Polymer Cage Research Articles

Recasting the wobbling-in-a-cone model for the rotational anisotropy of phenylselenocyanate in poly(methyl methacrylate): Effect of internal bond rotation and polymer segmental motion.

The rotational anisotropy of a molecule in a constrained environment is modeled by wobbling-in-a-cone (WIAC) motion, which describes the angular space sampled by the molecule. Recent polarization-selective IR pump-probe measurements have applied this model to phenylselenocyanate in amorphous polymers, aiming to probe the surrounding free volume. A faster rotational timescale was hypothesized to reflect the angular space within the static voids of the polymer matrix, while a slower timescale relates to constraint release by the polymer backbones. To better quantify the contributions of internal bond rotation and polymer segmental motion, we conduct molecular dynamics simulations on two phenylselenocyanate variants with different internal rotational barriers, as well as on p-chlorobenzonitrile, which lacks such internal rotational freedom, within a polymer matrix. Our analyses reveal that the faster (∼10ps) component of the cyano group's anisotropy decay arises from concurrent angular sampling due to internal bond rotation and WIAC motion. Conversely, polymer segmental motion was found to have a minimal influence on the slow (∼200ps) anisotropy component. Based on these findings, we refine the WIAC model to better link rotational diffusion with the distinct free volume elements accessed by the probe molecule. This revised model allows the quantification of free volume elements associated with both internal bond rotation and wobbling motion within the polymer cage.

Conformational Selection of Polymer Chains upon π-π Interactions with Small Molecules.

Conformational selection, pivotal in biological molecular recognition, remains underexplored in synthetic polymers, especially in the bulk states of polymers. This study reveals distinct conformational selection behavior in atactic polystyrene melts interacting with polycyclic aromatic hydrocarbons for the first time. Remarkably, despite structural similarities, anthracene and pyrene induce distinctly different conformations-trans and gauche, respectively. This divergence, attributed to the unique π-π interaction geometries, is captured by a "polymer cage" model, providing new insights into the precise structuring of polymers at the secondary structure level.

Modeling viscoelasticity and cyclic creep of PEEK by parallel rheological framework (PRF)

Although creep is usually regarded as a quasistatic phenomenon, in multiple engineering applications the load is not constant, hence creep under cyclic loading conditions should be considered. The current work presents the theoretical and experimental study on the viscoelasticity and cyclic creep of PEEK (Polyether ether ketone) – the polymer with good chemical and thermal stability. Among other demanding applications, PEEK is used in bearings industry for the fabrication of cages, which main function is to isolate and to guide rolling elements. In this application the polymer cage is subjected to the long-term load alternating in time, meaning that classical creep (under constant load) cannot be presumed. In the current study, the non-linear viscosity is included into the generalized Maxwell model, employing the Eyring equations which postulate that the viscosity coefficient is not constant but is dependent on stress. The model is implemented with the Parallel Rheological Framework (PRF) (the numerical technique recently implemented in the commercial software ABAQUS), used to construct the generalized Maxwell model with hyper-elastic springs and dashpots of non-linear viscosity. Initially, the viscoelastic material parameters are identified from the uniaxial test, and later these parameters are used to simulate the PEEK response under cyclic loading, to predict the time to creep/fatigue failure. Eventually, the numerical predictions are compared to the test results. The comparison indicates that the developed method and its numerical implementation by PRF can be successfully used to model the non-linear viscoelastic behavior of PEEK under uniaxial load. It is also found, that the simulation of cyclic creep can be reasonably performed by using the current material model and PRF.

A polymer cage as an efficient polysulfide reservoir for lithium-sulfur batteries.

Herein, we present a self-assembly strategy to prepare a cage-polymer coated sulfur sample. The sample embeds graphene as a new sulfur cathode. The cathode exhibits excellent electrochemical stability, maintaining a capacity of 546 mA h g-1 after 495 cycles at 1C, corresponding to an attenuation rate of 0.071% per cycle.

