AppliedChem

The monitoring and control of bioprocesses rely on the measurement of the main metabolite concentrations. To this end, infrared spectroscopy (IR) is a good candidate with which to perform rapid and non-destructive measurements. However, IR-based measurements rely on a calibration step linking the measured spectra to the concentrations of the compounds of interest. This calibration may suffer with problems of robustness when the measuring conditions change, such as when some chemicals not present in the calibration spectra are added when using the IR sensor. In this study, a method based on orthogonal projection, dynamic orthogonal projection (DOP), was tested for its ability to cope with the robustness problem caused by the addition of ammonia in a pilot-scale anaerobic digester, whose volatile fatty acid concentrations were monitored by mid-IR spectrometry. The results demonstrate that DOP has significant potential as a form of process analytical technology. Full article

The extensive use of synthetic pesticides and their addition to the field presents significant environmental problems that must be minimized. The use of natural insecticides and their addition using techniques that minimize their impact in the field are widely studied by the current scientific community. In this work an extraction method based on supercritical CO₂ to obtain a pyrethrin-rich natural extract from different varieties of chrysanthemum flowers is analyzed. This extract would be used in a supercritical solvent impregnation (SSI) process to produce a commercial polypropylene (PP) film with insecticidal properties to be used in greenhouses. The extract selected for the impregnation process was that obtained from the Atlantis variety at 35 °C and 10 MPa pressure. The amount of insecticide impregnated into the polymer at 55 °C and under two different pressure levels (10 MPa and 40 MPa) have been determined. A batch impregnation method (BM) with 5 h constant impregnation time and low depressurization rates were used to favor the impregnation process. The results demonstrated that this procedure was suitable to produce pyrethrin-loaded PP films that could to be used in greenhouses as a protection against pests, while allowing a more rational and moderate use of other chemical pesticides. Full article

Ibuprofen is a non-steroidal, anti-inflammatory drug that is widely prescribed for its analgesic, antipyretic, and anti-inflammatory actions to treat pain, symptoms of rheumatoid arthritis and fever, but it is also known to cause stomach-related side effects. The development of efficient drug delivery systems for this compound to prevent these side effects is hampered by its poor water solubility. In this work, we show that graphite oxide and its derivatives have great potential as effective drug delivery systems not only to overcome side effects but also to increase the short biological half-life of ibuprofen. We studied the adsorption capacity of graphite oxide and carboxylated and sulfonated graphene oxide for this drug and its release in simulated gastric and intestinal fluid. The obtained compounds were characterized by X-ray diffraction, thermogravimetric analysis and Fourier transform infrared spectroscopy. DFT calculations were conducted to elucidate the Ibuprofen/host interactions, to establish which properties of these carbon nanomaterials control the loading and release, as well as to provide a better understanding of the orientation of the drug molecules on the single-layer GO. Full article

Natural antioxidants have renewed value for human health and the food industry. Green labeling is becoming an important attribute for consumers and is impacting food processing and formulations. Clean label is another attribute that ranked third after the “free-from” claims and “a good source” of nutrient claims. Clean label attributes also are ranked higher than local, seasonal, and organic. Techniques that are able to preserve the valuable characteristics of natural antioxidants, while eliminating even trace amounts of solvent residues from their extraction and processing, are important. Supercritical fluids (SCF) are an effective green technology that can be adopted for extraction of natural antioxidants. This review is focused on the application of supercritical carbon dioxide (SCCO₂) for extracting hydrophobic antioxidant compounds with an emphasis on oilseed crops and carrots. The information provided about extraction parameters helps to guide optimization of the yield of tocopherols and carotenoids. Pressure is the most effective parameter for the extraction yield of tocopherol among the other parameters, such as temperature, time, and CO₂ flow rate. For carotenoid extraction, both pressure and temperature have a large impact on extraction yield. Higher yields of antioxidants, greater purity of the extracts, and larger retention of bioactivity are the main advantages of supercritical fluid extraction (SFE) in comparison to other conventional techniques. The benefits of SCF technology may open new opportunities for extracting valuable, natural and effective antioxidant compounds from food processing co-streams for use as bioactive compounds. Full article

