Efficacy of 3D printed anatomically equivalent thermoplastic polyurethane guide conduits in promoting the regeneration of critical-sized peripheral nerve defects.

Three-dimensional (3D) printing is an emerging tool for creating patient-specific tissue constructs analogous to the native tissue microarchitecture. In this study, anatomically equivalent 3D nerve conduits were developed using thermoplastic polyurethane (TPU) by combining reverse engineering and material extrusion (i.e., fused deposition modeling) technique. Printing parameters were optimized to fabricate nerve-equivalent TPU constructs. The TPU constructs printed with different infill densities supported the adhesion, proliferation, and gene expression of neuronal cells. Subcutaneous implantation of the TPU constructs for three months in rats showed neovascularization with negligible local tissue inflammatory reactions and was classified as a non-irritant biomaterial as per ISO 10993-6. To perform in vivo efficacy studies, nerve conduits equivalent to rat's sciatic nerve were fabricated and bridged in a 10 mm sciatic nerve transection model. After four months of implantation, the sensorimotor function and histological assessments revealed that the 3D printed TPU conduits promoted the regeneration in critical-sized peripheral nerve defects equivalent to autografts. This study proved that TPU-based 3D printed nerve guidance conduits can be created to replicate the complicated features of natural nerves that can promote the regeneration of peripheral nerve defects and also show the potential to be extended to several other tissues for regenerative medicine applications. .

Fabric structure and polymer composition as key contributors to micro(nano)plastic contamination in face masks.

The surge in face mask use due to COVID-19 has raised concerns about micro(nano)plastics (MNPs) from masks. Herein, focusing on fabric structure and polymer composition, we investigated MNP generation characteristics, mechanisms, and potential risks of surgical polypropylene (PP) and fashionable polyurethane (PU) masks during their wearing and photoaging based on stereomicroscope, µ-Fourier transform infrared spectroscopy (µ-FTIR), and scanning electron microscope (SEM) techniques. Compared with new PP and PU masks (66 ± 16 MPs/PP-mask, 163 ± 83 MPs/PU-mask), single- and multiple-used masks exhibited remarkably increased MP type and abundance (600-1867 MPs/PP-mask, 607-2167 MPs/PU-mask). Disinfection exacerbated endogenous MP generation in masks, with washing (416 MPs/PP-mask, 30,708 MPs/PU-mask) being the most prominent compared to autoclaving (219 MPs/PP-mask, 553 MPs/PU-mask) and alcohol spray (162 MPs/PP-mask, 18,333 MPs/PU-mask). Photoaging led to massive generation of MPs (8.8 × 104-3.7 × 105 MPs/PP-layer, 1.0 × 105 MPs/PU-layer) and NPs (5.2 × 109-3.6 × 1013 NPs/PP-layer, 3.5 × 1012 NPs/PU-layer) from masks, presenting highly fabric structure-dependent aging modes as "fragmentation" for fine fiber-structure PP mask and "erosion" for 3D mesh-structure PU mask. The MNPs derived from PP/PU mask caused significant deformities of Zebrafish (Danio rerio) larvae. These findings underscore the potential adverse effects of masks on humans and aquatic organisms, advocating to enhance proper use and rational disposal for masks.

The effects of submicron-textured surface topography on antibiotic efficacy against biofilms.

Submicron-textured surfaces have been a promising approach to mitigate biofilm development and control microbial infection. However, the use of the single surface texturing approach is still far from ideal for achieving complete control of microbial infections on implanted biomedical devices. The use of a surface topographic modification that might improve the utility of standard antibiotic therapy could alleviate the complications of biofilms on devices. In this study, we characterized the biofilms of Staphylococcus aureus and Pseudomonas aeruginosa on smooth and submicron-textured polyurethane surfaces after 1, 2, 3, and 7 days, and measured the efficacy of common antibiotics against these biofilms. Results show that the submicron-textured surfaces significantly reduced biofilm formation and growth, and that the efficacy of antibiotics against biofilms grown on textured surfaces was improved compared with smooth surfaces. The antibiotic efficacy appears to be related to the degree of biofilm development. At early time points in biofilm formation, antibiotic treatment reveals reasonably good antibiotic efficacy against biofilms on both smooth and textured surfaces, but as biofilms mature, the efficacy of antibiotics drops dramatically on smooth surfaces, with lesser decreases seen for the textured surfaces. The results demonstrate that surface texturing with submicron patterns is able to improve the use of standard antibiotic therapy to treat device-centered biofilms by slowing the development of the biofilm, thereby offering less resistance to antibiotic delivery to the bacteria within the biofilm community.