Benzophenone as a photoprobe of polymer films

The review article is devoted to kinetics of fast reactions following photoexcitation of benzophenone in polymer films. We observed three processes by ns laser flash photolysis in elastomers: (i) decay of a triple state of benzophenone with hydrogen abstraction from polymer matrix, (ii) formation and decay of geminate radical pairs, (iii) cross-termination of the formed radicals in the polymer bulk. Application of external magnetic field (MF) of B=0.2T essentially affects recombination of geminate (G-) and a bimolecular recombination of free radicals, which escaped polymer cage (F-pairs). Theoretical calculation of MF effects on G- and F-pairs is in agreement with corresponding experimental data. Elongation of elastomer leads to an unexpected observation: recombination in the bulk becomes slower. An explanation of this phenomenon based on elastomer free volume Vf approach was suggested.

Investigating the pH Dependence of Ultraviolet Radiation Induced Synthesis of TiO<sub>2</sub>/Poly(Acrylic Acid) Nanocomposites

In this work, Poly(Acrylic Acid) (PAA) was employed as nanoparticle stabilizer for TiO2. Adsorption and encapsulation of nanoparticles in polyelectrolytes impart stability due to stearic and electrostatic effects. Crosslinking of the polymer through UV-Irradiation permanently encapsulates the metal as well as reinforces the polymer cage. The efficient pH and ratio of reactants were optimized then assessed through Dynamic Light Scattering (DLS) for particle size and Zeta Potential Measurements for stability in aqueous solutions. Results showed that among the various TiO2/PAA ratios, the 1:3 ratio showed minimal changes on the size and Zeta Potential values even when exposed to various pH conditions. Meanwhile at pH 5, TiO2 attained a positive surface charge, while PAA exists in its deprotonated form, thus maximizing the electrostatic interaction between the two materials. Analysis revealed that in that particular ratio and pH range, particles size and zeta-potential value of 61.79 nm and -36 mV were obtained respectively. Physical morphology of the nanocomposites was characterized through Scanning Electron Microscopy, showing agglomerates of small particles, resulting to larger particles. Further studies shall be done to utilize the potential of the polymer-coated nanoparticles in dry form.

Polyhedral Oligomeric Silsesquioxane Polymer-Caged Silver Nanoparticle as a Smart Colorimetric Probe for the Detection of Hydrogen Sulfide

The rapid and accurate detection of hydrogen sulfide is of great concern due to its unique role on environmental pollution and signal transmission in physiological systems. Herein, we report a smart colorimetric probe for the selective detection of H2S. The probe is prepared via a surfactant-free route with cross-linked polyhedral oligomeric silsesquioxane (POSS) polymer cage as capping ligand and reducing agent under microwave irradiation, called poly-POSS-formaldehyde polymer (PPF) cage-AgNPs or PPF-AgNPs for short. The caged silver nanoparticles are well-dispersed with narrow size distribution within 6.0-8.4 nm. Chloride ions and aldehyde groups in PPF make the nucleation and growth of Ag nanoparticles accomplished within a very short time of 1 min. The positively charged PPF-AgNPs exhibit excellent selectivity to H2S against other anionic species and thiols due to the specific Ag-H2S interaction, where the favorable protection effect of PPF polymer cage from the nanoparticle aggregation is demonstrated. The colorimetric probe presents a quick response to H2S (<3 min) and favorable sensitivity within a linear range of 0.7-10 μM along with a detection limit of 0.2 μM. The probe is well demonstrated by analysis of H2S in various water and biological samples.

Reactivity of Benzophenone Ketyl Free Radicals in an Elongated Elastomer Film.

