Permanent tuning of optical resonant modes of chalcogenide-coated microresonators.

Chalcogenide materials are promising for optical resonant mode tuning of whispering gallery mode (WGM) microresonators due to their high nonlinearity. In this study, this phenomenon was demonstrated for Ge2Sb2Te5-coated toroidal microresonators using an optical postprocess, which utilizes the intrinsically photosensitive property of the Ge2Sb2Te5 coating. A signal laser was used to illuminate the resonator for permanent tuning of the WGMs in a sensitive manner. 0.01 nm and 0.02 nm permanent tuning of the WGMs was recorded for 5 nm and 10 nm coated resonators, respectively. This technique enables resonance matching of coupled optical resonators, which could pave the way for optoelectronic circuitries employing multiple optical microresonators.

Reversible decryption of covert nanometer-thick patterns in modular metamaterials.

Continuous development of security features is mandatory for the fight against forgery of valuable documents and products, the most notable example being banknotes. Such features demonstrate specific properties under certain stimuli such as fluorescent patterns glowing under ultraviolet light. These security features should also be hard to copy by unlicensed people and be interrogated by anyone using easily accessible tools. To this end, this Letter demonstrates the development of an ideal security feature enabled by the realization of modular metamaterials based on metal-dielectric-metal cavities that consist of two separate parts: metal nanoparticles on an elastomeric substrate and a bottom mirror coated with a thin dielectric. Patterns generated by creating nanometer-thick changes in the dielectric layer are invisible (encrypted) and can only be detected (decrypted) by sticking the elastomeric patch on. The observed optical effects such as visibility and colors can only be produced with the correct combination of materials and film thicknesses, making the proposed structures a strong alternative to compromised security features.

A comparison of peptide amphiphile nanofiber macromolecular assembly strategies.

Supramolecular peptide nanofibers that are composed of peptide amphiphile molecules have been widely used for many purposes from biomedical applications to energy conversion. The self-assembly mechanisms of these peptide nanofibers also provide convenient models for understanding the self-assembly mechanisms of various biological supramolecular systems; however, the current theoretical models that explain these mechanisms do not sufficiently explain the experimental results. In this study, we present a new way of modeling these nanofibers that better fits with the experimental data. Molecular dynamics simulations were applied to create model fibers using two different layer models and two different tilt angles. Strikingly, the fibers which were modeled to be tilting the peptide amphiphile molecules and/or tilting the plane were found to be more stable and consistent with the experiments.

The design and fabrication of supramolecular semiconductor nanowires formed by benzothienobenzothiophene (BTBT)-conjugated peptides.

π-Conjugated small molecules based on a [1]benzothieno[3,2-b]benzothiophene (BTBT) unit are of great research interest in the development of solution-processable semiconducting materials owing to their excellent charge-transport characteristics. However, the BTBT π-core has yet to be demonstrated in the form of electro-active one-dimensional (1D) nanowires that are self-assembled in aqueous media for potential use in bioelectronics and tissue engineering. Here we report the design, synthesis, and self-assembly of benzothienobenzothiophene (BTBT)-peptide conjugates, the BTBT-peptide (BTBT-C3-COHN-Ahx-VVAGKK-Am) and the C8-BTBT-peptide (C8-BTBT-C3-COHN-Ahx-VVAGKK-Am), as ß-sheet forming amphiphilic molecules, which self-assemble into highly uniform nanofibers in water with diameters of 11-13(±1) nm and micron-size lengths. Spectroscopic characterization studies demonstrate the J-type π-π interactions among the BTBT molecules within the hydrophobic core of the self-assembled nanofibers yielding an electrical conductivity as high as 6.0 × 10-6 S cm-1. The BTBT π-core is demonstrated, for the first time, in the formation of self-assembled peptide 1D nanostructures in aqueous media for potential use in tissue engineering, bioelectronics and (opto)electronics. The conductivity achieved here is one of the highest reported to date in a non-doped state.

The Predictor Role of the Aqueduct Cerebrospinal Fluid Flow on Endoscopic Third Ventriculostomy: Explication on Assumption Physical Model.

