Single-element Detection Research Articles

Spatial frequency modulation imaging for laser processing applications

Single element detection, spatial frequency modulation imaging (SPIFI) is deployed in a laser processing environment. SPIFI images are used to monitor a laser melting process, like that encountered during additive manufacturing, with an exposure time of 120μs, which enables real-time, in-situ monitoring of melt track formation coaxial with the processing laser. SPIFI images from a single photodiode are shown to be comparable to or better than white light camera images taken at the same numerical aperture. SPIFI deployed in this manner represents a disruptive new sensor metrology system that, when coupled with developing process models, can ultimately be used to validate statistically significant process parameter-signature-quality relationships with quantified uncertainty.

Dual signal-based electrochemical aptasensor for simultaneous detection of Lead(II) and Mercury(II) in environmental water samples

The Pb2+-binding aptamer (PBA) and Hg2+-binding aptamer (HBA) have been widely adopted as biosensing elements for lead(II) (Pb2+) and mercury (II) (Hg2+), due to the formation of stable and specific Pb2+-G-quadruplex and T-Hg2+-T structures. However, the currently developed electrochemical sensors are only applicable for single-element analysis of Pb2+ or Hg2+. Herein, a dual signal interface was realized by in-situ grafting the signal tags (Melamine-Cu2+ complex and Nile blue) bearing different redox potentials on the terminal of PBA and HBA that were co-immobilized on gold electrode. The results show that the interface has two pairs of independent redox peaks, ascribing to the melamine-Cu2+ complex and Nile blue, respectively. The sensor is not only applicable for single-element detection of Pb2+ or Hg2+, but also for simultaneous detection of them. The surface density of PBA and HBA on the gold electrode and the grafting efficiency of the electroactive tags on the aptamers have been determined. The detection limits for Pb2+ and Hg2+ were estimated to be 0.98 pM and 19 pM, respectively. The dual signal sensor is successfully applied for Pb2+ and Hg2+ determination in real water samples, showing its potential in the environmental monitoring of Pb2+ and Hg2+.

Herriott cell spot imaging increases the performance of tunable laser spectrometers.

With the availability of high-power (milliwatts) single-mode tunable laser sources that operate at room temperature across the infrared (IR) region, tunable laser spectrometers have seen an explosion of growth in applications that include commercial, Earth and planetary science, and medical and industrial sensing. While the laser sources themselves have shown steady improvement, the detection architecture of using a single-element detector at one end of a multipass cell has remained unchanged over the last few decades. We present here an innovative new approach using a detector array coupled to an IR-transmissive mirror to image all or part of the multipass spot pattern of the far mirror and record spectra for each pixel. This novel approach offers improved sensitivity, increased dynamic range, laser power normalization, contaminant subtraction, resilience to misalignment, and reduces the instrument power requirement by avoiding the need for "fringe-wash" heaters. With many tens of pixels representing each spot during the laser spectral scan, intensity and optical fringe amplitude and phase information are recorded. This allows selection and manipulation (e.g., co-addition, subtraction) of the pixel output spectra to minimize optical interference fringes thereby increasing sensitivity. We demonstrate a factor of ∼20 sensitivity improvement over traditional single-element detection. Dynamic range increase of a factor of ∼100 is also demonstrated through spot selection representing different pathlengths. Additionally, subtracting the spectrum of the first spot from that of the higher pass normalizes the laser power and removes the contribution of contaminant gas and fringes in the fore-optics region. These initial results show that this imaging method is particularly advantageous for multi-channel laser spectrometers, and, once the image field is analyzed, pixel selection can be used to minimize data rate and volume collection requirements. This technique could be beneficial to enhanced-cavity detection schemes.

Two-dimensional random access multiphoton spatial frequency modulated imaging.

