scholarly journals Supramolecular Triblock Copolymers Through the Formation of Hydrogen Bonds: Synthesis, Characterization, Association Effects in Solvents of Different Polarity

Polymers ◽  
2020 ◽  
Vol 12 (2) ◽  
pp. 468
Author(s):  
Spyridoula-Lida Bitsi ◽  
Margarita Droulia ◽  
Marinos Pitsikalis

Anionic polymerization techniques were employed for the synthesis of linear polystyrene (PS) and block copolymer of PS and polyisoprene (PI) PS-b-PI bearing end hydroxyl groups. Following suitable organic chemistry transformation, the –OH end groups were converted to moieties able to form complementary hydrogen bonds including 2,6-diaminopurine, Dap, thymine, Thy, and the so-called Hamilton receptor, Ham. The formation of hydrogen bonds was examined between the polymers PS-Dap and PS-b-PI-Thy, along with the polymers PS-Ham and PS-b-PI-Thy. The conditions under which supramolecular triblock copolymers are formed and the possibility to form aggregates were examined both in solution and in the solid state using a variety of techniques such as 1H-NMR spectroscopy, size exclusion chromatography (SEC), dilute solution viscometry, dynamic light scattering (DLS), thermogravimetric analysis (TGA), differential thermogravimetry (DTG), and differential scanning calorimetry (DSC).

Holzforschung ◽  
2015 ◽  
Vol 69 (3) ◽  
pp. 297-302 ◽  
Author(s):  
Maja Kandula ◽  
Tasja Schwenke ◽  
Stefan Friebel ◽  
Tunga Salthammer

Abstract Industrially produced lignins are by-products of the pulp and paper industry and depending on the source and pulping technology they have deviating functional groups, solubility behavior and reactivity. In the present paper, kraft lignin was pretreated by mechanical milling and polyesterified with ε-caprolactone to create hydroxyl groups that are more easily available for further reactions. The products obtained were analysed by size exclusion chromatography (SEC), differential scanning calorimetry (DSC) and functional group determination. The analytical data are presented as a function of reaction time, crosslinking reactions and the amount of ε-caprolactone input.


Polymers ◽  
2019 ◽  
Vol 11 (10) ◽  
pp. 1606 ◽  
Author(s):  
Nikovia ◽  
Sougioltzoupoulou ◽  
Rigas ◽  
Pitsikalis

Single and double poly(L-lactide) (PLLA) and poly(ε-caprolactone) (PCL) macromonomers having a norbornenyl polymerizable group were prepared by conventional Ring Opening Polymerization (ROP). These macromonomers were further subjected to ring opening metathesis polymerization (ROMP) reactions in order to produce double polymer brushes consisting of PLLA or PCL side chains on a polynorbornene (PNBE) backbone. Statistical or block ring opening metathesis copolymerization of the PLLA and PCL macromonomers afforded the corresponding random and block double brushes. Sequential ROMP of the single PLLA, PCL and PLLA macromonomers resulted in the synthesis of the corresponding triblock copolymer brush. The molecular characteristics of the macromolecular brushes were obtained by 1H-NMR spectroscopy and Size Exclusion Chromatography. The thermal properties of the samples were studied by thermogravimetric analysis, TGA, Differential Thermogravimetry, DTG and Differential Scanning Calorimetry, DSC.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Sam Wong ◽  
Simone Alidori ◽  
Barbara P. Mello ◽  
Bryan Aristega Almeida ◽  
David Ulmert ◽  
...  

AbstractCellulose nanocrystals (CNC) are linear organic nanomaterials derived from an abundant naturally occurring biopolymer resource. Strategic modification of the primary and secondary hydroxyl groups on the CNC introduces amine and iodine group substitution, respectively. The amine groups (0.285 mmol of amine per gram of functionalized CNC (fCNC)) are further reacted with radiometal loaded-chelates or fluorescent dyes as tracers to evaluate the pharmacokinetic profile of the fCNC in vivo. In this way, these nanoscale macromolecules can be covalently functionalized and yield water-soluble and biocompatible fibrillar nanoplatforms for gene, drug and radionuclide delivery in vivo. Transmission electron microscopy of fCNC reveals a length of 162.4 ± 16.3 nm, diameter of 11.2 ± 1.52 nm and aspect ratio of 16.4 ± 1.94 per particle (mean ± SEM) and is confirmed using atomic force microscopy. Size exclusion chromatography of macromolecular fCNC describes a fibrillar molecular behavior as evidenced by retention times typical of late eluting small molecules and functionalized carbon nanotubes. In vivo, greater than 50% of intravenously injected radiolabeled fCNC is excreted in the urine within 1 h post administration and is consistent with the pharmacological profile observed for other rigid, high aspect ratio macromolecules. Tissue distribution of fCNC shows accumulation in kidneys, liver, and spleen (14.6 ± 6.0; 6.1 ± 2.6; and 7.7 ± 1.4% of the injected activity per gram of tissue, respectively) at 72 h post-administration. Confocal fluorescence microscopy reveals cell-specific accumulation in these target tissue sinks. In summary, our findings suggest that functionalized nanocellulose can be used as a potential drug delivery platform for the kidneys.


