Signal and noise transfer in spatiotemporal quantum-based imaging systems

Fourier-based transfer theory is extended into the temporal domain to describe both spatial and temporal noise processes in quantum-based medical imaging systems. Lag is represented as a temporal scatter in which the release of image quanta is delayed according to a probability density function. Expressions describing transfer of the spatiotemporal Wiener noise power spectrum through quantum gain and scatter processes are derived. Lag introduces noise correlations in the temporal domain in proportion to the correlated noise component only. The effect of lag is therefore dependent on both spatial and temporal physical processes. A simple model of a fluoroscopic system shows that image noise is reduced by a factor that is similar to Wagner's information bandwidth integral, which depends on the temporal modulation transfer function.     

Use of a designed peptide array to infer dissociation trends for nontryptic peptides in quadrupole ion trap and quadrupole time-of-flight mass spectrometry

Observed peptide gas-phase fragmentation patterns are a complex function of many variables. To systematically probe this phenomenon, an array of 40 peptides was synthesized for study. The array of sequences was designed to hold certain variables (peptide length) constant and randomize or balance others (peptide amino acid distribution and position). A high-quality tandem mass spectrometry (MS/MS) data set was acquired for each peptide for all observed charge states on multiple MS instruments, quadrupole-time-of-flight and quadrupole ion trap. The data were analyzed as a function of total charge state and number of mobile protons. Previously known dissociation trends were observed, validating our approach. In addition, the general influence of basic amino acids on dissociation could be determined because, in contrast to the more widely studied tryptic peptides, the amino acids H, K, and R were positionally distributed. Interestingly, our results suggest that cleavage at all basic amino acids is suppressed when a mobile proton is available. Cleavage at H becomes favored only under conditions where a partially mobile proton is present, a caveat to the previously reported trend of enhanced cleavage at H. Finally, all acquired data were used as a benchmark to determine how well these sequences would have been identified in a database search using a common algorithm, Mascot.     

Corneal minimal visible lesion thresholds for 2.0 microm laser radiation

To support refinement of the ANSI Maximum Permissible Exposure safety limits, a series of experiments were conducted in vivo on Dutch Belted rabbit corneas to determine corneal minimum visible lesion thresholds for 2.0 microm continuous-wave laser irradiation. Single pulse radiant exposures were made at specified pulse durations of 0.1, 0.25, 0.5, 1.0, 2.0, and 4.0 s for spot 1/e(2) diameters of 1.17 mm and 4.02 mm. Threshold lesions were defined as the presence of a superficial surface whitening one hour after irradiation. Temperature measurements indicated that threshold peak temperatures were dependent on spot size and exposure duration. The exposure duration dependence of threshold average radiant exposure was described by an empirical power law equation: threshold radiant exposure[J/cm(2)]=a x exposure duration[s](b).     

Characteristics of a broadband dye laser using Pyrromethene and Rhodamine dyes

A broadband dye laser pumped by a frequency-doubled Nd:YAG laser with a full width at half-maximum from 592 to 610?nm was created for the use in a dual-pump broadband coherent anti-Stokes Raman spectroscopy (CARS) system called width increased dual-pump enhanced CARS (WIDECARS). The desired broadband dye laser was generated with a mixture of Pyrromethene dyes as an oscillator gain medium and a spectral selective optic in the oscillator cavity. A mixture of Rhodamine dyes was used in the amplifier dye cell. To create this laser, a study was performed to characterize the spectral behavior of broadband dye lasers created with Rhodamine dyes 590, 610, and 640 and Pyrromethene dyes 597 and 650, as well as mixtures of these dyes.     

DNA sensing by amplifying the number of near-infrared emitting, oligonucleotide-encapsulated silver clusters

A bifunctional oligonucleotide integrates in situ synthesis of a fluorogenic silver cluster with recognition of a target DNA sequence. With the template C(3)AC(3)AC(3)GC(3)A, a complex forms with 10 silver atoms that possesses electronic transitions in the near-infrared and that is detected at nanomolar concentrations using diode laser excitation. Pendant to this cluster encoding region, the recognition component binds a target DNA strand through hybridization, and decoupling of these two regions of the composite sensor renders a modular sensor for specific oligonucleotides. A target is detected using a quencher strand that bridges the cluster template and recognition components and disturbs cluster binding, as indicated by static quenching. Competitive displacement of the quencher by the target strand restores the favored cluster environment, and our key finding is that this exchange enhances emission through a proportional increase in the number of emissive clusters. DNA detection is also accomplished in serum-containing buffers by taking advantage of the high brightness of this fluorophore and the inherently low endogenous background in the near-infrared spectral region. Cluster stability in this biological environment is enhanced by supplementing the solutions with Ag(+).     

