Solubility In Most Organic Solvents Research Articles

Furanocoumarins as Enhancers of Antitumor Potential of Sorafenib and LY294002 toward Human Glioma Cells In Vitro.

Furanocoumarins are naturally occurring compounds in the plant world, characterized by low molecular weight, simple chemical structure, and high solubility in most organic solvents. Additionally, they have a broad spectrum of activity, and their properties depend on the location and type of attached substituents. Therefore, the aim of our study was to investigate the anticancer activity of furanocoumarins (imperatorin, isoimperatorin, bergapten, and xanthotoxin) in relation to human glioblastoma multiforme (T98G) and anaplastic astrocytoma (MOGGCCM) cell lines. The tested compounds were used for the first time in combination with LY294002 (PI3K inhibitor) and sorafenib (Raf inhibitor). Apoptosis, autophagy, and necrosis were identified microscopically after straining with Hoechst 33342, acridine orange, and propidium iodide, respectively. The levels of caspase 3 and Beclin 1 were estimated by immunoblotting and for the blocking of Raf and PI3K kinases, the transfection with specific siRNA was used. The scratch test was used to assess the migration potential of glioma cells. Our studies showed that the anticancer activity of furanocoumarins strictly depended on the presence, type, and location of substituents. The obtained results suggest that achieving higher pro-apoptotic activity is determined by the presence of an isoprenyl moiety at the C8 position of the coumarin skeleton. In both anaplastic astrocytoma and glioblastoma, imperatorin was the most effective in induction apoptosis. Furthermore, the usage of imperatorin, alone and in combination with sorafenib or LY294002, decreased the migratory potential of MOGGCCM and T98G cells.

Tropolone-Conjugated DNA: A Fluorescent Thymidine Analogue Exhibits Solvatochromism, Enzymatic Incorporation into DNA and HeLa Cell Internalization.

Tropolone is a non-benzenoid aromatic scaffold with unique photophysical and metal-chelating properties. Recently, it has been conjugated with DNA, and the photophysical properties of this conjugate have been explored. Tropolonyl-deoxyuridine (tr-dU) is a synthetic fluorescent DNA nucleoside analogue that exhibits pH-dependent emissions. However, its solvent-dependent fluorescence properties are unexplored owing to its poor solubility in most organic solvents. It would be interesting to incorporate it into DNA primer enzymatically. This report describes the solvent-dependent fluorescence properties of the silyl-derivative, and enzymatic incorporation of its triphosphate analogue. For practical use, its cell-internalization and cytotoxicity are also explored. tr-dU nucleoside was found to be a potential analogue to design DNA probes and can be explored for various therapeutic applications in the future.

New metallophthalocyanines including benzylphenoxy groups and investigation of their organic-field effect transistor (OFET) features

In this study, metal and metal-free novel phthalocyanines containing peripheral and non-peripheral tetra 2-benzylphenoxy groups were synthesized. The compounds were characterized by UV–Vis, FT-IR, 1H NMR, and MALDI-TOF mass spectrometry as well as elemental analysis. These new phthalocyanines exhibited excellent solubility in most organic solvents, and their redox behavior was investigated in different solvents such as dimethyl sulfoxide (DMSO) and dichloromethane (DCM). The redox behavior of the peripheral and non-peripheral phthalocyanine compounds 1a-c and 2a-c was determined by cyclic voltammetry and in situ spectroelectrochemistry. According to organic field-effect transistors (OFETs) measurements, the peripheral and non-peripheral phthalocyanine-cobalt complexes which have higher mobility than others were utilized top-gate bottom-contact OFETs fabrication. The output characteristics of the device show that its mobility is approximately 5 × 10−2 cm2/Vs with p-type accumulation.

