Development of a novel LED-IoT photoreactor for enhanced removal of carbamazepine waste driven by solar energy.

This study introduces an innovative LED-IoT photoreactor, representing a significant advancement in response to the demand for sustainable water purification. The integration of LED-IoT installations addresses the challenge of intermittent sunlight availability, employing LEDs with a spectrum mimicking natural sunlight. Passive Infra-Red (PIR) sensors and Internet of things (IoT) technology ensure consistent radiation intensity, with the LED deactivating in ample sunlight and activating in its absence. Utilizing a visible light-absorbing photocatalyst developed through sol-gel synthesis and mild-temperature calcination, this research demonstrates a remarkable carbamazepine removal efficiency exceeding 95% under LED-IoT system illumination, compared to less than 90% efficiency with sunlight alone, within a 6-h exposure period. Moreover, the designed photocatalytic system achieves over 60% mineralization of carbamazepine after 12 h. Notably, the photocatalyst demonstrated excellent stability with no performance loss during five further cycles. Furthermore, integration with renewable energy sources facilitated continuous operation beyond daylight hours, enhancing the system's applicability in real-world water treatment scenarios. A notable application of the LED-IoT system at an operating sewage treatment plant showed nearly 80% efficiency in carbamazepine removal from sewage in the secondary settling tank after 6 h of irradiation, coupled with nearly 40% mineralization efficiency. Additionally, physicochemical analyses such as XPS and STA-FTIR confirm that the carbamazepine photooxidation process does not affect the surface of the photocatalyst, showing no adsorption for degradation products.

The toxicological analysis and assessment of essential elements (Cu, Fe, Mn, Zn) in Food for Special Medical Purposes (FSMP) dedicated to oncological patients available in Polish pharmacies.

Foods for Special Medical Purposes (FSMP) for oncology patients, available in pharmacies, play a crucial role in providing nutrition and supplementation. However, the scientific literature lacks comprehensive research on the safety of essential trace elements in these products. This study aimed to assess Cu, Fe, Mn and Zn levels in commonly prescribed FSMPs (n = 23) from Polish pharmacies. Using ICP-MS after microwave-induced digestion (using concentrated nitric acid and hydrogen peroxide), we evaluated element levels. Our research used three approaches: the raw score for Cu, Fe, Mn, and Zn; single intake per serving; and the daily ration, compared with the reference values of the European Food Safety Authority. Discrepancies were found between the actual and declared product compositions, influenced by the route of administration and the recommended intake. Despite variations, all products were considered safe for oncological patients based on current evidence. However, it is recommended to have clear guidelines for FSMPs in cancer care. This pioneering study evaluates the safety and quality of prescription FSMPs for cancer patients from toxicological and nutritional perspectives, highlighting the need for standardised protocols in pharmacy-dispensed FSMPs.

Association of Metallic and Nonmetallic Elements with Fibrin Clot Properties and Ischemic Stroke.

Objectives-Metallic elements and fibrin clot properties have been linked to stroke. We examined metallic and nonmetallic elements, fibrin clot lysis time (CLT), and maximum absorbance (Absmax) in relation to ischemic stroke. Design-A case-control study of ischemic stroke patients vs. healthy individuals. Subjects and Methods-Plasma and serum were collected from 260 ischemic stroke patients (45.0% women; age, 68 ± 12 years) and 291 healthy controls (59.7% women; age, 50 ± 17 years). Fibrin CLT and Absmax were measured using a validated turbidimetric assay. Serum elements were quantified by inductively coupled plasma mass spectrometry (ICP-MS) and optical emission spectrometry (ICP-OES). Data were analyzed by bivariate correlations and multiple or logistic regression. Results-In female stroke patients, copper, lithium, and aluminum were significantly lower compared with controls; in male stroke patients, potassium was lower, and beryllium was elevated. In female and male stroke patients, iron, zinc, nickel, calcium, magnesium, sodium, and silicon were significantly lower, while strontium was elevated. Positive correlations between fibrin clot properties and metals, observed in healthy controls, were lost in ischemic stroke patients. In multivariate regression analysis, fibrin CLT and/or Absmax was associated with zinc, calcium, potassium, beryllium, and silicon in stroke patients and with sodium, potassium, beryllium, and aluminum in controls. In logistic regression analysis, stroke was independently associated with lithium, nickel, beryllium, strontium, boron, and silicon and with sodium, potassium, calcium, and aluminum but not with fibrin CLT/Absmax. Conclusions-Various elements were associated with fibrin clot properties and the risk of ischemic stroke. Lithium, sodium, calcium, and aluminum abrogated the association of fibrin clot properties with ischemic stroke.

