The impact of round window reinforcement on middle and inner ear mechanics with air and bone conduction stimulation.

The round window (RW) membrane plays an important role in normal inner ear mechanics. Occlusion or reinforcement of the RW has been described in the context of congenital anomalies or after cochlear implantation and is applied as a surgical treatment for hyperacusis. Multiple lumped and finite element models predict a low-frequency hearing loss with air conduction of up to 20 dB after RW reinforcement and limited to no effect on hearing with bone conduction stimulation. Experimental verification of these results, however, remains limited. Here, we present an experimental study measuring the impact of RW reinforcement on the middle and inner ear mechanics with air and bone conduction stimulation. In a within-specimen repeated measures design with human cadaveric specimens (n = 6), we compared the intracochlear pressures in scala vestibuli (PSV) and scala tympani (PST) before and after RW reinforcement with soft tissue, cartilage, and bone cement. The differential pressure (PDIFF) across the basilar membrane - known to be closely related to the hearing sensation - was calculated as the complex difference between PSV and PST. With air conduction stimulation, both PSV and PSTincreased on average up to 22 dB at frequencies below 1500 Hz with larger effect sizes for PST compared to PSV. The PDIFF, in contrast, decreased up to 11 dB at frequencies between 700 and 800 Hz after reinforcement with bone cement. With bone conduction, the average within-specimen effects were less than 5 dB for either PSV, PST, or PDIFF. The inter-specimen variability with bone conduction, however, was considerably larger than with air conduction. This experimental study shows that RW reinforcement impacts air conduction stimulation at low frequencies. Bone conduction stimulation seems to be largely unaffected. From a clinical point of view, these results support the hypothesis that delayed loss of air conduction hearing after cochlear implantation could be partially explained by the impact of RW reinforcement.

OCT-based intra-cochlear imaging and 3D reconstruction: ex vivo validation of a robotic platform.

PURPOSE: The small size of the cochlea, and its location deeply embedded in thick temporal bone, poses a challenge for intra-cochlear guidance and diagnostics. Current radiological imaging techniques are not able to visualize the cochlear microstructures in detail. Rotational optical coherence tomography (OCT) fibers show great potential for intra-cochlear guidance. The generated images could be used to map, and study, the tiny cochlear microstructures relevant for hearing. METHODS: This work describes the design of a rotational OCT probe with an outer diameter of 0.9 mm. It further discusses a robotic system, which features a remote center of motion mechanism, dedicated to the probe's positioning, fine manipulation and stable insertion into the cochlear micro-spaces. Furthermore, the necessary calibration steps for 3D reconstruction are described, followed by a detailed quantitative analysis, comparing the 3D reconstructions using a synthetic, 2:1 scaled scala tympani model with a reconstruction from micro-CT, serving as the ground truth. Finally, the potential of the system is demonstrated by scanning a single ex vivo cadaveric human cochlea. RESULTS: The study investigates five insertions in the same 2:1 scaled tympani model, along with their corresponding 3D reconstruction. The comparison with micro-CT results in an average root-mean-square error of 74.2 µm, a signed distance error of 38.1 µm and a standard deviation of 63.6 µm. The average F-score of the reconstructions, using a distance threshold of 100 and 74.2 µm, resulted in 83.0% and 71.8%, respectively. Insertion in the cadaveric human cochlea showed the challenges for straight insertion, i.e., navigating the hook region. CONCLUSION: Overall, the system shows great potential for intra-cochlear guidance and diagnostics, due to the system's capability for precise and stable insertion into the basal turn in the scala tympani. The system, combined with the calibration procedure, results in detailed and precise 3D reconstructions.

Objective preclinical measures for bone conduction implants.