Synthesis and characterization of a novel organo-soluble polyimide containing hydroxyl and bis-tert-butyl substituted triphenylpyridine units

A new diamine containing hydroxyl and bis-tert-butyl substituted triphenylpyridine units was synthesized and used in the synthesis of polyimides (PIs) via a one-step polymerization. The diamine and PIs were characterized by FTIR and 1H-NMR. The aggregated structure of PIs was amorphous by wide angle X-ray diffraction test and all of them exhibited excellent solubility in most organic solvents. The bis-tert-butyl and triphenylpyridine units endowed PIs excellent thermal stability with 10% weight loss temperatures in the range 493–525 °C and high glass transition temperature in the range 301–344 °C, while the existence of hydroxyl groups provided the possibility for further modification of polymer. The PI membranes had excellent mechanical properties with tensile strength in the range 65–93 MPa. The density of PIs was lower with density in the range 1.266–1.289 g/cm3. It was foreseeable that PIs will greatly promote the applications of heat-resistant and lightweight PI materials in the future.

Synthesis of a conjugated polymer for sensing ferric/ferrous cations based on dual responses

AbstractA conjugated polymer (PPETE‐RB) with poly[p‐(phenylene ethynylene)‐alt‐(thienylene‐ethynylene)] (PPETE) as the backbone with pendant rhodamine B (RB) groups in the close‐ring spirolactam form was synthesized. With long spacer between backbone and pedant groups as well as long solubilizing side chains, the polymer possesses good solubility in most organic solvents and relatively large molecular weight. The fluorescence of the conjugated polymer in THF exhibited selective dual responses upon adding Fe3+/Fe2+ but negligible response upon other cations. The emission around 481 nm (excited at 360 nm) decreased and that around 571 nm (excited at 520 nm) emerged and increased when increasing the concentration of iron ions. The responses to Fe3+ and Fe2+ are very similar. The limits of detection were found to fall in between 6 μM and 8 μM. The mechanism study showed that the quenching around 481 nm was due to the inner filter effect (IFE) between the Fe3+/Fe2+ and PPETE‐RB; while that enhancement around 571 nm could be attributed to the formation of fluorescent ring‐open structure from nonfluorescent spirolactam of pedant RB group upon Fe3+/Fe2+. Such dual and opposite responses provided more reliable information than single response for sensing applications.

Thioxanthone-based amidine: An efficient nonionic photobase generator for thiol-based click polymerization under visible LED light

With the fast development of the long-wavelength irradiation sources, such as light emitting diodes (LED), which possess advantages regarding irradiation safety and energy utilization efficiency, it is highly desired to develop efficient photobase generators (PBGs) sensitive to visible light. Currently, the reported efficient visible light PBGs mainly undergo photodecarboxylation to generate the super bases, while the released CO2 can potentially cause bubbles and cracks in the cured materials. Moreover, these ionic PBGs generally have poor solubility in organic media and limited thermal stability. In the present work, we have investigated a nonionic amidine PBG TX-DBN, which contains thioxanthone as a chromophore and a reduced form of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) as a latent base species. TX-DBN, with a strong absorption above 380 nm, showed excellent solubility in most organic solvents and commercial monomers/oligomers. Under irradiation with an LED lamp at 405 nm, TX-DBN undergoes a CN bond cleavage followed by a fast hydrogen transfer, leading to the generation of the super base DBN without the generation of CO2. The as-released active species, namely super bases and active free radicals, can trigger thiol-epoxy and thiol-ene polymerization to fabricate hybrid network.

Synthesis, Characterization and Antibacterial Assay of Some Schiff Base Metal (II) Complexes

The complexes of Co (II), Mn (II) and Ni (II) with Schiff base derived from pentane-2, 4-dione and 2-aminobenzoic acid were synthesized and characterized by molar conductivity, magnetic susceptibility, Infrared and elemental analyses. The solubility test on the Schiff base and its metal (II) complexes revealed their solubility in most organic solvents except chloroform and diethyl ether. The molar conductivity of the complexes was small indicating that they are non-electrolytes. The antibacterial susceptibility test conducted on the Schiff base and the metal (II) complexes showed a good activity except Ni (II) complex.

Colorless Semi-Alicyclic Copolyimides with High Thermal Stability and Solubility.

