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1
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Thermo-responsiveness of polysiloxanes grafted with poly(dimethyl acrylamide) segments

100%
Rusu Hodorog A., Ibanescu C., Moleavin I., Hurduc N.
Open Chemistry
|
2012
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vol. 10
|
issue 4
1338-1348
EN
Thermo-sensitive polymers are of outstanding importance due to their ability to undergo controlled major changes in their properties as a response to minor modifications in temperature. The syntheses of novel polymers by grafting polysiloxane containing chlorobenzyl groups in the side chain by the homopolymerization of N,N′-dimethyl acrylamide (DMA) or the copolymerization of DMA and methyl methacrylate (MMA) using SET-LRP technique are presented. The polymers were characterized by 1H-NMR, UV, and fluorescence spectroscopy, and DSC. The thermo-sensitivity and the lower critical solution temperature (LCST), as well as the aggregation phenomena during the phase transition are evidenced by dynamic light scattering (DLS) and rheology. [...]
2
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Azo-polysiloxane micelles charged with nifedipine

88%
Prisacaru A.-I., Grama S., Durdureanu-Angheluta A., Pinteala M., Hurduc N.
Open Chemistry
|
2013
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vol. 11
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issue 9
1431-1438
EN
Abstract One recent aspect of the research study on polymers is their capability to respond to external stimuli. Of importance are photosensitive polymers due to their application in drug delivery systems, sensors, therapeutic devices or optoelectronic switches. The present paper focuses on the azo-polysiloxane micelles capacity charged with hydrophobic drugs, such as nifedipine. Azo-polysiloxanes modified with quaternary ammonium groups and which are capable to generate photo-sensitive micelles were synthesized and characterized by 1H-NMR, UV-VIS and fluorescence spectroscopy. The critical concentration of the micellar aggregation (CCA) was evaluated as was the nifedipine embedding capacity. The CCA values were influenced only by the hydrophobic/hydrophilic balance and not by the chemical structure of the quaternary ammonium groups. The disaggregation capacity of the micelles under UV irradiation was investigated as well, and the best results were obtained for the samples with higher azobenzene content. The DLS measurements evidenced micelles diameters situated in the optimum range domain (70–130 nm). The capacity to incorporate nifedipine inside the micelles was demonstrated. The micelles proved to be stable in time, 21 days after preparation with the diameter having constant values. Graphical abstract [...]
3
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Thermal behavior of some aromatic copolyethers containing a propylenic spacer

88%
Hurduc N., Damian C., Tarus A., Toader V., Hurduc N.
Open Chemistry
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2005
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vol. 3
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issue 1
53-62
EN
The main objective of this paper is to study the thermal stability of some aromatic copolyethers containing a propylenic spacer. Some of the investigated copolyethers displayed a liquid crystalline (LC) behavior, with the presence of the mesogenic groups in the main chain, inducing high values of the thermal transition temperatures. As a consequence, a thermal stability study was necessary to establish the maximum temperature value for the LC behavior characterization. A thermal degradation mechanism is proposed, taking into consideration the azobenzenic unit as the weakest link in the polymer chain and thus, the starting point of the thermal degradation process. The degradation mechanisms were correlated with the chemical structure and the polarity and conformation of the chains. Conformational analysis was performed using molecular simulations. Freeman-Caroll and Coats-Redfern methods were used to calculate some kinetic characteristics.
4
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Thermal and kinetic characteristics in non-isothermal conditions of some aromatic copolyethers containing an octomethylenic spacer

88%
Prajinaru M., Hurduc N., Alazaroaie S., Catanescu O., Hurduc N.
Open Chemistry
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2003
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vol. 1
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issue 4
387-401
EN
The paper presents a study of the thermal properties of some aromatic polyethers obtained by phase trasfer catalysis technique. The polymes were synthesized starting from 1,8-dichloro-octane and various bisphenols: 4,4′-dihydroxyazobenzene, 4,4′-dihydroxydiphenyl, bisphenol A and 2,7-dihydroxynaphthalene. Molecular simulations were performed in order to obtain supplementary information concerning the chain conformation and inter-chain interactions. The presence of azobenzenic moieties induces high phase transition values, situated near the thermal stability limit. Therefore, the thermogravimetrical study of these polymers is very important for establishing the temperature limits for DSC and optical microscopy studies. All the polymers present a good thermal stability situated above the isotropization values. In these circumstances no special precautions are necessary for the characterization methods of the liquid crystalline behavior. The kinetic characteristics suggest a similar degradation mechanism by successive reactions. The inter-chain interactions do not influence the thermostability of the samples if the polar surface of the polymer is situated below a certain value.
5
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Synthesis and photochromic behavior of some azo-polysiloxanes modified with nucleobases or donor-acceptor groups

76%
Enea R., Resmeriţă A.-M., Petraru L., Grigoraş C., Scutaru D., Simionescu C., Hurduc N.
Open Chemistry
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2007
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vol. 5
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issue 4
981-995
EN
This paper presents the syntheses, characterization and photochromic behavior of some new azo-polysiloxanes modified with uracil, cytosine or nitro-phenolic groups. Taking into consideration the possibility of generating H-bonds or donor/acceptor interactions, this class of materials present a potential applicability in the immobilization of biomolecules and their nano-manipulations. Also, such compounds are capable of producing a fluid phase, with directional flowing capacity. For all these polymers, the molecular modeling simulations have shown disordered structures, which would generate amorphous phases, a very important aspect for molecules’ nano-manipulation. The photochromic behavior in the presence of UV irradiation was also evaluated. [...]
6
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Amphiphilic azopolymers capable to generate photo-sensitive micelles

76%
Moleavin I., Ibanescu C., Hodorog-Rusu A., Peptu E., Doroftei F., Hurduc N.
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EN
Amphiphilic macromolecular micelles are advantageous for drug delivery applications due to the decrease of side-effects, ease of screening drugs against degradation, long-term stability, targeted delivery and control of the amount of the released drug. A series of amphiphilic azo-polymers having a flexible or rigid main-chain were synthesized and characterized. The presence of chlorobenzyl side-groups allowed both the easy bonding of photo-sensitive or hydrophilic groups and good control of the degree of substitution. The chemical structure was confirmed by 1H-NMR. The critical concentration of aggregation (CCA) was calculated using the fluorescence emission spectrum of pyrene. The interest was focused on a preliminary study concerning the disaggregation capacity of micelles under UV irradiation. The presence of micellar aggregates was confirmed by DLS and SEM and different organization of the amphiphilic polymers was evidenced depending on polymers concentration and polymers structure. In low polymer concentrations in water predominantly globular aggregates were formed. The increase in concentration increased the polydispersity index due to the fusion of micelles and formation of associates of globular aggregates, inter-micellar associates (clusters) and vesicles. [...]
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