The study evaluates the accuracy of predicting intracochlear pressure during bone conduction stimulation using promontory velocity and ear canal pressure, as less invasive alternatives to intracochlear pressure. Stimulating with a percutaneous bone conduction device implanted in six human cadaveric ears, measurements were taken across various intensities, frequencies, and stimulation positions. Results indicate that intracochlear pressure linearly correlates with ear canal pressure (R2 = 0.43, RMSE = 6.85 dB), and promontory velocity (R2 = 0.47, RMSE = 6.60 dB). Normalizing data to mitigate the influence of stimulation position leads to a substantial improvement in these correlations. R2 values increased substantially to 0.93 for both the ear canal pressure and the promontory velocity, with RMSE reduced considerably to 2.02 (for ear canal pressure) and 1.94 dB (for promontory velocity). Conclusively, both ear canal pressure and promontory velocity showed potential in predicting intracochlear pressure and the prediction accuracy notably enhanced when accounting for stimulation position. Ultimately, these findings advocate for the continued use of intracochlear pressure measurements to evaluate future bone conduction devices and illuminate the role of stimulation position in influencing the dynamics of bone conduction pathways.

Lumped element models of sound conduction in the human ear: A systematic review.

Lumped element models facilitate investigating the fundamental mechanisms of human ear sound conduction. This systematic review aims to guide researchers to the optimal model for the investigated parameters. For this purpose, the literature was reviewed up to 12 July 2023, according to the PRISMA guidelines. Seven models are included via database searching, and another 19 via cross-referencing. The quality of the models is assessed by comparing the predicted middle ear transfer function, the tympanic membrane impedance, the energy reflectance, and the intracochlear pressures (ICPs) (scala vestibuli, scala tympani, and differential) with experimental data. Regarding air conduction (AC), the models characterize the pathway from the outer to the inner ear and accurately predict all six aforementioned parameters. This contrasts with the few existing bone conduction (BC) models that simulate only a part of the ear. In addition, these models excel at predicting one observable parameter, namely, ICP. Thus, a model that simulates BC from the coupling site to the inner ear is still lacking and would increase insights into the human ear sound conduction. Last, this review provides insights and recommendations to determine the appropriate model for AC and BC implants, which is highly relevant for future clinical applications.

Anatomically and mechanically accurate scala tympani model for electrode insertion studies.

The risk of insertion trauma in cochlear implantation is determined by the interplay between individual cochlear anatomy and electrode insertion mechanics. Whereas patient anatomy cannot be changed, new surgical techniques, devices for cochlear monitoring, drugs, and electrode array designs are continuously being developed and tested, to optimize the insertion mechanics and prevent trauma. Preclinical testing of these developments is a crucial step in feasibility testing and optimization for clinical application. Human cadaveric specimens allow for the best simulation of an intraoperative setting. However, their availability is limited and it is not possible to conduct repeated, controlled experiments on the same sample. A variety of artificial cochlear models have been developed for electrode insertion studies, but none of them were both anatomically and mechanically representative for surgical insertion into an individual cochlea. In this study, we developed anatomically representative models of the scala tympani for surgical insertion through the round window, based on microCT images of individual human cochleae. The models were produced in transparent material using commonly-available 3D printing technology at a desired scale. The anatomical and mechanical accuracy of the produced models was validated by comparison with human cadaveric cochleae. Mechanical evaluation was performed by recording insertion forces, counting the number of inserted electrodes and grading tactile feedback during manual insertion of a straight electrode by experienced cochlear implant surgeons. Our results demonstrated that the developed models were highly representative for the anatomy of the original cochleae and for the insertion mechanics in human cadaveric cochleae. The individual anatomy of the produced models had a significant impact on the insertion mechanics. The described models have a promising potential to accelerate preclinical development and testing of atraumatic insertion techniques, reducing the need for human cadaveric material. In addition, realistic models of the cochlea can be used for surgical training and preoperative planning of patient-tailored cochlear implantation surgery.

Human cochlear microstructures at risk of electrode insertion trauma, elucidated in 3D with contrast-enhanced microCT.

