A Dynamic Data Correction Method for Enhancing Resolving Power of Integrated Spectra in Spectroscopic Analysis.

A dynamic data correction method embedded in the process of data acquisition improves spectral quality. The method minimizes the impact of random errors in spectroscopic measurements by correcting peak positions in every single-scan spectrum. The method is fast enough to facilitate online data correction. The integration of corrected spectra improves resolving power and signal-to-noise ratio. The correction method can apply to most analytical spectra. In mass spectrometry and Raman spectroscopy, observations show that it improved the average resolving power by roughly 40-150% and revealed unresolved spectral features.

Protein Attachment on Nanodiamonds.

A recent advance in nanotechnology is the scale-up production of small and nonaggregated diamond nanoparticles suitable for biological applications. Using detonation nanodiamonds (NDs) with an average diameter of ∼4 nm as the adsorbents, we have studied the static attachment of three proteins (myoglobin, bovine serum albumin, and insulin) onto the nanoparticles by optical spectroscopy, mass spectrometry, and dynamic light scattering, and electrophoretic zeta potential measurements. Results show that the protein surface coverage is predominantly determined by the competition between protein-protein and protein-ND interactions, giving each protein a unique and characteristic structural configuration in its own complex. Specifically, both myoglobin and bovine serum albumin show a Langmuir-type adsorption behavior, forming 1:1 complexes at saturation, whereas insulin folds into a tightly bound multimer before adsorption. The markedly different adsorption patterns appear to be independent of the protein concentration and are closely related to the affinity of the individual proteins for the NDs. The present study provides a fundamental understanding for the use of NDs as a platform for nanomedical drug delivery.

Development of gas exchange and ion regulation in two species of air-breathing fish, Betta splendens and Macropodus opercularis.

Aquatic air-breathing anabantoids, a group of fish species characterized by the presence of a labyrinth organ and some gills, exhibit morphological variations. This study aimed to examine whether unequal gill growth begins during the early stages and described the sequence of the early gill developmental events in Betta splendens and Macropodus opercularis. To determine when the ion regulatory and gas exchange abilities first appear in the gills, mitochondria-rich cells (MRCs) and neuroepithelial cells (NECs) were examined in young B. splendens. To evaluate the relative importance of the gills and the labyrinth organ under different levels of oxygen uptake stress, the levels of carbonic anhydrase II (CAII) and Na(+)/K(+)-ATPase (NKA) protein expressions in 2 gills and the labyrinth organ were examined in M. opercularis. We found that the first 3 gills developed earlier than the 4th gill in both species, an indication that the morphological variation begins early in life. In B. splendens, the MRCs and NECs clearly appeared in the first 3 gills at 4 dph and were first found in the 4th gill until 11 dph. The oxygen-sensing ability of the gills was concordant with the ionoregulatory function. In M. opercularis, the hypoxic group had a significantly higher air-breathing frequency. CAII protein expression was higher in the labyrinth organ in the hypoxic group. The gills exhibited increased NKA protein expression in the hypoxic and restricted groups, respectively. Functional plasticity in CAII and NKA protein expressions was found between the gills and the labyrinth organ in adult M. opercularis.

Effects of hypoxia on ionic regulation, glycogen utilization and antioxidative ability in the gills and liver of the aquatic air-breathing fish Trichogaster microlepis.