AIM: To evaluate the cerebrospinal fluid (CSF) flow dynamics in the aqueductus sylvii of patients with obstructive hydrocephalus who underwent endoscopic third ventriculostomy (ETV) and to predict ventriculostomy patency via aqueduct flow measurements. MATERIAL AND METHODS: Twenty-four patients with obstructive hydrocephalus caused by primary aqueduct stenosis who underwent ETV were included in the study. All the patients underwent conventional and cine magnetic resonance imaging before and after treatment. The flow of CSF in the aqueduct of Sylvius and prepontine cistern was assessed, and the diameter of the third ventricle was also measured. Increase in the aqueduct flow velocity after a successful ETV was supported by the assumption physical model that highlights a possible mechanism that explains the clinical findings. RESULTS: The flow pattern and velocity in the prepontine cistern and aqueduct were normal in 17 out of 24 patients who responded to ETV clinically. However, seven patients who did not respond to ETV had an abnormal flow pattern in both the prepontine cistern and aqueduct. CONCLUSION: The flow pattern in the aqueduct was normalised and velocity was increased compared with those of preoperative values after a successful ETV. The flow of CSF in the prepontine cistern is routinely used for ventriculostomy patency assessment. In addition, aqueduct measurements may be useful in predicting ventriculostomy patency. The physical model provides valuable insights on a possible mechanism that affected the experimental data.

Force and time-dependent self-assembly, disruption and recovery of supramolecular peptide amphiphile nanofibers.

Biological feedback mechanisms exert precise control over the initiation and termination of molecular self-assembly in response to environmental stimuli, while minimizing the formation and propagation of defects through self-repair processes. Peptide amphiphile (PA) molecules can self-assemble at physiological conditions to form supramolecular nanostructures that structurally and functionally resemble the nanofibrous proteins of the extracellular matrix, and their ability to reconfigure themselves in response to external stimuli is crucial for the design of intelligent biomaterials systems. Here, we investigated real-time self-assembly, deformation, and recovery of PA nanofibers in aqueous solution by using a force-stabilizing double-pass scanning atomic force microscopy imaging method to disrupt the self-assembled peptide nanofibers in a force-dependent manner. We demonstrate that nanofiber damage occurs at tip-sample interaction forces exceeding 1 nN, and the damaged fibers subsequently recover when the tip pressure is reduced. Nanofiber ends occasionally fail to reconnect following breakage and continue to grow as two individual nanofibers. Energy minimization calculations of nanofibers with increasing cross-sectional ellipticity (corresponding to varying levels of tip-induced fiber deformation) support our observations, with high-ellipticity nanofibers exhibiting lower stability compared to their non-deformed counterparts. Consequently, tip-mediated mechanical forces can provide an effective means of altering nanofiber integrity and visualizing the self-recovery of PA assemblies.

Colorimetric detection of ultrathin dielectrics on strong interference coatings.

Metal films covered with ultrathin lossy dielectrics can exhibit strong interference effects manifested as the broad absorption of the incident light resulting in distinct surface colors. Despite their simple bilayer structures, such surfaces have only recently been scrutinized and applied mainly to color printing. Here, we report the use of such surfaces for colorimetric detection of ultrathin dielectrics. Upon deposition of a nanometer-thick dielectric on the surface, the absorption peak red shifts, changing the surface color. The color contrast between the bare and dielectric-coated surfaces can be detected by the naked eye. The optical responses of the surfaces are characterized for nanometer-thick SiO2, Al2O3, and bovine serum albumin molecules. The results suggest that strong interference surfaces can be employed as biosensors.

Probe microscopy methods and applications in imaging of biological materials.

Atomic force microscopy is an emerging tool for investigating the biomolecular aspects of cellular interactions; however, cell and tissue analyses must frequently be performed in aqueous environment, over rough surfaces, and on complex adhesive samples that complicate the imaging process and readily facilitate the blunting or fouling of the AFM probe. In addition, the shape and surface chemistry of the probe determine the quality and types of data that can be acquired from biological materials, with certain information becoming available only within a specific range of tip lengths or diameters, or through the assistance of specific chemical or biological functionalization procedures. Consequently, a broad range of probe modification techniques has been developed to extend the capabilities and overcome the limitations of biological AFM measurements, including the fabrication of AFM tips with specialized morphologies, surface coating with biologically affine molecules, and the attachment of proteins, nucleic acids and cells to AFM probes. In this review, we underline the importance of probe choice and modification for the AFM analysis of biomaterials, discuss the recent literature on the use of non-standard AFM tips in life sciences research, and consider the future utility of tip functionalization methods for the investigation of fundamental cell and tissue interactions.

Biocompatible Electroactive Tetra(aniline)-Conjugated Peptide Nanofibers for Neural Differentiation.

