Falcon Probe: A High-Pressure and Robust Sampling Interface for Coupling Lossless Liquid Chromatography Injection with In Situ Nanoliter-Scale Sample Pretreatment.

With the increasing demand for trace sample analysis, injecting trace samples into liquid chromatography-mass spectrometry (LC-MS) systems with minimal loss has become a major challenge. Herein, we describe an in situ LC-MS analytical probe, the Falcon probe, which integrates multiple functions of high-pressure sample injection without sample loss, high-efficiency LC separation, and electrospray. The main body of the Falcon probe is made of stainless steel and fabricated by the computer numerical control (CNC) technique, which has ultrahigh mechanical strength. By coupling a nanoliter-scale droplet reactor made of polyether ether ketone (PEEK) material, the Falcon probe-based LC-MS system was capable of operating at mobile-phase pressures up to 800 bar, which is comparable to those of conventional ultraperformance liquid chromatography (UPLC) systems. Using the probe pressing microamount in situ (PPMI) injection approach, the Falcon probe-based LC-MS system showed high separation efficiency and good repeatability with relative standard deviations (RSDs) of retention time and peak area of 1.8% and 9.9%, respectively, in peptide mixture analysis (n = 6). We applied this system to the analysis of a trace amount of 200 pg of HeLa protein digest and successfully identified an average of 766 protein groups (n = 5). By combining in situ sample pretreatment at the nanoliter range, we further applied the present system in single-cell proteomic analysis, and 241 protein groups were identified in single 293 cells, which preliminarily demonstrated its potential in the analysis of trace amounts of samples with complex compositions.

Propelling Multi-Modal Therapeutics of PEEK Implants through the Power of NO evolving Covalent Organic Frameworks (COFs).

The design and fabrication of NO-evolving core-shell nanoparticles (denoted as NC@Fe), comprised of BNN6-laden COF@Fe3 O4 nanoparticles, are reported. This innovation extends to the modification of 3D printed polyetheretherketone scaffolds with NC@Fe, establishing a pioneering approach to multi-modal bone therapy tailored to address complications such as device-associated infections and osteomyelitis. This work stands out prominently from previous research, particularly those relying on the use of antibiotics, by introducing a bone implant capable of simultaneous NO gas therapy and photothermal therapy (PPT). Under NIR laser irradiation, the Fe3 O4 NP core (photothermal conversion agent) within NC@Fe absorbs photoenergy and initiates electron transfer to the loaded NO donor (BNN6), resulting in controlled NO release. The additional heat generated through photothermal conversion further propels the NC@Fe nanoparticles, amplifying the therapeutic reach. The combined effect of NO release and PPT enhances the efficacy in eradicating bacteria over a more extensive area around the implant, presenting a distinctive solution to conventional challenges. Thorough in vitro and in vivo investigations validate the robust potential of the scaffold in infection control, osteogenesis, and angiogenesis, emphasizing the timeliness of this unique solution in managing complicated bone related infectious diseases.

Brushing Up on Cartilage Lubrication: Polyelectrolyte-Enhanced Tribological Rehydration.

This study presents new insights into the potential role of polyelectrolyte interfaces in regulating low friction and interstitial fluid pressurization of cartilage. Polymer brushes composed of hydrophilic 3-sulfopropyl methacrylate potassium salt (SPMK) tethered to a PEEK substrate (SPMK-g-PEEK) are a compelling biomimetic solution for interfacing with cartilage, inspired by the natural lubricating biopolyelectrolyte constituents of synovial fluid. These SPMK-g-PEEK surfaces exhibit a hydrated compliant layer approximately 5 µm thick, demonstrating the ability to maintain low friction coefficients (µ ∼ 0.01) across a wide speed range (0.1-200 mm/s) under physiological loads (0.75-1.2 MPa). A novel polyelectrolyte-enhanced tribological rehydration mechanism is elucidated, capable of recovering up to ∼12% cartilage strain and subsequently facilitating cartilage interstitial fluid recovery, under loads ranging from 0.25 to 2.21 MPa. This is attributed to the combined effects of fluid confinement within the contact gap and the enhanced elastohydrodynamic behavior of polymer brushes. Contrary to conventional theories that emphasize interstitial fluid pressurization in regulating cartilage lubrication, this work demonstrates that SPMK-g-PEEK's frictional behavior with cartilage is independent of these factors and provides unabating aqueous lubrication. Polyelectrolyte-enhanced tribological rehydration can occur within a static contact area and operates independently of known mechanisms of cartilage interstitial fluid recovery established for converging or migrating cartilage contacts. These findings challenge existing paradigms, proposing a novel polyelectrolyte-cartilage tribological mechanism not exclusively reliant on interstitial fluid pressurization or cartilage contact geometry. The implications of this research extend to a broader understanding of synovial joint lubrication, offering insights into the development of joint replacement materials that more accurately replicate the natural functionality of cartilage.