Cochlear implant restores hearing loss through electrical stimulation of the hearing nerve from within the cochlea. Unfortunately, surgical implantation of this neuroprosthesis often traumatizes delicate intracochlear structures, resulting in loss of residual hearing and compromising hearing in noisy environments and appreciation of music. To avoid cochlear trauma, insertion techniques and devices have to be adjusted to the cochlear microanatomy. However, existing techniques were unable to achieve a representative visualization of the human cochlea: classical histology damages the tissues and lacks 3D perspective; standard microCT fails to resolve the cochlear soft tissues; and previously used X-ray contrast-enhancing staining agents are destructive. In this study, we overcame these limitations by performing contrast-enhanced microCT imaging (CECT) with a novel polyoxometalate staining agent Hf-WD POM. With Hf-WD POM-based CECT, we achieved nondestructive, high-resolution, simultaneous, 3D visualization of the mineralized and soft microstructures in fresh-frozen human cochleae. This enabled quantitative analysis of the true intracochlear dimensions and led to anatomical discoveries, concerning surgically-relevant microstructures: the round window membrane, the Rosenthal's canal and the secondary spiral lamina. Furthermore, we demonstrated that Hf-WD POM-based CECT enables quantitative assessment of these structures as well as their trauma.

Sulfobetaine-based ultrathin coatings as effective antifouling layers for implantable neuroprosthetic devices.

Foreign body response (FBR), inflammation, and fibrotic encapsulation of neural implants remain major problems affecting the impedance of the electrode-tissue interface and altering the device performance. Adhesion of proteins and cells (e.g., pro-inflammatory macrophages, and fibroblasts) triggers the FBR cascade and can be diminished by applying antifouling coatings onto the implanted devices. In this paper, we report the deposition and characterization of a thin (±6 nm) sulfobetaine-based coating onto microfabricated platinum electrodes and cochlear implant (CI) electrode arrays. We found that this coating has stable cell and protein-repellent properties, for at least 31 days in vitro, not affected by electrical stimulation protocols. Additionally, its effect on the electrochemical properties relevant to stimulation (i.e., impedance, charge injection capacity) was negligible. When applied to clinical CI electrode arrays, the film was successful at inhibiting fibroblast adhesion on both the silicone packaging and the platinum/iridium electrodes. In vitro, in fibroblast cultures, coated CI electrode arrays maintained impedance values up to five times lower compared to non-coated devices. Our studies demonstrate that such thin sulfobetaine containing layers are stable and prevent protein and cell adhesion in vitro and are compatible for use on CI electrode arrays. Future in vivo studies should be conducted to investigate its ability to mitigate biofouling, fibrosis, and the resulting impedance changes upon long-term implantation in vivo.

An optically-guided cochlear implant sheath for real-time monitoring of electrode insertion into the human cochlea.

In cochlear implant surgery, insertion of perimodiolar electrode arrays into the scala tympani can be complicated by trauma or even accidental translocation of the electrode array within the cochlea. In patients with partial hearing loss, cochlear trauma can not only negatively affect implant performance, but also reduce residual hearing function. These events have been related to suboptimal positioning of the cochlear implant electrode array with respect to critical cochlear walls of the scala tympani (modiolar wall, osseous spiral lamina and basilar membrane). Currently, the position of the electrode array in relation to these walls cannot be assessed during the insertion and the surgeon depends on tactile feedback, which is unreliable and often comes too late. This study presents an image-guided cochlear implant device with an integrated, fiber-optic imaging probe that provides real-time feedback using optical coherence tomography during insertion into the human cochlea. This novel device enables the surgeon to accurately detect and identify the cochlear walls ahead and to adjust the insertion trajectory, avoiding collision and trauma. The functionality of this prototype has been demonstrated in a series of insertion experiments, conducted by experienced cochlear implant surgeons on fresh-frozen human cadaveric cochleae.

Intracochlear pressure as an objective measure for perceived loudness with bone conduction implants.