Peripheral nerve injuries cause devastating problems for the quality of patients' lives, and regeneration following damage to the peripheral nervous system is limited depending on the degree of the damage. Use of nanobiomaterials can provide therapeutic approaches for the treatment of peripheral nerve injuries. Electroactive biomaterials, in particular, can provide a promising cure for the regeneration of nerve defects. Here, a supramolecular electroactive nanosystem with tetra(aniline) (TA)-containing peptide nanofibers was developed and utilized for nerve regeneration. Self-assembled TA-conjugated peptide nanofibers demonstrated electroactive behavior. The electroactive self-assembled peptide nanofibers formed a well-defined three-dimensional nanofiber network mimicking the extracellular matrix of the neuronal cells. Neurite outgrowth was improved on the electroactive TA nanofiber gels. The neural differentiation of PC-12 cells was more advanced on electroactive peptide nanofiber gels, and these biomaterials are promising for further use in therapeutic neural regeneration applications.

Multivalent Presentation of Cationic Peptides on Supramolecular Nanofibers for Antimicrobial Activity.

Noncovalent and electrostatic interactions facilitate the formation of complex networks through molecular self-assembly in biomolecules such as proteins and glycosaminoglycans. Self-assembling peptide amphiphiles (PA) are a group of molecules that can form nanofibrous structures and may contain bioactive epitopes to interact specifically with target molecules. Here, we report the presentation of cationic peptide sequences on supramolecular nanofibers formed by self-assembling peptide amphiphiles for cooperative enhanced antibacterial activity. Antibacterial properties of self-assembled peptide nanofibers were significantly higher than soluble peptide molecules with identical amino acid sequences, suggesting that the tandem presentation of bioactive epitopes is important for designing new materials for bactericidal activity. In addition, bacteria were observed to accumulate more rapidly on peptide nanofibers compared to soluble peptides, which may further enhance antibacterial activity by increasing the number of peptide molecules interacting with the bacterial membrane. The cationic peptide amphiphile nanofibers were observed to attach to bacterial membranes and disrupt their integrity. These results demonstrate that short cationic peptides show a significant improvement in antibacterial activity when presented in the nanofiber form.

Supramolecular Peptide Nanofiber Morphology Affects Mechanotransduction of Stem Cells.

Chirality and morphology are essential factors for protein function and interactions with other biomacromolecules. Extracellular matrix (ECM) proteins are also similar to other proteins in this sense; however, the complexity of the natural ECM makes it difficult to study these factors at the cellular level. The synthetic peptide nanomaterials harbor great promise in mimicking specific ECM molecules as model systems. In this work, we demonstrate that mechanosensory responses of stem cells are directly regulated by the chirality and morphology of ECM-mimetic peptide nanofibers with strictly controlled characteristics. Structural signals presented on l-amino acid containing cylindrical nanofibers (l-VV) favored the formation of integrin ß1-based focal adhesion complexes, which increased the osteogenic potential of stem cells through the activation of nuclear YAP. On the other hand, twisted ribbon-like nanofibers (l-FF and d-FF) guided the cells into round shapes and decreased the formation of focal adhesion complexes, which resulted in the confinement of YAP proteins in the cytosol and a corresponding decrease in osteogenic potential. Interestingly, the d-form of twisted-ribbon like nanofibers (d-FF) increased the chondrogenic potential of stem cells more than their l-form (l-FF). Our results provide new insights into the importance and relevance of morphology and chirality of nanomaterials in their interactions with cells and reveal that precise control over the chemical and physical properties of nanostructures can affect stem cell fate even without the incorporation of specific epitopes.

Fabrication of Supramolecular n/p-Nanowires via Coassembly of Oppositely Charged Peptide-Chromophore Systems in Aqueous Media.

Fabrication of supramolecular electroactive materials at the nanoscale with well-defined size, shape, composition, and organization in aqueous medium is a current challenge. Herein we report construction of supramolecular charge-transfer complex one-dimensional (1D) nanowires consisting of highly ordered mixed-stack π-electron donor-acceptor (D-A) domains. We synthesized n-type and p-type ß-sheet forming short peptide-chromophore conjugates, which assemble separately into well-ordered nanofibers in aqueous media. These complementary p-type and n-type nanofibers coassemble via hydrogen bonding, charge-transfer complex, and electrostatic interactions to generate highly uniform supramolecular n/p-coassembled 1D nanowires. This molecular design ensures highly ordered arrangement of D-A stacks within n/p-coassembled supramolecular nanowires. The supramolecular n/p-coassembled nanowires were found to be formed by A-D-A unit cells having an association constant (KA) of 5.18 × 105 M-1. In addition, electrical measurements revealed that supramolecular n/p-coassembled nanowires are approximately 2400 and 10 times more conductive than individual n-type and p-type nanofibers, respectively. This facile strategy allows fabrication of well-defined supramolecular electroactive nanomaterials in aqueous media, which can find a variety of applications in optoelectronics, photovoltaics, organic chromophore arrays, and bioelectronics.