2018 ◽  
Vol 33 (2) ◽  
pp. 180-197 ◽  
Author(s):  
Khezrollah Khezri ◽  
Yousef Fazli

Pristine mesoporous diatomite was employed to prepare polystyrene/diatomite composites. Diatomite platelets were used for in situ polymerization of styrene by atom transfer radical polymerization to synthesize tailor-made polystyrene nanocomposites. X-Ray fluorescence spectrometer analysis and thermogravimetric analysis (TGA) were employed for evaluating some inherent properties of pristine diatomite platelets. Nitrogen adsorption/desorption isotherm is applied to examine surface area and structural characteristics of the diatomite platelets. Evaluation of pore size distribution and morphological studies were also performed by scanning and transmission electron microscopy. Conversion and molecular weight determinations were carried out using gas and size exclusion chromatography, respectively. Linear increase of ln ( M0/M) with time for all the samples shows that polymerization proceeds in a living manner. Addition of 3 wt% pristine mesoporous diatomite leads to an increase of conversion from 72% to 89%. Molecular weight of polystyrene chains increases from 11,326 g mol−1 to 14134 g mol−1 with the addition of 3 wt% pristine mesoporous diatomite; however, polydispersity index values increases from 1.13 to 1.38. Increasing thermal stability of the nanocomposites is demonstrated by TGA. Differential scanning calorimetry shows an increase in glass transition temperature from 81.9°C to 87.1°C by adding 3 wt% of mesoporous diatomite platelets.


e-Polymers ◽  
2010 ◽  
Vol 10 (1) ◽  
Author(s):  
Lenka Poláková ◽  
Jan Lokaj ◽  
Petr Holler ◽  
Larisa Starovoytova ◽  
Michal Pekárek ◽  
...  

AbstractNitroxide-terminated 4VP AN copolymers have been synthesized at 125 oC using an alkoxyamine (MAMA-SG1) as a unimolecular initiator. Their compositions were compared with those published for the conventional radical 4VP-AN copolymerization. To verify the initiation potential of the copolymers containing nitroxyl end groups, they were employed in chain extension with styrene (S). Both the prepared statistic copolymer macroinitiators and related diblock copolymers, poly(4VP-co-AN) and poly(4VP-co-AN)-block-poly(S), respectively, were quaternized with methyl iodide in N,N-dimethylformamide or methanol at ambient temperature. The size-exclusion chromatography and NMR were used for the characterization of the polymers; the completeness of the quaternization was checked by the IR spectrometry.


Author(s):  
Ian T. Cook ◽  
Thomas S. Leyh ◽  
Susan A. Kadlubar ◽  
Charles N. Falany

AbstractMammalian cytosolic sulfotransferases (SULTs) frequently show substrate inhibition during the sulfation of increasing concentrations of substrates. SULT2A1, a major human liver isoform responsible for the conjugation of hydroxysteroids, bile acids and aliphatic hydroxyl groups in drugs and xenobiotics, is a homodimer and displays substrate inhibition during the conjugation of dehydroepiandrosterone (DHEA). Maltose binding protein (MBP)-SULT2A1 fusion protein, produced as an intermediate step in the purification of the SULT2A1 homodimer, elutes during size exclusion chromatography as a monomer. The initial-rate parameters (


1999 ◽  
Vol 561 ◽  
Author(s):  
F. Sahlén ◽  
T. Geisler ◽  
S. Hvilsted ◽  
N. C. R. Holme ◽  
P. S. Ramanujam ◽  
...  

ABSTRACTNew combined main- and side-chain azobenzene polyesters, which exhibit an intensity dependent refractive index, have been prepared in order to optically fabricate nonlinear waveguides. Novel sulfone azobenzenes, a diester, (4-[[5-(ethoxycarbonyl)pentyl]sulfonyl]-4'-[[5-(ethoxycarbonyl)pentyl]methylamino] azobenzene, and a diol, 4-[[(8-hydroxy-7-methylhydroxy)-octyl]sulfonyl]-4'-N, N-dimethylamino azobenzene, have been used to prepare new polyesters by transesterification in the molten state. The polyesters have been characterized by UV-visible spectroscopy, differential scanning calorimetry (DSC), size exclusion chromatography (SEC), third harmonic generation (THG) and optical anisotropy measurements. The molar masses of the polyesters were in the range of 5000-10000 g mol−1, which was sufficient in order to spin coat thin films. From THG measurements the polymers are shown to possess an offresonance electronic X(3) of the order 10−12 esu corresponding to a nonlinear refractive index of 2.3×10−14 cm2/W.


Polymers ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1190 ◽  
Author(s):  
Valentina Sabatini ◽  
Eleonora Pargoletti ◽  
Valeria Comite ◽  
Marco Aldo Ortenzi ◽  
Paola Fermo ◽  
...  

In this work, new co- and ter-polymers of methyl methacrylate (MMA), ethyl methacrylate (EMA), and N-butyl methacrylate (nBuMA), containing just 1% mol × mol−1 of a fluorinated co-monomer, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyl methacrylate (POMA), were synthesized. After an UV accelerated aging test, the photo-chemical stability of the polymers prepared was determined by 1H NMR and FT-IR spectroscopy, size exclusion chromatography, differential scanning calorimetry and wettability measurements. The polymers were applied to Botticino tiles to achieve better performances in terms of water repellency and consequently deterioration resistance. One-year prolonged exposure to a real environment was conducted and the properties of the coated materials and their performances were studied using different surface techniques such as water contact angle (WCA) and colorimetric measurements (CIELaB), capillary absorption, permeability (RVP) tests and soluble salts determination. The effectiveness of the fluorinated methacrylic coatings was clearly demonstrated; among all the resins, the co-polymer MMA_POMA seems to be the most performing one. Furthermore, both the UV photo-chemical resistance and the easiness of removal was successfully studied.


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