Effect of a heat-treatment on the linear dimensional change of a hard chairside reline resin

Statement of problem. Little data are available regarding the effect of heat-treatments on the dimensional stability of hard chairside reline resins. Purpose. The objective of this in vitro study was to evaluate whether a heat-treatment improves the dimensional stability of the reline resin Duraliner II and to compare the linear dimensional changes of this material with the heat-polymerized acrylic resin Lucitone 550. Material and methods. The materials were mixed according to the manufacturer's instructions and packed into a stainless steel split mold (50.0 mm diameter and 0.5 mm thickness) with reference points (A, B, C, and D). Duraliner II specimens were polymerized for 12 minutes in water at 37°C and bench cooled to room temperature before being removed from the mold. Twelve specimens were made and divided into 2 groups: group 1 specimens (n=6) were left untreated, and group 2 specimens (n=6) were submitted to a heat-treatment in a water bath at 55°C for 10 minutes and then bench cooled to room temperature. The 6 Lucitone specimens (control group) were polymerized in a water bath for 9 hours at 71°C. The specimens were removed after the mold reached the room temperature. A Nikon optical comparator was used to measure the distances between the reference points (AB and CD) on the stainless steel mold (baseline readings) and on the specimens to the nearest 0.001 mm. Measurements were made after processing and after the specimens had been stored in distilled water at 37°C for 8 different periods of time. Data were subjected to analysis of variance with repeated measures, followed by Tukey's multiple comparison test (P<.05). Results. All specimens exhibited shrinkage after processing (control, -0.41%; group 1, -0.26%; and group 2, -0.51%). Group 1 specimens showed greater shrinkage (-1.23%) than the control (-0.23%) and group 2 (-0.81%) specimens after 60 days of storage in water (P<.05). Conclusion. Within the limitations of this study, a significant improvement of the long-term dimensional stability of the Duraliner II reline resin was observed when the specimens were heat-treated. However, the shrinkage remained considerably higher than the denture base resin Lucitone 550. Copyright © 2002 by The Editorial Council of The Journal of Prosthetic Dentistry.

Kinetic parameters for thermal decomposition of supramolecular polymers derived from diclofenac-meglumine supramolecular adducts

Meglumine is an aminocarbohydrate able to form supramolecular adducts with organic acids. The recognition is based on hydrogen bonds and the structures resulting from the complexation have high solubility in water. This property has been exploited by the pharmaceutical industry in the improvement of existing drugs, and the successful example of this approach involves the poorly soluble non-steroidal anti-inflammatory drugs (NSAIDs). Investigation of the thermal behavior of adduct obtained from meglumine and the NSAID diclofenac revealed that a polymer-like material is formed from the self-assembly of diclofenac-meglumine adducts in the melt. This polymer showed a high molecular weight around 2.0×105kDa. The kinetic parameters for the thermal decomposition step of the polymer were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and heating rates of 5, 10, 15 and 20°Cmin-1, the Eα and Bα terms could be determined, and consequently the pre-exponential factor, Aα, as well as the kinetic model, g(α). © 2012 Elsevier B.V.

A new biomimetic sensor based on molecularly imprinted polymers for highly sensitive and selective determination of hexazinone herbicide

A new selective sensor based on molecularly imprinted polymers (MIPs) was developed for the determination of hexazinone (HXZ) in environmental samples. MIPs were synthesized using a non-covalent approach, and selection of the monomers employed in the polymerization reaction was carried out by molecular modeling. Three functional monomers with high (2-vinylpyridine (MP17)) and intermediate (methacrylic acid (MP12) and acrylamide (MP5)) energies of binding to the template (HXZ) were selected for preparation of the MIPs, in order to conduct comparative studies and validate the theoretical data. For sensor construction, carbon pastes were modified with each MIP or NIP (non-imprinted polymer), and HXZ determination was performed using differential pulse adsorptive cathodic stripping voltammetry (DPAdCSV). All parameters affecting the sensor response were optimized. In HCl at pH 2.5, the sensor prepared with MP17 (5% w/w in the paste) showed a dynamic linear range between 1.9 × 10−11 and 1.1 × 10−10 mol L−1, and a detection limit of 2.6 × 10−12 mol L−1, under the following conditions: accumulation time of 200 s at a potential of −0.5V, scan rate of 50 mVs−1, pulse amplitude of 60 mV, and pulse width of 50 ms. The sensor was selective in the presence of other similar compounds, and was successfully applied to the analysis of HXZ in river water samples.

