State-of-the-art and future perspectives in infertility diagnosis: Conventional versus nanotechnology-based assays.

According to the latest World Health Organization statistics, around 50 to 80 million people worldwide suffer from infertility, amongst which male factors are responsible for around 20 to 30 % of all infertility cases while 50 % were attributed to the female ones. As it is becoming a recurrent health problem worldwide, clinicians require more accurate methods for the improvement of both diagnosis and treatment schemes. By emphasizing the potential use of innovative methods for the rapid identification of the infertility causes, this review presents the news from this dynamic domain and highlights the benefits brought by emerging research fields. A systematic description of the standard techniques used in clinical protocols for diagnosing infertility in both genders is firstly provided, followed by the presentation of more accurate and comprehensive nanotechnology-related analysis methods such as nanoscopic-resolution imaging, biosensing approaches and assays that employ nanomaterials in their design. Consequently, the implementation of nanotechnology related tools in clinical practice, as recently demonstrated in the selection of spermatozoa, the detection of key proteins in the fertilization process or the testing of DNA integrity or the evaluation of oocyte quality, might confer excellent advantages both for improving the assessment of infertility, and for the success of the fertilization process.

Insight and Recent Advances into the Role of Topography on the Cell Differentiation and Proliferation on Biopolymeric Surfaces.

It is well known that surface topography plays an important role in cell behavior, including adhesion, migration, orientation, elongation, proliferation and differentiation. Studying these cell functions is essential in order to better understand and control specific characteristics of the cells and thus to enhance their potential in various biomedical applications. This review proposes to investigate the extent to which various surface relief patterns, imprinted in biopolymer films or in polymeric films coated with biopolymers, by utilizing specific lithographic techniques, influence cell behavior and development. We aim to understand how characteristics such as shape, dimension or chemical functionality of surface relief patterns alter the orientation and elongation of cells, and thus, finally make their mark on the cell proliferation and differentiation. We infer that such an insight is a prerequisite for pushing forward the comprehension of the methodologies and technologies used in tissue engineering applications and products, including skin or bone implants and wound or fracture healing.

Single Crystals of Established Semiconducting Polymers.

In this work, we aim to deliver a comprehensive review of the past and current fabrication and subsequent structural characterization of single crystals of established semiconducting polymers and oligomers while maintaining extra emphasis on the crystals' resulting optoelectronic properties, including charge carrier mobility, conductivity, photovoltaic capability, and the ability to absorb light.

Morphological Characteristics of Biopolymer Thin Films Swollen-Rich in Solvent Vapors.

Biopolymers exhibit a large variety of attractive properties including biocompatibility, flexibility, gelation ability, and low cost. Therefore, especially in more recent years, they have become highly suitable for a wider and wider range of applications stretching across several key sectors such as those related to food packaging, pharmaceutic, and medical industries, just to name a few. Moreover, biopolymers' properties are known to be strongly dependent on the molecular arrangements adopted by such chains at the nanoscale and microscale. Fortunately, these arrangements can be altered and eventually optimized through a plethora of more or less efficient polymer processing methods. Here, we used a space-confined solvent vapor annealing (C-SVA) method to subject various biopolymers to rich swelling in solvent vapors in order to favor their further crystallization or self-assembly, with the final aim of obtaining thin biopolymer films exhibiting more ordered chain conformations. The results obtained by atomic force microscopy revealed that while the gelatin biopolymer nucleated and then crystallized into granular compact structures, other biopolymers preferred to self-assemble into (curved) lamellar rows composed of spherical nanoparticles (glycogen and chitosan) or into more complex helix-resembling morphologies (phytagel). The capability of the C-SVA processing method to favor crystallization and to induce self-assembly in various biopolymeric species or even monomeric units further emphasizes its great potential in the future structuring of a variety of biological (macro)molecules.

Large Enhancement of Photoluminescence Obtained in Thin Polyfluorene Films of Optimized Microstructure.

There is a clearly demonstrated relationship between the microstructure, processing and resulting optoelectronic properties of conjugated polymers. Here, we exploited this relationship by exposing polyfluorene thin films to various solvent vapors via confined-solvent vapor annealing to optimize their microstructure, with the final goal being to enhance their emission properties. Our results have demonstrated enlargements in photoluminescence intensity of up to 270%, 258% and 240% when thin films of polyfluorenes of average molecular weights of 105,491 g/mol, 63,114 g/mol and 14,000 g/mol, respectively, experienced increases in their ß-phase fractions upon processing.