Wafer-scale arrays of high-Q silica optical microcavities.

On-chip high-Q microcavities possess significant potential in terms of integration of optical microresonators into functional optoelectronic devices that could be used in various applications, including biosensors, photonic-integrated circuits, or quantum optics experiments. Yet, despite the convenience of fabricating wafer-scale integrated microresonators with moderate Q values using standard microfabrication techniques, surface-tension-induced microcavities (STIMs), which have atomic-level surface roughness enabling the observation of Q values larger than 106, could only be produced using individual thermal treatment of every single microresonator within the devised area. Here, we demonstrate a facile method for large-scale fabrication of silica STIMs of various morphologies. Q values exceeding 106 are readily obtained using this technique. This study represents a significant advancement toward fabrication of wafer-scale optoelectronic circuitries.

A Modular Antigen Presenting Peptide/Oligonucleotide Nanostructure Platform for Inducing Potent Immune Response.

The design and development of vaccines, which can induce cellular immunity, particularly CD8+ T cells hold great importance since these cells play crucial roles against cancers and viral infections. Covalent conjugation of antigen and adjuvant molecules has been used for successful promotion of immunogenicity in subunit vaccines; however, the stimulation of the CD8+ T-cell responses by this approach has so far been limited. This study demonstrates a modular system based on noncovalent attachment of biotinylated antigen to a hybrid nanofiber system consisting of biotinylated self-assembling peptide and CpG oligodeoxynucleotides (ODN) molecules, via biotin-streptavidin interaction. These peptide/oligonucleotide hybrid nanosystems are capable of bypassing prior limitations related with inactivated or live-attenuated virus vaccines and achieve exceptionally high CD8+ T-cell responses. The nanostructures are found to trigger strong IgG response and effectively modulate cross-presentation of their antigen "cargo" through close proximity between the antigen and peptide/ODN adjuvant system. In addition, the biotinylated peptide nanofiber system is able to enhance antigen uptake and induce the maturation of antigen-presenting cells. Due to its versatility, biocompatibility, and biodegradability with a broad variety of streptavidin-linked antigens, the nanosystem shown here can be utilized as an efficient strategy for new vaccine development.

Local delivery of doxorubicin through supramolecular peptide amphiphile nanofiber gels.

Peptide amphiphiles (PAs) self-assemble into supramolecular nanofiber gels that provide a suitable environment for encapsulation of both hydrophobic and hydrophilic molecules. The PA gels have significant advantages for controlled delivery applications due to their high capacity to retain water, biocompatibility, and biodegradability. In this study, we demonstrate injectable supramolecular PA nanofiber gels for drug delivery applications. Doxorubicin (Dox), as a widely used chemotherapeutic drug for breast cancer treatment, was encapsulated within the PA gels prepared at different concentrations. Physical and chemical properties of the gels were characterized, and slow release of the Dox molecules through the supramolecular PA nanofiber gels was studied. In addition, the diffusion constants of the drug molecules within the PA nanofiber gels were estimated using fluorescence recovery after the photobleaching (FRAP) method. The PA nanofiber gels did not show any cytotoxicity and the encapsulation strategy enhanced the activity of drug molecules on cellular viability through prolonged release compared to direct administration under in vitro conditions. Moreover, the local in vivo injection of the Dox encapsulated PA nanofiber gels (Dox/PA) to the tumor site demonstrated the lowest tumor growth rate compared to the direct Dox injection and increased the apoptotic cells within the tumor tissue for local drug release through the PA nanofiber gels under in vivo conditions.

Atomic force microscopy for the investigation of molecular and cellular behavior.

The present review details the methods used for the measurement of cells and their exudates using atomic force microscopy (AFM) and outlines the general conclusions drawn by the mechanical characterization of biological materials through this method. AFM is a material characterization technique that can be operated in liquid conditions, allowing its use for the investigation of the mechanical properties of biological materials in their native environments. AFM has been used for the mechanical investigation of proteins, nucleic acids, biofilms, secretions, membrane bilayers, tissues and bacterial or eukaryotic cells; however, comparison between studies is difficult due to variances between tip sizes and morphologies, sample fixation and immobilization strategies, conditions of measurement and the mechanical parameters used for the quantification of biomaterial response. Although standard protocols for the AFM investigation of biological materials are limited and minor differences in measurement conditions may create large discrepancies, the method is nonetheless highly effective for comparatively evaluating the mechanical integrity of biomaterials and can be used for the real-time acquisition of elasticity data following the introduction of a chemical or mechanical stimulus. While it is currently of limited diagnostic value, the technique is also useful for basic research in cancer biology and the characterization of disease progression and wound healing processes.