Efficiency comparison of hyperbranched polymers as toughening agents for a one-part epoxy resin

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Linear viscoelasticity of immiscible blends: The application of creep

A new method to characterize the long-time linear relaxation mechanisms of immiscible blends based on creep experiment was developed. Small-amplitude oscillatory shear and incomplete creep/recovery experiments were combined to characterize immiscible blends of polypropylene with dispersed droplets of polystyrene. An experimental protocol was defined such that the full creep compliance function could be obtained while minimizing morphological changes. Dynamic experiments were performed to characterize the shorter time relaxation processes, and creep and recovery measurements were used to detect the longer time portions of the relaxation spectra. Extended retardation and relaxation spectra were constructed by combining these data. It was found that using this technique, very long-time relaxation peaks which were inaccessible with dynamic experiments alone could be detected. (C) 2012 The Society of Rheology. [http://dx.doi.org/10.1122/1.4720081]

Single polymers at surfaces: adsorption and detachment

This thesis is concerned with the adsorption and detachment of polymers at planar, rigid surfaces. We have carried out a systematic investigation of adsorption of polymers using analytical techniques as well as Monte Carlo simulations with a coarse grained off-lattice bead spring model. The investigation was carried out in three stages. In the first stage the adsorption of a single multiblock AB copolymer on a solid surface was investigated by means of simulations and scaling analysis. It was shown that the problem could be mapped onto an effective homopolymer problem. Our main result was the phase diagram of regular multiblock copolymers which shows an increase in the critical adsorption potential of the substrate with decreasing size of blocks. We also considered the adsorption of random copolymers which was found to be well described within the annealed disorder approximation. In the next phase, we studied the adsorption kinetics of a single polymer on a flat, structureless surface in the regime of strong physisorption. The idea of a ’stem-flower’ polymer conformation and the mechanism of ’zipping’ during the adsorption process were used to derive a Fokker-Planck equation with reflecting boundary conditions for the time dependent probability distribution function (PDF) of the number of adsorbed monomers. The numerical solution of the time-dependent PDF obtained from a discrete set of coupled differential equations were shown to be in perfect agreement with Monte Carlo simulation results. Finally we studied force induced desorption of a polymer chain adsorbed on an attractive surface. We approached the problem within the framework of two different statistical ensembles; (i) by keeping the pulling force fixed while measuring the position of the polymer chain end, and (ii) by measuring the force necessary to keep the chain end at fixed distance above the adsorbing plane. In the first case we treated the problem within the framework of the Grand Canonical Ensemble approach and derived analytic expressions for the various conformational building blocks, characterizing the structure of an adsorbed linear polymer chain, subject to pulling force of fixed strength. The main result was the phase diagram of a polymer chain under pulling. We demonstrated a novel first order phase transformation which is dichotomic i.e. phase coexistence is not possible. In the second case, we carried out our study in the “fixed height” statistical ensemble where one measures the fluctuating force, exerted by the chain on the last monomer when a chain end is kept fixed at height h over the solid plane at different adsorption strength ε. The phase diagram in the h − ε plane was calculated both analytically and by Monte Carlo simulations. We demonstrated that in the vicinity of the polymer desorption transition a number of properties like fluctuations and probability distribution of various quantities behave differently, if h rather than the force, f, is used as an independent control parameter.