The effect of polymer film elongation leading to the thinning of the film up to three times on the decay of transients was studied. Kinetics of benzophenone (B) triplet state (3)B* and ketyl free radical BH• in soft rubber poly(ethylene-co-butylene) (abbreviated as E) was investigated by nanosecond laser flash photolysis. We monitored decay kinetics of the triplet state of (3)B* and of BH• decay in the polymer cage and decay of BH• in the polymer bulk. The fast exponential decay of (3)B*(lifetime τT ≈ 200 ns) is accompanied by hydrogen atom abstraction from E with the formation of BH• and a polymer free radical R•. The decay of BH• in the polymer cage occurs during τc ≈ 1 μs. Cage recombination, in turn, was followed by a cross-termination of BH• in the polymer bulk (τb ≈ 100 μs under our conditions) and is characterized by a rate constant kb ≈ 10(8) M(-1) s(-1). We studied changes of rates of transients decay upon elongation (thinning) of E. Decay of (3)B* is practically independent of elongation of the film. Recombination of BH• in the solvent bulk occurs with a two times lower kb than in a nonelongated E. The decrease in kb is ascribed mainly to a lower fractional polymer free volume Vf in elongated E compared with that in nonelongated E. Dependencies of log10 kb versus [Formula: see text], where [Formula: see text] is the thickness of the film, turned out to be linear with a negative slope. At the same [Formula: see text] recombination proceeds slower in the elongated elastomer compared with the nonelongated elastomer. Cage effect increases twice as well due to a lower rate of radicals escape from the polymer cage in the elongated film. We observed relatively large effects of external magnetic field (B = 0.2T) on the kinetics of cage recombination and recombination in the polymer bulk. Magnetic field effect on recombination rates in the cage and in the solvent bulk does not depend on elongation.

Polymer/Nanoparticle Hybrid Materials of Precise Dimensions by Size-Exclusive Fishing of Metal Nanoparticles.

Polymer cages prepared by etching of gold nanoparticles from polymer templates by the "grafting around" method are designed for selective separation of metal nanoparticles. The separation process is demonstrated as a fast biphasic ligand exchange reaction. The high separation efficiency and size selectivity of the polymer cage is verified by comparison with the linear block copolymer.

Kinetics of benzophenone ketyl free radicals recombination in a polymer: reactivity in the polymer cage vs. reactivity in the polymer bulk.

The decay kinetics of intermediates produced under photolysis of benzophenone (B) dissolved in soft rubber poly(ethylene-co-butylene) films (abbreviated as E) was studied by ns laser flash photolysis in the temperature range of 263-313 K. We monitored decay kinetics of the triplet state of (3)B* and of benzophenone ketyl free radical BH˙. The fast exponential decay of (3)B* (life-time τT ≈ 200 ns) is accompanied by hydrogen atom abstraction from E with a formation of BH˙ and a polymer free radical R˙. Decay of (3)B* was followed by decay of BH˙ in the polymer cage (geminate recombination) with τc ≈ 1 μs. Cage recombination in turn was followed by a decay of BH˙ in the polymer bulk (τb ≈ 100 μs). Fortunately, all three processes are separated in time. Both cage and bulk reactions were decelerated by the application of magnetic field (MF) of 0.2 T by approximately 20%. Geminate recombination was fit to the first-order kinetic law, and recombination in the solvent bulk fits well to the second-order law. Both geminate recombination and recombination in the solvent bulk are predominantly a reaction between BH˙ and R˙. It was assumed that the reaction radius ρ12 and a mutual diffusion coefficient D12 of BH˙ and R˙ are the same for the cage and bulk recombination, respectively. This led to an estimation of ρ12 = 3.3 nm and D12 = 1 × 10(-7) cm(2) s(-1). These values are discussed. We obtained activation energy, Eact, equal to 6 kcal mol(-1) and 7 kcal mol(-1) for cage decay and for recombination in the polymer bulk, respectively. These Eact coincide with each other within experimental error of their determination (±0.5 kcal mol(-1)). This indicates the same diffusion character in the cage and in the polymer bulk. It was demonstrated that an exponential model of cage effect sufficiently describes the obtained experimental data in rubber.

Fabrication of hydrophilic polymer nanocontainers by use of supramolecular templates.

Polymer-shelled vesicles are prepared by using cyclodextrin vesicles as supramolecular templates and an adamantane-functionalized poly(acrylic acid) additive anchored via host-guest recognition, followed by cross-linking of carboxylic acid groups on the polymer. The polymer-shelled nanocontainers are highly stable and effective for encapsulating small hydrophilic molecules. We also show that a hollow cross-linked polymer cage can be obtained after dissolution of the template vesicles. The size and shell thickness of the polymer cage can be tuned by variation of template size and polymer length.