A series of colorless copolyimide films with high thermal stability and good solubility are synthesized from (trifluoromethyl)biphenyl-4,4’-diamine (TFMB) with different 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA) to 2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane (6FDA) dianhydride mole ratios through one-pot solution polycondensation. These copolyimide films exhibit excellent optical transparency (T400 > 90% and λ0 ~305–333 nm) with a thickness of 15 μm and good solubility in most organic solvents. The excellent optical properties are mainly attributed to the low inter- and intra-molecular charge transfer interactions due to the alicyclic structure and the strong electronegative CF3 groups. The glass transition temperature increases from 332 to 352 °C with increasing HPMDA content in the copolymers, while the thermal decomposition temperature is improved with increasing 6FDA content. These results indicate that the copolyimide films can be successfully utilized in the development of novel heat-resistant plastic substrates for the optoelectronic engineering applications.

Chemical modification: Toward solubility and processability of graphdiyne

The perfect properties of graphdiyne (GDY) make it a good candidate for application in multi-fields such as energy storage and conversion, catalyst. However, the poor solubility and processability of GDY is main problem to limit its high level application in electronic devices. Chemical modification provides effective solutions to resolve the above issues. Herein, we report the application of the Huisgen cycloaddition to the functionalization of GDY with alkyl azide for synthesizing soluble and processable GDY. Three kinds of alkyl azide (CH3(CH2)16CH2N3, CH3(CH2)10CH2N3 and CH3(CH2)4CH2N3) were used to prepare the modified graphdiyne. And the resultant graphdiynes show excellent solubility in most organic solvents. The enhanced conductivity of GDY-Tz-CH2(CH2)16CH3 reveals that the functionalization of graphdiyne maintains both the structural integrity and the property of graphdiyne. The good solubility of GDY-Tz-CH2(CH2)16CH3 enables it easily processable application in the planar heterojunction (PHJ) perovskite solar cells serving as electron transport layer. The solar cells exhibit an increase of PCE from 16.24% to 19.26% and the Jsc increasing from 20.85 mA cm−2 to 23.7 mA cm−2. This cost-effective, simple, and scalable strategy for the synthesis of soluble and processable GDY presents a feasible way to expedite the development of GDY-based materials.

Dodecabromo- and Dodecaiodocentrohexaindane: Td -Symmetrical Key Building Blocks for Twelve-Fold Cross-Coupling Reactions and Six-Fold Orthogonal Extension.

Centrohexaindane was converted into its Td -symmetrical 2,3,6,7,10,11,14,15,20,21,26,27-dodecabromo and -dodecaiodo derivatives using N-bromo- and N-iodosuccinimide, respectively, in the presence of trifluoromethanesulfonic acid as a catalyst in single, highly efficient steps. Sonication or microwave irradiation was indispensable to enforce exhaustive halogenation of the twelve equivalent peripheral positions of this Cartesian polyaromatic hydrocarbon. Despite their extremely poor solubility in most organic solvents, the new dodecahalo derivatives were fully characterized, including single crystal X-ray structure analysis. Subsequent Pd0 -catalyzed twelve-fold C-C cross-coupling reactions furnished the corresponding dodecamethyl, dodeca(phenylethynyl) and dodecaphenyl derivatives in good to excellent yields. The latter hydrocarbon was also analyzed by X-ray diffraction.

Analysis of wax esters in seven commercial waxes using C30 reverse phase HPLC

Commercial waxes are difficult to analyze due to their limited solubility in most organic solvents. Recently, our laboratory published a new reverse phase HPLC-MS method using a C30 column, a gradient of methanol and chloroform, an evaporative light-scattering detector (ELSD), and atmospheric pressure chemical ionization mass spectrometry (APCI-MS) to analyze jojoba wax (jojoba oil), carnauba wax, and sorghum wax. In the current study, the published HPLC method was modified by reducing the solvent gradient program to 60 minutes and this new method was evaluated for its usefulness for the analysis of five other commercial waxes (beeswax, rice bran, sunflower, candelilla and paraffin waxes). The ELSD appeared to detect all types of wax components, whereas the APCI-MS was most useful for the identification of wax esters and was unable to detect hydrocarbons, such as those in candelilla wax and paraffin wax. Previous HPLC methods for waxes and most GC methods for waxes only separate wax esters with size up to 54 carbons (C54) but this method was able to separate those with size up to 60 carbon wax esters. This report presents the first HPLC chromatograms for rice bran, sunflower, candelilla, and paraffin waxes. The main contribution of this work is the evidence that a C30 reverse phase HPLC system provides acceptable chromatographic separation of major components in commercial waxes.