Triphenylene-based polymers for organic electronics

An efficient synthesis has been developed toward a novel series of conjugated blue emitting polymers containing triphenylene as repeating unit for polymer light emitting diodes (PLEDs). Soluble triphenylene-based co- and homo-polymers have been synthesized by the palladium-catalyzed Suzuki-Miyaura and the nickel-catalysed Yamamoto polycondensation reactions, respectively. The photophysical properties as well as the application of the polymers in PLED devices are presented here.rnIn addition a simple GNR fabrication method that allows for the production of atomically precise GNRs of different topologies and widths is introduced. This bottom-up approach consists in the surface-assisted coupling of suitably designed molecular triphenylene precursors into linear polyphenylenes and their subsequent cyclodehydrogenation and results in GNRs whose topology, width and edge periphery are defined by the precursor monomers. Various types of atomically precise GNRs thus eventually become available for experimental investigation and exploitation of their many predicted and technologically highly interesting properties. Furthermore, it is anticipated that this bottom-up approach of GNR fabrication will allow the engineering of chemical and electronic properties and the yet elusive realization of theoretically predicted structures such as intraribbon quantum dots, superlattice structures, or magnetic devices based on specific GNR edge states.rn

Thin films of polythiophene: Linear and nonlinear optical characterization

Wir haben die linearen und nichtlinearen optischen Eigenschaften von dünnen Schichten und planaren Wellenleitern aus mehreren konjugierten Polymeren (MEH-PPV und P3AT) und Polymeren mit -Elektronen Systemen in der Seitenkette (PVK und PS) untersucht und verglichen. PVK und PS haben relativ kleine Werte des nichtlinearen Brechungsindex n2 bei 532 nm, nämlich (1,2 ± 0,5)10-14 cm2/W und (2,6 ± 0,5) 10-14 cm2/W.rnWir haben die linearen optischen Konstanten von mehreren P3ATs untersucht, insbesondere den Einfluss der Regioregularität und Kettenlänge der Alkylsubstituenten. Wir haben das am besten geeignete Polymere für Wellenleiter Anwendungen identifiziert, welches P3BT-ra genannt ist. Wir haben die linearen optischen Eigenschaften dünner Schichten des P3BT-ra untersucht, die mit Spincoating aus verschiedenen Lösungsmitteln mit unterschiedlichen Siedetemperaturen präparieret wurden. Wir haben festgestellt, dass P3BT-ra Filme aus Toluol-Lösungen die am besten geeigneten Wellenleiter für die intensitätsabhängigen Prismen-Kopplungs Experimente sind, weil diese geringe Wellenleiterdämpfungsverluste bei = 1064 nm haben. rnWir haben die Dispersionen des Wellenleiterdämfungsverlustes gw, des nichtlinearen Brechungsindex n2 und des nichtlinearen Absorptionskoeffizienten 2 von Wellenleitern aus P3BT-ra im Bereich von 700 - 1500 nm gemessen. Wir haben große Werte des nichtlinearen Brechungsindex bis 1,5x10-13 cm2/W bei 1150 nm beobachtet. Wir haben gefunden, dass die Gütenkriterien (“figures of merit“) für rein optische Schalter im Wellenlängebereich 1050 - 1200 nm erfüllt sind. Dieser Bereich entspricht dem niederenergetischen Ausläufer der Zwei-Photonen-Absorption. Die Gütekriterien von P3BT-ra gehören zu den besten der bisher bekannten Werte von konjugierten Polymeren.rnWir haben gefunden, dass P3BT-ra ein vielversprechender Kandidat für integriert-optische Schalter ist, weil es eine gute Kombination aus großer Nichtlinearität dritter Ordnung, geringen Wellenleiterdämpfungverlusten und ausreichender Photostabilität zeigt. rnWir haben einen Vergleich der gemessenen Dispersion von gw, n2 und 2 mit der Theorie durchgeführt. Durch Kurvenanpassung der Dispersion von gw haben wir gefunden, dass Rayleigh-Streuung der dominierende Dämpfungsmechanismus in MEH-PPV und P3BT-ra Wellenleitern ist. Ein quantenmechanischer Ansatz wurde zur Berechnung der nichtlinearen Suszeptibilität dritter Ordnung (3) verwendet, um die gemessenen Spektren von n2 und 2 von P3BT-ra und MEH-PPV zu simulieren. Dies kann erklären, dass sättigbare Absorption und Zwei-Photonen Absorption die hauptsächlichen Effekte sind, welche die Dispersion von n2 und 2 verursachen. rn