From Single Atoms to Nanocrystals: Photoreduction of [PtCl6]2– in Aqueous and Tetrahydrofuran Solutions of PVP

Structured platinum nanoclusters Ptn (n = 5–30) capped by poly(N-vinylpyrrolidone) (PVP) have unique and highly attractive properties as potential selective catalysts. We show that the assembly of Pt mononuclear compounds in aqueous and tetrahydrofuran (THF) solutions under UV irradiation proceed via several steps: formation of linear Ptn clusters (n = 2–8), coalescence into mesocrystals, and transformation into Pt nanocrystals. The “quantum” size range of Ptn (n = 5–100) clusters is intermediate between those clusters with molecular properties and those with metallic properties. The PVP “cage” acts as a nano reactor and can hinder diffusion of photoexcited Pt atoms. The diffusion of the Pt from the polymer cage is strongly affected by the hydrophobic or hydrophilic property of the solution. An aqueous solution of [PtCl6]2– + PVP transforms into noncrystalline aggregates of molecules of less than 1.5–2 nm in diameter, whereas in THF solution Pt nanocrystals increase proportional to the UV irradiation time...

First Pseudohalogen Polymer Electrolyte for Dye-Sensitized Solar Cells Promising forIn SituPhotopolymerization

The incorporation of selenocianated-based redox couple in a polymer electrolyte for dye-sensitized solar cells is reported for the first time. The pseudohalogen redox mediator was integrated in two kinds of acrylic/methacrylic membranes prepared by photocopolymerization of multifunctional monomers. Before activation, the obtained membranes were transparent, self-standing and flexible, and the physicochemical characterizations of the films showed the formation of highly crosslinked architectures. Membranes were activated by swelling in an optimized solution containing the SeCN–/(SeCN)2 redox mediator with 4-tert-butylpyridine in acetonitrile, and the electrochemical behavior of the electrolytes revealed fast charge transfer kinetics. The photovoltaic performances of quasi-solid dye-sensitized solar cells were evaluated and compared with the results of the liquid counterpart, showing promising photoharvesting properties. No diminution in photoconversion efficiencies was evidenced in the comparison between solid and liquid cells, demonstrating an optimal kinetics of the redox species in the polymer cage, associated with a noteworthy increase in device durability, as demonstrated by aging tests. In addition, the in situ photopolymerization in the presence of the redox mediator is presented with outstanding results: this process, hardly feasible for the traditional I–/I3– couple (inhibitor of radical polymerization processes), enables at the same time the creation of an excellent electrode/electrolyte interface and the sealing of the device.

Tissue engineering rib with the incorporation of biodegradable polymer cage and BMSCs/decalcified bone: an experimental study in a canine model

BackgroundThe reconstruction of large bone defects, including rib defects, remains a challenge for surgeons. In this study, we used biodegradable polydioxanone (PDO) cages to tissue engineer ribs for the reconstruction of 4cm-long costal defects.MethodsPDO sutures were used to weave 6cm long and 1cm diameter cages. Demineralized bone matrix (DBM) which is a xenograft was molded into cuboids and seeded with second passage bone marrow mesenchymal stem cells (BMSCs) that had been osteogenically induced. Two DBM cuboids seeded with BMSCs were put into the PDO cage and used to reconstruct the costal defects. Radiographic examination including 3D reconstruction, histologic examination and mechanical test was performed after 24 postoperative weeks.ResultsAll the experimental subjects survived. In all groups, the PDO cage had completely degraded after 24 weeks and been replaced by fibrous tissue. Better shape and radian were achieved in PDO cages filled with DBM and BMSCs than in the other two groups (cages alone, or cages filled with acellular DBM cuboids). When the repaired ribs were subjected to an outer force, the ribs in the PDO cage/DBMs/BMSCs group kept their original shape while ribs in the other two groups deformed. In the PDO cage/DBMs/BMSCs groups, we also observed bony union at all the construct interfaces while there was no bony union observed in the other two groups. This result was also confirmed by radiographic and histologic examination.ConclusionsThis study demonstrates that biodegradable PDO cage in combination with two short BMSCs/DBM cuboids can repair large rib defects. The satisfactory repair rate suggests that this might be a feasible approach for large bone repair.