Synthesis of Polyquinolines via One-Pot Polymerization of Alkyne, Aldehyde, and Aniline under Metal-Free Catalysis and Their Properties

A novel synthetic route to polyquinolines with 6-substituted quinoline as the structural unit was developed based on the polymerization of alkyne–aldehyde monomers and aniline derivatives under the catalysis of Lewis acid B(C6F5)3. The polymerization was conducted in dichloroethane at 100 °C for 36 h under air atmosphere, affording polyquinolines with molecular weights up to 13 100 and good solubility in most organic solvents. The substituents in aniline exhibited significant effects on the molecular weight, yield, and solubility of the produced polyquinolines. The structures of prepared polymers were characterized and confirmed by GPC, NMR, and FT-IR. The thermogravimetry (TGA) and differential scanning calorimetry (DSC) analysis suggests that the polyquinolines are highly thermal stable. Further photoluminescence behaviors of the prepared polyquinolines were investigated. Based on the characterization results and small molecule reaction mechanism, the polymerization pathway of the polyquinolines was pro...

Synthesis and Characterization of Isotactic Poly(1-hexene)/Branched Polyethylene Multiblock Copolymer via Chain Shuttling Polymerization Technique

Understanding from the underlying mechanism of chain shuttling polymerization (CSP) is limited due to scarceness of successful reports and incompetence of traditional characterization techniques to distinguish blocky structures. Here, a simple synthesis approach for production of an isotactic poly(1-hexene)/branched polyethylene multiblock copolymer from a 1-hexene monomer is presented. Resulting copolymers can be easily characterized because of their solubility in most organic solvents. This novel blocky architecture is synthesized using ansa-ethylenebis(1-η5-indenyl)zirconium dichloride and α-diimine nickel(II) bromide catalysts. While the former participates in 1,2-enchainment of monomers and produces amorphous segments, the latter forms methylene sequences through chain walking reaction. A quasi-living polymerization is established by reversible transfer of growing chains between catalyst components, as manifested by narrowing molecular weight distribution. 13C NMR analysis confirms that the blocky st...

Zinc(II) and chloroindium(III) phthalocyanines bearing ethyl 7-oxy-6-chloro-4-methylcoumarin-3-propanoate groups: Synthesis, characterization and investigation of their photophysicochemical properties

In this study, ethyl 7-hydroxy-6-chloro-4-methylcoumarin-3-propanoate (1), ethyl 7-(2,3-dicyanophenoxy)-6-chloro-4-methylcoumarin-3-propanoate (2), ethyl 7-(3,4-dicyanophenoxy)-6-chloro-4-methylcoumarin-3-propanoate (3), ethyl 4-chloro-5-(7-oxy-6-chloro-4-methylcoumarin-3-propanoate)phthalonitrile (4) were synthesized. The phthalonitrile derivatives (2, 3 and 4) were converted to their peripheral tetra, non-peripheral tetra and peripheral chlorocta substituted zinc(II) and chloroindium phthalocyanine derivatives. All novel compounds were characterized by elemental analysis, FT-IR, [Formula: see text]H-NMR, MALDI-TOF mass spectrometry and UV-vis spectral data. Additionally, the spectral, photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of the resulting substituted phthalocyaninatozinc(II) and indium(III) chloride complexes (5–10) were investigated in DMF, and the obtained results were compared for determination of the effects of the substituents’ positions and the variety of the central metal atom on these properties. The fluorescence quenching behavior of these phthalocyanines (5–10) were also investigated using 1,4-benzoquinone as a quencher. The obtained ethyl 7-oxy-6-chloro-4-methylcoumarin-3-propanoate bearing phthalocyaninatozinc(II) (5, 7 and 9) and indium(III) chloride (6, 8 and 10) complexes showed excellent solubility in most organic solvents. They produced high singlet-oxygen and showed appropriate photodegradation which is very important for photodynamic therapy applications.