From amphiphilic block copolymers to ferrocenyl-functionalized polymers for biosensoric applications

The present thesis can be divided in three main parts. In all parts new polymer architecturesrnwere synthesized and characterized concerning their special features.rnThe first part will emphasize the advantage of a polystyrene-block-(hyperbranchedrnpolyglycerol) copolymer in comparison to an analogue polystyrene-block-(linear polyglycerol)rncopolymer. Therefore a synthethic route to prepare linear block copolymersrnhas been developed. Two strategies were examined. One strategy was based on thernclassic, sequential anionic polymerization; the second strategy was based on arn“Click-Chemistry” coupling reaction. In a following step glycidol was hypergraftedrnfrom these block copolymers by applying a hypergrafting reaction with glycidol. Thernbehavior of the amphiphilic block copolymers synthesized was studied in differentrnsolvents. Furthermore the polarity of the solvent was changed to form the correspondingrninverse micelles. DLS, SLS, SEC-MALLS-VISCO, AFM and Cyro TEMrnmeasurements were performed to obtain a visual image from the appearance of thernaggregates. It was found that a linear-hyperbranched architecture is necessary, ifrnwell defined, monodisperse aggregates are required, e.g. for the preparation of orderedrnnanoarrays. Linear-linear block copolymers formed only polydisperse aggregates.rnAdditionally it was found that size distribution could be improved dramaticallyrnby passing the aggregates through a SEC column with large pores. The SEC columnsrnacted like a template in which the aggregates adopt a more stable conformation.rnIn the second part anionic polymerization was employed to synthesize silaneendfunctionalizedrnmacromonomers with different molecular weights based on polybutadienernand polyisoprene. These were polymerized by a hydrosilylation reaction inrnbulk to obtain branched polymers, using Karstedt’s catalyst. Surprisingly the additionrnof monofunctional silanes during the polymerization had only a minimal effect concerningrnthe degree of polymerization. It was possible to introduce silanes without increasingrnthe overall number of reaction steps by a very convenient “pseudo-copolymerization”rnmethod. All branched polymers were analyzed by SEC, SEC-MALLS,rnSEC-viscometry, 1H-NMR-spectroscopy and DSC concerning their branching ratio.rnThe branching parameters for the branched polymers exhibited similar characteristicsrnas hyperbranched polymers based on AB2 monomers. Detailed kinetic study showedrnthat the polymerization occurred very rapidly in comparison to the hydrosilylation polymerizationrnof classical AB2 type carbosilanes monomers.rnThe last part will deal with ferrocenyl-functionalized polymers. On the one hand,rnferrocenyl-functionalized polyglycerols (PG) were studied. Esterification of PGs withrndifferent molecular weight using ferrocenemonocarboxylic acid gave the ferrocenylrnfuntionalized polymers in high yields. On the other hand three different block copolymersrnwere prepared with different ratios of styrene to butadiene units (10:1, 4:1, 2:1).rnThe double bonds of the 1,2-PB block were hydrosilylated using silanes bearing onern(HSiMe2Fc) or two (HSiMeFc2) ferrocene units. High degrees of functionalizationrnwere obtained (up to 83 %). In this manner, six different ferrocenyl-rich block copolymersrnwith different fractions of ferrocene were prepared and analyzed, employingrnNMR-spectroscopy, SEC, SEC/MALLS/viscometry, DLS and cyclic voltammetry. Thernredox properties of the studied polymers varied primarily with the nature of the silanernunit attached. Additionally, the redox properties in solution of the studied polymersrnwere influenced by the block length ratio of the block copolymers. Unexpectedly, withrnincreasing block length of the ferrocenyl block the fraction of active ferrocenes decreased.rnNevertheless, in case of thin monolayer films this behaviour was not observed.rnAll polymers (PG and PS-b-PB based) exhibited good electrochemical propertiesrnin a wide range of solvents, which rendered them very interesting for biosensoricrnapplications.