Three musketeers of PDA-based MRI contrasting and therapy.

Polydopamine (PDA) stands as a versatile material explored in cancer nanomedicine for its unique properties, offering opportunities for multifunctional drug delivery platforms. This study explores the potential of utilizing a one-pot synthesis to concurrently integrate Fe, Gd and Mn ions into porous PDA-based theranostic drug delivery platforms called Ferritis, Gadolinis and Manganis, respectively. Our investigation spans the morphology, magnetic properties, photothermal characteristics and cytotoxicity profiles of those potent nanoformulations. The obtained structures showcase a spherical morphology, robust magnetic response and promising photothermal behaviour. All of the presented nanoparticles (NPs) display pronounced paramagnetism, revealing contrasting potential for MRI imaging. Relaxivity values, a key determinant of contrast efficacy, demonstrated competitive or superior performance compared to established, used contrasting agents. These nanoformulations also exhibited robust photothermal properties under near infra-red irradiation, showcasing their possible application for photothermal therapy of cancer. Our findings provide insights into the potential of metal-doped PDA NPs for cancer theranostics.

Speciation analysis of arsenic in honey using HPLC-ICP-MS and health risk assessment of water-soluble arsenic.

It is well known that arsenic is one of the most toxic elements. However, measuring total arsenic content is not enough, as it occurs in various forms that vary in toxicity. Since honey can be used as a bioindicator of environmental pollution, in the present study the concentration of arsenic and its species (As(III), As(V), DMA, MMA and AsB) was determined in honey samples from mostly Poland and Ukraine using HPLC-ICP-MS hyphenated technique. The accuracy of proposed methods of sample preparation and analysis was validated by analyzing certified reference materials. Arsenic concentration in honey samples ranged from 0.12 to 13 µg kg-1, with mean value of 2.3 µg kg-1. Inorganic arsenic forms, which are more toxic, dominated in honey samples, with Polish honey having the biggest mean percentage of inorganic arsenic species, and Ukrainian honey having the lowest. Furthermore, health risks resulting from the consumption of arsenic via honey were assessed. All Target Hazard Quotient (THQ) values, for total water-soluble arsenic and for each form, were below 1, and all Carcinogenic Risk (CR) values were below 10-4, which indicates no potential health risks associated with consumption of arsenic via honey at average or recommended levels.

Copper(II) phosphate as a promising catalyst for the degradation of ciprofloxacin via photo-assisted Fenton-like process.

This work aims to unravel the potential of copper(II) phosphate as a new promising heterogenous catalyst for the degradation of ciprofloxacin (CIP) in the presence of H2O2 and/or visible light (λ > 400 nm). For this purpose, copper(II) phosphate was prepared by a facile precipitation method and fully characterized. Of our particular interest was the elucidation of the kinetics of CIP degradation on the surface of this heterogeneous catalyst, identification of the main reactive oxygen species responsible for the oxidative degradation of CIP, and the evaluation of the degradation pathways of this model antibiotic pollutant. It was found that the degradation of the antibiotic proceeded according to the pseudo-first-order kinetics. Copper(II) phosphate exhibited ca. 7 times higher CIP degradation rate in a Fenton-like process than commercial CuO (0.00155 vs. 0.00023 min-1, respectively). Furthermore, the activity of this metal phosphate could be significantly improved upon exposure of the reaction medium to visible light (reaction rate = 0.00445 min-1). In a photo-assisted Fenton-like process, copper(II) phosphate exhibited the highest activity in CIP degradation from among all reference samples used in this study, including CuO, Fe2O3, CeO2 and other metal phosphates. The main active species responsible for the degradation of CIP were hydroxyl radicals.

Determination of Metal Content by Inductively Coupled Plasma-Mass Spectrometry in Polish Red and White Wine Samples in Relation to Their Type, Origin, Grape Variety and Health Risk Assessment.