Processing of Thin Films Based on Cellulose Nanocrystals and Biodegradable Polymers by Space-Confined Solvent Vapor Annealing and Morphological Characteristics.

L-poly(lactic acid), poly(3-hydroxybutyrate), and poly-hydroxybutyrate-co-hydroxyvalerate are biodegradable polymers that can be obtained from renewable biomass sources. The aim of this study was to develop three types of environmentally friendly film biocomposites of altered microstructure by combining each of the above-mentioned polymers with cellulose nanocrystal fillers and further processing the resulting materials via space-confined solvent vapor annealing. Cellulose was previously obtained from renewable biomass and further converted to cellulose nanocrystals by hydrolysis with the lactic acid. The solutions of biodegradable polymers were spin-coated onto solid substrates before and after the addition of cellulose nanocrystals. The obtained thin film composites were further processed via space-confined solvent vapor annealing to eventually favor their crystallization and, thus, to alter the final microstructure. Indeed, atomic force microscopy studies have revealed that the presence of cellulose nanocrystals within a biodegradable polymer matrix promoted the formation of large crystalline structures exhibiting fractal-, spherulitic- or needle-like morphologies.

Growth of Hybrid Perovskite Crystals from CH3NH3PbI3-xClx Solutions Subjected to Constant Solvent Evaporation Rates.

In this work, we subjected hybrid lead-mixed halide perovskite (CH3NH3PbI3-xClx) precursor inks to different solvent evaporation rates in order to facilitate the nucleation and growth of perovskite crystals. By controlling the temperature of perovskite solutions placed within open-air rings in precise volumes, we established control over the rate of solvent evaporation and, thus, over both the growth rate and the shape of perovskite crystals. Direct utilization of diluted lead-mixed halide perovskites solutions allowed us to control the nucleation and to favor the growth of only a low number of perovskite crystals. Such crystals exhibited a clear sixfold symmetry. While crystals formed at a lower range of temperatures (40-60 °C) exhibited a more compact dendritic shape, the crystals grown at a higher temperature range (80-110 °C) displayed a fractal dendritic morphology.

Self-Assembly of Block Copolymers in Thin Films Swollen-Rich in Solvent Vapors.

In this study we have employed a polymer processing method based on solvent vapor annealing in order to condense relatively large amounts of solvent vapors onto thin films of block copolymers and thus to promote their self-assembly into ordered nanostructures. As revealed by the atomic force microscopy, a periodic lamellar morphology of poly(2-vinylpyridine)-b-polybutadiene and an ordered morphology comprised of hexagonally-packed structures made of poly(2-vinylpyridine)-b-poly(cyclohexyl methacrylate) were both successfully generated on solid substrates for the first time.

Phonon-Assisted Tunneling through Quantum Dot Systems Connected to Majorana Bound States.

We theoretically analyze phonon-assisted tunneling transport in a quantum dot side connected to a Majorana bound state in a topological superconducting nanowire. We investigate the behavior of the current through the dot, for a range of experimentally relevant parameters, in the presence of one long-wave optical phonon mode. We consider the current-gate voltage, the current-bias voltage and the current-dot-Majorana coupling characteristics under the influence of the electron-phonon coupling. In the absence of electron-phonon interaction, the Majorana bound states suppress the current when the gate voltage matches the Fermi level, but the increase in the bias voltage counteracts this effect. In the presence of electron-phonon coupling, the current behaves similarly as a function of the renormalized gate voltage. As an added feature at large bias voltages, it presents a dip or a plateau, depending on the size of the dot-Majorana coupling. Lastly, we show that the currents are most sensitive to, and depend non-trivially on the parameters of the Majorana circuit element, in the regime of low temperatures combined with low voltages. Our results provide insights into the complex physics of quantum dot devices used to probe Majorana bound states.

Controllable processes for generating large single crystals of poly(3-hexylthiophene).

Sowing the seeds: A simple strategy based on self-seeding allows large single crystals of long regioregular poly(3-hexylthiophene) chains to be grown from solution. When appropriately crystallized, materials differing in their degrees of regioregularity and molecular weights formed monoclinic form II crystals with interdigitated hexyl side groups (see picture).