Nine years of patch testing with isocyanates in a clinic of occupational dermatology.

BACKGROUND: Isocyanates are used as starting materials of polyurethane (PU) products. They are relatively important occupational skin sensitizers. OBJECTIVES: To analyse results of a large isocyanate patch test series of 19 isocyanate test substances and 4,4'-diaminodiphenylmethane (MDA), a marker of 4,4'-diphenylmethane diisocyanate (MDI) hypersensitivity. METHODS: Test files were screened for positive reactions in the isocyanate series. Patients with positive reactions were analysed for occupation, exposure and diagnosis. RESULTS: In 2010-2019, 53 patients had positive reactions in the series (16% of 338 patients tested). MDA, the well-established screening substance for MDI allergy, was positive in 30 patients, an in-house monomeric MDI test substance in 23 patients and 3 different polymeric MDI test substances in 19-21 patients. We diagnosed 16 cases of occupational allergic contact dermatitis (OACD) from MDI including 3 pipe reliners. Hexamethylene-1,6-diisocyanate (HDI) oligomers in paint hardeners caused 5 cases of OACD, more cases than 2,4-toluene diisocyanate (TDI; n = 3) and isophorone diisocyanate (IPDI; n = 1) put together. CONCLUSIONS: In contrast to previous studies, polymeric MDI test substances were not superior to a monomeric MDI. Pipe reliners may get sensitised not only by epoxy products and acrylates but also by MDI in hardeners of PU pipe coatings. HDI oligomers were the second most important causes of OACD after MDI.

Nickel ferrite decorated noble metal containing nitrogen-doped carbon nanotubes as potential magnetic separable catalyst for dinitrotoluene hydrogenation.

The 2,4-toluenediamine (TDA) is one of the most important chemicals in the polyurethane industry, produced by the catalytic hydrogenation of 2,4-dinitrotoluene (DNT). The development of novel catalysts that can be easily recovered from the reaction mixture is of paramount importance. In our work, a NiFe2O4/N-BCNT supported magnetic catalyst was prepared by a modified coprecipitation method. The catalyst support alone also showed activity in the synthesis of TDA. Platinum nanoparticles were deposited on the catalyst support surface by a fast, relatively simple, and efficient sonochemical method, resulting in a readily applicable catalytically active system. The prepared catalyst exhibited high activity in hydrogenation tests, which was proved by the exceptionally high DNT conversion (100% for 120 min at 333 K) and TDA yield (99%). Furthermore, the magnetic catalyst can be easily recovered from the reaction medium by the action of an external magnetic field, which can greatly reduce catalyst loss during separation.

Imparting Ultrahigh Strength to Polymers via a New Concept Strategy of Construction of up to Duodecuple Hydrogen Bonding among Macromolecular Chains.