Polysaccharide Aldehydes and Ketones: Synthesis and Reactivity.

Polysaccharides are biodegradable, abundant, sustainable, and often benign natural polymers. The achievement of selective modification of polysaccharides is important for targeting specific properties and structures and will benefit future development of highly functional, sustainable materials. The synthesis of polysaccharides containing aldehyde or ketone moieties is a promising tool for achieving this goal because of the rich chemistry of aldehyde or ketone groups, including Schiff base formation, nucleophilic addition, and reductive amination. The obtained polysaccharide aldehydes or ketones themselves have rich potential for making useful materials, such as self-healing hydrogels, polysaccharide-protein therapeutic conjugates, or drug delivery vehicles. Herein, we review recent advances in synthesizing polysaccharides containing aldehyde or ketone moieties and briefly introduce their reactivity and corresponding applications.

Improved Mobility-Stretchability Properties of Diketopyrrolopyrrole-Based Conjugated Polymers with Diastereomeric Conjugation Break Spacers.

Stretchable conjugated polymers with conjugation break spacers (CBSs) synthesized via random terpolymerization have gained considerable attention because of their efficacy in modulating mobility and stretchability. This study incorporates a series of dianhydrohexitol diastereomers of isosorbide (ISB) and isomannide (IMN) units into the diketopyrrolopyrrole-based backbone as CBSs. It is found that the distorted CBS (IMN) improves the mobility-stretchability properties of the polymer with a highly coplanar backbone, whereas the extended CBS (ISB) enhances those of the polymer with a noncoplanar backbone. Additionally, the different configurations of ISB and IMN sufficiently affect the solid-state packing, aggregation capabilities, crystallographic parameters, and mobility-stretchability properties of the polymer. The IMN-based polymers exhibit the highest mobility of 1.69 cm2 V-1 s-1 and crystallinity retentions of (85.7, 78.6)% under 20% and 60% strains, outperforming their ISB-based or unmodified counterparts. The improvement is correlated with a robust aggregation capability. Furthermore, the CBS content affects aggregation behavior, notably affecting mobility. This result indicates that incorporating CBSs into the polymer can enhance backbone flexibility via movement and rotation of the CBS without affecting the crystalline regions.

Clinical and radiological results of TLIF surgery with titanium-coated PEEK or uncoated PEEK cages: a prospective single-centre randomised study.

BACKGROUND: A comparison of fusion rates and clinical outcomes of instrumented transforaminal interbody fusion (TLIF) between polyetheretherketone (PEEK) and titanium-coated PEEK (Ti-PEEK) cages is not well documented. METHODS: A single-centre, prospective, randomised study included patients who underwent one-level TLIF between L3-S1 segments. Patients were randomised into one of two groups: TLIF surgery with the PEEK cage and TLIF surgery with the Ti-PEEK cage. Clinical results were measured. All patients were assessed by repeated X-rays and 3D CT scans. Cage integration was assessed using a modified Bridwell classification. The impact of obesity and smoking on fusion quality was also analysed. Patients in both groups were followed up for 2 years. RESULTS: Altogether 87 patients were included in the study: of these 87 patients, 81 (93.1%) completed the 2-year follow-up. A significant improvement in clinical outcome was found in the two measurements scales in both groups (RM: p = 0.257, VAS: p = 0.229). There was an increase in CobbS and CobbL angle in both groups (p = 0.172 for CobbS and p = 0.403for CobbL). Bony fusion was achieved in 37 of 40 (92.5%) patients in the TiPEEK group and 35 of 41 (85.4%) in the PEEK group (p = 0.157). Cage subsided in 2 of 40 patients (5%) in the TiPEEK group and 11 of 41 (26.8%) in the PEEK group (p = 0.007). Body mass index > 30 and smoking were not predictive factors of bony fusion achievement. CONCLUSION: There is no significant advantage of TiPEEK cages over PEEK cages in clinical outcome and fusion rate 2 years after surgery.

