Synthetic Approaches to Flexible Fluorescent Conjugated Polymers

Conjugated polymers (CPs) are intrinsically fluorescent materials that have been used for various biological applications including imaging, sensing, and delivery of biologically active substances. The synthetic control over flexibility and biodegradability of these materials aids the understanding of the structure-function relationships among the photophysical properties, the self-assembly behaviors of the corresponding conjugated polymer nanoparticles (CPNs), and the cellular behaviors of CPNs, such as toxicity, cellular uptake mechanisms, and sub-cellular localization patterns. Synthetic approaches towards two classes of flexible CPs with well-preserved fluorescent properties are described. The synthesis of flexible poly(p-phenylenebutadiynylene)s (PPBs) uses competing Sonogashira and Glaser coupling reactions and the differences in monomer reactivity to incorporate a small amount (~10%) of flexible, non-conjugated linkers into the backbone. The reaction conditions provide limited control over the proportion of flexible monomer incorporation. Improved synthetic control was achieved in a series of flexible poly(p-phenyleneethynylene)s (PPEs) using modified Sonogashira conditions. In addition to controlling the degree of flexibility, the linker provides disruption of backbone conjugation that offers control of the length of conjugated segments within the polymer chain. Therefore, such control also results in the modulation of the photophysical properties of the materials. CPNs fabricated from flexible PPBs are non-toxic to cells, and exhibit subcellular localization patterns clearly different from those observed with non-flexible PPE CPNs. The subcellular localization patterns of the flexible PPEs have not yet been determined, due to the toxicity of the materials, most likely related to the side-chain structure used in this series. The study of the effect of CP flexibility on self-assembly reorganization upon polyanion complexation is presented. Owing to its high rigidity and hydrophobicity, the PPB backbone undergoes reorganization more readily than PPE. The effects are enhanced in the presence of the flexible linker, which enables more efficient π-π stacking of the aromatic backbone segments. Flexibility has minimal effects on the self-assembly of PPEs. Understanding the role of flexibility on the biophysical behaviors of CPNs is key to the successful development of novel efficient fluorescent therapeutic delivery vehicles.

Silicon photonic device for wavelength sensing and monitoring

Over the last decade advances and innovations from Silicon Photonics technology were observed in the telecommunications and computing industries. This technology which employs Silicon as an optical medium, relies on current CMOS micro-electronics fabrication processes to enable medium scale integration of many nano-photonic devices to produce photonic integrated circuitry. ^ However, other fields of research such as optical sensor processing can benefit from silicon photonics technology, specially in sensors where the physical measurement is wavelength encoded. ^ In this research work, we present a design and application of a thermally tuned silicon photonic device as an optical sensor interrogator. ^ The main device is a micro-ring resonator filter of 10 μm of diameter. A photonic design toolkit was developed based on open source software from the research community. With those tools it was possible to estimate the resonance and spectral characteristics of the filter. From the obtained design parameters, a 7.8 × 3.8 mm optical chip was fabricated using standard micro-photonics techniques. In order to tune a ring resonance, Nichrome micro-heaters were fabricated on top of the device. Some fabricated devices were systematically characterized and their tuning response were determined. From measurements, a ring resonator with a free-spectral-range of 18.4 nm and with a bandwidth of 0.14 nm was obtained. Using just 5 mA it was possible to tune the device resonance up to 3 nm. ^ In order to apply our device as a sensor interrogator in this research, a model of wavelength estimation using time interval between peaks measurement technique was developed and simulations were carried out to assess its performance. To test the technique, an experiment using a Fiber Bragg grating optical sensor was set, and estimations of the wavelength shift of this sensor due to axial strains yield an error within 22 pm compared to measurements from spectrum analyzer. ^ Results from this study implies that signals from FBG sensors can be processed with good accuracy using a micro-ring device with the advantage of ts compact size, scalability and versatility. Additionally, the system also has additional applications such as processing optical wavelength shifts from integrated photonic sensors and to be able to track resonances from laser sources.^