The main objective of the research was to assess the influence of selected factors (type of wine, grape variety, origin, alcohol content and daily consumption) on the concentration levels of 26 elements in 53 Polish wine samples, also using chemometric analysis tools. Concentration of Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Ni, Pb, Sb, Se, Sr, Ti, V, Zn and Zr was analyzed by ICP-MS, while concentration of Ca, Na, K and Mg was determined by ICP-OES. White wines were characterized by higher concentrations of Al, As, Be, Ca, Co, Cu, Fe, Hg, Li, Mg, Na, Pb, Sb, Ti, V, Zn and Zr (mean values: 0.075-86,403 µg·L-1 in white wines, 0.069-81,232 µg·L-1 in red wines). Red wines were characterized by higher concentrations of Ba, Cd, Cr, K, Mn, Se and Sr (mean values: 0.407-1,160,000 µg·L-1 in white wines, 0.448-1,521,363 µg·L-1 in red wines). The results obtained for the health risk assessment indices, including the Target Hazard Quotient (THQ, mean values per glass of wine: 2.097 × 10-5 (Cr)-0.041 (B) in all wines), indicate that the analyzed elements do not show a potential toxic effect resulting from wine consumption. The chemometric analysis confirmed that elements such as Li, Ti, Ca, Mn, Sr, Ba, Zn, Mg, Cu, Se and B were closely related to local conditions and soil properties, and the presence of Fe, Cr, V and Pb was related to contamination of the soil.

Sea spray as a secondary source of chlorinated persistent organic pollutants? - Conclusions from a comparison of seven fresh snowfall events in 2019 and 2021.

Secondary sources of persistent organic pollutants (POPs) gain in importance worldwide as primary sources decline. In this work, we aim to determine whether sea spray may be a secondary source of chlorinated POPs to the terrestrial Arctic, since a similar mechanism was proposed there only for the more water-soluble POPs. To this end, we have determined polychlorinated biphenyls and organochlorine pesticides concentrations in fresh snow and seawater collected in the vicinity of the Polish Polar Station in Hornsund in two sampling periods covering spring 2019 and 2021. To support our interpretations, we include also metal and metalloid, and stable hydrogen and oxygen isotopes analysis in those samples. A significant correlation was found between the concentrations of POPs and the distance from the sea at the sampling point, yet the confirmation of sea spray impact lies more in capturing an event with negligible long-range transport influence where the detected chlorinated POPs (Cl-POPs) matched in composition the compounds enriched in the sea surface microlayer, which is both a source of sea spray and a seawater microenvironment rich in hydrophobic substances.

Rainwater chemistry composition in Bellsund: Sources of elements and deposition discrepancies in the coastal area (SW Spitsbergen, Svalbard).

Discrepancies in rainfall chemistry in Bellsund were found to be influenced by the orographic barrier and related to the variability in the inflow of air masses as well as to the distance of sampling sites from the sea and thus the extent of sea spray impact. This study covers measurements of rainfall (P) and air temperature (T), physicochemical parameters (pH, specific electrolytic conductivity (SEC), major ions (Cl-, NO3-, SO42-) and elements (Na, Ca, Mg,K), as well as trace elements (i.a. As, Cd, Cr, Fe, Co, Pb, Ni, Zn) and dissolved organic carbon (DOC) in 22 rainfall samples collected in August on the Calypsostranda marine terrace and in the forefield of a land-terminating glacier (NW Wedel Jarlsberg Land). The comparison of chemical parameters in the samples revealed major discrepancies, including statistically significant higher rainwater pH and SEC, and the levels of Ag, As, Bi, Ca, Co, Fe, Li, Mn, Mo, Ni, Pb, Sb, and V, deposited near the seashore (Calypsostranda) than in the glacier forefield. Cluster analysis (CA) showed that elements deposited in lower concentrations at the glacier forefield site came from predominately anthropogenic sources. Conversely, CA results of metals and metalloids deposited on the Calypsostranda marine terrace indicate both natural and anthropogenic sources. A correlation matrix and principal component analysis (PCA) permitted identifying two primary factors affecting rainfall chemistry at each of the study sites. In Calypsostranda, these were the inflow of relatively unpolluted cold air (F1 = 35.1%) and sea spray (F2 = 27.6%), while in the glacier forefield the factors were an orographic barrier (F1 = 37.3%) and the inflow of polluted warm air (F2 = 25.2%).