Influence of instrumentation type on outcomes after surgical management of spondylodiscitis: a systematic review and meta-analysis.

OBJECTIVE: Spondylodiscitis refers to infection of the intervertebral disk and neighboring structures. Outcomes based on instrumentation type are not well reported in the literature, but are important in establishing guidelines for surgical management of spondylodiscitis. This study aims to clarify the effect of instrumentation material selection on clinical and radiographic outcomes in patients with spondylodiscitis. METHODS: Studies that evaluated the use of polyetheretherketone (PEEK), titanium, allograft, and/or autologous bone grafts for spondylodiscitis were identified in the literature. Radiographic and clinical data were analyzed using a meta-analysis of proportions, with estimated risk and confidence intervals reported for our primary study outcomes. RESULTS: Thirty-two retrospective studies totaling 1088 patients undergoing surgical management of spondylodiscitis with PEEK, TTN, allograft, and autologous bone graft instrumentation were included. There were no differences in fusion rates (p-interaction = 0.55) with rates of fusion of 93.4% with TTN, 98.6% with allograft, 84.2% with autologous bone graft, and 93.9% with PEEK. There were no differences in screw loosening (p-interaction = 0.52) with rates of 0.33% with TTN, 0% with allograft, 1.3% with autologous bone graft, and 8.2% with PEEK. There were no differences in reoperation (p-interaction = 0.59) with rates of 2.64% with TTN, 0% with allograft, 1.69% with autologous bone graft, and 3.3% with PEEK. CONCLUSIONS: This meta-analysis demonstrates that the choice of instrumentation type in the surgical management of spondylodiscitis resulted in no significant differences in rate of radiographic fusion, screw loosening, or reoperation. Future comparative studies to optimize guidelines for the management of spondylodiscitis are needed.

Retrieval analysis of PEEK rods pedicle screw system: three cases analysis.

PURPOSE: To analyze the characteristics of PEEK rods retrieved in vivo, specifically their wear and deformation, biodegradability, histocompatibility, and mechanical properties. METHOD: Six PEEK rods were retrieved from revision surgeries along with periprosthetic tissue. The retrieved PEEK rods were evaluated for surface damage and internal changes using Micro-CT, while light and electron microscopy were utilized to determine any histological changes in periprosthetic tissues. Patient history was gathered from medical records. Two intact and retrieved PEEK rods were used for fatigue testing analysis by sinusoidal load to the spinal construct. RESULTS: All implants showed evidence of plastic deformation around the screw-rod interface, while the inner structure of PEEK rods appeared unchanged with no visible voids or cracks. Examining images captured through light and electron microscopy indicated that phagocytosis of macrophages around PEEK rods was less severe in comparison to the screw-rod interface. The results of an energy spectrum analysis suggested that the distribution of tissue elements around PEEK rods did not differ significantly from normal tissue. During fatigue testing, it was found that the retrieved PEEK rods cracked after 1.36 million tests, whereas the intact PEEK rods completed 5 million fatigue tests without any failure. CONCLUSION: PEEK rods demonstrate satisfactory biocompatibility, corrosion resistance, chemical stability, and mechanical properties. Nevertheless, it is observed that the indentation at the junction between the nut and the rod exhibits relatively weak strength, making it susceptible to breakage. As a precautionary measure, it is recommended to secure the nut with a counter wrench, applying the preset torque to prevent overtightening.

Clinical performance of implanted devices used in surgical treatment of patients with spinal tumors: a systematic review.

