     

新型环氧聚氨酯的合成与表征

聚氮酯是一类性能优异的高分子材料,利用聚氨酯对环氧树脂进行改性,可以形成各种性能优良的材料。本文以常见的甲苯二异氰酸酯（TDI）和环氧氯丙烷（EPH）为起始原料,首先通过阳离子开环聚合合成出中间产物（Ⅰ）聚环氧氯丙烷二醇（PECH）,然后用PECH封端TDI,制备出端基为氯醇基团的中间产物（Ⅱ）,最后在碱性条件下进行关环,合成出端基为环氧基团、分子中具有氨基甲酸酯结构的环氧封端聚氨酯-环氧氨酯（EPU）。中间产物和目标产物的结构经红外光谱法和端基滴定分析来确定。环氧氨酯作为增韧剂对环氧树脂的增韧改性将另行讨论。     

新型含氟聚醚酰亚胺的合成与表征

利用对苯二酚、2-氯-5-硝基三氟甲苯合成得到1,4-双(2-三氟甲基-4-硝基苯氧基)苯,再在钯/炭、水合肼和有机溶剂的作用下,合成得到了1,4-双(2-三氟甲基-4-氨基苯氧基)苯,并对其性能进行了表征,包括其本身的熔点、红外吸收特征等。合成得到的1,4-双(2-三氟甲基-4-氨基苯氧基)苯与4,4'-二氨基二苯醚、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐反应,制得了含氟聚醚酰亚胺,并对其性能进行了表征。     

Synthesis,Characterization and Properties of Novel Poly(urethane‐imide) Networks as Electrical Insulators with Improved Thermal Stability

Summary: A new series of thermoplastic poly(urethane‐imide)s (TPUI1‐4) containing hydroxyl groups in the backbone was synthesized from the reaction of epoxy‐terminated polyurethane prepolymers (EPU1‐4) and an imide containing diacid (DIDA) chain extender under optimized reaction conditions. EPU1‐4 was prepared through end‐functionalization of NCO‐terminated polyurethanes based on polyester polyol (CAPA) and hexamethylene diisocyanate with glycidol. A blocked isocyanate (BIC) was made from the reaction of trimethylol propane (TMP), toluene diisocyanate (TDI) and N‐methylaniline (NMA). Polymer networks were prepared from the reaction of librated isocyanate groups of BIC with hydroxyl groups of TPUIs. The starting materials and polymers were characterized by conventional spectroscopic methods and the physical, thermal and electrical properties of crosslinked networks were studied. Investigation of the recorded properties for these samples showed considerable improvement in thermal and electrical properties in comparison to common polyurethanes.

Synthetic route for preparation of TPUIs.