Cage Effect in Poly(alkyl methacrylate) Thin Films Studied by Nile Red Single Molecule Fluorescence Spectroscopy

Interactions in a probe–polymer cage were monitored by spectral fluctuations in the emission spectroscopy of single molecules of Nile Red in poly(alkyl methacrylate) thin films (25–200 nm) in the 278–323 K temperature range. Three types of emission spectra were identified. The highest emission energy spectra show small amplitude fluctuations and a very low probability of changing their spectral emission features. On the other hand, the other two types of emission profiles exchange more frequently. The fluctuations are analyzed by the complementary cumulative distribution function of spectral emission energy difference between successive spectra in a time trace. The fluctuations show three components: two of them with zero mean average and distinctly different standard deviations and a third component with much lower frequency and an amplitude absolute value of 0.13–0.15 eV. This amplitude is the same in all conditions, pointing to a common feature of the probe–polymer cage as responsible for their presence: complex cage rearrangements, involving the carbonyl side chain of the polymer as the common actor are postulated to be the cause of these spectral fluctuations in the time range of seconds.

An In Vitro Biomechanical Comparison of Single-Rod, Dual-Rod, and Dual-Rod With Transverse Connector in Anterior Thoracolumbar Instrumentation

After thoracolumbar corpectomy, standard anterolateral instrumentation may consist of dual rods with cross-connectors. However, when the vertebral bodies are small or involved with disease, only 1 rod may be possible. To compare the biomechanics of an in vitro L1 corpectomy model using 1 rod, 2 rods, or 2 rods with 2 cross-connectors. Eight fresh frozen human cadaveric spines were potted from T9 to L3. Pure moments of 1.5, 3, and 4.5 Nm were applied, and the motion of the spine was measured using 3 infrared cameras. Loads were applied in flexion and extension, right and left lateral bending, and right and left axial rotation. Each spine was first tested in the intact state. After performing an L1 corpectomy and replacement with a carbon fiber reinforced polymer cage, 3 constructs were tested: single rod (1R), dual rod (2R), and dual rod with 2 transverse connectors (CC). Analysis of variance suggests significant main effects of load (P < .0001), axis (P = .022), construct (P =.0019), and individual spine (P < .0001). Overall, the single-rod construct is significantly less rigid than the intact spine in axial rotation. There is no significant difference between the intact spine and either the dual-rod construct or the dual-rod cross-connector construct. In our in vitro model of anterior spinal stabilization after corpectomy and grafting, a single-rod construct is significantly less rigid than the intact spine. Addition of a second rod returns the rigidity of the spine to the intact state. A dual-rod cross-connector construct is significantly more rigid than a single-rod construct.

Triggered Release of Pharmacophores from [Ni(HAsO3)]-Loaded Polymer-Caged Nanobin Enhances Pro-apoptotic Activity: A Combined Experimental and Theoretical Study

Nanoscale drug delivery platforms can provide an attractive therapeutic strategy for cancer treatments, as they can substantially reduce the adverse side effects associated with toxic small-molecule anticancer agents. For enhanced therapeutic efficacy to be achieved with such platforms, a tumor-specific drug-release trigger is a critical requirement. This article reports the use of a pH-sensitive polymer network that surrounds a nanoscale liposome core to trigger the release of both encapsulated hydrophilic, membrane-impermeable Ni(II) cations and amphipathic, membrane-permeable As(III) anticancer agents under acidic conditions commonly encountered in hypoxic tumor tissues and late endosomes. Computational modeling studies provide clear evidence that the acid-triggered drug-release mechanism for this polymer-caged nanobin (PCN) platform arises from a pH- and temperature-responsive conformation change of the cross-linked polymer cage. As a result, the simultaneous release of both of the active agents in this multicomponent therapeutic enhances the pro-apoptotic activity of As(III) while diminishing its acute toxicity, potentially reducing the undesirable side effects commonly associated with this free drug. The ability to engender acid-triggered release of drugs co-encapsulated inside a liposomal template makes drug delivery using PCN an attractive strategy for triggered drug release.