PURPOSE: Implanted devices used in metastatic spine tumor surgery (MSTS) include pedicle screws, fixation plates, fixation rods, and interbody devices. A material to be used to fabricate any of these devices should possess an array of properties, which include biocompatibility, no toxicity, bioactivity, low wear rate, low to moderate incidence of artifacts during imaging, tensile strength and modulus that are comparable to those of cortical bone, high fatigue strength/long fatigue life, minimal or no negative impact on radiotherapy (RT) planning and delivery, and high capability for fusion to the contiguous bone. The shortcomings of Ti6Al4V alloy for these applications with respect to these desirable properties are well recognized, opening the field for an investigation about novel biomaterials that could replace the current gold standard. Previously published reviews on this topic have exhibited significant shortcomings in the studies they included, such as a small, heterogenous sample size and the lack of a cost-benefit analysis, extremely useful to understand the practical possibility of applying a novel material on a large scale. Therefore, this review aims to collect information about the clinical performance of these biomaterials from the most recent literature, with the objective of deliberating which could potentially be better than titanium in the future, with particular attention to safety, artifact production and radiotherapy planning interference. The significant promise showed by analyzing the clinical performance of these devices warrants further research through prospective studies with a larger sample size also taking into account each aspect of the production and use of such materials. METHODS: The Preferred Reporting Items for Systematic reviews and Meta-Analyses (PRISMA) guidelines were used to improve the reporting of the review. The search was performed from March 2022 to September 2023. RESULTS: At the end of the screening process, 20 articles were considered eligible for this study. Polyetheretherketone (PEEK), Carbon-fibre reinforced polyetheretherketone (CFR-PEEK), long carbon fiber reinforced polymer (LCFRP), Polymethylmethacrylate (PMMA), and carbon screw and rods were used in the included studies. CONCLUSION: CFR-PEEK displays a noninferior safety and efficacy profile to titanium implanted devices. However, it also has other advantages. By decreasing artifact production, it is able to increase detection of local tumor recurrence and decrease radiotherapy dose perturbation, ultimately bettering prognosis for patients necessitating adjuvant treatment. Nonetheless, its drawbacks have not been explored fully and still require further investigation in future studies. This does not exclude the fact that CFR-PEEK could be a valid alternative to titanium in the near future.

Anterior Cruciate Ligament Reconstruction: Fixation Techniques.

Anterior cruciate ligament reconstruction (ACLR) is among the most common procedures performed by orthopaedic sports medicine surgeons and has inherent challenges due to the complex anatomy and biomechanical properties required to reproduce the function and stability of the native ACL. Awareness of the anatomic and biomechanical factors, including graft selection and tunnel placement, along with graft tensioning and fixation techniques, is vital in achieving a successful clinical outcome. Common techniques for ACLR graft fixation include intratunnel fixation with interference screws, suspensory fixation, or hybrid fixation strategies, along with several supplemental fixation techniques. Interference screw fixation may decrease graft-tunnel motion, tunnel widening, and graft creep and may be performed with metallic, PEEK (polyether ether ketone), or bioabsorbable screws. Suspensory fixation techniques primarily include suture-buttons, anchors, staples, and screws/washers. Suspensory fixation allows adequate biomechanical strength, although some techniques have been linked to increased graft-tunnel motion and potential tunnel widening. Supplemental fixation techniques may be performed in the setting of concerns for adequacy of primary fixation and includes the use of suture anchors, staples, and screw/washer devices. Regardless of the implant chosen for fixation, secure fixation is paramount to avoid displacement of the graft and allow for integration into the bone tunnel and facilitates early postoperative rehabilitation. It is important for orthopaedic sports medicine surgeons performing primary and revision ACLR to be familiar with multiple fixation techniques.

Biomechanical comparison of polyetheretherketone rods and titanium alloy rods in transforaminal lumbar interbody fusion: a finite element analysis.

BACKGROUND: Whether polyetheretherketone (PEEK) rods have potential as an alternative to titanium alloy (Ti) rods in transforaminal lumbar interbody fusion (TLIF) remains unclear, especially in cases with insufficient anterior support due to the absence of a cage. The purpose of this study was to investigate biomechanical differences between PEEK rods and Ti rods in TLIF with and without a cage. METHODS: An intact L1-L5 lumbar finite element model was constructed and validated. Accordingly, four TLIF models were developed: (1) Ti rods with a cage; (2) PEEK rods with a cage; (3) Ti rods without a cage; and (4) PEEK rods without a cage. The biomechanical properties were then compared among the four TLIF constructs. RESULTS: With or without a cage, no obvious differences were found in the effect of PEEK rods and Ti rods on the range of motion, adjacent disc stress, and adjacent facet joint force. Compared to Ti rods, PEEK rods increase the average bone graft strain (270.8-6055.2 µE vs. 319.0-8751.6 µE). Moreover, PEEK rods reduced the stresses on the screw-rod system (23.1-96.0 MPa vs. 7.2-48.4 MPa) but increased the stresses on the cage (4.6-35.2 MPa vs. 5.6-40.9 MPa) and endplates (5.7-32.5 MPa vs. 6.6-37.6 MPa). CONCLUSIONS: Regardless of whether a cage was used for TLIF, PEEK rods theoretically have the potential to serve as an alternative to Ti rods because they may provide certain stability, increase the bone graft strain, and reduce the posterior instrumentation stress, which might promote bony fusion and decrease instrumentation failure.