Spatial frequency modulated imaging (SPIFI) enables the use of an extended excitation source for linear and nonlinear imaging with single element detection. To date, SPIFI has only been used with fixed excitation source geometries. Here, we explore the potential for the SPIFI method when a spatial light modulator (SLM) is used to program the excitation source, opening the door to a more versatile, random access imaging environment. In addition, an in-line, quantitative pulse compensation and measurement scheme is demonstrated using a new technique, spectral phase and amplitude retrieval and compensation (SPARC). This enables full characterization of the light exposure conditions at the focal plane of the random access imaging system, an important metric for optimizing, and reporting imaging conditions within specimens.

Optimized EDXRF system for simultaneous detection of gold and silver nanoparticles in tumor phantom

An energy-dispersive X-ray fluorescence system (EDXRF) was optimized for simultaneous detection of gold and silver nanoparticles inside water-equivalent phantoms applied to theranostics. The optimization process was carried out in order to maximize the fluorescence detection, keeping dose levels as low as possible. Gold and silver fluorescent emissions were simultaneously detected emerging from phantom's volume, allowing the future development of multi-parametric imaging associated to specific tumor characteristics. For fluorescence detection, gold LIII-edge and silver K-edge emission lines were used, exited with a conventional X-ray source with a tungsten target. Several combinations of filters of different thickness were used to hardening the Bremsstrahlung spectrum, thus producing energetically narrow beams with central energy according to both excitation edges. In the case of gold, incident spectrum was optimized by means of strontium (Sr) and yttrium (Y) filters to relatively incrementing photons capable of exciting gold LIII-edge, while silver K-edge excitation was improved using a tin (Sn) filter. Filtering combinations made of 212.0 μm Sr with 94.5 μm Sn, and 130.2 μm Y with 94.5 μm Sn maximized fluorescence detection sensitivity and minimized delivered dose, resulting in doses 2.24 and 2.36 times lower than individual gold or silver fluorescent detection. Furthermore, when dual gold and silver fluorescent detection was performed, the minimum detectable concentration was lower than single element detection: 0.042 ± 0.002 mg/mL of Au and 0.024 ± 0.005 mg/mL of Ag in dual detection against 0.058 ± 0.003 mg/mL of Au and 0.124 ± 0.007 mg/mL of Ag when measured independently.

Interferometric spatial frequency modulation imaging.

Interferometric spatial frequency modulation for imaging (I-SPIFI) is demonstrated for the first time, to our knowledge. Significantly, this imaging modality can be seamlessly combined with nonlinear SPIFI imaging and operates through single-element detection, making it compatible for use in scattering specimens. Imaging dynamic processes with submicrometer axial resolution through long working distance optics is shown, and high contrast images compared to traditional wide-field microscopy images. Finally, enhanced lateral resolution is achieved in I-SPIFI. To our knowledge, this is the first single platform that enables multimodal linear and nonlinear imaging, with enhanced resolution, all of which can be performed simultaneously.

Mapping multidimensional electronic structure and ultrafast dynamics with single-element detection and compressive sensing.

Compressive sensing allows signals to be efficiently captured by exploiting their inherent sparsity. Here we implement sparse sampling to capture the electronic structure and ultrafast dynamics of molecular systems using phase-resolved 2D coherent spectroscopy. Until now, 2D spectroscopy has been hampered by its reliance on array detectors that operate in limited spectral regions. Combining spatial encoding of the nonlinear optical response and rapid signal modulation allows retrieval of state-resolved correlation maps in a photosynthetic protein and carbocyanine dye. We report complete Hadamard reconstruction of the signals and compression factors as high as 10, in good agreement with array-detected spectra. Single-point array reconstruction by spatial encoding (SPARSE) Spectroscopy reduces acquisition times by about an order of magnitude, with further speed improvements enabled by fast scanning of a digital micromirror device. We envision unprecedented applications for coherent spectroscopy using frequency combs and super-continua in diverse spectral regions.

Simultaneous spatial frequency modulation imaging and micromachining with a femtosecond laser.

