Current Analytical Chemistry - Current Issue

This study introduces basil seeds as a novel, low-cost, and environmentally friendly adsorbent for the removal of ciprofloxacin from aqueous solutions. The primary innovation of this work lies in the use of readily available basil seeds, which have not been widely explored for this purpose, to achieve high adsorption capacity and efficiency.

The adsorption process was systematically optimized by adjusting parameters such as time, temperature, pH, and ciprofloxacin concentration, with results showing maximum adsorption at 40 minutes, 70°C, and pH 7. Additionally, the study investigates the influence of interfering factors like competing ions and organic matter in water, providing a more realistic assessment of the material’s effectiveness.

The findings demonstrate that basil seeds offer a promising alternative to conventional adsorbents, presenting both environmental and economic advantages for water treatment applications.

This work significantly advances current knowledge by proposing a sustainable solution for pharmaceutical pollutant removal from contaminated water.

Liubao tea residues, often discarded as waste, may contain valuable bioactive compounds as polysaccharides. To characterize the physicochemical properties of polysaccharides extracted by 4 mol/L KOH (KTP) and investigate its effects on macrophage activation and immune response.

KTP was extracted using an alkaline method. Physicochemical characterization was performed using monosaccharide analysis, molecular weight assessment, FT-IR spectroscopy, XRD, and NMR spectroscopy. Immunomodulatory effects were evaluated through macrophage activation assays, focusing on NO production, cytokine release, and NF-κB pathway modulation.

Monosaccharide analysis identified KTP as a composite of arabinose, mannose, galactose, glucose, and xylose with distinct variations in abundance. Molecular weight analysis revealed KTP as a heterogeneous polysaccharide with fractions KTP-1 and KTP-2 of different molecular sizes. Structural characterization analysis showed specific functional groups, bond arrangements, and helical conformations, elucidating KTP’s intricate surface morphologies and semi-crystalline nature. Additionally, immunomodulatory studies demonstrated KTP’s activation of macrophage pathways via the NF-κB pathway, increasing nitric oxide (NO) and pro-inflammatory cytokine production dose-dependently.

This study reveals KTP's rich structural diversity and potent immunomodulatory activity, highlighting its potential as a natural immune booster and possible application in developing functional foods.

The main areas of research in the field of document dating, mainly focused on chromatographic methods. These methods are based on studying the dynamics of evaporation of volatile ink components. There is also a variety of chromatography techniques, including gas chromatography, ion chromatography, high performance liquid chromatography, thin layer chromatography and gas chromatography-mass spectrometry. This indicates the wide range of approaches and techniques used to determine the age of written materials. However, all these methods are used mainly during the first two years after writing the document details, which does not allow examining documents that are more than two years old.

Raman spectroscopy was used as the main research method. The object of the study was sheets of white A4 paper with printed text printed on them, produced on a laser printer. The subject of the study was areas of paper free of text, as well as areas of paper under toner. The integrated fluorescence of a paper optical brightener based on stilbene was studied in the wavelength range of 400–500 nm. Also, all objects were studied using optical microscopy.

The comparison of peak intensity values averaged over 10 brands over the years made it possible to reveal the following regularities: – the ratio of peaks in the paper spectra from which the toner was removed is greater than in the blank paper spectra, and the difference becomes less noticeable as the age of the paper decreases. The ratio of the intensity of the 330 cm-1 peak to the intensity of the 1603 cm-1 peak: the older the document becomes, the lower the average ratios of these peaks in both the blank paper spectra and in the spectra of paper from which the toner has been removed. –the intensity of the peak in the region of 280 cm-1 and 1 086 cm-1 of the Raman shift increases with decreasing the age of the toner-free paper.– a gradual increase in the intensity of the 380 cm-1 peak is observed when comparing the paper samples from which the toner was removed for 2016, 2018, 2020, and 2022. Regularity was also found in the change in the ratio of the average statistical values of the peak at 280 cm-1 in the spectra of the paper under the toner to a similar peak in the spectra of the paper free from text: the value of this ratio decreases with decreasing the paper age. At the same time, the paper fluorescence signal is an informative parameter that makes it possible to establish some facts from the document’s history. With artificial document aging, a significant broadening of the dispersion region and the appearance of its “splitting” into two or three strata are observed in the distribution of the fluorescence signal level of a paper sheet relative to the average value. The average fluorescence signal of a naturally aged sheet decreases with the age of the document.