This work reports the new method of Rauhut-Currier reaction (RC) with the use of lithium selenolates, which provided up to 80% yield in a non-asymmetric IRC reaction. Therefore, our paper involves the search for an efficient chiral additive in the asymmetric version. The influence of various reaction parameters, such as solvent, additives, temperature, and time, was examined. The results for the non-asymmetric version were significantly higher with the presence of water, but surprisingly different observations were obtained in the asymmetric version. Here, the chiral scandium complex with tertiary amine played an important role. The reaction carried out in the presence of chiral complexes gave the expected product with up to 60% yield and up to 70% ee. Full article

The influence of soaking and germination on the physicochemical characteristics of tigernut tubers (Cyperus esculentus L.) are investigated. Tubers (Ø > 1 cm) were soaked in an ascorbic acid solution (0.1%) for 48 h at 40 °C before undergoing germination for 6 days. The textural profile, the capacity and germination energy and the biochemical composition of these tubers were determined. The germination energy varied from 76.18 to 79.48% for the quantities of solution of 24 and 48 mL, respectively. The textural profile of the tubers varied depending on the type of treatment. Germination resulted in a considerable reduction in amylose content from 14.15% for the native tigernut tuber to 9.98% for the sprouted one. This treatment also increased the protein, ascorbic acid and ash contents, which ranged from 7.54 to 8.82 g/100 g DM, 250 to 275.39 mg/100 g DM and 2.60 to 3.84 g/100 g DM, respectively. The starch content of the tubers following germination remained high, which could come up against the pasteurization of the milk from these tubers. Full article

The determination of the true molar mass distribution (MMD) of lignin is highly important to understand the physicochemical characteristics for lignin-based value-added applications. It is imperative to develop a universal method to quantify accurate MMD of lignin using size exclusion chromatography (SEC), as the conventional method with polymer standards provides irregular MMD results. This work aims to evaluate the MMD of five lignin samples (Protobind 1000, Organosolv, Indulin, Pine Kraft and Eucalyptus Kraft) in THF. Different derivatization methods (acetylation, fluorobenzylation and fluorobenzoylation) were performed. FTIR and ¹⁹F NMR analyses were used to follow derivatization. The MMDs of derivatized and underivatized lignins were determined by the conventional method and compared with the universal calibration method developed using intrinsic viscosity. The ¹⁹F NMR spectra provided the information to quantify the degree of substitution of lignin hydroxyl groups, to calculate the true molar mass of the derivatives of lignin monomers. The obtained MMDs values for all the derivatized lignin by universal calibration were found to be three to five times higher than that of the conventional calibration. The polydispersity values obtained with the acetylation method were higher than the fluoro-derivatives. The results demonstrated that fluoro-derivatization is an appropriate method to apply to higher molar mass technical lignins and lacks solubility and aggregation issues. Full article

Cat’s claw (Uncaria tomentosa (Willd. ex Schults) DC.), a plant that is exceptionally rich in phytochemicals, has been used for centuries by the indigenous people of South and Central America as a therapeutic and is currently widely exported for medicinal purposes. Extracts and individual components have shown considerable potential as antibacterials in the literature. The purpose of this review is twofold: first, to provide a substantiated, comprehensive collection of the known chemical constituents of U. tomentosa, including their detailed structures; second, to identify those components that offer some promise as antibacterials based on the research to date. Bacterial resistance to currently available antibiotics continues to increase and is widely recognized as an impending, potentially catastrophic, problem. There is research to suggest that U. tomentosa components may have antibacterial potential individually or synergistically with established antibiotics against microbes, including Borrelia burgdorferi, the causative agent of Lyme disease. It is our intention that this review will provide a valuable resource to investigators in search of new antimicrobials to meet the daunting challenge of antibiotic resistance. Full article

Probiotics are microorganisms that have a beneficial influence on the human gastrointestinal tract. Unfortunately, their viability can be negatively affected by manufacturing, storage conditions and gastrointestinal tract conditions. Therefore, there is a need to develop delivery systems, which can protect probiotics against adverse conditions. Previously, we reported on hydrogels made of poly-γ-glutamic acid (γ-PGA) and selected PEGs with the potential application as probiotic delivery vehicles. In the next step of research, we decided to develop fully biobased hydrogels with the potential application as probiotic oral-delivery systems. Selected sugar alcohols, erythritol, xylitol and sorbitol, have been used as cross-linkers in the synthesis of γ-PGA-based hydrogels. It was examined if obtained hydrogels enhanced the survival rate of entrapped probiotic strains subjected to acidic conditions. Results have been discussed in relation to the previously reported γ-PGA-PEG hydrogels. Moreover, the possibility of using developed hydrogels as a cryoprotectant was investigated during freeze drying of entrapped probiotic cells. Full article