A Thermally Wavelength-tunable Photonic Switch Based on Silicon Microring Resonator

Silicon photonics is a very promising technology for future low-cost high-bandwidth optical telecommunication applications down to the chip level. This is due to the high degree of integration, high optical bandwidth and large speed coupled with the development of a wide range of integrated optical functions. Silicon-based microring resonators are a key building block that can be used to realize many optical functions such as switching, multiplexing, demultiplaxing and detection of optical wave. The ability to tune the resonances of the microring resonators is highly desirable in many of their applications. In this work, the study and application of a thermally wavelength-tunable photonic switch based on silicon microring resonator is presented. Devices with 10µm diameter were systematically studied and used in the design. Its resonance wavelength was tuned by thermally induced refractive index change using a designed local micro-heater. While thermo-optic tuning has moderate speed compared with electro-optic and all-optic tuning, with silicon’s high thermo-optic coefficient, a much wider wavelength tunable range can be realized. The device design was verified and optimized by optical and thermal simulations. The fabrication and characterization of the device was also implemented. The microring resonator has a measured FSR of ~18 nm, FWHM in the range 0.1-0.2 nm and Q around 10,000. A wide tunable range (>6.4 nm) was achieved with the switch, which enables dense wavelength division multiplexing (DWDM) with a channel space of 0.2nm. The time response of the switch was tested on the order of 10 us with a low power consumption of ~11.9mW/nm. The measured results are in agreement with the simulations. Important applications using the tunable photonic switch were demonstrated in this work. 1×4 and 4×4 reconfigurable photonic switch were implemented by using multiple switches with a common bus waveguide. The results suggest the feasibility of on-chip DWDM for the development of large-scale integrated photonics. Using the tunable switch for output wavelength control, a fiber laser was demonstrated with Erbium-doped fiber amplifier as the gain media. For the first time, this approach integrated on-chip silicon photonic wavelength control.

Sub-wavelength resonators as seismic Rayleigh waves shield

We explore the thesis that tall structures can be protected by means of seismic metamaterials. Seismic metamaterials can be built as some elements are created over soil layer with different shapes, dimensions, patterns and from different materials. Resonances in these elements are acting as locally resonant metamaterials for Rayleigh surface waves in the geophysics context. Analytically we proved that if we put infinite chain of SDOF resonator over the soil layer as an elastic, homogeneous and isotropic material, vertical component of Rayleigh wave, longitudinal resonance of oscillators will couple with each other, they would create a Rayleigh bandgap frequency, and wave will experience attenuation before it reaches the structure. As it is impossible to use infinite chain of resonators over soil layer, we considered finite number of resonators throughout our simulations. Analytical work is interpreted using finite element simulations that demonstrates the observed attenuation is due to bandgaps when oscillators are arranged at sub-wavelength scale with respect to the incident Rayleigh wave. For wavelength less than 5 meters, the resulting bandgaps are remarkably large and strongly attenuating when impedance of oscillators matches impedance of soil. Since longitudinal resonance of SDOF resonator are proportional to its length inversely, a formed array of resonators that attenuates Rayleigh waves at frequency ≤10 Hz could be designed starting from vertical pillars coupled to the ground. Optimum number of vertical pillars and their interval spacing called effective area of resonators are investigated. For 10 pillars with effective area of 1 meter and resonance frequency of 4.9 Hz, bandgap frequency causes attenuation and a sinusoidal impulsive force illustrate wave steering down phenomena. Simulation results proved analytical findings of this work.