As a result of research, it has been established that Raman spectroscopy can be successfully used as a method for dating documents. When comparing the degree of degradation of the surface of open areas of paper and areas protected by toner of printed text, different effects of external factors on these areas were established, leading to different rates of degradation processes. The use of Raman peak intensity ratios for paper components in exposed areas compared to peaks under printed text further expands the methodology. The emphasis on spectral methods, in particular fluorescence signal distribution and Raman spectroscopy, to detect surface changes is well justified. It demonstrates a holistic approach to document analysis, taking into account both the chemical changes observed using Raman spectroscopy and the fluorescence signal distribution that may indicate signs of artificial aging through light exposure. This combination of methods appears to be reliable for assessing the age of documents and can make significant contributions to the field of forensic document examination.

The present work aims to synthesize, characterize, and DNA binding properties of copper, nickel, zinc, and iron complexes of a well-known polyphenol drug curcumin. The metal ion complexes of curcumin's synthesized transition metal ion complexes were characterized by UV-vis spectroscopy and FTIR.

The complexation of curcumin with transition metal ion complexes changes the color of the curcumin based on the metal incorporated. Moreover, the shift in the absorption maxima of curcumin metal ion complexes may confirm the formation of coordination complexes. Then, FTIR results indicated that the coordination of curcumin with metal ions in the ketone group of curcumin confirms the formation of 1:2 (M: L) complexes.

Then, we evaluated the DNA binding properties of synthesized metal ion complexes of curcumin using electronic absorption spectra and agarose gel electrophoresis. The results indicated that the curcumin zinc complex exhibited less DNA binding constant among the four metal ion complexes than all the other compounds tested, confirming its weak interaction.

Moreover, all the compounds degrade plasmid DNA, confirming their DNA cleavage activity. From our findings, these compounds will pave the way for developing new anticancer drugs with less toxicity.

The Iraqi ecosystem, particularly in the southern area, has been polluted due to human activity. Analyzing biological materials is the most common method for detecting the presence of toxic substances in the human body.

Heavy metal levels of Pb, Ni, and Cd in urine specimens collected from individuals with renal failure and healthy individuals residing in Al-Muthanna province were measured by using atomic absorption spectroscopy. Urine Specimens were collected from two cohorts of male and female participants: the group of individuals with renal failure and the group of individuals who are in good condition. The specimens of urine from both the group of patients with renal failure and the group of healthy individuals were taken from the Al-Muthanna governorate in southern Iraq. This governorate served as a focal point for extensive military operations throughout the Gulf War.

The concentrations of toxic substances (Pb, Ni, and Cd) in the urine specimens of the cohort of patients suffering from renal failure are 0.411, 0.197, and 0.113 mg/l, respectively. Concentrations of (Pb, Ni, and Cd) in the healthy group are 0.249, 0.101, and 0.0294 mg/l, respectively. The toxic metals found in urine samples can be organized in the following order: Pb > Ni > Cd.

The findings indicated that the concentrations of toxic substances in specimens of urine from individuals with renal failure are considerably greater than those in the control group of healthy individuals. According to the findings, patients' incidence of renal failure may be related to the prevalence of harmful compounds in southern Iraq.

The problem of nuclear water pollution is becoming serious worldwide. Uranium, as a metal substance with long half-life radioactivity, is commonly treated by various methods. Adsorption is considered to be one of the most promising methods for treating uranium-containing wastewater.

Magnetic nanoparticles MnFe2O4 were prepared via the coprecipitation method, followed by modification of silica using the improved Stöber method. Subsequently, amino was functionalized and grafted onto graphene oxide to prepare a novel magnetic graphene oxide composite MnFe2O4@SiO2-NH2@GO.