Synthesis and characterization of temperature- and light-responsive polymers and block copolymers

In summary, thermoresponsive polyacrylamides with various amounts of different photoswitchable side groups, i. e. azobenzene, salicylideneaniline and fulgimide were successfully prepared. As such, in a first step three different chromophores with an amine functionality were synthesized. The synthesis of the stimuli-responsive materials was based on the RAFT polymerization of activated ester acrylates followed by a polymer analogous reaction with different amines. The procedure has been designed to allow the synthesis of well-defined materials with functional groups. All copolymers prepared in this way showed a LCST in aqueous solution. The LCST was in general decreased by increasing the amount of hydrophobic dye incorporated into the thermoresponsive polymer. However, in the case of the fulgimide, the LCST was hardly affected by the chromophore. For azobenzene containing PNIPAM polymers and analogues, higher LCST values were measured after irradiation of the polymer sample solutions with UV-light (Delta LCSTmax = 7.3°C). A reversible light-induced solubility change within a certain temperature range was possible. In contrast to this, irradiated samples of salicylideneaniline containing thermoresponsive copolymers showed an irreversible increase in the LCST (Delta LCSTmax = 13.0°C). Fulgimide chromophores did not influence the LCST of PNIPAM based copolymers after UV-light exposure.rnSimilar to the thermoresponsive polyacrylamides with azobenzene side groups, poly(oligo(ethylene glycol) methyl ether methacrylate) [P(OEGMA)] polymers with azobenzene end groups showed a LCST shift upon UV-irradiation. These polymers were synthesized by RAFT polymerization using a functional chain transfer agent (CTA). For this, PFP-CTA was used as a RAFT-agent for end group functionalization of (thermoresponsive) polymers. In contrast to the statistically arranged copolymers with azobenzene side groups, P(OEGMA) polymers with terminal azobenzene showed a linear increase of the LCST shifts with increasing amount of chromophore (Delta LCSTmax = 4.3°C). Noteworthy, the chemical nature of the end group exhibited a strong influence on the LCST in the case of short thermoresponsive P(OEGMA) polymers.rnThe investigation on temperature- and lightresponsive polymers was transferred onto block copolymers capable to self-assemble into polymeric micelles. Therefore, PEO-b-PNIPAM block copolymers with azobenzene moieties were synthesized successfully. These polymers showed a “smart” behavior in aqueous solution, as the reversible formation and disruption of the micelles could either be controlled by temperature or using light as a stimulus. The usefulness of these materials was demonstrated by encapsulation of a hydrophobic dye in the core of the micelle. Such materials might have a great potential as a model system for several technical or biological applications.rnFinally, double thermoresponsive block copolymers forming micellar structures in a certain temperature range with functional end groups could successfully be synthesized. These “smart materials” based on POEGMA-b-PNIPMAM have been demonstrated to be very promising for a temperature selective immobilization on a protein surface. This might be a suitable concept for further biological applications.rnConcluding, different thermoresponsive copolymers and block copolymers with lightresponsive moieties arranged along the backbone or located at the chain ends were successfully prepared and investigated. By controlling the nature of functional groups and their respective incorporation ratios, the LCST could be dialed in precisely. Further, the LCST of the polymers could be triggered by light. A light-controlled disruption of micellar structures could be shown for functional block copolymers. The importance of end groups of thermoresponsive polymers was demonstrated by a temperature-controlled protein-polymer binding of a terminal biotin-functionalized double thermoresponsive polymer. The synthetic approaches and the material properties presented here should be promising for further research and applications beyond this dissertation.rn