Interconnecting macromolecules via multiple hydrogen bonds (H-bonds) can simultaneously strengthen and toughen polymers, but material synthesis becomes extremely difficult with increasing number of H-bonding donors and acceptors; therefore, most reports are limited to triple and quadruple H-bonds. Herein, this bottleneck is overcome by adopting a quartet-wise approach of constructing H-bonds instead of the traditional pairwise method. Thus, large multiple hydrogen bonds can be easily established, and the supramolecular interactions are further reinforced. Especially, when such multiple H-bond motifs are embedded in polymers, four macromolecular chains-rather than two as usual-are tied, distributing the applied stress over a larger volume and more significantly improving the overall mechanical properties. Proof-of-concept studies indicate that the proposed intermolecular multiple H-bonds (up to duodecuple) are readily introduced in polyurethane. A record-high tensile strength (105.2 MPa) is achieved alongside outstanding toughness (352.1 MJ m-3), fracture energy (480.7 kJ m-2), and fatigue threshold (2978.4 J m-2). Meantime, the polyurethane has acquired excellent self-healability and recyclability. This strategy is also applicable to nonpolar polymers, such as polydimethylsiloxane, whose strength (15.3 MPa) and toughness (50.3 MJ m-3) are among the highest reported to date for silicones. This new technique has good expandability and can be used to develop even more and stronger polymers.

An Acellular, Self-Healed Trilayer Cryogel for Osteochondral Regeneration in Rabbits.

Osteochondral regeneration remains formidable challenges despite significant advances in microsurgery. Herein, an acellular trilayer cryogel (TC) with injectability, tunable pore sizes (80-200 µm), and appropriate compressive modulus (10.8 kPa) is manufactured from self-healable hydrogel under different gelling times through Schiff reaction between chitosan and difunctionalized polyurethane (DFPU). Bioactive molecules (Y27632 and dexamethasone) are respectively loaded in the top and bottom layers to form the Y27632/dexamethasone-loaded trilayer cryogel (Y/DEX-TC). Mesenchymal stem cells (MSCs) seeded in Y/DEX-TC proliferated ≈350% in vitro and underwent chondrogenesis or osteogenesis in response to the respective release of Y or DEX in 14 days. Acupuncture is administered to animals in an attempt to modulate the innate regulatory system and mobilize endogenous MSCs for osteochondral defect regeneration. In vivo rabbit experiments using Y/DEX-TC combined with acupuncture successfully regulate SDF-1 and TGF-ß1 levels, which possibly cause MSC migration toward Y/DEX-TC. The synergistic effect of cryogel and acupuncture on immunomodulation is verified with a ≈7.3-fold enhancement of the M2-/M1-macrophage population ratio by treatment of Y/DEX-TC combining acupuncture, significantly greater than ≈1.5-fold increase by acupuncture or ≈2.2-fold increase by Y/DEX-TC alone. This novel strategy using acellular drug-loaded cryogel and accessible acupuncture shows promise in treating osteochondral defects of joint damage.

Unraveling the Impact of Boron Nitride and Silicon Nitride Nanoparticles on Thermoplastic Polyurethane Fibers and Mats for Advanced Heat Management.

The urgent challenges posed by the energy crisis, alongside the heat dissipation of advanced electronics, have embarked on a rising demand for the development of highly thermally conductive polymer composites. Electrospun composite mats, known for their flexibility, permeability, high concentration and orientational degree of conductive fillers, stand out as one of the prime candidates for addressing this need. This study explores the efficacy of boron nitride (BN) and its potential alternative, silicon nitride (SiN) nanoparticles, in enhancing the thermal performance of the electrospun composite thermoplastic polyurethane (TPU) fibers and mats. The 3D reconstructed models obtained from FIB-SEM imaging provided valuable insights into the morphology of the composite fibers, aiding the interpretation of the measured thermal performance through scanning thermal microscopy for the individual composite fibers and infrared thermography for the composite mats. Notably, we found that TPU-SiN fibers exhibit superior heat conduction compared to TPU-BN fibers, with up to a 6 °C higher surface temperature observed in mats coated on copper pipes. Our results underscore the crucial role of arrangement of nanoparticles and fiber morphology in improving heat conduction in the electrospun composites. Moreover, SiN nanoparticles are introduced as a more suitable filler for heat conduction enhancement of electrospun TPU fibers and mats, suggesting immense potential for smart textiles and thermal management applications.

"One for two" strategy to construct an organic-inorganic polymer colloid for flame-retardant modification of flax fabric and rigid polyurethane foam.