Patterning at the micro/nano-scale: Polymeric scaffolds for medical diagnostic and cell-surface interaction applications.

Future-oriented material fabrication technologies would aim to reproduce features characteristic to the natural materials into the synthetic ones. Various bio-mimicking strategies can be already used in medical industry since they can mimic the desired surface design with the help of surface patterning techniques. In this review, we highlight the most common patterning methodologies employed for the fabrication of polymeric substrates having micro or nano-features by presenting their advantages and potential utility for applications in the biomedical field. Top-down and bottom-up fabrication techniques including lithographic approaches such as photolithography, electron, proton, ion beam and block copolymer lithography, soft lithography and some advanced methods as scanning probe and particle lithography are firstly described, followed by a brief presentation of the alternative patterning techniques using biomolecule crystallization or DNA self-assembly. The potential use of synthetic- and bio-polymer patterned substrates and the so-far reported studies including analysis of molecule and cell-interface interactions, cell development, migration and differentiation are further described with emphasis onto their implementation on circulating blood cells and blood disorders. The last chapter summarizes the results found regarding the advantages of using such substrates as component parts in biosensing devices, with foreseen applicability in medical diagnosis and the clinical healthcare domain.

Spheres-in-Grating Assemblies with Altered Photoluminescence and Wetting Properties.

In this work, we report the fabrication of spheres-in-grating assemblies consisting of equally spaced parallel rectangular grooves filled with fluorescent spheres, by employing embossing and convective self-assembly methods. The developed hierarchical assemblies, when compared to spheres spin-cast on glass, exhibited a blueshift in the photoluminescence spectra, as well as changes in wetting properties induced not only by the patterning process, but also by the nature and size of the utilized spheres. While the patterning process led to increased hydrophobicity, the utilization of spheres with larger diameter improved the hydrophilicity of the fabricated assemblies. Finally, by aiming at the future integration of the spheres-in-grating assemblies as critical components in different technological and medical applications, we report a successful encapsulation of the incorporated spheres within the grating with a top layer of a functional polymer.

Multifunctional Structured Platforms: From Patterning of Polymer-Based Films to Their Subsequent Filling with Various Nanomaterials.

There is an astonishing number of optoelectronic, photonic, biological, sensing, or storage media devices, just to name a few, that rely on a variety of extraordinary periodic surface relief miniaturized patterns fabricated on polymer-covered rigid or flexible substrates. Even more extraordinary is that these surface relief patterns can be further filled, in a more or less ordered fashion, with various functional nanomaterials and thus can lead to the realization of more complex structured architectures. These architectures can serve as multifunctional platforms for the design and the development of a multitude of novel, better performing nanotechnological applications. In this work, we aim to provide an extensive overview on how multifunctional structured platforms can be fabricated by outlining not only the main polymer patterning methodologies but also by emphasizing various deposition methods that can guide different structures of functional nanomaterials into periodic surface relief patterns. Our aim is to provide the readers with a toolbox of the most suitable patterning and deposition methodologies that could be easily identified and further combined when the fabrication of novel structured platforms exhibiting interesting properties is targeted.

Antimicrobial Polymeric Structures Assembled on Surfaces.

Pathogenic microbes are the main cause of various undesired infections in living organisms, including humans. Most of these infections are favored in hospital environments where humans are being treated with antibiotics and where some microbes succeed in developing resistance to such drugs. As a consequence, our society is currently researching for alternative, yet more efficient antimicrobial solutions. Certain natural and synthetic polymers are versatile materials that have already proved themselves to be highly suitable for the development of the next-generation of antimicrobial systems that can efficiently prevent and kill microbes in various environments. Here, we discuss the latest developments of polymeric structures, exhibiting (reinforced) antimicrobial attributes that can be assembled on surfaces and coatings either from synthetic polymers displaying antiadhesive and/or antimicrobial properties or from blends and nanocomposites based on such polymers.

Understanding hierarchical spheres-in-grating assembly for bio-inspired colouration.

The vivid iridescent response from particular butterflies is as an excellent example of how micro-engineered hierarchical architectures that combine physical structures and pigmentary inclusions create unique colouration. To date, however, detailed knowledge is missing to replicate such sophisticated structures in a robust, reliable manner. Here, we deliver spheres-in-grating assemblies with colouration effects as found in nature, exploiting embossed polymer gratings and self-assembled light-absorbing micro-spheres.