Digital wear analysis and retention of poly-ether-ether-ketone retentive inserts versus conventional nylon inserts in locator retained mandibular overdentures: in-vitro study.

OBJECTIVE: this study aimed to digitally compare wear behavior and retention between PEEK and nylon retentive inserts used in locator-retained, mandibular implant overdentures when attachment design and size were standardized. MATERIALS AND METHODS: A total of sixty-four inserts (32 PEEK and 32 nylon inserts); were picked-up in implant overdentures. Overdentures of both groups were submerged in artificial saliva and mounted to chewing simulator. After 480,000 chewing cycles (equivalent to 2 years of clinical use) all inserts were scanned by scanning electron microscope (SEM), then all acquired images were digitally analyzed by software to detect and compare quantitative and qualitative changes of inserts in both groups. On the other hand, retention of both groups was measured by universal testing machine and the collected data was statistically analyzed using one-way Analysis of Variance (ANOVA) test with significance level set at P ≤ 0.05. RESULTS: PEEK inserts showed significantly higher mean retentive values compared to the nylon inserts in the control group. Also, PEEK retentive inserts exhibited statistically lower mean wear values than the control group P ≥ 0.000. Qualitative investigation revealed significant and more pronounced changes in the surface roughness of nylon inserts compared to PEEK ones. CONCLUSIONS: Regarding retention, wear behavior and dimension stability, PEEK can be recommended as retentive insert material in cases of locator-retained mandibular implant overdentures. CLINICAL RELEVANCE: PEEK inserts offer enhanced retention, reduced wear, and greater dimensional stability over two years time interval. Clinically, this reduces prosthodontic maintenance and adjustments, improving patient satisfaction and long-term prosthetic success.

Dental implant and abutment in PEEK: stress assessment in single crown retainers on anterior region.

OBJECTIVE: Stress distribution assessment by finite elements analysis in poly(etheretherketone) (PEEK) implant and abutment as retainers of single crowns in the anterior region. MATERIALS AND METHODS: Five 3D models were created, varying implant/abutment manufacturing materials: titanium (Ti), zirconia (Zr), pure PEEK (PEEKp), carbon fiber-reinforced PEEK (PEEKc), glass fiber-reinforced PEEK (PEEKg). A 50 N load was applied 30o off-axis at the incisal edge of the upper central incisor. The Von Mises stress (σvM) was evaluated on abutment, implant/screw, and minimum principal stress (σmin) and maximum shear stress (τmax) for cortical and cancellous bone. RESULTS: The abutment σvM lowest stress was observed in PEEKp group, being 70% lower than Ti and 74% than Zr. On the implant, PEEKp reduced 68% compared to Ti and a 71% to Zr. In the abutment screws, an increase of at least 33% was found in PEEKc compared to Ti, and of at least 81% to Zr. For cortical bone, the highest τmax values were in the PEEKp group, and a slight increase in stress was observed compared to all PEEK groups with Ti and Zr. For σmin, the highest stress was found in the PEEKc. Stress increased at least 7% in cancellous bone for all PEEK groups. CONCLUSION: Abutments and implants made by PEEKc concentrate less σvM stress, transmitting greater stress to the cortical and medullary bone. CLINICAL RELEVANCE: The best stress distribution in PEEKc components may contribute to decreased stress shielding; in vitro and in vivo research is recommended to investigate this.

Is Polyetheretherketone an Effective Alloplastic Material in Comparison to Titanium in Calvarial Reconstruction.