Lanthanide Fluorobenzoates as Bio-Probes: a Quest for the Optimal Ligand Fluorination Degree.

The thorough study of fluorinated benzoates of lanthanides (Eu, Tb, Nd, Er, Yb, Gd, La, Lu) is reported. Their composition in single crystal and powder state revealed two predominant structural motifs. An in-depth luminescence study has been performed on the reported fluorobenzoates, showing, that terbium and europium complexes in solid state possess high luminescence intensity with the quantum yield of up to 69 %. High solubility in most organic solvents, as well as in water, combined with the high luminescence intensity in water solution and non-toxicity allowed the testing of europium complexes as bioprobes in cellulo. Among all tested fluorobenzoates, europium 2-fluorobenzoate dihydrate combined the best luminescent properties, thermodynamic stability, aqueous solubility, and non-toxicity, and was shown to be a viable bio-marker.

Grid-type complexes of M2+ (M = Co, Ni, and Zn) with highly soluble bis(hydrazone)thiopyrimidine-based ligands: Spectroscopy and electrochemical properties

Herein we present the syntheses of two types of two-site symmetric bis(hydrazone) ligands (1 and 2) which contain two tridentate subunits suitable for metal ion complexation, with remarkable solubility in most organic solvents, contrary to other pyrimidine-based bis(hydrazones) used for the preparation of metallogrids. As expected, compounds 1 and 2 exhibit conformational changes when coordinated metal ions (Zn2+, Ni2+, Co2+) through the two terpyridine-like sites leading to the metal complexes 1a–c and 2a–c. The absorption spectra and redox properties of ligands 1 and 2 and of the metal complexes 1a–c and 2a–c were studied. Compounds 1 and 2 exhibit absorption spectra dominated by intense π–π∗ bands in the UV region, while the absorption spectra of the metal complexes 1a–c and 2a–c show intense bands in the UV region, due to the spin-allowed ligand-centred (LC) transitions, and in the visible region, due to spin-allowed metal-to-ligand charge transfer (MLCT) transitions. Cyclic voltammetry and square wave voltammetry were carried out in order to establish the relevance of the complexation, and the grid formation in the redox potentials of the ligands 1 and 2.

Poly(ionic liquid)-based polyurethanes having imidazolium, ammonium, morpholinium or pyrrolidinium cations

The synthesis of cationic polyelectrolytes based on condensation-derived backbone is rarely performed due to the difficulty obtaining of the respective ionic monomers in high purity. Despite such an approach is favorable as it results in ionic polymers with well-defined chemical structure and ionic group distribution. In this work two efficient methods are presented for the synthesis of ionic diols in high purity, namely the technique with pyranyl protection of OH-groups and the direct quaternization of tertiary amine alcohols. Applying these methods five novel ionic diols bearing various cations, namely, 1,1-bis(2-hydroxyethyl)pyrrolidin-1-ium bromide, 4,4-bis(2-hydroxyethyl)morpholin-4-ium bromide, N, N-bis(2-hydroxyethyl)-N-methylethanammonium, 1,1′-(pentane-1,5-diyl)bis(1-(2-hydroxyethyl)pyrrolidin-1-ium) dibromide, and 3-(2-hydroxyethyl)-1-(5-(3-(3-hydroxypropyl)-1H-imidazol-3-ium-1-yl)pentyl)-1H-imidazol-3-ium dibromide, were synthesized in high purity and high yields. The tin(II) mediated solution polycondensation of ionic diols with commercial hexamethylene diisocyanate or 4,4′-methylenebis(cyclohexyl isocyanate) resulted in a series of ionic, high molecular weight ( Mw = 2.3 × 104 −8.0 × 104) polyurethanes (PUs). The influence of various reaction parameters including reaction temperature and time, catalyst concentration and solvent nature upon PUs molecular weight was investigated. After the exchange of bromide to (CF3SO2)2N- anion the obtained poly(ionic liquid)s exhibit high thermal stability with onset mass loss above 225°C and demonstrate glass transition temperatures in the wide range from −22°C to 76°C depending on the nature of ionic diol used. Ionic PUs present excellent solubility in most organic solvents and are capable to form tough, flexible films with tensile strength up to 29.7 MPa.

