Cryogenic Modulator Research Articles

All optical operation of a superconducting photonic interface.

Quantum photonic processing via electro-optic components typically requires electronic links across different operation environments, especially when interfacing cryogenic components such as superconducting single photon detectors with room-temperature control and readout electronics. However, readout and driving electronics can introduce detrimental parasitic effects. Here we show an all-optical control and readout of a superconducting nanowire single photon detector (SNSPD), completely electrically decoupled from room temperature electronics. We provide the operation power for the superconducting detector via a cryogenic photodiode, and readout single photon detection signals via a cryogenic electro-optic modulator in the same cryostat. This method opens the possibility for control and readout of superconducting circuits, and feedforward for photonic quantum computing.

Determination of Nonylphenol in Selected Foods and Identification of Single Isomers in a Coffee Sample by Comprehensive Two-Dimensional Gas Chromatography-Time of Flight Mass Spectrometry

Nonylphenols (NPs) are a degradation product of nonylphenol ethoxylate surfactants, which occur in many samples from the environment, food, and human organism. NPs are persistent and toxic and exhibit estrogenic activity. One of the challenges in understanding the estrogenic effects of NPs is the large number of isomers that may exist in different samples. After analyzing selected foods from different countries by high-performance liquid chromatography coupled with tandem mass spectrometry, NPs were detected in 8 of the 12 food samples. The concentration of NPs, based on fresh weight, ranged from 0.5 to 18.9 μg kg−1. The highest NP contents were found in coffee samples, and therefore an isomer-specific analysis was carried out by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GCxGC-TOF-MS). Fourteen pure isomers of NP were used as standards for cross-referencing the NP isomers. We identified the two main NP isomers in the coffee samples as 4-[3-ethyl-1,1-dimethylpentyl]-phenol and 4-[1-ethyl-1,3-dimethylpentyl]-phenol or NP128 and NP111 (Juelich nomenclature), respectively. The GCxGC-TOF-MS system with a liquid nitrogen cryogenic modulator used in this study is suitable for the isomer-specific analysis of NP and can be applied and further optimized for future routine analysis in food control.

Top-Down Approach to Retention Time Prediction in Comprehensive Two-Dimensional Gas Chromatography-Mass Spectrometry.

In this contribution, we describe a novel modeling approach to predicting retention times (tr) in comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-ToF-MS) with a particular emphasis on the second-dimension (2D) retention time predictions (2tr). This approach is referred to as a "top-down" approach in that it breaks down the complete GC × GC separation into two independent one-dimensional gas chromatography separations (1D-GC). In this regard, both dimensions, that is, first dimension (1D) and second dimension (2D) are treated separately, and the cryogenic modulator is simply considered as a second consecutive injection device. Separate 1D-GC tr predictions are performed on both dimensions using the same flow rate as the one deployed in the conventional GC × GC system. The separate tr predictions are then combined to account for the two-dimensional separation. This model was applied to 24 analytes from 2 standard mixtures (Grob Test Mix and Fragrance Materials Test Mix) and assessed across 9 GC × GC chromatographic conditions. The experimental and predicted chromatographic retention space occupations were assessed by using the convex hull approach defined by the Delaunay triangulation. The predicted percentage of space occupation corresponded favorably with the experimental values. Furthermore, the top-down approach enabled an accurate prediction of the 2tr of all investigated analytes, providing an average 2tr modeling error of 0.26 ± 0.01 s.