The highest adsorption rate of MnFe2O4@SiO2-NH2@GO for uranium can reach 97.27% in 1 mg·L^-1 uranium solution, and the adsorption process conformed to the quasi-second-order kinetic model and Langmuir adsorption isotherm model, indicating that it was a monolayer adsorption dominated by chemisorption. The adsorption thermodynamic parameters demonstrated that the adsorption process was a spontaneous endothermic reaction.

MnFe2O4@SiO2-NH2@GO had excellent adsorption properties for uranium, which has great application potential in the treatment of low-concentration uranium-containing wastewater.

The Iraqi environment, especially in the southern region, has been contaminated as a result of human activities. The detection of heavy metals in water samples is the preferred method for monitoring the toxic levels, which are very important for environmental protection and human health.

Heavy metal concentrations of lead (Pb), cadmium (Cd), and nickel (Ni) were investigated in water samples from Al-Muthanna governorate, southern Iraq. The selected water samples were taken from different sources of tap water and river samples from the Euphrates and collected from various locations: residential, agricultural, and industrial.

The mean values of Pb, Cd, and Ni in tap water samples are 3.76, 2.62, and 84.88 μg/L, respectively, while the corresponding element levels in river water are 11.21, 7.58, and 104.31 μg/L, respectively. Rivers water samples recorded higher levels of toxic metals than tap water samples. Concentrations of toxic elements in water samples from industrial locations of Al-Muthanna governorate are higher than in the agricultural and residential places. Toxic metals in water samples can be arranged in the following sequence: Ni > Pb > Cd.

The levels of heavy metals in most water samples were above the permissible levels according to USEPA; therefore, it is recommended that the water samples should be regularly monitored for heavy metals to prevent the effect of heavy metals contamination in the human food chain.

Silver nanoparticles possess distinctive characteristics, including chemical stability, high thermal and electrical conductivity, and linear optical properties, making them unique and fascinating. The rise of green synthesis methods for silver nanoparticles is garnering significant interest among researchers, surpassing traditional chemical and physical approaches due to the environmentally friendly, cost-effective, and convenient nature of synthesis. This approach stands as a viable alternative across various sectors, encompassing research, industry, and environmental safety initiatives.

Parmotrema permutatum was utilized in the synthesis of silver nanoparticles, followed by their characterization using ultraviolet-visible spectroscopy, Fourier-transformed infrared spectroscopy, X-ray diffraction, energy dispersive X-ray analysis, and scanning electron microscopy. These nanoparticles are subsequiently employed for detecting methylene blue, formaldehyde, and hazardous mercury metal ions as well as photocatalytically degrading methylene blue.

The silver nanoparticle synthesized was confirmed by a color change and the maximum peak of the SPR band was at 420 nm in the UV spectrum. The crystal has face-centered cubic (FCC) structure with an average size of 12.78 nm. The lichen extract contains polyphenolic groups which act as capping agents. synthesized silver nanoparticles were used to detect formaldehyde and hazardous Hg²⁺ ions separately. A color change was observed. The detection limit of Hg²⁺ was 600 μL. Likewise, silver nanoparticles were used to degrade methylene blue. The blue color of methylene blue disappeared. The efficiency of silver nanoparticles was found to be 72% in 4 hours and 87.82% in 24 hours.

Parmotrema permutatum has the potential to reduce Ag⁺¹ to Ag^o and acts as a capping and stabilizing agent, it can be used to biosynthesize silver nanoparticles and can detect formaldehyde, and Hg²⁺ ions, in addition, it also degrades methylene blue photolytically.

The Asteraceae family comprises the largest flowering plant species, which have also been proven to have medicinal value for various illnesses due to the presence of numerous volatile and non-volatile constituents.

The study aims to compare the volatile phytoconstiteunts presence in the essential oils of Asteraceae family plants including Roman Chamomile Oil (Chamaemelum nobile), German Chamomile Oil (Matricaria chamomilla), Davana Oil (Artemisia pallens), Wormwood Oil (Artemisia absinthium), Armoise Oil (Artemisia vulgaris), Tansy Oil (Tanacetum vulgare), Yarrow Oil (Achillea millefolium), Tarragon Oil (Artemisia dracunculus), Tagetes Oil (Tagetes erecta) and Immortelle Absolute Oil (Helichrysum italicum) as simultaneous estimation using the novel methods.