Minimizing lateral domain collapse in etched poly(3-hexylthiophene)-block-polylactide thin films for improved optoelectronic performance.

Thin films of poly(3-hexylthiophene)-block-polylactide block copolymer exhibiting ordered lamellar morphology have been selectively etched to produce structured films that could be used in fabrication of idealized bulk heterojunctions for organic or hybrid solar energy devices. Etched poly(3-hexylthiophene) films, after being rinsed in water to remove degraded polylactide fragments, were dried using various drying approaches that reduce or alleviate surface tension forces generated during liquid evaporation from the film. As emphasized by atomic force microscopy, X-ray diffraction, and emission photoluminescence, a reduction in domain collapse leads to improved molecular ordering in the plane perpendicular to the substrate and enhanced photoluminescence quenching when paired with fullerene C(60) hydroxide electron acceptors.

Enhancing Photoluminescence Quenching in Donor-Acceptor PCE11:PPCBMB Films through the Optimization of Film Microstructure.

We show that a precise control of deposition speed during the fabrication of polyfullerenes and donor polymer films by convective self-assembly leads to an optimized film microstructure comprised of interconnected crystalline polymer domains comparable to molecular dimensions intercalated with similar polyfullerene domains. Moreover, in blended films, we have found a correlation between deposition speed, the resulting microstructure, and photoluminescence quenching. The latter appeared more intense for lower deposition speeds due to a more favorable structuring at the nanoscale of the two donor and acceptor systems in the resulting blend films.

The influence of protic non-solvents present in the environment on structure formation of poly(γ-benzyl-l-glutamate) in organic solvents.

We present an experimental study of structure formation in a polypeptide hetero-arm star block copolymer solution, obtained by swelling thin films in chloroform solvent vapor to variable poly(γ-benzyl-l-glutamate) (PBLGlu) concentrations (cp). Direct observation by optical microscopy allowed us to follow in real time nucleation and growth of ordered three-dimensional structures of ellipsoidal shape. At low cp, growth stopped when cp decreased below the solubility limit (ccritical) but additional structures were formed when cp was rapidly increased to a higher value. Although water is not a solvent for this polymer, we demonstrate that water, even in trace amounts, is nonetheless considerably affecting solubility and consequently the process of structure formation. We have varied systematically the amount of water present in the environment. ccritical changed from about 0.53 (dry, i.e. desiccated surrounding vapour phase) viaccritical ≈ 0.16-0.25 for 30-50% humidity of the vapour phase to ccritical ≈ 0.03 for a vapour phase at 100% humidity. We attribute this change in solubility to complexation of water molecules with PBLGlu α-helix, which increases the interfacial tension between the polymer and the solvent. We have tested our hypothesis by replacing water with other non-solvents for the polymer. Only protic non-solvents changed the solubility of PBLGlu in chloroform.

Influence of Molecular Conformations and Microstructure on the Optoelectronic Properties of Conjugated Polymers.

It is increasingly obvious that the molecular conformations and the long-range arrangement that conjugated polymers can adopt under various experimental conditions in bulk, solutions or thin films, significantly impact their resulting optoelectronic properties. As a consequence, the functionalities and efficiencies of resulting organic devices, such as field-effect transistors, light-emitting diodes, or photovoltaic cells, also dramatically change due to the close structure/property relationship. A range of structure/optoelectronic properties relationships have been investigated over the last few years using various experimental and theoretical methods, and, further, interesting correlations are continuously revealed by the scientific community. In this review, we discuss the latest findings related to the structure/optoelectronic properties interrelationships that exist in organic devices fabricated with conjugated polymers in terms of charge mobility, absorption, photoluminescence, as well as photovoltaic properties.

Enhancing the photoluminescence emission of conjugated MEH-PPV by light processing.

We show here that treatment of thin films of conjugated polymers by illumination with light leads to an increase of the intensity of their photoluminescence by up to 42%. The corresponding enhancement of absorbance was much less pronounced. We explain this significant enhancement of photoluminescence by a planarization of the conjugated polymer chains induced by photoexcitations even below the glass transition temperature, possibly due to an increased conjugation length. Interestingly, the photoluminescence remains at the enhanced level for more than 71 h after treatment of the films by illumination with light, likely due to the fact that below the glass transition temperature no restoring force could return the conjugated chains into their initial conformational state.