In recent years, the amount of produced petrochemical plastic waste has been growing at an alarming rate. According to the Plastics Europe Market Research Group (PEMRG)/Conversio Market & Strategy GmbH, in 2018 the global production of plastics amounts to 359 million tons, and in Europe—61.8 million tons. More than 80% of all marine litter is plastic, which accumulates in the environment due to its durability. Due to the growing problem, biodegradable polymer products are introduced to the market. Therefore, it is necessary to conduct research on degradation products in order to estimate the risk arising from their presence in the environment. This paper discusses research on compounds that may potentially remain in the soil after the degradation of the double green PLA polymer. The aim of the research was to prove whether products made of PLA, e.g., packaging, films and other waste can release substances harmful to the environment. Therefore, soil was selected as a medium to characterize the substances potentially released from the polymer under conditions simulating the degradation process in the environment. The soil was always used from the same producer. Before the polymer biodegradation process, it was additionally checked for pH, C and N content, number of microorganisms, etc. PLA degradation in soil was carried out in a laboratory accredited by the Polish Accreditation Center (PCA). During the research, soil samples at various stages of the degradation process under laboratory conditions were subjected to both extraction in an aqueous environment and organic solvent extraction The studies used the gas chromatography coupled with mass spectrometry (GC/MS), as well as pyrolysis gas chromatography (Py-GC/MS). In addition, the study used the gel permeation chromatography (GPC/SEC) allowing to determine the distribution of molar masses, average molar masses and polydispersity, and the infrared spectroscopy (FTIR). Full article

The deamidation of glutamine (Gln) residues, which occurs non-enzymatically under physiological conditions, triggers protein denaturation and aggregation. Gln residues are deamidated via the cyclic glutarimide intermediates to l-α-, d-α-, l-β-, and d-β-glutamate residues. The production of these biologically uncommon amino acid residues is implicated in the pathogenesis of autoimmune diseases. The reaction rate of Gln deamidation is influenced by the C-terminal adjacent (N +1) residue and is highest in the Gln-glycine (Gly) sequence. Here, we investigated the effect of the (N + 1) Gly on the mechanism of Gln deamidation and the activation barrier using quantum chemical calculations. Energy-minima and transition-state geometries were optimized by the B3LYP density functional theory, and MP2 calculations were used to obtain the single-point energy. The calculated activation barrier (85.4 kJ mol⁻¹) was sufficiently low for the reactions occurring under physiological conditions. Furthermore, the hydrogen bond formation between the catalytic ion and the main chain of Gly on the C-terminal side was suggested to accelerate Gln deamidation by stabilizing the transition state. Full article

An ion-associate phase (IAP) microextraction/ back-microextraction system was applied for the enrichment, separation, and detection of trace amounts of nickel from environmental water samples. Thenoyltrifluoroacetone (HTTA) acted not only as a chelating reagent for nickel, but also as a component of the extraction phase, i.e., IAP. Nickel in a 40 mL sample solution was pH-adjusted with phenolsulfonate (PS⁻) and tetramethylammonium hydroxide and converted by chelation reaction in the presence of thenoyltrifluoroacetonate (TTA⁻). When benzyldodecyldimethylammonium ion (C₁₂BzDMA⁺) was added, a suspension of IAP formed in the solution. The IAP consisted of TTA⁻, a chelating reagent, the PS⁻, a component of pH buffer, and C₁₂BzDMA⁺, which helps extract the chelating complex. When the solution was centrifuged, the IAP separated from the suspension and the nickel-TTA chelate was extracted into the bottom phase of the centrifuge tube. After the aqueous phase was taken away, 100 µL of nitric acid (2 M) solution containing phosphate was used to back-microextract nickel from the IAP. The acid phase was measured via graphite-furnace atomic-absorption spectrometry (GF-AAS). The proposed method facilitated a 400-fold enrichment. The limit of detection was 0.02 µg L⁻¹. The proposed method was applied for the determination of nickel in river water and seawater samples. Full article