We examined the hypothesis that Trichogaster microlepis, a fish with an accessory air-breathing organ, uses a compensatory strategy involving changes in both behavior and protein levels to enhance its gas exchange ability. This compensatory strategy enables the gill ion-regulatory metabolism to maintain homeostasis during exposure to hypoxia. The present study aimed to determine whether ionic regulation, glycogen utilization and antioxidant activity differ in terms of expression under hypoxic stresses; fish were sampled after being subjected to 3 or 12h of hypoxia and 12h of recovery under normoxia. The air-breathing behavior of the fish increased under hypoxia. No morphological modification of the gills was observed. The expression of carbonic anhydrase II did not vary among the treatments. The Na(+)/K(+)-ATPase enzyme activity did not decrease, but increases in Na(+)/K(+)-ATPase protein expression and ionocyte levels were observed. The glycogen utilization increased under hypoxia as measured by glycogen phosphorylase protein expression and blood glucose level, whereas the glycogen content decreased. The enzyme activity of several components of the antioxidant system in the gills, including catalase, glutathione peroxidase, and superoxidase dismutase, increased in enzyme activity. Based on the above data, we concluded that T. microlepis is a hypoxia-tolerant species that does not exhibit ion-regulatory suppression but uses glycogen to maintain energy utilization in the gills under hypoxic stress. Components of the antioxidant system showed increased expression under the applied experimental treatments.

The absence of ion-regulatory suppression in the gills of the aquatic air-breathing fish Trichogaster lalius during oxygen stress.

The strategy for most teleost to survive in hypoxic or anoxic conditions is to conserve energy expenditure, which can be achieved by suppressing energy-consuming activities such as ion regulation. However, an air-breathing fish can cope with hypoxic stress using a similar adjustment or by enhancing gas exchange ability, both behaviorally and physiologically. This study examined Trichogaster lalius, an air-breathing fish without apparent gill modification, for their gill ion-regulatory abilities and glycogen utilization under a hypoxic treatment. We recorded air-breathing frequency, branchial morphology, and the expression of ion-regulatory proteins (Na(+)/K(+)-ATPase and vacuolar-type H(+)-ATPase) in the 1(st) and 4(th) gills and labyrinth organ (LO), and the expression of glycogen utilization (GP, glycogen phosphorylase protein expression and glycogen content) and other protein responses (catalase, CAT; carbonic anhydrase II, CAII; heat shock protein 70, HSP70; hypoxia-inducible factor-1α, HIF-1α; proliferating cell nuclear antigen, PCNA; superoxidase dismutase, SOD) in the gills of T. lalius after 3 days in hypoxic and restricted conditions. No morphological modification of the 1(st) and 4(th) gills was observed. The air-breathing behavior of the fish and CAII protein expression both increased under hypoxia. Ion-regulatory abilities were not suppressed in the hypoxic or restricted groups, but glycogen utilization was enhanced within the groups. The expression of HIF-1α, HSP70 and PCNA did not vary among the treatments. Regarding the antioxidant system, decreased CAT enzyme activity was observed among the groups. In conclusion, during hypoxic stress, T. lalius did not significantly reduce energy consumption but enhanced gas exchange ability and glycogen expenditure.

Capillary action-driven surface-enhanced Raman spectroscopy (SERS) for the identification of phthalocyanine blue in modern paintings based on the BPG spot test.

A method for the extraction and accumulation of Ag nanoparticles utilizing capillary action through a piece of triangular-shaped cotton paper is reported. This method allowed the integration of SERS and the BPG spot test, which are typically employed for examining pigments on paper or in books. Malachite green oxalate was used as the model material for investigating the extent of enhancement when SERS was applied. The dynamic behavior of the Ag nanoparticles was also studied. When the cotton paper was pre-treated with malachite green oxalate, Ag nanoparticles could be extracted and accumulated on the triangular top, resulting in a dramatic SERS improvement. When malachite green oxalate (at a concentration of 10-6 M) was applied using this method, a dramatic analytical enhancement factor of approximately 3000% was obtained. Finally, the method developed in this study was successfully applied to the analysis of pigments in paintings from a university collection. The findings revealed that phthalocyanine blue was a popular pigment used in numerous paintings during the 1950s.

Quantification of peracetic acid (PAA) in the H2O2 + acetic acid reaction by the wavelength shift analysis in near-UV/visible absorption region.