Historical global map of NH4+ and NO3- application in synthetic nitrogen fertilizer, link to NetCDF files

This paper provides a method for constructing a new historical global nitrogen fertilizer application map (0.5° × 0.5° resolution) for the period 1961-2010 based on country-specific information from Food and Agriculture Organization statistics (FAOSTAT) and various global datasets. This new map incorporates the fraction of NH+4 (and NONO-3) in N fertilizer inputs by utilizing fertilizer species information in FAOSTAT, in which species can be categorized as NH+4 and/or NO-3-forming N fertilizers. During data processing, we applied a statistical data imputation method for the missing data (19 % of national N fertilizer consumption) in FAOSTAT. The multiple imputation method enabled us to fill gaps in the time-series data using plausible values using covariates information (year, population, GDP, and crop area). After the imputation, we downscaled the national consumption data to a gridded cropland map. Also, we applied the multiple imputation method to the available chemical fertilizer species consumption, allowing for the estimation of the NH+4/NO-3 ratio in national fertilizer consumption. In this study, the synthetic N fertilizer inputs in 2000 showed a general consistency with the existing N fertilizer map (Potter et al., 2010, doi:10.1175/2009EI288.1) in relation to the ranges of N fertilizer inputs. Globally, the estimated N fertilizer inputs based on the sum of filled data increased from 15 Tg-N to 110 Tg-N during 1961-2010. On the other hand, the global NO-3 input started to decline after the late 1980s and the fraction of NO-3 in global N fertilizer decreased consistently from 35 % to 13 % over a 50-year period. NH+4 based fertilizers are dominant in most countries; however, the NH+4/NO-3 ratio in N fertilizer inputs shows clear differences temporally and geographically. This new map can be utilized as an input data to global model studies and bring new insights for the assessment of historical terrestrial N cycling changes.

Integral field spectroscopy and multi-wavelength imaging of nearby spiral galaxies: NGC 5668 as a pilot case for MEGARA

MEGARA (Multi-Espectrógrafo en GTC de Alta Resolución para Astronomía) is an optical Integral-Field Unit (IFU) and Multi-Object Spectrograph (MOS) designed for the GTC 10.4 m telescope in La Palma. MEGARA will be a 3rd generation instrument for GTC. It is led by the University Complutense of Madrid with the collaboration of INAOE, IAA, UPM and comprises more than 50 researchers from a large number of institutions worldwide.

Pupillary behavior in relation to wavelength and age

Pupil light reflex can be used as a non-invasive ocular predictor of cephalic autonomic nervous system integrity. Spectral sensitivity of the pupil's response to light has, for some time, been an interesting issue. It has generally, however, only been investigated with the use of white light and studies with monochromatic wavelengths are scarce. This study investigates the effects of wavelength and age within three parameters of the pupil light reflex (amplitude of response, latency, and velocity of constriction) in a large sample of younger and older adults (N = 97), in mesopic conditions. Subjects were exposed to a single light stimulus at four different wavelengths: white (5600° K), blue (450 nm), green (510 nm), and red (600 nm). Data was analyzed appropriately, and, when applicable, using the General Linear Model (GLM), Randomized Complete Block Design (RCBD), Student's t-test and/or ANCOVA. Across all subjects, pupillary response to light had the greatest amplitude and shortest latency in white and green light conditions. In regards to age, older subjects (46-78 years) showed an increased latency in white light and decreased velocity of constriction in green light compared to younger subjects (18-45 years old). This study provides data patterns on parameters of wavelength-dependent pupil reflexes to light in adults and it contributes to the large body of pupillometric research. It is hoped that this study will add to the overall evaluation of cephalic autonomic nervous system integrity.

Broadly tunable dual-wavelength InAs/GaAs quantum-dot laser for THz generation

We demonstrate an ultra-compact, room-Temperature, continuous-wave, broadly-Tunable dual-wavelength InAs/GaAs quantum-dot external-cavity diode laser in the spectral region between 1150 nm and 1301 nm with maximum output power of 280 mW. This laser source generating two modes with tunable difference-frequency (300 GHz-30 THz) has a great potential to replace commonly used bulky lasers for THz generation in photomixer devices.