Multivariate Statistical Analysis for Mutual Dependence Assessment of Selected Polyphenols, Organic Acids and Metals in Cool-Climate Wines.

Polyphenols, organic acids and metal ions are an important group of compounds that affect the human health and quality of food and beverage products, including wines. It is known that a specific correlation between these groups exist. While wines coming from the New World and the Old World countries are extensively studied, wines coming from cool-climate countries are rarely discussed in the literature. One of the goals of this study was to determine the elemental composition of the wine samples, which later on, together as polyphenols and organic acids content, was used as input data for chemometric analysis. The multivariate statistical approach was applied in order to find specific correlations between the selected group of compounds in the cool-climate wines and the features that distinguish the most and differ between red and white wines and rosé wines. Moreover, special attention was paid to resveratrol and its correlation with selected wine constituents.

Ferritin-mediated iron detoxification promotes hypothermia survival in Caenorhabditis elegans and murine neurons.

How animals rewire cellular programs to survive cold is a fascinating problem with potential biomedical implications, ranging from emergency medicine to space travel. Studying a hibernation-like response in the free-living nematode Caenorhabditis elegans, we uncovered a regulatory axis that enhances the natural resistance of nematodes to severe cold. This axis involves conserved transcription factors, DAF-16/FoxO and PQM-1, which jointly promote cold survival by upregulating FTN-1, a protein related to mammalian ferritin heavy chain (FTH1). Moreover, we show that inducing expression of FTH1 also promotes cold survival of mammalian neurons, a cell type particularly sensitive to deterioration in hypothermia. Our findings in both animals and cells suggest that FTN-1/FTH1 facilitates cold survival by detoxifying ROS-generating iron species. We finally show that mimicking the effects of FTN-1/FTH1 with drugs protects neurons from cold-induced degeneration, opening a potential avenue to improved treatments of hypothermia.

Phosphate doping as a promising approach to improve reactivity of Nb2O5 in catalytic activation of hydrogen peroxide and removal of methylene blue via adsorption and oxidative degradation.

This study is devoted to the evaluation of the influence of phosphate dopants on the reactivity of Nb2O5-based nanomaterials in the combined catalytic activation of H2O2 and the elimination of methylene blue (MB) from an aqueous solution via adsorption and chemical degradation. For this purpose, several niobia-based catalysts doped with various amounts of phosphate were prepared by a facile hydrothermal method and subsequent calcination. Phosphate doping was shown to strongly enhance the ability of Nb2O5 to activate H2O2, as well as to adsorb and degrade MB. The most pronounced differences in the reactivity of the parent Nb2O5 and phosphate-doped samples were observed under strongly acidic conditions (pH ~ 2.4), at which the most active modified catalysts (Nb/P molar ratio = 5/1) was approximately 6 times more efficient in the removal of MB. The observed enhancement of reactivity was attributed to the increased generation of singlet oxygen 1O2, which was identified as the main oxidizing agent responsible for efficient degradation of MB. To our knowledge, it is the first report revealing that phosphate doping of Nb2O5 resulted in an improved activity of niobia in the adsorption and degradation of organic pollutants.

Sex- and Age-Related Dynamic Changes of the Macroelements Content in the Femoral Bone with Hip Osteoarthritis.

BACKGROUND: The content of macroelements in bones varies with age and depends on sex. The aim of the study was to evaluate the content of macroelements and its correlation with age and sex in the femoral bone obtained during total hip arthroplasty. METHODS: In the 86 patients, the content of macroelements (Ca, P, Mg, and Na) in the femoral head and neck (cancellous and cortical bone) was assessed by means of the inductively coupled plasma optical emission spectrometry analytical technique (ICP-OES). RESULTS: There was a decrease in the content of macroelements in the cortical bone with age in the women in the 51-60 years (statistically significant: -0.59 for Ca, -0.65 for P) and over 70 years age groups (correlation not statistically significant: -0.29 for Ca, -0.38 for P). A significant decrease in the content of macroelements in the cortical bone was found in men over 70 years of age. CONCLUSIONS: Patterns of increased loss of macronutrients (Ca, P, and Mg) in the femoral neck (cortical bone) were demonstrated in the following patients with osteoarthritis: women aged 51-60 years and patients of both sexes over 70 years of age.