Roman chamomile, German chamomile, davana, wormwood, armoire, tansy, yarrow, tarragon, tagetes, and immortelle absolute oils were extracted by steam distillation from their respective Asteraceae species and carried out the gas chromatography analysis.

The result was that GC-MS analysis of selected essential oils contains terpenes and terpenoids in major amounts. Among the detected volatile constituents in crucial oils Methyl Chavicol was found higher 75.63% in Tarragon Oil compared to other constituents followed Neryl acetate (60.25%) found in the immortelle absolute oil, Cis davanone (55.36%) was found in the davana oil, Ocimene (45.58%) in the tagetes oil, α-bisabololoxide B (45.26%) in the German chamomile oil, Beta thujone (50.65%) in the tansy oil, Alpha thujone (40.21%) in the wormwood oil and Camphor (38.65%) in the armoise oil. 1,8-Cineole, Alpha pinene, and Camphene were found in three oils (Wormwood oil, Armoise oil and Yarrow oil) among the selected oils.

Finally, we concluded that species from the same family (Asteraceae) were biologically synthesized with different volatile constituents. Hence, each essential oil has a unique biochemical fingerprint. These findings will help the food industry in relation to natural flavoring.

In this study, the effect of different weighing material such as olivine, barite and calcium carbonate on cutting carrying of water-based drilling fluids was investigated. Initially, characterization studies were performed for the additive materials.

Then, spud type muds were prepared with bentonite and the weighing materials were added at different rates ranging from wt.1-6%. After the sample preparation, mud weight, 600 and 300 rpm dial reading, plastic viscosity, yield point, flow behavior index and power law consistency factor values were measured/calculated.

With these results, cutting carrying index of the muds was calculated and the effect of the additive materials was compared. According to the results, it was determined that the barite added muds had better cutting carrying capacity than others and the calcium carbonate added muds showed worse cutting carrying capacity. Optimal CCI results were obtained from O-5 as 3.7869 and, from B-6 as 5.9417 and from C-4 as 2.7113.

Results of this study show that olivine can be used as low additive ratios in drilling muds to clean the hole.

Different C-3 substituted flavonoids have different biological activities and applications in food pharmacology, toxicology, and medicine. Thus, the rapid identification and classification of substitution patterns at C-3 of flavonoids can benefit the processing of flavonoid-related food and medicine.

This study aimed to classify flavonoids with different C3 substituents using Raman spectroscopy, providing a feasible approach for identifying flavonoids in plants.

Eighteen flavonoid samples were selected and dissolved in different solvents. The corresponding Raman spectra were collected by a portable Raman spectrograph. After preprocessing, feature reduction and machine learning were used for the accurate classification of three flavonoids based on 66 Raman spectra.

The signals of flavone at 1002, 1245, 1590, and 1609 cm^-1 were identified as the characteristic peaks. Peaks at 1298, 1586, and 1605 cm^-1 were the special features observed of flavonol. The fingerprint features of isoflavone appeared at 894, 1227, 1321, and 1620 cm^-1. All combinations achieved a good classification accuracy of 85%, and the accuracy of the neural network reached 93.3%.

The results have demonstrated machine learning to be applicable for the detection and classification of C-3 substituted flavonoids and that feature reduction can aid in the discrimination of Raman spectra variations among diverse C-3 substituted flavonoids, thereby facilitating their further application.

Lung adenocarcinoma (LUAD) exhibits high incidence and mortality rates globally. Mitophagy exerts a critical role in cancer development, including LUAD. The present work set out to classify the molecular subtypes of LUAD and to develop a mitophagy-related gene (MRG) signature to assess the prognostic outcomes of LUAD patients.