Polymeric materials such as fabric and foam have high flammability which limits their application in the field of fire protection. To this end, an organic-inorganic polymer colloid constructed from carboxymethyl chitosan and ammonium polyphosphate was used to improve the flame retardancy of flax fabric (FF) and rigid polyurethane foam (RPUF) based on a "one for two" strategy. The modification processes of FF and RPUF relied on pad-dry-cure method and UV-curing technology, respectively, and the modified FF and RPUF were severally designated as CMC/APP-FF and RFR-RPUF. Flame retardancy studies showed that CMC/APP-FF and RFR-RPUF exhibited limiting oxygen index values as high as 39.4 % and 42.6 %, respectively, and both achieved self-extinguishing behavior when external ignition source was removed. Thermogravimetric analysis and cone calorimetry test confirmed that CMC/APP-FF and RFR-RPUF had good charring ability and demonstrated reduced peak heat release rate values of 90.1 % and 10.8 %, respectively, distinct from before they were modified. In addition, condensed phase analysis showed that after burning, CMC/APP-FF became an integration char structure, whereas RFR-RPUF turned into a sandwiched char structure. In summary, the "one for two" strategy reported in this work provides a new insight into the economical fabrication of flame-retardant polymeric materials.

Microstructure Evolution of Reactive Polyurethane Films During In Situ Polyaddition and Film-Formation Processes.

Due to the advantages of low energy consumption, no air and water pollutions, the reactive polyurethane films (RPUFs) are replacing the solvated and waterborne PUFs nowadays, which significantly promotes the green and low-carbon production of PU films. However, the microstructure evolution and in situ film-formation mechanism of RPUFs in solvent-free media are still unclear. Herein, according to time-temperature equivalence principle, the in situ polyaddition and film-formation processes of RPUFs generated by the typical polyaddition of diisocyanate terminated prepolymer (component B) and polyether glycol (component A) are thoroughly investigated at 25 °C. According to the temporal change of viscosity, the RPUFs gradually transfer from liquid to gel and finally to solid state. Further characterizing the molecular weight, hydrogen bonds, crystallinity, gel content, and phase images, the polyaddition and film-formation processes can be divided into three stages as 1) chain extension and microcrystallization; 2) gelation and demicrocrystallization; 3) microphase separation and film-formation. This work promotes the understanding of the microstructure evolution and film-formation mechanism of RPUFs, which can be used as the theoretical guidance for the controllable preparation of high-performance products based on RPUFs.

Bio-based melamine formaldehyde resins for flame-retardant polyurethane foams.

The polyurethane (PU) foams can be functionally tailored by modifying the formulation with different additives. One such additive is melamine (MA) formaldehyde resin for improving their flame-retardant properties. In this work, the glycerol-modified (GMF), sodium alginate (SGMF)- and lignosulfonate-modified melamine formaldehyde (LGMF) were prepared and used as flame retardants reacting with isocyanate to prepare the corresponding rigid polyurethane foams (GMF-PU, SGMF-PU and LGMF-PU). The thermomechanical properties and flame-retardant properties of the foams were characterized. The results showed that the specific compression strength of GMF-PU, SGMF-PU and LGMF-PU increased substantially compared to the foams from physical addition of MA, sodium alginate and lignosulfonate, all of which were greater than that of the foam without any flame retardant (PPU). Meanwhile, the cell wall of the foam pores became thicker and the closed pore ratio increased. The sodium alginate and lignosulfonate played a key role in enhancing foam thermal stability. The limiting oxygen index values and cone calorimetry results indicated the flame-retardant efficiency of GMF-PU, SGMF-PU and LGMF-PU was significantly enhanced relative to PPU. Meanwhile, the heat and smoke release results indicated sodium alginate and lignosulfonate could reduce the amount of smoke generation to different degrees during the combustion of the foam.

Preparation of Gradient Polyurethane and Its Performance for Flexible Sensors.