INTRODUCTION AND AIM: Polyetheretherketone (PEEK) and titanium (Ti) cranioplasty implants ideal outcomes are good esthetics, long-term stability, and protection of the fragile brain tissue. However, it is unclear whether PEEK implants can offer an equal alternative to Ti implants. This work aimed to critically review papers and case series published on both Ti and PEEK Cranioplasty regarding complications, clinical outcomes, ease of use, esthetics, manufacture and availability, cost and time-saving factors, postoperative quality of life (QOL), as well as their suitability for the fronto-orbito region reconstruction. METHODS: PubMed database was sourced for published literature in the period 2007 to the end of 2023; a further manual search for articles was carried out on the reference lists of each paper. RESULTS: A total of 48980 papers were found during the initial search, but only 33 articles met the inclusion criteria. A total of 6023 cranial implants, with 3879 being Ti and 1205 PEEK. Titanium was the material of choice in over 64.4% of cases; however, Ti has been in application for many years compared to PEEK. Out of the 33 papers, there was 27 retrospective cohort/analysis/case series and reviews: 1 meta-analysis, 2 systematic reviews and 3 randomized control trials. Four articles commented on the QOL, 15 on esthetics, 7 discussed cost and time-saving without measurable variables, and 7 articles looked explicitly at the complex fronto-orbito region, of which 49% were primary 1-stage surgical reconstructions, 54% were reconstructed with PEEK and 7% Ti (CAD/CAM). CONCLUSION: There is no absolute consensus for the preference of either material, however, in the fronto-orbito region, PEEK is the material of choice for ease of use, esthetics, and time-saving. However, there are no long-term studies on PEEK cranioplasty, and fewer in comparison with Ti implants. Further research is required in this field. No reliable or measurable data was found to determine the QOL, esthetics, cost, or time-saving elements.

Endoscopic-Assisted Forehead Augmentation with Polyetheretherketone (PEEK) Patient-Specific Implant (PSI) for Aesthetic Considerations.

BACKGROUND: Forehead augmentation have become popular aesthetic procedures among Asians in recent years. However, the use of polyetheretherketone (PEEK) patient-specific implant (PSI) in the facial contouring surgery for aesthetic considerations is not well documented in the existing studies. The purpose of this study was to develop a novel method for forehead augmentation and assess the clinical outcomes and complications in patients who underwent forehead augmentation with PEEK PSI assisted by endoscopy. METHODS: The PEEK PSIs were fabricated using the virtual surgical planning (VSP) and the computer-aided manufacturing (CAM) for each patient, preoperatively. The implant pockets were dissected in the subperiosteal plane, and PEEK PSIs were placed in their designed position and fixed assisting by endoscopy via small incision within the hairline. All patients were asked to complete the FACE-Q questionnaire before and 6 months after the operation. Pre- and postoperative demographics, photographs, and other clinical data of patients were collected and analyzed. RESULTS: 11 patients underwent forehead augmentation were enrolled in this study. All procedures were completed successfully with the help of endoscope. The average patient age was 30.63 ± 2.54 years. The mean thickness and size of PEEK PSI were 4.44 ± 1.77 mm and 38.43 ± 22.66 cm2, respectively. The mean operative time was 83.00 ± 29.44 min, and the mean postoperative follow-up period was 11.00 ± 6.50 months. No implant exposure, extrusion or removal were reported. The FACE-Q scores of patients in satisfaction with the forehead increased from 47.64 ± 7.15 to 78.81 ± 6.35. CONCLUSIONS: PEEK PSIs can be prefabricated to achieve accurate remodeling of the frontal contour with good esthetic outcomes. The endoscope provides direct and magnified vision, which allow easy access to the supraorbital rim and lateral edge of the eyebrow arch and confirming the position of the implants without damaging nerves and vessels. Endoscopic-assisted forehead augmentation with PEEK PSI is safe and effective. LEVEL OF EVIDENCE IV: This journal requires that authors assign a level of evidence to each article. For a full description of these evidence-based medicine ratings, please refer to the Table of contents or the online Instructions to Authors www.springer.com/00266 .

Theoretical and Experimental Study of Different Side Chains on 3,4-Ethylenedioxythiophene and Diketopyrrolopyrrole-Derived Polymers: Towards Organic Transistors.