BACKGROUND: The generally accepted method to assess the functionality of novel bone conduction implants in a preclinical stage is to experimentally measure the vibratory response of the cochlear promontory. Yet, bone conduction of sound is a complex propagation phenomenon, depending on both frequency and amplitude, involving different conduction pathways. OBJECTIVES: The aim of this study is to validate the use of intracochlear sound pressure (ICP) as an objective indicator for perceived loudness for bone conduction stimulation. It is investigated whether a correlation exists between intracochlear sound pressure measurements in cadaveric temporal bones and clinically obtained results using the outcome of a loudness balancing experiment. METHODS: Ten normal hearing subjects were asked to balance the perceived loudness between air conducted (AC) sound and bone conducted (BC) sound by changing the AC stimulus. Mean balanced thresholds were calculated and used as stimulation levels in a cadaver trial (N = 4) where intracochlear sound pressure was measured during AC and BC stimulation to assess the correlation with the measured clinical data. The intracochlear pressure was measured at the relatively low stimulation amplitude of 80 dBHL using a lock-in amplification technique. RESULTS: Applying AC and BC stimulation at equal perceived loudness on cadaveric heads yield a similar differential intracochlear pressure, with differences between AC and BC falling within the range of variability of normal hearing test subjects. CONCLUSION: Comparing the perceived loudness at 80 dB HL for both AC and BC validates intracochlear pressure as an objective indicator of the cochlear drive. The measurement setup is more time-intensive than measuring the vibratory response of the cochlear promontory, yet it provides direct information on the level of the cochlear scalae.

The Impact of Location and Device Coupling on the Performance of the Osia System Actuator.

Active transcutaneous bone conduction (BC) devices offer the benefit of improved power output compared to passive transcutaneous devices and remove the risk of skin infections that are more common in traditional percutaneous BC devices. Despite these advantages, more research is needed on implant location, device coupling, and their influence on device performance. This study is aimed at quantifying the extent to which certain parameters affect device output when using the Osia® system actuator. Parameters under study are (1) implant location, (2) comparison with the actuator of a state-of-the-art BC device, (3) bone undergrowth simulation, and (4) skull fixation. Five human cadaveric heads were implanted with the actuator at three different implant locations: (1) recommended, (2) posterior Osia® positions, and (3) standard Baha® position. At each location, the cochlear promontory velocity and the intracochlear pressure difference were measured. A percutaneous bone conduction actuator was used as a reference for the obtained measurements. Stimulation levels corresponded to a hearing level of 60 dB HL for frequencies between 250 and 6000 Hz. In addition, bone cement was used as a simulation for reactive bone growth. Results obtained in four heads indicate an improved power transmission of the transcutaneous actuator when implanted at the recommended position compared to the actuator of the percutaneous device on its respective recommended location when stimulating at an identical force level. A correlation was found between the promontory vibration and the actuator position, indicating that the same level of stimulation leads to higher promontory vibrations when the device is implanted closer to the ear canal. This is mainly reflected at frequencies higher than 1 kHz, where an increase was observed in both measurement modalities. At lower frequencies (<1 kHz), the power transmission is less influenced by the implant position and differences between the acquired responses are limited. In addition, when no rigid coupling to the skull is provided, power transfer losses of up to 30 dB can be expected.

Optical Coherence Tomography-Based Atlas of the Human Cochlear Hook Region.

Advancements in intracochlear diagnostics, as well as prosthetic and regenerative inner ear therapies, rely on a good understanding of cochlear microanatomy. The human cochlea is very small and deeply embedded within the densest skull bone, making nondestructive visualization of its internal microstructures extremely challenging. Current imaging techniques used in clinical practice, such as MRI and CT, fall short in their resolution to visualize important intracochlear landmarks, and histological analysis of the cochlea cannot be performed on living patients without compromising their hearing. Recently, optical coherence tomography (OCT) has been shown to be a promising tool for nondestructive micrometer resolution imaging of the mammalian inner ear. Various studies performed on human cadaveric tissue and living animals demonstrated the ability of OCT to visualize important cochlear microstructures (scalae, organ of Corti, spiral ligament, and osseous spiral lamina) at micrometer resolution. However, the interpretation of human intracochlear OCT images is non-trivial for researchers and clinicians who are not yet familiar with this novel technology. In this study, we present an atlas of intracochlear OCT images, which were acquired in a series of 7 fresh and 10 fresh-frozen human cadaveric cochleae through the round window membrane and describe the qualitative characteristics of visualized intracochlear structures. Likewise, we describe several intracochlear abnormalities, which could be detected with OCT and are relevant for clinical practice.