Flexible sensors are prone to the problems of slow recovery rate and large residual strain in practical use. In this paper, a polyurethane functional composite with a gradient change in elastic modulus is proposed as a flexible sensor to meet the recovery rate and residual strain without affecting the motion. Different hard and soft segment ratios are used to synthesize a gradient polyurethane structure. The conductive percolation threshold was obtained between 45 wt% and 50 wt% of flake silver powder. Both gradient polyurethane and gradient polyurethane composites demonstrated that gradient materials can increase the recovery rate and reduce residual strain. The gradient polyurethane composites had a tensile strength of 3.26 MPa, an elastic modulus of 2.58 MPa, an elongation at break of 245%, a sensitivity coefficient of 1.20 at 0-25% deformation, a sensitivity coefficient of 11.38 at 25-75% deformation, a rate of recovery of 1.95 s at a time, and a resistance to fatigue (over 1000 cycles at a fixed strain of 20% showed a stable electrical response). The sensing performance under different cyclic strain frequencies was also investigated. The process has practical applications in the field of wearable skin motion and health monitoring.

Mechanochemical Recycling of Flexible Polyurethane Foam Scraps for Quantitative Replacement of Polyol Using Wedge-Block-Reinforced Extruder.

Recycling flexible polyurethane foam (F-PUF) scraps is difficult due to the material's high cross-linking structure. In this work, a wedge-block-reinforced extruder with a considerable enhanced shear extrusion and stretching area between the rotating screw and the stationary wedge blocks was utilized to recycle F-PUF scraps into powder containing surface-active hydroxyl groups. The powder was then utilized for the quantitative replacement of polyol in the foaming process. Characterizations showed that the continuous shear extrusion and stretching during the extrusion process reduced the volume mean diameter (VMD) of the F-PUF powder obtained by extruding it three times at room temperature to reach 54 µm. The -OH number (OHN) of the powder prepared by extruding it three times reached 19.51 mgKOH/g due to the mechanochemical effect of the powdering method. The F-PUF containing recycled powder used to quantitively replace 10 wt.% polyol was similar in microstructure and chemical structure to the original F-PUF, with a compression set of 2%, indentation load deflection of 21.3 lbf, resilience of 43.4%, air permeability of 815.7 L/m2·s, tensile strength of 73.0 Kpa, and tear strength of 2.3 N/cm, indicating that the recycling method has potential for industrial applications.

In Vivo Durability of Polyurethane Insulated Implantable Cardioverter Defibrillator (ICD) Leads.

The 6935M Sprint Quattro Secure S and 6947M Sprint Quattro Secure are high voltage leads designed to administer a maximum of 40 joules of energy for terminating ventricular tachycardia or ventricular fibrillation. Both leads utilize silicone insulation and a polyurethane outer coating. The inner coil is shielded with polytetrafluoroethylene (PTFE) tubing, while other conductors are enveloped in ethylene tetrafluoroethylene (ETFE), contributing to the structural integrity and functionality of these leads. Polyurethane is a preferred material for the outer insulation of cardiac leads due to its flexibility and biocompatibility, while silicone rubber ensures chemical stability within the body, minimizing inflammatory or rejection responses. Thirteen implantable cardioverter defibrillator (ICD) leads were obtained from the Wright State University Anatomical Gift Program. The as-received devices exhibited varied in vivo implantation durations ranging from less than a month to 89 months, with an average in vivo duration of 41 ± 27 months. Tests were conducted using the Test Resources Q series system, ensuring compliance with ASTM Standard D 1708-02a and ASTM Standard D 412-06a. During testing, a load was applied to the intact lead, with careful inspection for surface defects before each test. Results of load to failure, percentage elongation, percentage elongation at 5 N, ultimate tensile strength, and modulus of elasticity were calculated. The findings revealed no significant differences in these parameters across all in vivo exposure durations. The residual properties of these ICD leads demonstrated remarkable stability and performance over a wide range of in vivo exposure durations, with no statistically significant degradation or performance changes observed.