A Ti:Al2O3 chirped-pulse amplification system is used to simultaneously image and machine. By combining simultaneous spatial and temporal focusing (SSTF) with spatial frequency modulation for imaging (SPIFI), we are able to decouple the imaging and cutting beams to attain a resolution and a field-of-view that is independent of the cutting beam, while maintaining single-element detection. This setup allows for real-time feedback with the potential for simultaneous nonlinear imaging and imaging through scattering media. The novel SSTF machining platform uses refractive optics that, in general, are prohibitive for energetic, amplified pulses that might otherwise compromise the integrity of the focus as a result of nonlinear effects.

Eliminating the scattering ambiguity in multifocal, multimodal, multiphoton imaging systems

In this work we present how to entirely remove the scattering ambiguity present in existing multiphoton multifocal systems. This is achieved through the development and implementation of single-element detection systems that incorporate high-speed photon-counting electronics. These systems can be used to image entire volumes in the time it takes to perform a single transverse scan (four depths simultaneously at a rate of 30 Hz). In addition, this capability is further exploited to accomplish single-element detection of multiple modalities (two photon excited fluorescence and second harmonic generation) and to perform efficient image deconvolution. Finally, we demonstrate a new system that promises to significantly simplify this promising technology.

Remote focusing for programmable multi-layer differential multiphoton microscopy.

We present the application of remote focusing to multiphoton laser scanning microscopy and utilize this technology to demonstrate simultaneous, programmable multi-layer imaging. Remote focusing is used to independently control the axial location of multiple focal planes that can be simultaneously imaged with single element detection. This facilitates volumetric multiphoton imaging in scattering specimens and can be practically scaled to a large number of focal planes. Further, it is demonstrated that the remote focusing control can be synchronized with the lateral scan directions, enabling imaging in orthogonal scan planes.

Nonmetals in the argon-inductively coupled plasma-optical emission spectrometry: I. Phosphorus, sulfur and carbon.

The behavior of phosphorus, sulfur and carbon in the argon-ICP-OES was systematically investigated for a wide range of nebulizer gas flows and observation heights. Five lines of phosphorus, four lines of sulfur and three lines of carbon, which have analytical usable detection limits, were taken into consideration. The further parameter set was inspired by the needs of every-day-analysis in the laboratory, especially the low integration time that is necessary for analysis of large amounts of samples. For each element line a signal-to-noise plot was obtained with a method described earlier. The optimum conditions for the combined analysis were determined from signal-to-noise plots of those element lines with the lowest detection limits. The lowest detection limits for phosphorus (0.13 mg/L) and carbon (0.01 mg/L) are useful for solving many analytical problems. However, even the best detection limit for sulfur (2.97 mg/L) is only of limited use without further preconcentration. A major problem was the background of carbon, most probably from carbon dioxide, which increased the available detection limit to about 0.04 mg/L. Surprisingly, the best detection limits were obtained at very low observation heights, which were only a couple of millimeters above the load coil. Fortunately, all elements showed a similar behavior and so the detection limits at compromise conditions were only slightly higher compared with the single-element detection limits.

Sagnac-type fiber-optic array sensor for detection of bulk ultrasonic waves

In this paper, we describe a fiber optic array sensor suitable for detection of bulk ultrasonic waves. This sensor is based on an intrinsic fiber optic Sagnac interferometer. The fiber array is formed by multiple folding of a continuous length of an optical fiber into flat coils. Depending on the orientation of the fiber array with respect to the ultrasonic wave, the proposed sensor can act as a conventional in-phase detector or as a narrowband detector. In the narrowband mode, the center frequency of detection can be tuned by adjusting the spacing of the fiber array elements to be equal to the ultrasonic wavelength of interest. This feature distinguishes this array sensor from conventional hydrophones in which a receiver is typically much smaller than the acoustical wavelength. It is shown that the array sensor provides an enhanced signal-to-noise ratio (SNR) compared with a single element detection scheme. Results are presented for detection of ultrasonic waves in water arising from both piezoelectric and laser ultrasonic sources. Potential areas of application of this sensor include process monitoring, smart structures, bio-medical ultrasound, and chemical sensing.