Synthesis of Macrocyclic Polymers Formed via Intramolecular Radical Trap-Assisted Atom Transfer Radical Coupling

The synthesis of cyclic polystyrene (Pst) with an alkoxyamine functionality has been accomplished by intramolecular radical coupling in the presence of a nitroso radical trap Linear alpha,omega-dibrominated polystyrene, produced by the atom transfer radical polymerization (ATRP) of styrene using a dibrominated initiator, was subjected to chain-end activation via the atom transfer radical coupling (ATRC) process under pseudodilute conditions in the presence of 2-methyl-2-nitrosopropane (MNP). This radical trap-assisted, intramolecular ATRC (RTA-ATRC) produced cyclic polymers in greater than 90% yields possessing < G > values in the 0.8-0.9 range as determined by gel permeation chromatography (GPC). Thermal-induced opening of the cycles, made possible by the incorporated alkoxyamine, resulted in a return to the original apparent molecular weight, further supporting the formation of cyclic polymers in the RTA-ATRC reaction. Liquid chromatography-mass spectrometry (LC-MS) provided direct confirmation of the cyclic architecture and the incorporation of the nitroso group into the macrocycle RTA-ATRC cyclizations carried out with faster rates of polymer addition into the redox active solution and/or in the presence of a much larger excess of MNP (up to a 250:1 ratio of MNP:C-Br chain end) still yielded cyclic polymers that contained alkoxyamine functionality.

Synthesis, structure and magnetic properties of cobalt(II) and copper(II) coordination polymers assembled by phthalate and 4-methylimidazole

New coordination polymers [M(Pht)(4-MeIm)2(H2O)]n (M=Co (1), Cu (2); Pht2−=dianion of o-phthalic acid; 4-MeIm=4-methylimidazole) have been synthesized and characterized by IR spectroscopy, X-ray crystallography, thermogravimetric analysis and magnetic measurements. The crystal structures of 1 and 2 are isostructural and consist of [M(4-MeIm)2(H2O)] building units linked in infinite 1D helical chains by 1,6-bridging phthalate ions which also act as chelating ligands through two O atoms from one carboxylate group in the case of 1. In complex 1, each Co(II) atom adopts a distorted octahedral N2O4 geometry being coordinated by two N atoms from two 4-MeIm, three O atoms of two phthalate residues and one O atom of a water molecule, whereas the square-pyramidal N2O3 coordination of the Cu(II) atom in 2 includes two N atoms of N-containing ligands, two O atoms of two carboxylate groups from different Pht, and a water molecule. An additional strong O–H⋯O hydrogen bond between a carboxylate group of the phthalate ligand and a coordinated water molecule join the 1D helical chains to form a 2D network in both compounds. The thermal dependences of the magnetic susceptibilities of the polymeric helical Co(II) chain compound 1 were simulated within the temperature range 20–300 K as a single ion case, whereas for the Cu(II) compound 2, the simulations between 25 and 300 K, were made for a linear chain using the Bonner–Fisher approximation. Modelling the experimental data of compound 1 with MAGPACK resulted in: g=2.6, |D|=62 cm−1. Calculations using the Bonner–Fisher approximation gave the following result for compound 2: g=2.18, J=–0.4 cm−1.