Synthesis, Characterization and Reactivity of Iodosylbenzene Nanoparticles as a New Nano–reagent

AbstractIodosylbenzene (PhIO) and its derivatives are efficient terminal oxidants that have gained considerable attention. However, it suffers from limited solubility in most organic solvents and water. In the present study, the nanoparticles of iodosylbenzene has been synthesized with the aim of enhancing solubility in different solvents and its reactivity in oxidation reactions without any change in its chemical composition. Controlled alkaline hydrolysis of iodobenzene diacetate in the presence of (triethyleneglycol)monomethyl ether as stabilizer produced the nanoparticles. The average radius of the nanostructures determined by dynamic light scattering (DLS) and atomic force microscopy (AFM), was 149 and 71 nm, respectively. Also, the maximum height of nanoparticles measured from AFM images was 16 nm. Furthermore, scanning electron microscopy‐energy dispersive X‐ray analysis (SEM‐EDX) confirmed the formation of non‐spherical iodosylbenzene nanoparticles. The results of 1H and 13C NMR studies in DMSO‐d6 are in accord with the existence of different oligomeric iodosylbenzene particles in solution. This observation was also confirmed by the superimposed FT‐IR spectra of the bulk and nano‐sized products. Non‐catalytic oxidation of 1,5‐naphthalenediol to juglone with the bulk and nano‐sized oxidants, also the oxidation of styrene in the absence and presence of meso‐tetraphenylporphyrinatomanganese(III) acetate, confirmed the increased oxidizing ability of the nano‐sized oxidant.

Synthesis and characterization of organosoluble, transparent, and hydrophobic fluorinated polyimides derived from 3,3′-diisopropyl-4,4′-diaminodiphenyl-4′′-trifluoromethyltoluene

A novel aromatic fluorinated diamine monomer, 3,3′-diisopropyl-4,4′-diaminodiphenyl-4′′-trifluoromethyltoluene, was synthesized by coupling of 2-isopropylaniline and 4-(trifluoromethyl)benzaldehyde and its structure was confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance, elemental analysis, and mass spectrometry, and then used to prepare a series of fluorinated polyimides (FPIs) by polycondensation reaction with various commercial dianhydrides via conventional one-step method. The obtained FPIs present excellent solubility in most organic solvents and enough to cast into tough and flexible films. All the FPI films show good optical transparency and light color with the cutoff wavelengths in range of 307–362 nm and the average transmittance above 86%. These polymer films also exhibit high glass transition temperature in range of 261–331°C and thermal stability with 10% weigh loss above 463°C under nitrogen atmosphere. Furthermore, they exhibit outstanding mechanical properties with tensile strengths of 65.9–94.3 MPa, elongation at break of 11.4–13.8%, Young’s modulus of 1.6–1.9 GPa, and low dielectric constants in range of 2.75–3.10 at 1 MHz as well as prominent hydrophobicity with the contact angle in the range of 87.3–93.9°.

Structural and electrical characterization of spin-coated polyurea thin films

Thin-film fabrication of polyurea is hindered by poor solubility in most organic solvents. We fabricated spin-coated thin films of polyurea and investigated the structural and electrical properties of the films. The as-spun films had rough surfaces and relatively high crystallinity with 4.5 nm grains, while melt-quenched films were smooth and lower in crystallinity with 2.7 nm grains. Residual solvent remained in the films at temperatures above the boiling point of the solvent. The quenched polyurea films exhibited large current peaks originating from activated impurity charges from the residual solvent in the current density-electric field curves. The pyroelectric coefficient of the spin-coated polyurea films was estimated to be 4.13 μC/m2K. The polyurea films maintained pyroelectricity even after the application of an electric field, thereby exhibiting potential applicability in pyroelectric devices with annealing to remove the impurity charges.