In this research, two polymers of P1 and P2 based on monomers consisting of thiophene, 3,4-Ethylenedioxythiophene (EDOT) and diketopyrrolopyrrole (DPP) are designed and obtained via Stille coupling polycondensation. The material shows excellent coplanarity and structural regularity due to the fine planarity of DPP itself and the weak non-covalent bonding interactions existing between the three units. Two different lengths of non-conjugated side chains are introduced and this has an effect on the intermolecular chain stacking, causing the film absorption to display different characteristic properties. On the other hand, the difference in the side chains does not have a significant effect on the thermal stability and the energy levels of the frontier orbitals of the materials, which is related to the fact that the materials both feature extremely high conjugation lengths and specific molecular compositions. Microscopic investigations targeting the side chains provide a contribution to the further design of organic semiconductor materials that meet device requirements. Tests based on organic transistors show a slight difference in conductivity between the two polymers, with P2 having better hole mobility than P1. This study highlights the importance of the impact of side chains on device performance, especially in the field of organic electronics.

Marginal fit and fracture resistance of polyetheretherketone, zirconia, and titanium implant-supported prosthesis frameworks for a partially edentulous arch after thermomechanical aging.

STATEMENT OF PROBLEM: Although polyetheretherketone (PEEK) and zirconia (Zir) have been used as implant-supported prosthesis (ISP) frameworks, the long-term effects of thermomechanical aging on the marginal fit and fracture resistance of PEEK and Zir ISP frameworks with titanium (Ti) bases for patients with a partially edentulous arch are not clear. PURPOSE: The purpose of this in vitro study was to determine the marginal fit and fracture resistance of PEEK and Zir ISP frameworks with Ti bases and Ti ISP frameworks for partially edentulous arches after aging. MATERIAL AND METHODS: A total of 30 ISP epoxy resin casts were obtained from a typodont with 1 straight implant (Nobel Biocare) in the mandibular right canine region and 1 implant with a 30-degree distal tilt in the mandibular right first molar region. All frameworks (n=10) were fabricated on their own epoxy resin cast with multiunit abutment replicas by using a computer-aided design and computer-aided manufacturing system (exocad-Yenadent). The PEEK and Zir frameworks were fabricated with Ti-bases. Primer (MKZ) and resin cement (DTK adhesive) were used to cement the frameworks to the Ti-bases under a static load of 10 N. After thermomechanical aging (1.2×106 cycles, 120 N, 5 °C-55 °C), marginal gaps between the Ti-bases and cemented frameworks and vertical and passive fits between the Ti-bases and framework and multi-unit abutments were measured by using a stereomicroscope (Euromex) at ×100 magnification. Fracture resistances and types were then determined by using a universal test machine and a stereomicroscope at ×40 magnification. Data were analyzed by using 1-way analysis of variance (ANOVA) and the Tukey HSD and Fisher-Freeman-Halton tests (α=.05). RESULTS: The marginal gaps of the PEEK and Zir frameworks were respectively 83.5 ±27.1 and 81.8 ±17.8 µm. PEEK (23.7 ±4.6) and Zir (32.9 ±8.7) had a better vertical fit (µm) than Ti (52.5 ±10.6) (P<.001). Zir (49.3 ±16.2) (P<.001) and PEEK (70.9 ±19.6) (P>.05) frameworks had better passive fit (µm) than Ti (91.3 ±24.2). Ti had the highest mean fracture resistance (N) (14800.2 ±3442.3) followed by Zir (7318.7 ±1385.1) and PEEK (3448.9 ±486.6) (P<.001). Fracture types were different in different groups (P<.001). CONCLUSIONS: The PEEK and Zir frameworks with Ti bases had better vertical and passive fit than the Ti frameworks. All ISP frameworks represented mean marginal fit below 92 µm and withstood physiologic occlusal forces after thermomechanical aging.

Comparative analysis of the retention force and deformation of PEEK and PEKK removable partial denture clasps with different thicknesses and undercut depths.

STATEMENT OF PROBLEM: The retentive force and deformation of milled polyetheretherketone (PEEK) and polyetherketoneketone (PEKK) removable partial denture (RPD) frameworks are not well understood. PURPOSE: The purpose of this in vitro study was to assess the retentive force and deformation of PEEK and PEKK Akers clasps with different designs and undercut depths. MATERIAL AND METHODS: A master model containing the first and second molar abutments was used to design Akers clasps of different cross-sectional dimensions, undercut depths (0.5 and 0.75 mm), and materials. The components of the removable partial denture framework also included an occlusal rest and were manufactured using a milling machine (n=5). The fatigue resistance of the Akers clasps was measured before and after deformation regarding the retentive forces. RESULTS: The PEEK2-U50 clasp had the largest retentive force with no significant difference among all groups before and after the insertion and removal cycle. In addition, the increased cross-sectional dimensions of the design resulted in significant differences in retentive forces between the PEEK1 and PEEK2 groups and between the PEEK and PEKK materials. CONCLUSIONS: Increasing the clasp's cross-sectional dimensions significantly impacted retentive forces, especially between different PEEK groups and between PEEK and PEKK materials.