Hierarchical self-assembly of the DNA-grafted supramolecular polymers

Conjugation of functional entities with a specific set of optical, mechanical or biological properties to DNA strands allows engineering of sophisticated DNA-containing architectures. Among various hybrid systems, DNA-grafted polymers occupy an important place in modern materials science. In this contribution we present the non-covalent synthesis and properties of DNA-grafted linear supramolecular polymers (SPs), which are assembled in a controllable manner from short chimeric DNA-pyrene oligomers. The synthetic oligomers consist of two parts: a 10 nucleotides long DNA chain and a covalently attached segment of variable number of phosphodiester-linked pyrenes. The temperature-dependent formation of DNA-grafted SPs is described by a nucleation-elongation mechanism. The high tendency of pyrenes to aggregate in water, leads to the rapid formation of SPs. The core of the assemblies consists of stacked pyrenes. They form a 1D platform, to which the DNA chains are attached. Combined spectroscopic and microscopic studies reveal that the major driving forces of the polymerization are π-stacking of pyrenes and hydrophobic interactions, and DNA pairing contributes to a lesser extent. AFM and TEM experiments demonstrate that the 1D SPs appear as elongated ribbons with a length of several hundred nanometers. They exhibit an apparent helical structure with a pitch-to-pitch distance of 50±15 nm. Since DNA pairing is a highly selective process, the ongoing studies are aimed to utilize DNA-grafted SPs for the programmable arrangement of functional entities. For example, the addition of non-modified complementary DNA strands to the DNA-grafted SPs leads to the cooperative formation of higher-order assemblies. Also, our experiments suggest that the fluorescent pyrene core of 1D ribbons serves as an efficient donor platform for energy transfer applications.

Hierarchical self-assembly of the DNA-grafted supramolecular polymers

Conjugation of functional entities with a specific set of optical, mechanical or biological properties to DNA strands allows engineering of sophisticated DNA-containing architectures. Among various hybrid systems, DNA-grafted polymers occupy an important place in modern materials science. In this contribution we present the non-covalent synthesis and properties of DNA-grafted linear supramolecular polymers (SPs), which are assembled in a controllable manner from short chimeric DNA-pyrene oligomers. The synthetic oligomers consist of two parts: a 10 nucleotides long DNA chain and a covalently attached segment of variable number of phosphodiester-linked pyrenes. The temperature-dependent formation of DNA-grafted SPs is described by a nucleation-elongation mechanism. The high tendency of pyrenes to aggregate in water, leads to the rapid formation of SPs. The core of the assemblies consists of stacked pyrenes. They form a 1D platform, to which the DNA chains are attached. Combined spectroscopic and microscopic studies reveal that the major driving forces of the polymerization are π-stacking of pyrenes and hydrophobic interactions, and DNA pairing contributes to a lesser extent. AFM and TEM experiments demonstrate that the 1D SPs appear as elongated ribbons with a length of several hundred nanometers. They exhibit an apparent helical structure with a pitch-to-pitch distance of 50±15 nm. Since DNA pairing is a highly selective process, the ongoing studies are aimed to utilize DNA-grafted SPs for the programmable arrangement of functional entities. For example, the addition of non-modified complementary DNA strands to the DNA-grafted SPs leads to the cooperative formation of higher-order assemblies. Also, our experiments suggest that the fluorescent pyrene core of 1D ribbons serves as an efficient donor platform for energy transfer applications.

Smart Hybrid Polymers for Advanced Damascene Electroplating: Combination of Superfill and Leveling Properties

A successful bottom-up fill of single Damascene test features is achieved by using a two-component additive package consisting of bis-(sodium-sulfopropyl)-disulfide (SPS) and Imep polymers (polymerizates of imidazole and epichlorohydrin). In addition, a remarkable leveling effect is observed. Clearly, the Imep additive combines bottom-up fill capabilities with leveling characteristics in one single polymer component. These unique hybrid properties of the Imep are rationalized on the basis of an extended N-NDR (N-shaped negative differential resistance) being present in the linear-sweep voltammogram of the SPS/Imep additive system during Cu electrodeposition.