Ultralow voltage, high-speed, and energy-efficient cryogenic electro-optic modulator

Photonic integrated circuits (PICs) at cryogenic temperatures enable a wide range of applications in scalable classical and quantum systems for computing and sensing. A promising application of cryogenic PICs is to provide optical interconnects by upconverting signals from the electrical to the optical domain, allowing a massive data transfer from 4 K superconducting (SC) electronics to the room temperature environment. Such a solution can overcome a major bottleneck in the scalability of cryogenic systems that currently rely on bulky coaxial cables that suffer from limited bandwidth, a large heat load, and poor scalability. A key element to realize a cryogenic-to-room temperature optical interconnect is a high-speed, electro-optic (EO) modulator operating at 4 K with a modulation voltage at the mV scale, compatible with SC electronics. Although several cryogenic EO modulators have been demonstrated, their driving voltages are substantially large (several hundred mV to a few V) compared to the mV scale voltage provided by SC circuits. Here, we demonstrate a cryogenic modulator with ∼ 10 m V peak-to-peak driving voltage and Gb/s data rate, with an ultralow electric energy consumption of ∼ 10.4 a J / b i t and an optical energy consumption of ∼ 213 f J / b i t . We achieve this record performance by designing and fabricating a compact optical ring resonator modulator in a heterogeneous InP-on-Si platform, where we optimize a multi-quantum-well layer of InAIGaAs to achieve a strong EO effect at 4 K. Unlike other semiconductors such as silicon, our platform benefits from the high-carrier mobility and minimal free-carrier freezing of III-V compounds at low temperatures, with a moderate doping level and a correspondingly low loss (intrinsic resonator Q ∼ 272 , 000 ). These modulators can pave the path for complex cryogenic photonic functionalities and massive data transmission between cryogenic and room-temperature electronics.

QUBIC V: Cryogenic system design and performance

Current experiments aimed at measuring the polarization of the Cosmic Microwave Background (CMB) use cryogenic detector arrays with cold optical systems to boost their mapping speed. For this reason, large volume cryogenic systems with large optical windows, working continuously for years, are needed. The cryogenic system of the QUBIC (Q & U Bolometric Interferometer for Cosmology) experiment solves a combination of simultaneous requirements: very large optical throughput (∼40 cm2sr), large volume (∼1 m3) and large mass (∼165 kg) of the cryogenic instrument. Here we describe its design, fabrication, experimental optimization and validation in the Technological Demonstrator configuration. The QUBIC cryogenic system is based on a large volume cryostat that uses two pulse-tube refrigerators to cool the instrument to ∼3 K. The instrument includes the cryogenic polarization modulator, the corrugated feedhorn array, and the lower temperature stages: a 4He evaporator cooling the interferometer beam combiner to ∼1 K and a 3He evaporator cooling the focal-plane detector arrays to ∼0.3 K. The cryogenic system has been tested and validated for more than 6 months of continuous operation. The detector arrays have reached a stable operating temperature of 0.33 K, while the polarization modulator has operated at a ∼10 K base temperature. The system has been tilted to cover the boresight elevation range 20°-90° without significant temperature variations. The instrument is now ready for deployment to the high Argentinean Andes.

A low-noise on-chip coherent microwave source

The scaleup of quantum computers operating in the microwave domain requires advanced control electronics, and the use of integrated components that operate at the temperature of the quantum devices is potentially beneficial. However, such an approach requires ultra-low power dissipation and high signal quality in order to ensure quantum-coherent operations. Here, we report an on-chip device that is based on a Josephson junction coupled to a spiral resonator and is capable of coherent continuous-wave microwave emission. We show that characteristics of the device accurately follow a theory based on a perturbative treatment of the capacitively shunted Josephson junction as a gain element. The infidelity of typical quantum gate operations due to the phase noise of this cryogenic 25-pW microwave source is less than 0.1% up to 10-ms evolution times, which is below the infidelity caused by dephasing in state-of-the-art superconducting qubits. Together with future cryogenic amplitude and phase modulation techniques, our approach may lead to scalable cryogenic control systems for quantum processors.

Pulse Dipolar EPR Reveals Double-Histidine Motif CuII-NTA Spin-Labeling Robustness against Competitor Ions.