In our study, we present an innovative method for the analysis and real-time monitoring of peracetic acid (PAA) formation within the near-UV/Vis (visible) wavelength region. PAA's absorption spectrum, influenced by its presence in a complex quaternary equilibrium mixture with hydrogen peroxide (H2O2), acetic acid, and water, lacks discernible peaks. This inherent complexity challenges conventional analytical techniques like Beer's law, which rely on absorption intensity as a foundation. To address this challenge, we introduce a novel approach that centers on the analysis of blue shifts in absorption wavelengths, particularly at an absorbance of 0.8 a.u. This method significantly enhances the precision of calibration curves for both diluted PAA and H2O2, unveiling an exponential correlation between wavelength and the logarithm of concentration for both components. Significantly, our approach allows for real-time and accurate measurements, especially during the dynamic PAA formation reaction. Our results exhibit excellent agreement with data obtained from Fourier-transform infrared (FT-IR) spectroscopy, validating the reliability of our method. It's noteworthy that under stable PAA concentration conditions (after 12 h of solution interaction), both traditional absorption method and our approach closely align with the FT-IR method. However, in dynamic scenarios (0-12 h), the absorption method exhibits higher error rates compared to our approach. Additionally, the increased concentration of a catalyst, sulfuric acid (H2SO4), significantly reduces the errors in both methods, a finding that warrants further exploration. In summary, our study not only advances our understanding of PAA and its spectral behavior but also introduces innovative and precise methods for determining PAA concentration in complex solutions. These advancements hold the potential to revolutionize the field of chemical analysis and spectroscopy.

Use of an accelerometer and a microphone as gas detectors in the online quantitative detection of hydrogen released from ammonia borane by gas chromatography.

The use of an accelerometer as a gas detector in gas chromatography (GC) is described for the first time. A milli-whistle was connected to the outlet of the GC capillary. When the eluted and GC carrier gases pass through the capillary and milli-whistle, a sound is produced. After a fast Fourier transform (FFT), the sound wave generated from the milli-whistle is picked up by a microphone and the resulting vibration of the milli-whistle body can be recorded by an accelerometer. The release of hydrogen gas, as the result of thermal energy, from ammonia borane (NH3BH3), which has been suggested as a storage medium for hydrogen, was selected as the model sample. The findings show that the frequencies generated, either by sound or by the vibration from the whistle body, were identical. The concentration levels of the released hydrogen gas can be determined online, based on the frequency changes. Ammonia borane was placed in a brass reservoir, heated continually, and the released hydrogen gas was directly injected into the GC inlet at 0.5 min intervals, using a home-built electromagnetic pulse injector. The concentration of hydrogen for each injection can be calculated immediately. When the ammonia borane was encapsulated within a polycarbonate (PC) microtube array membrane, the temperature required for the release of hydrogen can be decreased, which would make such a material more convenient for use. The findings indicate that 1.0 mg of ammonia borane can produce hydrogen in the range of 1.0-1.25 mL, in the temperature range of 85-115 °C.

The use of RGB-tracking of color changes during indigo-reduction processes based on LabVIEW machine vision.

The use of an RGB-tracking chart for monitoring the reduction of indigo (color changes) based on the LabVIEW machine vision is demonstrated for the first time. In contrast to a normal analytical chromatographic chart, the time scale is used on the X-axis, but the sum of "RGB-pixels" is used on the Y-axis, instead of "signal intensity". The RGB-tracking chart was obtained from an investigation of the process involved in the reduction of indigo, in which a PC camera was used as a detector and LabVIEW machine vision was simultaneously operated. As a result, when sodium dithionite (Na2S2O4) and yeast were used, respectively, during the indigo-reduction processes, two types of reduction processes were found; the optimized timing for dyeing can be easily determined from the RGB-tracking charts. Furthermore, based on the changes in HSV (hue, saturation, lightness), the use of sodium dithionite provides a higher number of hue and saturation when clothes & fabric were dyed. In contrast to this, a longer time was required for the yeast solution to reach the same high number for hue and saturation. After comparing several series of dyed fabrics, we found that the use of an RGB-tracking chart is indeed a reliable novel tool for measuring color changes that occur during the chemical reactions that are associated with this process.