Xanthan-Polyurethane Conjugates: An Efficient Approach for Drug Delivery.

The antifungal agent, ketoconazole, and the anti-inflammatory drug, piroxicam, were incorporated into matrices of xanthan or oleic acid-esterified xanthan (Xn) and polyurethane (PU), to develop topical drug delivery systems. Compared to matrices without bioactive compounds, which only showed a nominal compressive stress of 32.18 kPa (sample xanthan-polyurethane) at a strain of 71.26%, the compressive resilience of the biomaterials increased to nearly 50.04 kPa (sample xanthan-polyurethane-ketoconazole) at a strain of 71.34%. The compressive strength decreased to around 30.67 kPa upon encapsulating a second drug within the xanthan-polyurethane framework (sample xanthan-polyurethane-piroxicam/ketoconazole), while the peak sustainable strain increased to 87.21%. The Weibull model provided the most suitable fit for the drug release kinetics. Unlike the materials based on xanthan-polyurethane, those made with oleic acid-esterified xanthan-polyurethane released the active ingredients more slowly (the release rate constant showed lower values). All the materials demonstrated antimicrobial effectiveness. Furthermore, a higher volume of piroxicam was released from oleic acid-esterified xanthan-polyurethane-piroxicam (64%) as compared to xanthan-polyurethane-piroxicam (44%). Considering these results, materials that include polyurethane and either modified or unmodified xanthan showed promise as topical drug delivery systems for releasing piroxicam and ketoconazole.

Solidification of Polyurethane Model Foams via Catalyst Drainage from a Secondary Foam.

Due to their unique mechanical and thermal properties, polyurethane foams are widely used in multiple fields of applications, including cushioning, thermal insulation or biomedical engineering. However, the way polyurethane foams are usually manufactured - via chemical foaming - produces samples where blowing and gelling occurs at the same time, resulting in a morphology control achieved by trial and error processes. Here, we introduce a novel strategy to build model homogeneous polyurethane foams of controlled density with millimetric bubbles from liquid templates. We show that by producing a polyurethane foam via physical bubbling without a catalyst and gently depositing a secondary foam containing catalyst on the top of this first foam, we can take advantage of drainage mechanisms to trigger the solidification of the bottom foam. The characterisation of our samples performed by X-ray microtomography allows us to study quantitatively the structure of the final solid foam, at the global and at the local scale. Using the tomographic three-dimensional images of the foam architectures, we show that the superimposed foam technique introduced in this article is promising to produce foams with a good homogeneity along the vertical direction, with a density controlled by varying the concentration of catalyst in the secondary foam. This article is protected by copyright. All rights reserved.

Thermoplastic Polyurethane-poly(N-isopropylacrylamide) Copolymer for Selective Uptake of Alcohol from Aqueous Solution.

Ethanol possesses high economic value, but as an industrial waste, it poses harm to human health and the environment. The paper describes the preparation of a thermoplastic polyurethane-poly(n-isopropylacrylamide) (TPU-PNIPAM) copolymer designed to selectively uptake alcohol in aqueous solution. The material was created by bonding TPU and PNIPAM together through intermolecular hydrogen bonds, enhancing its hydrophobic properties and making it easier to interact with alcohol molecules. As the amount of PNIPAM in TPU increases, the number of hydrophobic isopropyl groups in TPU-PNIPAM also increases, leading to an enhanced selective uptake ability of TPU-PNIPAM for alcohols in aqueous solution. When the temperature reaches 55 °C, the hydrophobic groups in TPU-PNIPAM are more exposed, further enhancing the selective uptake ability of TPU-PNIPAM for alcohols in aqueous solution. TPU-PNIPAM demonstrates selective preferential uptake for various concentrations and types of alcohol in aqueous solutions. The material's selective uptake performance for alcohols increases with their hydrophobicity, so TPU-PNIPAM exhibited the best adsorption performance for a 10 wt% n-propanol solution under the combined effect of steric hindrance. In addition, TPU-PNIPAM exhibited selective adsorption for other organic solvents, which demonstrated the universality of TPU-PNIPAM in removing contaminants from aqueous solutions.