Pulse-dipolar EPR is an appealing strategy for structural characterization of complex systems in solution that complements other biophysical techniques. Significantly, the emergence of genetically encoded self-assembling spin labels exploiting exogenously introduced double-histidine motifs in conjunction with CuII-chelates offers high precision distance determination in systems nonpermissive to thiol-directed spin labeling. However, the noncovalency of this interaction exposes potential vulnerabilities to competition from adventitious divalent metal ions, and pH sensitivity. Herein, a combination of room-temperature isothermal titration calorimetry (ITC) and cryogenic relaxation-induced dipolar modulation enhancement (RIDME) measurements are applied to the model protein Streptococcus sp. group G. protein G, B1 domain (GB1). Results demonstrate double-histidine motif spin labeling using CuII-nitrilotriacetic acid (CuII–NTA) is robust against the competitor ligand ZnII–NTA at >1000-fold molar excess, and high nM binding affinity is surprisingly retained under acidic and basic conditions even though room temperature affinity shows a stronger pH dependence. This indicates the strategy is well-suited for diverse biological applications, with the requirement of other metal ion cofactors or slightly acidic pH not necessarily being prohibitive.

Progress Report on the Large-Scale Polarization Explorer

The large-scale polarization explorer (LSPE) is a cosmology program for the measurement of large-scale curl-like features (B-modes) in the polarization of the cosmic microwave background. Its goal is to constrain the background of inflationary gravity waves traveling through the universe at the time of matter-radiation decoupling. The two instruments of LSPE are meant to synergically operate by covering a large portion of the northern microwave sky. LSPE/STRIP is a coherent array of receivers planned to be operated from the Teide Observatory in Tenerife, for the control and characterization of the low-frequency polarized signals of galactic origin; LSPE/SWIPE is a balloon-borne bolometric polarimeter based on 330 large throughput multi-moded detectors, designed to measure the CMB polarization at 150 GHz and to monitor the polarized emission by galactic dust above 200 GHz. The combined performance and the expected level of systematics mitigation will allow LSPE to constrain primordial B-modes down to a tensor/scalar ratio of $$10^{-2}$$ . We here report the status of the STRIP pre-commissioning phase and the progress in the characterization of the key subsystems of the SWIPE payload (namely the cryogenic polarization modulation unit and the multi-moded TES pixels) prior to receiver integration.

Towards the determination of an equivalent standard column set between cryogenic and flow-modulated comprehensive two-dimensional gas chromatography

This preliminary research is focused on the task of defining an equivalent standard column set between cryogenic and flow-modulation comprehensive two-dimensional gas chromatography (GC × GC) combined with mass spectrometry (MS). Cryogenic modulation (CM) was carried out by using a loop-type device, while the flow modulator used was a seven-port wafer chip, equipped with an external accumulation loop.Initially, a common low-polarity + mid-polarity CM GC × GC column set was selected (30 m × 0.25 mm ID × 0.25 μm df + 1.5 m × 0.25 mm ID × 0.25 μm df), a method was developed, and a GC × GC-MS fingerprint was attained (on a sample of bio-oil derived from coconut fibers). After, a column set with the same stationary phases was selected for the flow modulation GC × GC-MS method (20 m × 0.18 mm ID × 0.18 μm df + 5 m × 0.32 mm ID × 0.25 μm df), with the capability to provide a-similar-as-possible separation. A side-by-side measurement of several chromatography parameters (efficiency, peak capacity, resolution, peak widths, retention factors, elution temperatures) was made.

In-Depth Qualitative Analysis of Lime Essential Oils Using the Off-Line Combination of Normal Phase High Performance Liquid Chromatography and Comprehensive Two-Dimensional Gas Chromatography-Quadrupole Mass Spectrometry.

The present research is focused on the in-depth qualitative analysis of three types of lime essential oil (EO), viz., Key (A and B) and Persian, using the off-line combination of normal phase high performance liquid chromatography (NP-HPLC) and comprehensive two-dimensional gas chromatography–quadrupole mass spectrometry (GC × GC-QMS). The first analytical dimension (NP-HPLC) was exploited for the isolation of the hydrocarbon constituents from the oxygenated ones. Each fraction was then reduced in volume and analyzed using (cryogenic modulation) GC × GC-QMS. Peak assignment was carried out through the combined use of mass spectral database and linear retention index matching processes. The powerful four-dimensional technology enabled the separation and identification of a very high number (153) of lime essential oil volatile compounds.