Two datasets were acquired from Gene Expression Omnibus (GEO) and The Cancer Genome Atlas (TCGA) databases. MRGs were extracted from the MSigDB. The somatic gene mutation landscape was developed using the “maftools” package. Molecular subtypes were classified by employing the “ConsensusClusterPlus” package. Functional enrichment analysis was performed using the “clusterProfiler” package. Mitophagy-related module genes were identified using the “WGCNA” package and used to develop a prognostic MRG signature employing LASSO Cox regression analysis. Then, a RiskScore model was formulated and validated. Immune cell infiltration in different groups was compared. The expressions of the prognostic MRGs in LUAD cells were detected by in vitro tests. CCK-8, wound healing, and transwell assays were carried out to measure the cell viability, and migratory and invasive capabilities of LUAD cells.

Somatic gene mutation was detected in 77 (13.58%) out of 567 LUAD patients and 10 (50%) out of 20 prognosis-related MRGs. Based on 20 prognosis-related MRGs, three molecular LUAD subtypes with distinct prognostic outcomes, clinical features, immune cell infiltration, and biological pathways were classified. Next, a 9-MRG signature composed of 3 “protective” genes (PDIK1L, SNX30, PLEKHM1) and 6 “risk” genes (FEZ2, FAF2, HNRNPA2B1, PCMTD1, STK24, ALG13) was established. Then, a RiskScore model with excellent prognostic predictive power for LUAD was constructed. The high-risk group showed worse outcomes and decreased immune cell infiltration in comparison to the low-risk group. Further, the relative mRNA expressions of PDIK1L, SNX30, and PLEKHM1 were significantly downregulated, while those of FEZ2, FAF2, HNRNPA2B1, PCMTD1, STK24, and ALG13 were notably upregulated in LUAD cells. In addition, silencing SKT24 and PDIK1L significantly affected the invasive and migratory capacities of LUAD cells.

We delineated three molecular subtypes and developed a 9-MRG signature in LUAD, providing a valuable framework for the prognosis evaluation of LUAD patients.

Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Imaging (MALDI-MSI) technique has been reported in the literature for fingermark analysis and forensic purposes. One of the greatest challenges in this field involves the aging of fingermarks, which has an essential role in criminal investigation.

This study presents an approach to preservation fingermarks analysis through the MALDI-Fourier transform ion cyclotron resonance mass spectrometry method, comparing different matrix samples.

For MALDI analysis, the efficiency of three MALDI matrices (α-cyano-4-hydroxycinnamic acid (CHCA), 2-mercaptobenzothiazole (MBT), and 2,5-dihydroxybenzoic acid (DHB) in the ionization process of monitored analytes (m/z 368.4, m/z 522.6 and m/z 550.6) was initially evaluated, along with the spatial resolution (80 × 80 µm and 100 × 100 µm).

The CHCA matrix, and the resolution of 100 × 100 µm were chosen for the MALDI MSI analysis. The fingermark collections were analyzed at eight intervals from zero hours to fifty days. Additionally, photochemical aging (from zero hours to five days) of fingermarks, performed by applying constant light for five days to three different samples from the same donor, resulted in loss of chemical material and deformation of the image obtained by MALDI FT-ICR MSI analysis. On the other hand, in natural aging, the most expressive result showed that it is possible to visualize fingermark ridges of up to fifty days elapsed.

The method proposed showed a potential for fingermark examination and application in forensic routine. Chemical imaging of fingermarks can be a useful tool in detecting and comparing evidence, even after a considerable period.

This study presented new sensitive and selective modified carbon paste (MCPE) potentiometric sensors modified with different ion pairs for the determination of the antihypertensive drug diltiazem hydrochloride (DTM-HCl) in biological fluids, pharmaceutical preparations, and in its pure form.

Plasticizers, ion pair type, ion pair content, response time, temperature, and pH were just a few of the experimental factors evaluated that were found to affect electrode efficiency. The two electrodes that show the best sensitivity were prepared by mixing diltiazem-tetraphenyl borate (DTM-TPB) ion pair, graphite, and TCP or o-NPOE as a plasticizer.

Over the concentration ranges of 1.0x10^-5–1.0x10^-2, the produced electrodes I and II demonstrated monovalent Nernstian responses of 55.7±0.902 and 57.6±0.451 mV decade^-1. The selectivity property of the suggested electrodes was used to study the interference ions. The concentration of DTM-HCl in pharmaceutical formulations and biological fluids was measured using these modified electrodes. During the validation procedure, metrics like linearity, accuracy, precision, limit of detection, limit of quantification, and specificity were used.