Rapid screening and determination of 4-chloroamphetamine in saliva by paper spray-mass spectrometry and capillary electrophoresis-mass spectrometry.

A novel drug-screening system, consisting of paper spray-MS (PS-MS) and a CE-ESI-MS method was developed. This system can be easily switched either to PS-MS for rapidly screening samples or to the traditional CE-ESI-MS method for separation and to obtain detailed mass spectral information, while sharing the same mass spectrometer. In the former case, when a sharp (15°-tip) chromatography paper was used, the optimized distance from the paper tip to the mass inlet was 7.7 mm, whereas the optimized distance for the CE-ESI tip was ∼13.5 mm. Using 4-chloroamphetamine as a model compound, the LODs for PS-MS and CE-ESI-MS were determined to ∼0.1 and 0.25 ppm, respectively. Comparisons of results obtained using PS-MS and CE-ESI-MS and the experimental conditions are described.

Rapid screening and determination of designer drugs in saliva by a nib-assisted paper spray-mass spectrometry and separation technique.

A method for the rapid screening and determination of amphetamine-type designer drugs in saliva by a novel nib-assisted paper spray-mass spectrometry procedure is described. Under optimized conditions, the limit of detections for amphetamine derivatives (model samples: o-, m-, p-chloroamphetamine and o-, m-, p-fluoroamphetamine, respectively) were determined to 0.1 µg/mL by the nib-assisted paper spray-mass spectrometry method. This method is easier and has a higher sensitivity than similar methodologies, including atmospheric pressure/matrix-assisted laser desorption ionization mass spectrometry and electrospray-assisted laser desorption ionization/mass spectrometry. Data obtained using more classical separation methods, including liquid chromatography and capillary electrophoresis, are also reported.

Comparison and characterization of pigments and dyes by Raman spectroscopy.

This review provides a general understanding of Raman spectroscopy for use in the identification of pigments and dyes. The methodologies associated with a number of different related applications are also summarized. The first part of this review clarifies our basic knowledge regarding natural minerals and pigments. The second part discusses the fundamentals of currently used Raman spectroscopy, including surface-enhanced Raman scattering, µ-Raman spectroscopy, Raman imaging and spatially offset Raman spectroscopy. The third part focuses on recent applications, including the identification and analysis of various pigments and dyes that are used in paintings and related artworks. These studies show that Raman spectroscopy has great potential for use as a method for the rapid, non-destructive identification of such substances.

Investigation of optimal conditions needed for the production of indigo and subsequent dyeing using CO2/O2 sensors and a cellphone camera.

An investigation of the process involved in the production of and dyeing with indigo based on a CO2/O2 sensor device and a cellphone-camera is reported. The former involves transforming indican to indigo, and the latter the process by which indigo and indigo-white are produced. During the process of indigo production, a clear and positive correlation can be observed between the concentration of gas levels (either the production of CO2 or the consumption of O2) and the final yield. The authors found that for the first time that the change in the concentration levels of CO2/O2 can be used as important parameters for indigo dyeing. The optimal time required to produce indigo can be decided by the change of CO2/O2 concentration level. It is no long should depending on the experience of a craftsperson. Furthermore, the optimal time needed to produce indigo also can be decided by the concentration levels of glucose. The color analysis of indigo dyeing can be performed by using a camera and by calculating the RGB and HSV (hue, saturation, value) values.

Development and application of a milli-whistle for use in gas chromatography detection.