Effect of material and antagonist type on the wear of occlusal devices with different compositions fabricated by using conventional, additive, and subtractive manufacturing.

STATEMENT OF PROBLEM: Additive (AM) and subtractive (SM) manufacturing have become popular for fabricating occlusal devices with materials of different chemical compositions. However, knowledge on the effect of material and antagonist type on the wear characteristics of occlusal devices fabricated by using different methods is limited. PURPOSE: The purpose of this in vitro study was to evaluate the effect of material and antagonist type on the wear of occlusal devices fabricated by using conventional manufacturing, AM, and SM. MATERIAL AND METHODS: Two-hundred and forty Ø10×2-mm disk-shaped specimens were fabricated by using heat-polymerized polymethylmethacrylate (control, CM), AM clear device resin fabricated in 3 different orientations (horizontal [AMH], diagonal [AMD], and vertical [AMV]), SM polymethylmethacrylate (SMP), and SM ceramic-reinforced polyetheretherketone (SMB) (n=40). Specimens were then divided into 4 groups based on the antagonists: steatite ceramic (SC); multilayered zirconia (ZR); lithium disilicate (EX); and zirconia-reinforced lithium silicate (ZLS) used for thermomechanical aging (n=10). After aging, the volume loss (mm3) and maximum wear depth (µm) were digitally evaluated. Data were analyzed with 2-way analysis of variance and Tukey honestly significant difference tests (α=.05). RESULTS: The interaction between the device material and the antagonist affected volume loss and maximum depth of wear (P<.001). AMH had volume loss and depth of wear that was either similar to or higher than those of other materials (P≤.044). When SC was used, CM had higher volume loss and depth of wear than AMV, and, when EX was used, AMD had higher volume loss and depth of wear than SMP (P≤.013). SC and ZR led to higher volume loss of CM and AMH than EX and led to the highest depth of wear for these materials, while ZR also led to the highest volume loss and depth of wear of AMD and AMV (P≤.019). EX led to the lowest volume loss and depth of wear of AMV and SMP and to the lowest depth of wear of AMH (P≤.021). Regardless of the antagonist, SMB had the lowest volume loss and depth of wear (P≤.005). CONCLUSIONS: AMH mostly had higher volume loss and depth of wear, while SMB had the lowest volume loss, and its depth of wear was not affected by the tested antagonists. ZR mostly led to higher volume loss and maximum depth of wear, while EX mostly led to lower volume loss and maximum depth of wear of the tested occlusal device materials.

Mechanical failure of distal femur mega prosthesis due to polyaryl-ether-ether-ketone (PEEK) hinge component.

BACKGROUND: Polyaryl-ether-ether-ketone (PEEK) has gained popularity as a substrate for orthopaedic hardware due to its desirable properties such as heat and deformation resistance, low weight, and ease of manufacturing. However, we observed a relatively high failure rate of PEEK-based hinges in a distal femur reconstruction system. In this study, we aimed to evaluate the proportion of patients who experienced implant failure, analyse the mechanism of failure, and document the associated clinical findings. METHODS: We conducted a retrospective cohort study, reviewing the medical charts of 56 patients who underwent distal femur resection and reconstruction with a PEEK Optima hinge-based prosthesis between 2004 and 2018. Concurrently, we performed a clinical and biomechanical failure analysis. RESULTS: PEEK component failure occurred in 21 out of 56 patients (37.5%), with a mean time to failure of 63.2 months (range: 13-144 months, SD: 37.9). The survival distributions of PEEK hinges for males and females were significantly different (chi-square test, p-value = 0.005). Patient weight was also significantly associated with the hazard of failure (Wald's test statistic, p-value = 0.031). DISCUSSION: Our findings suggest that PEEK hinge failure in a distal femur reconstruction system is correlated with patient weight and male gender. Retrieval analysis revealed that failure was related to fretting and microscopic fractures due to cyclic loading, leading to instability and mechanical failure of the PEEK component in full extension. Further assessment of PEEK-based weight bearing articulating components against metal is warranted.