Electropolymerized Receptor Coatings for the Quantitative Detection of Histamine with a Catheter-Based, Diagnostic Sensor.

In this article, we report on the development of a catheter-based, biomimetic sensor as a step toward a minimally invasive diagnostic instrument in the context of functional bowel disorders. Histamine is a key mediator in allergic and inflammatory processes in the small intestines; however, it is a challenge to determine histamine levels at the duodenal mucosa, and classical bioreceptors are unsuitable for use in the digestive medium of bowel fluid. Therefore, we have developed molecularly imprinted polypyrrole coatings for impedimetric sensing electrodes, which enable the quantification of histamine in nondiluted, human bowel fluid in a broad concentration range from 25 nM to 1 µM. The electrodes show negligible cross-sensitivity to histidine as a competitor molecule and, for comparison, we also evaluated the response of nonimprinted and taurine-imprinted polypyrrole to histamine. Furthermore, using equivalent-circuit modeling, we found that the molecular recognition of histamine by polypyrrole primarily increases the resistive component of the electrode-liquid interface while capacitive effects are negligible. The sensor, integrated into a catheter, measures differentially to correct for nonspecific adsorption effects in the complex matrix of bowel fluids, and a single triggering frequency is sufficient to determine histamine concentrations. Together, these features are beneficial for real-time diagnostic tests.

Physicochemical study of diethylmethylammonium methanesulfonate under anhydrous conditions.

The protic ionic liquid diethylmethylammonium methanesulfonate ([DEMA][OMs]) was analyzed in depth by differential scanning calorimetry (DSC), nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, and broadband dielectric spectroscopy (BDS) under anhydrous conditions. Karl Fischer titration, NMR, and FT-IR spectra confirmed the high purity of [DEMA][OMs]. The melting point (37.7 °C) and the freezing point (14.0 °C) obtained by DSC agree well with the values determined by BDS (40.0 °C and 14.0 °C). The dc conductivity (σdc) above the melting/freezing point obeys the Vogel-Fulcher-Tammann (VFT) equation well, and thus, the proton conduction in [DEMA][OMs] is assumed to be dominated by the vehicle mechanism. In contrast, the σdc below the melting/freezing point can be fitted by the Arrhenius equation separately, and therefore, the proton conduction is most likely governed by the proton hopping mechanism. The non-negligible influence of previously reported low water content on the physicochemical properties of [DEMA][OMs] is found, indicating the importance of reducing water content as much as possible for the study of "intrinsic" properties of protic ionic liquids.

Towards a catheter-based impedimetric sensor for the assessment of intestinal histamine levels in IBS patients.

In this work, we report on the development of a catheter-based sensor designed for measuring the concentration of histamine in the human duodenum. Certain gut disorders, such as the irritable bowel syndrome (IBS), are associated with elevated levels of intestinal histamine due to chronic immune activation. As it is still impossible to determine histamine concentrations in vivo, a nasointestinal catheter with histamine-sensing capabilities has the potential to become a valuable diagnostic instrument. Regarding the sensing principle, we selected impedance spectroscopy using voltages that are compatible with intra-body applications with molecularly imprinted polymers (MIPs) as recognition elements. MIPs are synthetic receptors that offer the advantages of robustness, high specificity and selectivity for histamine as a target. In this specific case, the MIPs were synthesized from acryclic acid monomers, which guarantees a uniform binding capacity within the pH range of intestinal fluid. We have validated the catheter sensor on human intestinal liquids spiked with histamine in a testing setup that mimics the environment inside the duodenum. The dose-response curves show an analytical range between 5 and 200 nM of histamine, corresponding to physiologically normal conditions while higher concentrations correlate with disease. The key output signal of the sensor is the resistive component of the MIP-functionalized titanium electrodes as derived from the equivalent-circuit modelling of full-range impedance spectra. Future applications could be catheters tailored to cardiovascular, urological, gastrointestinal, and neurovascular applications. This, in combination with the versatility of the MIPs, will make this sensor platform a versatile diagnostic tool.