A simple milli-whistle was developed for the use in GC (gas chromatography) detection, in which, compared to a thermal conductivity detector (TCD), 1 order of magnitude superior sensitivity can be obtained. The milli-whistle can be connected to the outlet of a GC capillary. The gas and makeup gas passing through the capillary produces a sound as it passes through the milli-whistle (i.e., the gas of the GC eluate). The sound can easily be detected by a microphone, which, after a Fourier transform (FT) by means of a LabVIEW (Laboratory Virtual Instrumentation Engineering Workbench) built-in program, a very sharp frequency peak (full width at half-maximum, approximately 1.6 Hz) can be simultaneously observed. As a result, GC elutes can be qualitatively determined on the basis of their retention times, and a quantitative analysis can be achieved on the basis of the frequency shifts. When the makeup and carrier gases used were nitrogen, in the case of gas samples, including hydrogen, helium, argon, and carbon dioxide, the limits of detection were found to be approximately 3 microL/each injection; in the case of liquid samples, including methanol, cyclohexane, tetrahydrofuran, hexane, and acetone, the limits of detection were determined to be approximately 10 microg/each injection, respectively. When the gases were changed to hydrogen, the limits of detection were dramatically improved. When acetone was selected as the model sample, a linear relationship was found in the range of 0.2-200 microg/injection.

Application of Hadamard transform to gas chromatography/nonresonant multiphoton ionization/time-of-flight mass spectrometry.

The technique of Hadamard transform was successfully coupled with GC/nonresonant multiphoton ionization/TOFMS, for the first time. 1,4-Dichlorobenzene and the fourth harmonic generation (266 nm) of a Nd:YAG laser were employed as a model sample and an ionization laser, respectively. A Hadamard-injector coupled with a capillary-based supersonic jet nozzle (capillary-injector) was also developed in this study. The Hadamard-injector was used to obtain the chromatogram, which was encoded by successive sample introduction based on Hadamard codes, and the capillary-injector was used for injection of GC-elutes into TOFMS. Compared with a conventional single injection method, the S/N ratios were substantially improved after inverse Hadamard transformation of the encoded chromatogram. Under optimized conditions, when Hadamard matrices of 103 and 255 were used, the S/N ratios of the signals for 1,4-dichlorobenzene (concentration level, 4 microg/1 mL ACN) were substantially improved to 4.1- and 6.6-fold, respectively, and those improvements are in good agreement with those obtained by theory (5.1- and 8.0-fold).

Non-invasive and Time-dependent Blood-sugar Monitoring via Breath-derived CO2 Correlation Using Gas Chromatograph with a Milli-whistle Gas Analyzer.

A clear and positive correlation between the CO2 concentration and the blood-sugar level has been observed via a non-invasive and time-dependent monitoring of CO2 concentration from human breath, which is carried out by using a home-made gas chromatography (GC)/milli-whistle compact analyzer. The time-dependent sampling of the CO2 concentration correlated between 5.0 to 5.6% (1% = 104 ppm) in accordance with blood-sugar level variations of 80 to 110 mg/dL. The analytical method results in a rapid, continuous and non-invasive determination of blood-sugar level via measurement of the CO2 concentration exhaled from the lungs.

Determination of nitroaromatic explosives residue at military shooting ranges using a sweeping-MEKC method.

We report on the application of sweeping-MEKC, for the first time, using the Environmental Protection Agency Method 8330 stock standard (a mixture of 14 explosives). The use of a traditional MEKC mode provided the LODs (at S/N=3) ranging from 1.5 to 2.9 microg/mL for the 14 explosives standards, which were improved by as low as 3.1-6.5 ng/mL when a sweeping-MEKC technique was used. A set of 21 soil samples were collected from surface soil at military shooting ranges located at Kinmen County in Taiwan, and the findings showed that hexahydro-1,3,5-trini-tro-1,3,5-triazine and 2,4,6-trinitrotoluene made up the explosives residue present at the highest concentrations. This study is very useful for determining current levels of explosives residue and as a reference for making appropriate recommendations concerning future site characterization techniques.

Optimization of separation and online sample concentration of N,N-dimethyltryptamine and related compounds using MEKC.