Retracted: Atomic Absorption Spectrometry Analysis of Trace Elements in Degenerated Intervertebral Disc Tissue.

Medical Science Monitor is retracting the following publication on the basis of duplicated published content. 1) Kubaszewski L, Ziola-Frankowska A, Frankowski M, Rogala P, Gasik Z, Kaczmarczyk J, Nowakowski A, Dabrowski M, Labedz W, Miekisiak G, Gasik R. Comparison of trace element concentration in bone and intervertebral disc tissue by atomic absorption spectrometry techniques. J Orthop Surg Res. 2014 Oct 25;9: 99. doi: 10.1186/s13018-014-0099-y. PMID: 25342441; PMCID: PMC4220064. 2) Kubaszewski L, Ziola-Frankowska A, Frankowski M, Nowakowski A, Czabak-Garbacz R, Kaczmarczyk J, Gasik R. Atomic absorption spectrometry analysis of trace elements in degenerated intervertebral disc tissue. Med Sci Monit. 2014 Nov 4;20: 2157-64. doi: 10.12659/MSM.890654. PMID: 25366266; PMCID: PMC4301216. 3) Nowakowski A, Kubaszewski L, Frankowski M, Wilk-Franczuk M, Ziola-Frankowska A, Czabak-Garbacz R, Kaczmarczyk J, Gasik R. Analysis of trace element in intervertebral disc by Atomic Absorption Spectrometry techniques in degenerative disc disease in the Polish population. Ann Agric Environ Med. 2015;22(2): 362-7. doi: 10.5604/12321966.1152096. PMID: 26094540. We have reviewed the content of all three similar publications. We note that Medical Science Monitor was the second to publish this study, in November 2014. At that time, the Corresponding Author gave no declaration of submitting this study to any other journal, nor of previously publishing this study. Reference: Lukasz Kubaszewski, Anetta Ziola-Frankowska, Marcin Frankowski, Andrzej Nowakowski, Róza Czabak-Garbacz, Jacek Kaczmarczyk, Robert Gasik. Atomic Absorption Spectrometry Analysis of Trace Elements in Degenerated Intervertebral Disc Tissue. Med Sci Monit, 2014; 20: 2157-2164. DOI: 10.12659/MSM.890654.

Removal of Heavy Metal Ions from One- and Two-Component Solutions via Adsorption on N-Doped Activated Carbon.

This paper deals with the adsorption of heavy metal ions (Cu2+ and Zn2+) on the carbonaceous materials obtained by chemical activation and ammoxidation of Polish brown coal. The effects of phase contact time, initial metal ion concentration, solution pH, and temperature, as well as the presence of competitive ions in solution, on the adsorption capacity of activated carbons were examined. It has been shown that the sample modified by introduction of nitrogen functional groups into carbon structure exhibits a greater ability to uptake heavy metals than unmodified activated carbon. It has also been found that the adsorption capacity increases with the increasing initial concentration of the solution and the phase contact time. The maximum adsorption was found at pH = 8.0 for Cu(II) and pH = 6.0 for Zn(II). For all samples, better fit to the experimental data was obtained with a Langmuir isotherm than a Freundlich one. A better fit of the kinetic data was achieved using the pseudo-second order model.

New Method for Simultaneous Arsenic and Selenium Speciation Analysis in Seafood and Onion Samples.

This paper presents a new method for the simultaneous speciation analysis of arsenic (As(III)-arsenite, As(V)-arsenate, DMA-dimethylarsinic acid, MMA-methylarsonic acid, and AsB-arsenobetaine) and selenium (Se(IV)-selenite, Se(VI)-selenate, Se-Methionine, and Se-Cystine), which was applied to a variety of seafood and onion samples. The determination of the forms of arsenic and selenium was undertaken using the High-Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) analytical technique. The separation of both organic and inorganic forms of arsenic and selenium was performed using two analytical columns: an anion exchange column, Dionex IonPac AS22, containing an alkanol quaternary ammonium ion, and a double bed cation-anion exchange guard column, Dionex Ion Pac CG5A, containing, as a first layer, fully sulfonated latex for cation exchange and a fully aminated layer for anion exchange as the second layer. The ammonium nitrate, at pH = 9.0, was used as a mobile phase. The method presented here allowed us to separate the As and Se species within 10 min with a suitable resolution. The applicability was presented with different sample matrix types: seafood and onion.