Surface waves in mesh synthetic photonic lattices

Eigenmodes and dispersion curves in different configurations of synthetic photonic lattices are studied numerically. Eigenmodes localized on borders between areas with different optical potential are found. Stability of these eigenmodes against potential disturbances of different type is studied.

Constructing eigenmode excitation spectrum in synthetic photonic lattices using optical heterodyning

A method based on optical heterodyning is proposed for measuring relative optical phases of pulses circulating in a synthetic photonic lattices. The knowledge of the phases can be further used for qualitative reconstruction of an eigenmode excitation spectrum in the synthetic photonic lattice.

Multi-wavelength ultra-long Raman fibre laser based on Rayleigh-scattering feedback

We experimentally demonstrate a Raman fiber laser with linear cavity based on point-action fibre Bragg grating reflectors and random distributed feedback via Rayleigh scattering in the long fibre providing stable multiple wavelengths (close to ITU grid) output at Watts level. ©2010 IEEE.

Mode-locked laser pulse sources for wavelength division multiplexing

Recent theoretical investigations have demonstrated that the stability of mode-locked solution of multiple frequency channels depends on the degree of inhomogeneity in gain saturation. In this paper, these results are generalized to determine conditions on each of the system parameters necessary for both the stability and existence of mode-locked pulse solutions for an arbitrary number of frequency channels. In particular, we find that the parameters governing saturable intensity discrimination and gain inhomogeneity in the laser cavity also determine the position of bifurcations of solution types. These bifurcations are completely characterized in terms of these parameters. In addition to influencing the stability of mode-locked solutions, we determine a balance between cubic gain and quintic loss, which is necessary for existence of solutions as well. Furthermore, we determine the critical degree of inhomogeneous gain broadening required to support pulses in multiple frequency channels. © 2010 Copyright SPIE - The International Society for Optical Engineering.

Synthesis of a PbTx-2 photoaffinity and fluorescent probe and an alternative synthetic route to photoaffinity probes

A natural phenomenon characterized by dense aggregations of unicellular photosynthetic marine organisms has been termed colloquially as red tides because of the vivid discoloration of the water. The dinoflagellate Karenia brevis is the cause of the Florida red tide bloom. K. brevis produces the brevetoxins, a potent suite of neurotoxins responsible for substantial amounts of marine mammal and fish mortalities. When consumed by humans, the toxin causes Neurotoxic Shellfish Poisoning (NSP). The native function of brevetoxin within the organism has remained mysterious since its discovery. There is a need to identify factors which contribute to and regulate toxin production within K. brevis. These toxins are produced and retained within the cell implicating a significant cellular role for their presence. Localization of brevetoxin and identification of a native receptor may provide insight into its native role as well as other polyether ladder type toxins such as the ciguatoxins, maitotoxins, and yessotoxins. In higher organisms these polyether ladder molecules bind to transmembrane proteins with high affinity. We anticipated the native brevetoxin receptor would also be a transmembrane protein. Photoaffinity labeling has become increasingly popular for identifying ligand receptors. By attaching ligands to these photophors, one is able to activate the molecule after the ligand binds to its receptor to obtain a permanent linkage between the two. Subsequent purification provides the protein with the ligand directly attached. A molecule that is capable of fluorescence is a fluorophore, which upon excitation is capable of re-emitting light. Fluorescent labeling uses fluorophores by attaching them covalently to biologically active compounds. The synthesis of a brevetoxin photoaffinity probe and its application in identifying a native brevetoxin receptor will be described. The preparation of a fluorescent derivative of brevetoxin will be described and its use in localizing the toxin to an organelle within K. brevis. In addition, the general utility of a synthesized photoaffinity label with other toxins having similar functionality will be described. An alternative synthetic approach to a general photoaffinity label will also be discussed whose goal was to accelerate the preparation and improve the overall synthetic yields of a multifunctional label.