The optimal separation conditions and online sample concentration for N,N-dimethyltryptamine (DMT) and related compounds, including alpha-methyltryptamine (AMT), 5-methoxy-AMT (5-MeO-AMT), N,N-diethyltryptamine (DET), N,N-dipropyltryptamine (DPT), N,N-dibutyltryptamine (DBT), N,N-diisopropyltryptamine (DiPT), 5-methoxy-DMT (5-MeO-DMT), and 5-methoxy-N,N-DiPT (5-MeO-DiPT), using micellar EKC (MEKC) with UV-absorbance detection are described. The LODs (S/N = 3) for MEKC ranged from 1.0 1.8 microg/mL. Use of online sample concentration methods, including sweeping-MEKC and cation-selective exhaustive injection-sweep-MEKC (CSEI-sweep-MEKC) improved the LODs to 2.2 8.0 ng/mL and 1.3 2.7 ng/mL, respectively. In addition, the order of migration of the nine tryptamines was investigated. A urine sample, obtained by spiking urine collected from a human volunteer with DMT, was also successfully examined.

Applications of Hadamard transform to gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry.

Successful application of the Hadamard transform (HT) technique to gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/mass spectrometry (LC/MS) is described. Novel sample injection devices were developed to achieve multiple sample injections in both GC and LC instruments. Air pressure was controlled by an electromagnetic valve in GC, while a syringe pump and Tee connector were employed for the injection device in LC. Two well-known, abused drugs, 3,4-methylenedioxy-N-methylamphetamine (MDMA) and N, N-dimethyltryptamine (DMT), were employed as model samples. Both of the injection devices permitted precise successive injections, resulting in clearly modulated chromatograms encoded by Hadamard matrices. After inverse Hadamard transformation of the encoded chromatogram, the signal-to-noise (S/N) ratios of the signals were substantially improved compared with those expected from theoretical values. The S/N ratios were enhanced approximately 10-fold in HT-GC/MS and 6.8 in HT-LC/MS, using the matrices of 1023 and 511, respectively. The HT-GC/MS was successfully applied to the determination of MDMA in the urine sample of a suspect.

Comparison of the separation of nine tryptamine standards based on gas chromatography, high performance liquid chromatography and capillary electrophoresis methods.

Nine tryptamines, including alpha-methyltryptamine (AMT), N,N-dimethyltryptamine (DMT), 5-methoxy-alpha-methyltryptamine (5-MeO-AMT), N,N-diethyltryptamine (DET), N,N-dipropyltryptamine (DPT), N,N-dibutyltryptamine (DBT), N,N-diisopropyltryptamine (DIPT), 5-methoxy-N,N-dimethyltryptamine (5-MeO-DMT), and 5-methoxy-N,N-diisopropyltryptamine (5-MeO-DIPT) were selected as model compounds. Comparisons of their sensitivity, selectivity, time, cost and the order of migration are described based on different separation techniques (GC, HPLC and CE, respectively). As a result, the limit of detection (S/N=3) obtained by GC/MS and LC/UV-absorption ranged from 0.5 to 15 microg/mL and 0.3 to 1.0 microg/mL, respectively. In contrast to this, based on the CZE/UV-absorption method, the limit of detection (S/N=3) was determined to 0.5-1 microg/mL. However, when the sweeping-MEKC mode was applied, it dramatically improved to 2-10 ng/mL. In the case of GC, HPLC and CE, migration times of the nine standards ranged from 11 to 15 min and 8 to 23 min by GC and HPLC, respectively; ranged from 20 to 26 min by sweeping-MEKC. The order of migration of DMT, DET, DPT and DBT follows the molecular weight, whereas the order of migration of AMT and 5-MeO-AMT (primary amines), DIPT (an isomer of DPT) and 5-methoxy-tryptamines (5-MeO-AMT, 5-MeO-DMT and 5-MeO-DIPT) can be altered by changing the separation conditions.