Perfectly absorbing ultra thin interference coatings for hydrogen sensing.

Here we numerically demonstrate a straightforward method for optical detection of hydrogen gas by means of absorption reduction and colorimetric indication. A perfectly absorbing metal-insulator-metal (MIM) thin film interference structure is constructed using a silver metal back reflector, silicon dioxide insulator, and palladium as the upper metal layer and hydrogen catalyst. The thickness of silicon dioxide allows the maximizing of the electric field intensity at the Air/SiO2 interface at the quarter wavelengths and enabling perfect absorption with the help of highly absorptive palladium thin film (∼7 nm). While the exposure of the MIM structure to H2 moderately increases reflection, the relative intensity contrast due to formation of metal hydride is extensive. By modifying the insulator film thickness and hence the spectral absorption, the color is tuned and eye-visible results are obtained.

Virus-like nanostructures for tuning immune response.

Synthetic vaccines utilize viral signatures to trigger immune responses. Although the immune responses raised against the biochemical signatures of viruses are well characterized, the mechanism of how they affect immune response in the context of physical signatures is not well studied. In this work, we investigated the ability of zero- and one-dimensional self-assembled peptide nanostructures carrying unmethylated CpG motifs (signature of viral DNA) for tuning immune response. These nanostructures represent the two most common viral shapes, spheres and rods. The nanofibrous structures were found to direct immune response towards Th1 phenotype, which is responsible for acting against intracellular pathogens such as viruses, to a greater extent than nanospheres and CpG ODN alone. In addition, nanofibers exhibited enhanced uptake into dendritic cells compared to nanospheres or the ODN itself. The chemical stability of the ODN against nuclease-mediated degradation was also observed to be enhanced when complexed with the peptide nanostructures. In vivo studies showed that nanofibers promoted antigen-specific IgG production over 10-fold better than CpG ODN alone. To the best of our knowledge, this is the first report showing the modulation of the nature of an immune response through the shape of the carrier system.

Rounding corners of nano-square patches for multispectral plasmonic metamaterial absorbers.

Multispectral metamaterial absorbers based on metal-insulator-metal nano-square patch resonators are studied here. For a geometry consisting of perfectly nano-square patches and vertical sidewalls, double resonances in the visible regime are observed due to simultaneous excitation of electric and magnetic plasmon modes. Although slightly modifying the sizes of the square patches makes the resonance wavelengths simply shift, rounding corners of the square patches results in emergence of a third resonance due to excitation of the circular cavity modes. Sidewall angle of the patches are also observed to affect the absorption spectra significantly. Peak absorption values for the triple resonance structures are strongly affected as the sidewall angle varies from 90 to 50 degrees. Rounded corners and slanted sidewalls are typical imperfections for lithographically fabricated metamaterial structures. The presented results suggest that imperfections caused during fabrication of the top nano-structures must be taken into account when designing metamaterial absorbers. Furthermore, it is shown that these fabrication imperfections can be exploited for improving resonance properties and bandwidths of metamaterials for various potential applications such as solar energy harvesting, thermal emitters, surface enhanced spectroscopies and photodetection.

Portable microfluidic integrated plasmonic platform for pathogen detection.

Timely detection of infectious agents is critical in early diagnosis and treatment of infectious diseases. Conventional pathogen detection methods, such as enzyme linked immunosorbent assay (ELISA), culturing or polymerase chain reaction (PCR) require long assay times, and complex and expensive instruments, which are not adaptable to point-of-care (POC) needs at resource-constrained as well as primary care settings. Therefore, there is an unmet need to develop simple, rapid, and accurate methods for detection of pathogens at the POC. Here, we present a portable, multiplex, inexpensive microfluidic-integrated surface plasmon resonance (SPR) platform that detects and quantifies bacteria, i.e., Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) rapidly. The platform presented reliable capture and detection of E. coli at concentrations ranging from ~10(5) to 3.2 × 10(7) CFUs/mL in phosphate buffered saline (PBS) and peritoneal dialysis (PD) fluid. The multiplexing and specificity capability of the platform was also tested with S. aureus samples. The presented platform technology could potentially be applicable to capture and detect other pathogens at the POC and primary care settings.