Effects of Different Techniques of Malolactic Fermentation Induction on Diacetyl Metabolism and Biosynthesis of Selected Aromatic Esters in Cool-Climate Grape Wines.

The effects of different malolactic bacteria fermentation techniques on the bioconversion of aromatic compounds in cool-climate grape wines were examined. During three wine seasons, red and white grape wines were produced using various malolactic fermentation induction techniques: Coinoculation, sequential inoculation, and spontaneous process. Volatile compounds (diacetyl and the products of its metabolism, and selected ethyl fatty acid esters) were extracted by solid phase microextraction. Compounds were identified with a multidimensional gas chromatograph—GC × GC-ToFMS with ZOEX cryogenic (N2) modulator. Sensory evaluation of the wines was also performed. It was found that the fermentation-derived metabolites studied were affected by the malolactic bacteria inoculation regime. Quantitatively, ethyl lactate, diethyl succinate, and ethyl acetate dominated as esters with the largest increase in content. The total concentration of ethyl esters was highest for the coinoculation technique, while the highest concentration of diacetyl was noted for the spontaneous technique. Controlled malolactic fermentation, especially using the coinoculation technique, can be proposed as a safe and efficient enological practice for producing quality cool-climate grape wines enriched with fruity, fresh, and floral aromas.

Cryogenic modulation fast GC × GC-MS using a 10m microbore column combination: Concept, method optimization, and application.

The present research is based on the concept of using a 10m × 0.1mm id column for cryogenic-modulation fast comprehensive two-dimensional gas chromatography with quadrupole mass spectrometry. Specifically, an 8.9m × 0.1mm id low-polarity column was used as the first dimension, and a 1.1m × 0.1mm id medium-polarity column was used as the second dimension. The main scope of the investigation was to develop a high peak-capacity method, with an analysis time of approximately 10min. Various aspects related to method optimization are discussed, as well as separation parameters such as peak capacity (in each dimension, and as a total value), first-dimension sample capacity, peak widths, modulation ratio, sensitivity enhancement, and number of spectra per peak. The fast approach was evaluated in applications involving a mixture of cosmetic allergens and a sample of perfume. The approach proposed enables high-resolution separations in a short time (across the C8 -C23 alkane range), as well as a considerable reduction of the consumption of gases for modulation cooling and heating.

Thermal analysis of a prototype cryogenic polarization modulator for use in a space-borne CMB polarization experiment

We report a thermal analysis of a polarization modulator unit (PMU) for use in a space-borne cosmic microwave background (CMB) project. A measurement of the CMB polarization allows us to probe the physics of early universe, and that is the best method to test the cosmic inflation experimentally. One of the key instruments for this science is to use a halfwave plate (HWP) based polarization modulator. The HWP is required to rotate continuously at about 1 Hz below 10 K to minimize its own thermal emission to a detector system. The rotating HWP system at the cryogenic environment can be realized by using a superconducting magnetic bearing (SMB) without significant heat dissipation by mechanical friction. While the SMB achieves the smooth rotation due to the contactless bearing, an estimation of a levitating HWP temperature becomes a challenge. We manufactured a one-eighth scale prototype model of PMU and built a thermal model. We verified our thermal model with the experimental data. We forecasted the projected thermal performance of PMU for a full-scale model based on the thermal model. From this analysis, we discuss the design requirement toward constructing the full-scale model for use in a space environment such as a future CMB satellite mission, LiteBIRD.