Papillae mimetic hairy composite spheres towards lotus leaf effect coatings

An effective approach is proposed to fabricate a robust superhydrophobic coating constructed from hairy composite spheres. The hairy spheres mimic structure of the papillae on the surface of lotus leaf. The synthesis is based on template method and the corresponding PANi hairy spheres are prepared by polymerization induced diffusion growth via nanosized channels of a polymer cage. The composite spheres become more robust by coating a layer of inorganic materials onto the PANi hairy spheres. By using a middle adhesive layer of epoxy resin, the hairy spheres can be tightly attached to the substrate. The superhydrophobic coating is achieved with a contact angle of 159.9 ± 1.9° and tilt angle below 2° by a post hydrophobic modification with octadecyltrichlorosilane. Such coating is robust enough to resist water flushing and organic solvents. This method can be scaled up for almost all kinds of substrates.

A Multicenter Study to Evaluate the Safety and Efficacy of a Stand-Alone Anterior Carbon I/F Cage for Anterior Lumbar Interbody Fusion

Two-year prospective multicenter clinical trial. To determine the safety and efficacy of the anterior I/F Cage in the primary treatment of single-level degenerative disc disease. A carbon fiber-reinforced polymer cage was designed to replace the traditional allograft/autograft structural graft used in an anterior lumbar interbody fusion (ALIF). Although the outcomes of various types of ALIF cages have previously been reported, the safety and efficacy of the I/F cage are unknown. Between June 2000 and June 2004, 112 patients were prospectively enrolled at 12 study sites for the current study. Efficacy was evaluated clinically and radiographically. "Patient success" was declared only when the following 4 criteria were present at final follow-up: (1) "clinical success": improvement of 15 points on Oswestry Disability Index, (2) absence of a new neurologic abnormality, (3) successful radiographic fusion, and (4) no subsequent secondary surgical intervention at 24-month follow-up. Safety was inferred by way of an objective summary of complications and adverse events, as reported at regular intervals throughout the course of the study. A total of 112 patients (mean age: 41.7 years) underwent a single-level ALIF procedure (L5-S1: 95 patients, L4-L5: 17 patients). The mean surgical time was 126 minutes, the mean estimated blood loss was 134 mL, and the mean duration of hospitalization was 3.3 days. There were 80 patients available for 24-month follow-up. Overall patient success was 25% (20/80). Clinical success was present in 46.3% (37/80), fusion success was 57.5% (46/80), and 87.5% of patients (70/80) avoided a subsequent secondary surgical intervention. Disc space height had significantly increased after surgery, and this increase was maintained at 2 years follow-up period. Complications and adverse events included the following: 8 infections (7.1%) (7 superficial, 1 deep), 2 vascular injuries (1.8%) (left common iliac vein), and 12 secondary surgical interventions (15%). This safety and efficacy study suggests that the anterior I/F Cage is a safe surgical option in the treatment of single-level lumbar degenerative disc disease. As a stand-alone construct, the I/F Cage yields suboptimal radiographic and clinical outcomes. Additional benefit may be gained from adjunctive posterior stabilization.

Kinetic characteristics of the photoreduction of benzophenone in solid polymers in the presence of 4-halophenols

Benzophenone photoreduction in the presence of 4-halophenols (RC6H4OH; R = Cl, Br, and I) in a polymer glass is studied in terms of steady-state and nanosecond laser photolysis. The experimental data on the kinetics of the decay of the ketone triplet state are treated using a polychronous kinetic model in the assumption that two concurrent processes (hydrogen atom abstraction from the polymer and from the phenol) occur. The proton transfer rate constants averaged over the distribution and the parameter n that characterizes the distribution width were determined. The value of kav for the halophenols is shown to be more than an order of magnitude higher. No heavy atom effect is observed. The reaction product composition is demonstrated to change upon addition of a halophenol. The photoreduction in glass polymers is controlled by hydrogen atom abstraction from the respective donor by triplet ketone molecules. The reaction occurs predominantly in a polymer cage, a kind of polymer nanoreactor.