The obtained results showed good agreement with the HPLC technique as indicated by the F and t-test values and can conclude the possibility of using this potentiometric method in the routine analysis of DTM-HCl.

This study aims to identify key genes by analyzing gene expression changes induced by prolonged sleep deprivation (SD) and to explore their potential relationship with immune regulation and neurobehavioral disorders.

Microarray data of SD at different time points were obtained to screen differentially expressed genes (DEGs). The functions of DEGs and the biological pathways involved were explored. Additionally, significant DEGs were screened as key genes for SD. Finally, immune scores and immune cell scores were calculated. The relationships between key genes, immune scores, and immune-related pathways were explored.

The relevant DEGs were identified, including USP32P1, TREML1, PF4V1, GPR146, DEFA1B, and CLEC1B. Among these, CLEC1B, GPR146, PF4V1, and TREML1 were upregulated in SD samples, while DEFA1B and USP32P1 were downregulated. These key genes were involved in the biological processes, including DNA repair, KRAS signaling, and the PI3K-AKT signaling pathway. Furthermore, PF4V1, GPR146, TREML1, and CLEC1B exhibited a significant negative correlation with immune scores and were closely associated with various immune regulatory pathways, like antigen processing and presentation, B cell receptor signaling, and T cell receptor signaling pathways.

This study, based on microarray data, investigated the dynamic changes in gene expression induced by SD and their underlying mechanisms. Six key genes with differential expression levels and distinct enriched biological processes were identified.

The altered expression of 6 identified genes induced by SD and their underlying molecular mechanisms may provide a foundation for the early diagnosis and personalized treatment of SD-related diseases.

The recognition of the health hazards of azo dyes has highlighted the need to develop efficient, rapid, and reliable analytical methods for dye determination.

In this work, electrochemical probing of the azo group of Tartrazine (TZ) and Carmoisine (CR) in food dyes was carried out. Synthesized bismuth and zinc oxide nanoparticles were used to modify Graphite Electrode (GE).

Electrochemical analysis showed a much better electrochemical response using ZnO+Bi/GE as a modifier than individually nanoparticle-modified graphite electrodes. From the CV analysis, it was found that both the dyes exhibited irreversible electrochemical behavior, and the redox parameters were calculated. The Limit of Detection (LOD) values recorded for TZ and CR for ZnO+Bi/GE-based sensors were 0.84 µM and 2.80 µM, respectively. The obtained sensitivity values were 11.86 µA/µM/cm² for TZ and 17.3 µA/µM/cm² for CR.

The sensor evidently demonstrated reliable simultaneous detection of both dyes, making it suitable for practical applications in food safety analysis.

Accurate shooting distance estimation is critical in forensic investigations. Traditional color tests like the Modified Griess Test (MGT) and Sodium Rhodizonate Test (SRT) are commonly used but lack sensitivity and objectivity, necessitating improvements in reproducibility and validation.

A 7.62x39 mm cartridge was fired using an assault rifle (Sarsılmaz® SAR 308) at fabric samples from distances ranging from 0 to 100 cm. MGT and SRT were employed to estimate shooting distances, and the presence of inorganic and organic gunshot residues was confirmed using Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDS) and Fourier Transform Infrared Spectroscopy with Attenuated Total Reflection (FTIR-ATR). Inter-laboratory reproducibility was assessed through Relative Standard Deviation (RSD), paired t-tests, and Pearson Correlation Coefficient (PCC).

MGT and SRT showed high reproducibility at short distances (RSD <11% up to 30 cm), but sensitivity decreased at longer distances, with an RSD of 28.6% for SRT at 100 cm. Paired t-tests revealed statistically significant consistency between laboratories (p < 0.05), and a strong negative correlation (PCC = -0.72) was found between shooting distance and residue area.

Integrating SEM-EDS and FTIR-ATR with MGT and SRT enhances the sensitivity, objectivity, and reproducibility of shooting distance estimations. This multi-method approach provides more reliable forensic evidence for criminal investigations.