Structural elucidation of direct analysis in real time ionized nerve agent simulants with infrared multiple photon dissociation spectroscopy

Infrared multiple photon dissociation (IRMPD) was used to generate vibrational spectra of ions produced with a direct analysis in real time (DART) ionization source coupled to a 4.7 T Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The location of protonation on the nerve agent simulants diisopropyl methylphosphonate (DIMP) and dimethyl methylphosphonate (DMMP) was studied while solutions of the compounds were introduced for extended periods of time with a syringe pump. Theoretical vibrational spectra were generated with density functional theory calculations. Visual comparison of experimental mid-IR IRMPD spectra and theoretical spectra could not establish definitively if a single structure or a mixture of conformations was present for the protonated parent of each compound. However, theoretical calculations, near-ir IRMPD spectra, and frequency-to-frequency and statistical comparisons indicated that the protonation site for both DIMP and DMMP was predominantly, if not exclusively, the phosphonyl oxygen instead of one of the oxygen atoms with only single bonds.     

An X-ray beam position monitor based on the photoluminescence of helium gas

A new method for white beam position monitoring for both bend magnet and wiggler synchrotron X-ray radiation has been developed. This method utilizes visible light luminescence generated as a result of ionization by the intense X-ray flux. In video beam position monitors (VBPMs), the luminescence of helium gas at atmospheric pressure is observed through a view port using a CCD camera next to the beam line. The beam position, profile, integrated intensity and FWHM are calculated from the distribution of luminescence intensity in each captured image by custom software. Misalignment of upstream apertures changes the image profile making VBPMs helpful for initial alignment of upstream beam line components. VBPMs can thus provide more information about the X-ray beam than most beam position monitors (BPMs). A beam position calibration procedure, employing a tilted plane-parallel glass plate placed in front of the camera lens, has also been developed. The accuracy of the VBPM system was measured during a bench-top experiment to be better than 1 μm. The He-luminescence-based VBPM system has been operative on three CHESS beam lines (F hard-bend and wiggler, A-line wiggler and G-line wiggler) for about a year. The beam positions are converted to analog voltages and used as feedback signals for beam stabilization. In our paper we discuss details of VBPM construction and describe further results of its performance.     

Diffusivity of solutes measured in glass capillaries using Taylor's analysis of dispersion and a commercial CE instrument

We present a strategy for the rapid, efficient, and accurate measurement of the coefficient of diffusion (D) of solutes using a commercial capillary electrophoresis (CE) instrument. This approach utilizes the classic analysis of Taylor of the dispersion of solutes pumped hydrostatically through glass capillaries. To obtain accurate values of D, we modified Taylor's analysis of dispersion to account for the finite time required to reach steady-state flow in the capillary when using a CE instrument. Neglecting this effect results in measured diffusivities of phenylalanine, a model solute, that are in error by as much as 60% when compared with published values. We provide an analysis of this effect and a simple strategy for avoiding these errors. Using this approach, we analyze profiles of concentration fronts and measured values of D for phenylalanine to within 5% of published values. We also analyze profiles of pulses of solute. To determine values of D accurately, measurements of dispersion first need to be made as a function of injection volume to correct for the finite width of the injection plug, before they are corrected for unsteady-state flow. This approach also yields values of D for phenylalanine to within 5% of published values. In contrast to other techniques used for the determination of D, this approach requires no fluorescent labeling and is applicable to solutes of any molecular weight.     

Fabrication of metallic nanodots in large-area arrays by mold-to-mold cross imprinting (MTMCI)

We have developed a mold-to-mold cross imprint (MTMCI) process, which redefines an imprint mold with another imprint mold. By performing MTMCI on two identical imprint molds with silicon spacer nanowires in a perpendicular arrangement, we fabricated a large array of sub-30-nm silicon nanopillars. Large-area arrays of Pt dots are then produced using nanoimprint lithography with the silicon nanopillar mold.     

Nanowire lithography: fabricating controllable electrode gaps using Au-Ag-Au nanowires

A method to fabricate nanowire electrodes possessing controllable gaps is described. The method relies on electrochemical deposition and selective chemical etching or heating to selectively remove the Ag segment of Au-Ag-Au nanowires. Because the thickness of the Ag segment directly dictates the size of the nanogap, the gap width can be easily controlled during the nanowire fabrication process. Herein, we demonstrate gaps with 2 microm, 100 nm and 20 nm widths via the above-mentioned approaches. In addition, we observed that small gaps (approximately 20 nm) can be formed through annealing Au-Ag-Au nanowires at 200 degrees C in air. Electrical contact between nanowire electrodes and contact pads is studied. Using nanowire electrodes with a 100 nm gap, we subsequently fabricate organic field effect transistors (FETs) with regioregular poly(3-hexylthiophene).