High-resolution Imaging of the Human Cochlea through the Round Window by means of Optical Coherence Tomography.

The human cochlea is deeply embedded in the temporal bone and surrounded by a thick otic capsule, rendering its internal structure inaccessible for direct visualization. Clinical imaging techniques fall short of their resolution for imaging of the intracochlear structures with sufficient detail. As a result, there is a lack of knowledge concerning best practice for intracochlear therapy placement, such as cochlear implantation. In the past decades, optical coherence tomography (OCT) has proven valuable for non-invasive, high-resolution, cross-sectional imaging of tissue microstructure in various fields of medicine, including ophthalmology, cardiology and dermatology. There is an upcoming interest for OCT imaging of the cochlea, which so far was mostly carried out in small animals. In this temporal bone study, we focused on high-resolution imaging of the human cochlea. The cochlea was approached through mastoidectomy and posterior tympanotomy, both standard surgical procedures. A commercially available spectral-domain OCT imaging system was used to obtain high-resolution images of the cochlear hook region through the intact round window membrane in four cadaveric human temporal bones. We discuss the qualitative and quantitative characteristics of intracochlear structures on OCT images and their importance for cochlear implant surgery.

Reducing Artifacts in Intracochlear Pressure Measurements to Study Sound Transmission by Bone Conduction Stimulation in Humans.

HYPOTHESIS: Intracochlear pressure (ICP) measurements during bone conduction (BC) stimulation may be affected by motion of the pressure sensor relative to the cochlear promontory bone, demonstrating the need to cement the sensor firmly to the cochlear bone. BACKGROUND: ICP is a promising measurement tool for investigating the cochlear drive in BC transmission, but its use is not yet standardized. Previous ICP studies have reported artificially increased pressure due to motion of the sensor relative to the temporal bone. The artifact can be reduced by firmly cementing the sensor to the bone, but this is destructive for the sensor. Previous studies used a custom-made sensor; the use of commercially available sensors, however, is more generic, but also more challenging to combine with the cement. Therefore, the goals of the current study are: firstly, to evaluate a non-destructive cementing method suitable for a commercially available sensor, and secondly, to investigate ICP measurements during BC stimulation in more detail. METHODS: To study the effect of sensor cementing, three fixation conditions were investigated on six fresh-frozen temporal bones: 1) alginate, 2) alginate and dental composite, 3) alginate and dental composite, released from micromanipulators. Pressures in scala tympani and vestibuli were measured simultaneously, while velocity measurements were performed on the cochlear promontory and sensor. The ratio between sensor and promontory bone velocity was computed to quantify the relative motion. RESULTS: For air conduction stimulation, results were in line with those from previous ICP studies, indicating that baseline measurements were valid and could be used to interpret the results obtained with BC stimulation. Results showed that cementing the sensors and releasing them from the micromanipulators is crucial for valid ICP measurements. When the sensors were only sealed with alginate, the pressure was overestimated, especially at low and mid-frequencies. When the sensors were cemented and held in the micromanipulators, the pressure was underestimated. Compared with the scala tympani measurements, ICP measurements showed a lower scala vestibuli pressure below 1 kHz, and a higher pressure above 1 kHz. CONCLUSION: Dental composite is effective as a cement to attach commercially available sensors to the cochlear promontory bone. When sensors are firmly attached, valid ICP measurements can be obtained with BC stimulation.