Optimizing loop-type cryogenic modulation in comprehensive two-dimensional gas chromatography using time-variable combination of the dual-stage jets for analysis of crude oil

The enhanced chromatographic capability of the comprehensive two-dimensional gas chromatography (GC×GC) has already found several applications in analytical chemistry comprising complex samples. However, setting the appropriate chromatographic conditions that maximize sensitivity and separation efficiency in GC×GC may be more difficult than in conventional one-dimension gas chromatography, mainly due to the additional parameters strictly related to the modulation. Loop-type cryogenic modulators have been currently used for crude oil analysis using GC×GC, requiring sometimes a laborious try-and-error procedure to properly tune the dual-jets elapsed times on modulation. In this work, the advantages of choosing a time-variable combination of cold and hot jets pulses in a loop-type cryogenic modulator is presented when performing the fingerprinting analysis of crude oils using GC×GC-QMS, contrary to the conventional procedure based on a single combination for the dual-stage jets. A design of experiments approach is proposed to most effectively optimize the time-variable combination of the dual-jets elapsed times while modulating the wide hydrocarbons range along the GC×GC analysis. The most abundant classes of hydrocarbons contained in the maltenes fraction of a crude oil sample, such as paraffins, aromatics, steranes and hopanes were successfully resolved.

Analysis of underivatised low volatility compounds by comprehensive two-dimensional gas chromatography with a short primary column

Comprehensive two-dimensional gas chromatography (GC×GC) approaches with cryogenic modulation were developed for the qualitative analysis of selected low volatility compounds in raw coffee bean extracts, without derivatisation. The approaches employed short first (1D) and second (2D) dimension columns, specifically a 1D 65% phenyl methyl siloxane column (11m) and a 2D 5% phenyl methyl siloxane column (1m), which allowed elution of high molar mass compounds (e.g.>600Da). Solutes included hydrocarbons, fatty acids, diterpenes, tocopherols, sterols, diterpene esters, and di- and triacylglycerides. An oven temperature program up to 370°C was employed. The effects of experimental conditions were investigated, revealing that the GC×GC results strongly depended on the cryogenic trap T, and oven T program. An appropriate condition was selected and further applied for group type analysis of low volatility compounds in green Arabica coffee beans. Retention indices were compiled for 1D GC analysis and were similar for the composite column data in GC×GC. The elution of some compounds was confirmed by use of authentic standards. The approach allowed direct analysis of coffee extract in ethyl acetate solution, with improved analyte peak capacity (approximately 200 compounds were detected) without prior fractionation or pre-treatment of the sample. This avoided potential hydrolysis of high molar mass conjugate esters as well as degradation of thermally labile compounds such as the derivatives of the diterpenes cafestol and kahweol.

Untargeted metabolic profiling of Eucalyptus spp. leaf oils using comprehensive two-dimensional gas chromatography with high resolution mass spectrometry: Expanding the metabolic coverage

Chromatography with mass spectrometry (MS) is a technique of choice for metabolomic analysis of plant extracts. Single dimension gas chromatography (1DGC) with MS leads to poorly resolved metabolites of complex Eucalyptus spp. leaf oil secondary metabolites and consequently limited metabolic coverage of secondary compounds. Multidimensional chromatography with high resolution MS can contribute to advances in this field. Deeper insight into metabolite composition and variation for Eucalyptus spp. leaf oils through systematic untargeted metabolic profiling using comprehensive two-dimensional GC (GC × GC) with high resolution time-of-flight MS (accTOFMS), using generalised processes for metabolite identification. GC × GC separation used cryogenic modulation, with standard length polar first dimension and short fast analysis non-polar 2D columns. Compound tentative identification incorporated 1D and 2D retention information, retention indices, mass spectrum matching, and accurate mass MS data. Global metabolic profiles were interpreted through 2D contour plots and chemometric analysis. Strategies for metabolite screening and identification using GC × GC-accTOFMS were proposed. Considerably more components are detected and recognised than for 1DGC. Structured 2D molecular composition chromatographic patterns aid identification. ca. 400 metabolites were detected, 183 compounds were identified or tentatively identified, representing between 50.8–90.0% of the total ion count, comprising various chemical families. PCA revealed discriminating metabolites, allowing chemotaxonomic classification of species. Expansion of metabolic coverage by using GC × GC-accTOFMS, and detailed 2D metabolic fingerprints of E. polybractea, E. citriodora, E. radiata and E. globulus leaf oils were established. This high resolution analytical platform, and identification strategy can be adapted to metabolic analysis of other plant extracts. Phytoconstituents of four Australian eucalypt leaf oils were profiled using high resolution GC × GC-accurate mass TOFMS. Two-dimensional plots illustrated significant expansion of metabolic coverage. PCA discriminated metabolites of the eucalypts.