Polyurethane Composites Recycling with Styrene-Acrylonitrile and Calcium Carbonate Recovery.

The glycolysis process of flexible polyurethane foams containing styrene-acrylonitrile and calcium carbonate as fillers was explored in detail. The use of DABCO as a catalyst allowed us to reduce the catalyst concentration and the polyurethane-to-glycol mass ratio to 0.1% and 1:1, respectively. The glycolysis process allowed us to obtain a high-purity polyol (99%), which can totally replace raw polyols in the synthesis of new flexible polyurethane foams, maintaining the standard mechanical properties of the original one and modifying the ratio of isocyanates employed to correct the closed cell structure caused by the impurities present in the recovered polyol. This isocyanate mixture was also optimized, resulting in a ratio of 30 and 70% of the isocyanates TDI80 and TDI65, respectively. Additionally, the fillers incorporated in the glycolyzed foams were recovered. Both recovered fillers, styrene-acrylonitrile and calcium carbonate, were fully characterized, showing a quality very similar to that of commercial compounds. Finally, the replacement of commercial fillers by the recovered ones in the synthesis of new polyurethane foams was studied, demonstrating the feasibility of using them in the synthesis of new foams without significantly altering their properties.

Alternative Method for Determination of Vibroacoustic Material Parameters for Building Applications.

The development of urbanization and the resulting expansion of residential and transport infrastructures pose new challenges related to ensuring comfort for city dwellers. The emission of transport vibrations and household noise reduces the quality of life in the city. To counteract this unfavorable phenomenon, vibration isolation is widely used to reduce the propagation of vibrations and noise. A proper selection of vibration isolation is necessary to ensure comfort. This selection can be made based on a deep understanding of the material parameters of the vibration isolation used. This mainly includes dynamic stiffness and damping. This article presents a comparison of the method for testing dynamic stiffness and damping using a single degree of freedom (SDOF) system and the method using image processing, which involves tracking the movement of a free-falling steel ball onto a sample of the tested material. Rubber granules, rubber granules with rubber fibers, and rebound polyurethanes were selected for testing. Strong correlations were found between the relative indentation and dynamic stiffness (at 10-60 MN/m3) and the relative rebound and damping (for 6-12%). Additionally, a very strong relationship was determined between the density and fraction of the critical damping factor/dynamic stiffness. The relative indentation and relative rebound measurement methods can be used as an alternative method to measure the dynamic stiffness and critical damping factor, respectively.

Incorporation of Cu-TATAB metal-organic framework within polyurethane nanocomposite for enhanced thin film microextraction of some chlorinated pesticides.

In this research, electrospun nanofibers based on copper-based metal organic framework (MOF)/polyurethane (PU) were prepared in order to achieve an applicable and superior extractive phase. The incorporation of MOF, in the synthesized nanocomposite contributed to the enhanced sorption efficiency. The prepared sorbent was implemented for the thin film microextraction (TFME) of target compounds with subsequent quantification using gas chromatography-mass spectrometry (GC-MS). To obtain the maximum efficiency of the synthesized sorbent, the influential parameters on extraction and desorption steps, including the MOF percentage in nanocomposite, desorption solvent type and its volume, desorption time, solution ionic strength and extraction time were optimized. After method development, the linear dynamic range (0.02-700 µg L-1), limits of detection (LODs) (0.005-0.1 µg L-1) and limits of quantification (LOQs))0.02-0.33 µg L-1(were calculated. The relative standard deviations values for intra-day and inter-day analysis were found to be in the range of 4.3-5.3 % and 6.2-8.1 %, respectively. The developed method was validated for the TFME of model organochlorine (OC) pesticide residues in fish, soil and water samples. the recovery values for the spiked samples at two concentration levels of 5 and 100 µg l-1 were found in the range of 72-110 %.