Investigation of synthetic spider silk crystallinity and alignment via electrothermal, pyroelectric, literature XRD, and tensile techniques.

The processes used to create synthetic spider silk greatly affect the properties of the produced fibers. This paper investigates the effect of process variations during artificial spinning on the thermal and mechanical properties of the produced silk. Property values are also compared to the ones of the natural dragline silk of the N. clavipes spider, and to unprocessed (as-spun) synthetic silk. Structural characterization by scanning pyroelectric microscopy is employed to provide insight into the axial orientation of the crystalline regions of the fiber and is supported by XRD data. The results show that stretching and passage through liquid baths induce crystal formation and axial alignment in synthetic fibers, but with different structural organization than natural silks. Furthermore, an increase in thermal diffusivity and elastic modulus is observed with decreasing fiber diameter, trending towards properties of natural fiber. This effect seems to be related to silk fibers being subjected to a radial gradient during production.

Switchable Charge Injection Barrier in an Organic Supramolecular Semiconductor.

We disclose a supramolecular material that combines semiconducting and dipolar functionalities. The material consists of a discotic semiconducting carbonyl-bridged triarylamine core, which is surrounded by three dipolar amide groups. In thin films, the material self-organizes in a hexagonal columnar fashion through π-stacking of the molecular core and hydrogen bonding between the amide groups. Alignment by an electrical field in a simple metal/semiconductor/metal geometry induces a polar order in the interface layers near the metal contacts that can be reversibly switched, while the bulk material remains nonpolarized. On suitably chosen electrodes, the presence of an interfacial polarization field leads to a modulation of the barrier for charge injection into the semiconductor. Consequently, a reversible switching is possible between a high-resistance, injection-limited off-state and a low-resistance, space-charge-limited on-state. The resulting memory diode shows switchable rectification with on/off ratios of up to two orders of magnitude. This demonstrated multifunctionality of a single material is a promising concept toward possible application in low-cost, large-area, nonvolatile organic memories.

Second harmonic generation microscopy reveals hidden polar organization in fluoride doped MIL-53(Fe).

Polar metal-organic frameworks have potential applications as functional non-linear optical, piezoelectric, pyroelectric and ferroelectric materials. Using second harmonic generation microscopy we found that fluoride doping of the microporous iron(iii) terephthalate MOF MIL-53(Fe) induces a polar organization in its structure, which was not previously detected with XRD. The polar order is only observed when both fluoride and guest molecules are present, and may be related to a complex interplay between the adsorbates and the framework, leading to a modification of the positioning of fluoride in the inorganic Fe-chains. Combined polarized second harmonic generation microscopy and scanning pyroelectric microscopy show that the polar axis is unidirectional and of the same sense over the whole crystal, extending up to 100 micrometers. This finding shows how MOF materials can be endowed with useful properties by doping MOFs with fluoride.

Polar Nature of Biomimetic Fluorapatite/Gelatin Composites: A Comparison of Bipolar Objects and the Polar State of Natural Tissue.

The correspondence of the state of alignment of macromolecules in biomimetic materials and natural tissues is demonstrated by investigating a mechanism of electrical polarity formation: An in vitro grown biomimetic FAp/gelatin composite is investigated for its polar properties by second harmonic (SHGM) and scanning pyroelectric microscopy (SPEM). Hexagonal prismatic seed crystals formed in gelatin gels represent a monodomain polar state, due to aligned mineralized gelatin molecules. Later growth stages, showing dumbbell morphologies, develop into a bipolar state because of surface recognition by gelatin functionality: A reversal of the polar alignment of macromolecules, thus, takes place close to that basal plane of the seed. In natural hard tissues (teeth and bone investigated by SPEM) and the biomimetic FAp/gelatin composite, we find a surprising analogy in view of growth-induced states of polarity: The development of polarity in vivo and in vitro can be explained by a Markov-type mechanism of molecular recognition during the attachment of macromolecules.