Josephson junction microwave modulators for qubit control

We demonstrate Josephson junction based double-balanced mixer and phase shifter circuits operating at 6–10 GHz and integrate these components to implement both a monolithic amplitude/phase vector modulator and an I/Q quadrature mixer. The devices are actuated by flux signals, dissipate no power on chip, exhibit input saturation powers in excess of 1 nW, and provide cryogenic microwave modulation solutions for integrated control of superconducting qubits.

Improved Flow Modulator Construction for GC × GC with Quadrupole Mass Spectrometry.

Improvement and testing of a flow modulator for the application in comprehensive two-dimensional gas chromatography separations is the subject of the presented paper. This improved setup constructed from two independent capillary branches each consisting of a pressure regulator, a pressure sensor, a two-way solenoid valve and a microfluidic T-connector, allows an independent and easy settings of the pressures and flow velocities in the modulator and provides system flexibility in an operation without need of any component exchange. The estimated flow rates were 0.4 mL/min in the first column and 3.2 mL/min in the second column. This setup was compared with the commercial Zoex cryogenic modulator for the separation of 17 selected solvents at isothermal conditions. Modulator working conditions were optimized and its separation power was demonstrated on the analysis of a lavender extract under an application of two orthogonal capillary column sets (nonpolar-polar vs. polar-nonpolar) and temperature program. The results were evaluated by two commercial software packages and discussed with respect to the identification compliance.

Evaluation of a miniaturised single-stage thermal modulator for comprehensive two-dimensional gas chromatography of petroleum contaminated soils

A novel miniaturised single-stage resistively heated thermal modulator was investigated as an alternative to cryogenic modulation for use in comprehensive two-dimensional gas chromatography (GC×GC). The single-stage thermal modulator described herein yielded average retention time relative standard deviations (RSD) of ≤0.2% RSD (first-dimension) and ≤3.4% RSD (second-dimension). The average peak widths generated by the modulator were 72±3ms, and the peak area precision was better than 5.3% RSD for a range of polar and non-polar test analytes. GC×GC analysis can be performed using this modulator without the requirement for cryogenic cooling or additional pressure control modules for flow modulation. The modulator and associated electronics are compact and amenable towards field analysis. The modulator was used for qualitative and quantitative characterisation of petroleum-contaminated soils derived from a sub-Antarctic research station at Macquarie Island. The limit of detection compared to standard 1D GC analysis was improved from 64 to 11mgkg−1. An automated method of analysing and categorising samples using principal component analysis is presented.

Development and Design of a Single-Stage Cryogenic Modulator for Comprehensive Two-Dimensional Gas Chromatography

A new liquid nitrogen-based single-stage cryogenic modulator was developed and characterized. In addition, a dedicated liquid nitrogen delivery system was developed. A well-defined restriction placed inside a deactivated fused silica capillary was used to increase the cooling surface area and provide very efficient trapping. At the same time, it enabled modulation of the carrier gas flow owing to changes in gas viscosity with temperature. Gas flow is almost unimpeded at the trapping temperature but reduced to nearly zero at the desorption temperature, which prevents analyte breakthrough. Peak widths for n-alkanes of 30-40 ms at half height were obtained. Most importantly, even the solvent peak could be modulated, which is not feasible with any commercially available thermal modulator. Evaluation of the newly developed system in two-dimensional gas chromatography (GC × GC) separations of some real samples such as regular gasoline and diesel fuel showed that the analytical performance of this single-stage modulator is fully competitive to those of the more complicated dual-stage modulators.