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.

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.

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.

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.

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.

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.

The Use of a Gas Chromatography/Milli-whistle Technique for the On-line Monitoring of Ethanol Production Using Microtube Array Membrane Immobilized Yeast Cells.

Hollow, poly(L-lactic acid) microtube array membranes (MTAM) were used in preparing membranes that contained immobilized yeast cells. To evaluate the performance of the developed system for continuous and fed-batch fermentation, a gas chromatography/milli-whistle device was used to on-line monitor the production of ethanol. The milli-whistle was connected to the outlet of a GC capillary, and when the fermentation gases and the GC carrier gas passed through it, a sound with a fundamental frequency was produced. The online data obtained for frequency-change vs. retention time can be recorded after a fast Fourier transform. In typical bioethanol fermentation, the yeast cells cannot be recycled, whereas the artificial yeast-MTAMs can be. The hollow-MTAM containing immobilized yeast cells significantly enhanced to bioethanol productivity, and represent a novel, promising technology for bioethanol fermentation. Our data indicate that the gas chromatography/milli-whistle device, which is economical and stable, is a very useful detector for long-term monitoring.

Development and Application of a Brush-Spray Derived from a Calligraphy-Brush-Style Synthetic Hair Pen for Use in ESI/MS.

The development of a novel type of a sampling/ionization kit for use in electrospray ionization/mass spectrometry is reported. Using a small calligraphy-brush-style synthetic hair pen (nylon-brush), and analogous to paper-spray mass spectrometry, the analytes can be collected, elution/desorption and then ionized from the surface of the nylon-brush. The body of the kit was produced by means of a commercial 3D-printer, in which ABS (acrylonitrile butadiene styrene) was used as the starting material. Meanwhile, a small nylon-brush was embedded inside a 3D-printed plastic cell, in which a solvent was supplied to rinse the brush by means of capillary action. The size and weight of the kit were 1 g and 4 cm, respectively. The kit is disposable and it has various functions, including non-invasive sampling, sample-evaporation and ionization. As a result, when a type of pesticide was selected as the test sample (dimethoate; C5H12NO3PS2), the limit of detection was determined to be 0.1 µg/mL. Collecting the pesticide from a leaf-surface (lettuce) was also successful. The process for fabricating the nylon-brush kit and the optimized experimental conditions are reported herein.

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.

Applications of Hadamard transform-gas chromatography/mass spectrometry to the detection of acetone in healthy human and diabetes mellitus patient breath.

The Hadamard transform-gas chromatography/mass spectrometry (HT-GC/MS) technique was successfully employed to detect acetone, a biomarker for diabetes mellitus (DM) prediction, in human breath. Samples of exhaled breath were collected from four DM patients (one type-I and three type-II) and eight volunteers (nondiabetic healthy subjects), respectively. The gas samples, without any pretreatment, were simultaneously injected into a GC column through a Hadamard-injector based on Hadamard codes. Under optimized conditions, when cyclic S-matrix orders of 255, 1023 and 2047 were used, the S/N ratios of the acetone signals were substantially improved by 8.0-, 16.0- and 22.6-fold, respectively; these improvements are in good agreement with theoretically calculated values. We found that the breath acetone concentration levels in the four DM patients and the eight volunteers ranged from 1 to 10 ppmv and 0.1 to 1 ppmv, respectively.

The use of a milli-whistle as a detector in gas analysis by gas chromatography.

This mini-review introduces a general understanding of the use of a milli-whistle as a gas chromatography (GC) detector in gas analysis, including our research on the methodology and theory associated with a number of different related applications. The milli-whistle is connected to the outlet of a GC capillary, and when the eluted gases and the GC carrier gas pass through it, a sound with a fundamental frequency is produced. The sound wave can be picked up by a microphone or an accelerometer, and after a fast Fourier transform, the online data obtained for frequency-change vs. retention time constitute a new method for detecting gases. The first part of this review discusses the fundamentals of the milli-whistle. Some modifications are also discussed, including various types of whistles and an attempt to maximize the sensitivity and stability of the method. The second part then focuses on several practical applications, including an analysis of hydrogen released from ammonia borane, inorganic gases produced from fireworks, the CO2/O2 ratio from expired human breath and a purity test for alcohols. These studies show that the GC-whistle method has great potential for use as a fast sampling ionization method, and for the direct analysis of biological and chemical samples at under ambient conditions.

Paper spray-MS for bioanalysis.

This Review provides a general understanding of paper spray-MS, including the methodology and theory associated with a number of different related applications. This method has become a direct sampling/ionization method for mass spectrometric analysis at ambient conditions and, as a result, it has greatly simplified and increased the speed of mass-spectrum analysis. It has now become an increasingly popular and important method for MS. The first part of this review discusses the fundamentals of paper spray. Some modifications are also reviewed, including nib-assisted paper spray, droplet monitoring, high-throughput paper spray, leaf spray, tissue spray and wooden tip spray. The second part focuses on recent applications, including the analysis of DBS, foodstuffs, drugs and oil. These studies show that paper spray-MS has great potential for use as a fast sampling ionization method, and for the direct analysis of biological and chemical samples at ambient conditions.

Screening of inorganic gases released from firework-rockets by a gas chromatography/whistle-accelerometer method.

The use of an accelerometer for detecting inorganic gases in gas chromatography (GC) is described. A milli-whistle was connected to the outlet of the GC capillary and was used instead of a classical GC detector. When the GC carrier gases and the sample gases pass through the milli-whistle, a sound is produced, leading to vibrational changes, which can be recorded using an accelerometer. Inorganic gases, including SO2, N2 and CO2, which are released from traditional Chinese firework-rockets at relatively high levels as the result of burning the propellant and explosive material inside could be rapidly determined using the GC/whistle-accelerometer system. The method described herein is safe, the instrumentation is compact and has potential to be modified so as to be portable for use in the field. It also can be used in conjunction with FID (flame ionization detector) or TCD (thermal conductivity detector), in which either no response for FID (CO2, N2, NO2, SO2, etc.) or helium gas is needed for TCD, respectively.

A microwave-assisted fluorescent labeling method for the separation and detection of amphetamine-like designer drugs by capillary electrophoresis.

A microwave-assisted fluorescence labeling method for use in CE-LIF (capillary electrophoresis-laser induced fluorescence) is described. Six amphetamine-like designer drugs, namely, o-, m-, p-chloro- and o-, m-, p-fluoro-amphetamine derivatives, were synthesized and used as model compounds. FITC (fluorescein isothiocyanate isomer I) and a blue-laser were used as the fluorescent labeling reagent and excitation source, respectively. When a microwave oven was used, the reaction was complete within ∼5 min, while the classical method required at least 20 h (usually, an overnight reaction). A mimic oral fluid sample was obtained by spiking oral fluid from a volunteer with the six standards, and after liquid-liquid extraction and microwave-derivatization, it was possible to process the analytes by CE-LIF within a period of ∼10 min; the wavelength of the blue-laser used was 473 nm. For comparison, data obtained using classical methods, including CZE-UV (capillary zone electrophoresis-UV absorbance detection), sweeping-MEKC-UV (micellar electrokinetic chromatography-UV absorbance detection) and LC-Q-TOFMS (liquid chromatography/electrospray ionization quadrupole time-of-flight mass spectrometry) are also reported.

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.

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.