Impact of the oxidative and enzymatic metals in degenerated intervertebral disc disease.

INTRODUCTION: The degenerative process of the intervertebral disc is a heterogeneous process that may exist in two forms, and involves dominant degenerative changes within the nucleus pulposus and the annulus fibrosus. In degenerative disc disease, the oxidative stress factor can play an important role. OBJECTIVE: The aim of research was to present a new approach to understanding the role of the analyzed elements in the process of degeneration of the intervertebral disc. MATERIAL AND METHODS: Selected elements from oxidative groups (Fe, Zn, Mo, As, Se), associated with enzymatic processes (Fe, Mo, Se, Zn, Ag, As, Bi), metals (Fe, Zn, Mo, Li) and metalloids (As, Bi) and their content was analyzed depending on the changes in the radiological images of the intervertebral disc. Elemental content analysis was performed by Inductively Coupled Plasma Mass Spectrometry analytical technique. RESULTS: The similarity between Fe and Se has been demonstrated during different stages of the analysis of groups of patients with degenerative disc disease. There was a negative correlation between Li and degenerative disc disease. The results also suggest that Fe and Ag are involved in degenerative changes within the intervertebral disc. A potential relationship between As/Bi and Fe/Mo in the degeneration of the intervertebral disc was demonstrated. CONCLUSIONS: Only some of the correlations can be explained by the metabolism of morphological elements of the intervertebral disc. The relationships indicate new directions for further studies on the degeneration process of the intervertebral disc. The presented study may reflect metabolic changes in the intervertebral disc and adjacent structures in response to the progressive degenerative process.

Sources and composition of chemical pollution in Maritime Antarctica (King George Island), part 2: Organic and inorganic chemicals in snow cover at the Warszawa Icefield.

The study area is located on King George Island, where 90% of the area is permanently glaciated. This study provides a comprehensive analysis of the inorganic and organic chemistry of snow cover in the icefield and a comparison against previous results obtained in fresh water. Snow samples were collected in the summer of 2017 in the Warszawa Icefield area. Sampling points are located along two transects: between the Arctowski Polish Polar Station and the Carlini Base (N = 4), and from the forefield to the upper part of Ecology Glacier (N = 5). In the snow samples, (1) basic ions, (2) major trace metals and metalloids (and B), and (3) polycyclic aromatic hydrocarbons (PAHs) were detected and quantified. Additionally, the parameters of pH, specific electrolytic conductivity (SEC25) and total organic carbon (TOC) were determined. The results show a low concentration of inorganic elements (<30 mg/L), TOC (<1 mg/L) and PAHs (0.11-1.4 ng/L) in collected snow samples. A slight increase in PAHs and heavy-metals concentration has been observed at the marginal parts of the icefield, which suggests the impact of scientific stations. Based on this result there is a need to conduct research on pollutant levels in ice cores on King George Island to assess the risk associated with rapid glacier thawing and pollution remobilisation.

The Role of Sulphate and Phosphate Ions in the Recovery of Benzoic Acid Self-Enhanced Ozonation in Water Containing Bromides.

The ozonation of aromatic compounds in low-pH water is ineffective. In an acidic environment, the decomposition of ozone into hydroxyl radicals is limited and insufficient for the degradation of organic pollutants. Radical processes are also strongly inhibited by halogen ions present in the reaction medium, especially at low pH. It was shown that even under such unfavorable conditions, some compounds can initiate radical chain reactions leading to the formation of hydroxyl radicals, thus accelerating the ozonation process, which is referred to as so-called "self-enhanced ozonation". This paper presents the effect of bromides on "self-enhanced ozonation" of benzoic acid (BA) at pH 2.5. It is the first report to fully and quantitatively describe this process. The presence of only 15 µM bromides in water inhibits ozone decomposition and completely blocks BA degradation. However, the effectiveness of this process can be regained by ozonation in the presence of phosphates or sulphate. The addition of these inorganic salts to the bromide-containing solution helps to recover ozone decomposition and BA degradation efficiency. As part of this research, the fractions of hydroxyl, sulphate and phosphate radicals reacting with benzoic acid and bromides were calculated.