Optimization of atomic fluorescence measurements with a microcomputer-based time-multiplex multiple-slit spectrometer

An automated multielement flame atomic fluorescence (AF) spectrometer is described. The instrument employs a multiple exit slit monochromator and a single detector. Each element is excited to fluoresce with a single-element hollow cathode lamp (HCL) and a time-multiplex mode is used for pulsing the HCLs and gated data acquisition. A microcomputer controls the pulsing of HCLs, sample introduction into the flame and data acquisition. Optimization of the HCL pulse width and peak current is shown to be critical. With an air/H 2 flame sheathed with Ar, the following single-element detection limits (in μg/ml) were obtained: Au, 0.2; Cd, 0.005; Co, 0.03; Cu, 0.003; Fe, 0.05; Mg, 0.0008; Mn, 0.007; Ni, 0.04; Pb, 1 and Zn, 0.02. Some multielement detection limits were a factor of 2–5 worse. At higher analyte concentrations, the signal to noise ratio decreased due to an increase in the relative analyte fluorescence flicker noise.

Continuum-source atomic-absorption spectroscopy with an echelle spectrometer adapted to a charge injection device

An instrumental system for continuum-source atomic absorption spectroscopy has been developed for simultaneous multielement determinations. The system consists of an electrothermal atomizer and a charge injection device adapted to an echelle spectrometer to achieve multiplex detection. A continuous 40-nm spectral range in the two-dimensional echelle spectrum was acquired simultaneously through the capability of the charge injection device to integrate signals in its MOS capacitors. Novel methods were developed to compute absorbances by "scanning" through all orders in the entire echelle spectrum or selecting absorption lines randomly. In the range 300-430 nm, characteristic concentrations (1% absorption) were 1.6, 2.6, 2.9, and 3.8 ng mL-1 respectively for Cu, Mn, and two Cr lines; these values are similar to those (1.3, 2.2, 1.2, and 3.6 ng mL-1) obtained for single-element detection with an image-dissector system.

Construction and performance of a time-multiplex multiple-slit flame atomic fluorescence spectrometer for multi-element analysis

The design and performance characteristics of a new multi-element flame atomic fluorescence spectrometer are presented. Radiation from four hollow-cathode tubes is directed onto an unsheathed air—hydrogen flame. The resulting atomic fluorescence is viewed by a special monochromator with a separate exit slit for each element. The light exiting from all slits is directed to a single photomultiplier tube. The fluorescence signals from different elements are distinguished by a time multiplex approach. Single-element detection limits for ten elements and multi-element detection limits for four elements are presented. The degradation of detection limits by flame background emission noise and effect of flame composition on performance are discussed. Better than 1% precision is obtained for moderate analyte concentrations.

Evaluation of an echelle spectrometer/image dissector system for simultaneous multielement determinations by atomic absorption spectroscopy.

The performance characteristics of an image dissector coupled to an echelle grating spectrometer for simultaneous multielement determinations by atomic absorption are presented here. Because the image dissector and echelle grating spectrometer are not commonly used in clinical practice, the basic concepts and characteristics of these components are discussed. A comparison with a silicon target vidicon suggests that the image dissector has a luminous sensitivity that is 130 to 190 times greater than that of the vidicon. Multielement detection limits for Cu, Cr, Mn, Fe, Co, and Ni with the image dissector/echelle spectrometer are lower than with the silicon vidicon by a factor ranging from four to 27, and are comparable to, or better than, single-element detection limits reported for a silicon vidicon and conventional optics. We give analyses of the photometric errors encountered with these detectors, which reveals that the image dissector exhibits significant advantages over the silicon vidicon for multielemont determinations by atomic absorption spectroscopy. The fundamental noise characteristics of both detectors are identified and can be used to estimate detection limit ratios for any element. The conditions for simultaneous determination of the above-mentioned elements are also established. Additionally, we compare results by atomic absorption spectroscopy and atomic emission spectroscopy with a dc plasma source. AddItional Keyphrases: analytical error - intermethod comparison . trace elements . silicon target vidicon - tool for study of inter-element relationships in vivo