Group contribution (GC) methods to predict thermochemical properties are eminently important to process design. We present a group contribution parametrization for the heat of formation of organic molecules exhibiting chemical accuracy, maximum 1 kcal/mol (4.2 kJ/mol) difference between experiment and model values while minimizing the number of parameters avoiding overfitting and therewith avoiding reduced predictability. Compared to the contemporary literature, this was successfully achieved by employing available literature high-quality and consistent experimental data, optimizing parameters group by group, and introducing additional parameters when chemical understanding was obtained supporting these. A further important result is the observation that the applicability of the group contribution approach breaks down with increasing substitution levels, i.e., more heavily alkyl-substituted molecules, the reason being a serious influence of substitution on the conformation of the flexible part of the entire molecule within particular valence angles and torsional angles affected, which cannot be accounted for by additional GC parameters with fixed numerical values. Full article

The work presents a comprehensive profile of the physicochemical characteristics of opoka sedimentary rock in the context of its use as a hybrid filler for thermoplastics. Determining the functional parameters of the studied filler was the main aim of this research. Thermal treatment leads to changes in its morphology and phase composition. A wide range of physicochemical techniques was used, such as low-temperature nitrogen adsorption, FT-IR, TGA, XRD, optical, and electron microscopy. The susceptibility of the material to micronisation was also tested (ball milling). Due to its widespread occurrence, opoka can be an attractive alternative to fillers such as silica or chalk. In order to verify this statement, polypropylene composites thereof were prepared by melt blending and injection molding, and studied by mechanical testing and microscopic imaging. Full article

Cross-coupling reactions leading to carbon–heteroatom bonds yield compounds that attract substantial interest due to their role as structural units in many synthetic protocols for bioactive and natural products. Therefore, many research works aim at the improvement of heterogeneous catalytic protocols. We have studied the use of magnetite nanoparticles and solid base compounds in organic synthetic reactions in carbon–heteroatom bond formation because they can be flocculated and dispersed, and reversibly controlled by applying a magnetic field. In this work, we have developed an efficient and simple synthetic approach for the C–O/C–N cross-coupling reaction under ligand-free conditions by using CuI as a catalyst and KF/Fe₃O₄ as a base. We performed the nucleophilic aromatic substitution of electron-deficient aryl halides and phenols. It was found that both the solvent nature and the base have a profound influence on the reaction process. This approach affords good to excellent yields of arylated products. KF/Fe₃O₄ displayed convenient magnetic properties and could be easily separated from the reaction using a magnet and recycled several times without significant loss of catalytic activity. This method has been successfully investigated for the Ullmann coupling reaction. Full article

Food quality is a topic of utmost importance as more and more emphasis is placed on quality rather than quantity of products. Previous studies have pointed out the interaction of quality with the harvest year. In this study, 22 Pistacia vera (Greek ‘Aegina’ variety) samples (11 from 2017 and 11 from 2018) were differentiated using Fourier transform infrared spectroscopy (FTIR) and (a) diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and (b) KBr/sample disk techniques. In both years, the pistachios trees’ growing followed standard cultivation methods and similar agronomic conditions. Two chemometric models were developed using partial least squares-discrimination analysis (PLS-DA). DRIFTS proved unable to statistically differentiate the samples (R² = 0.96266, Q² = 0.63152). On the contrary, the disk technique completely differentiated the pistachio samples (R² = 0.99705, Q² = 0.97719). The 1720–1800 cm⁻¹ region mostly contributed to the discrimination. The disk-FTIR chemometric model is fast, robust, economical, and environmentally friendly for determining pistachio matrix quality. Full article

In order to afford the required level of broad-spectrum photoprotection against UV-B and UV-A radiation, sunscreens must contain a combination of UV filters. It is important that any interactions between UV filters do not adversely affect their photostability nor the overall photostability of the sunscreen formulation. In this work, we explore the feasibility of using methyl anthranilate (MA) as an alternative to the photo-unstable UV-A filter, avobenzone. From the in vitro studies presented here, we conclude that MA does not provide sufficient UV-A protection on its own but that it is more photostable in formulation than avobenzone. In addition, we found that both octocrylene (OCR) and ethylhexyl methoxycinnamate (EHMC), two commonly used UV-B filters, can stabilize MA through quenching of its triplet states, as previously reported, which has a demonstrable effect in formulation. In contrast with previously reported observations for mixtures of EHMC and avobenzone, we found no evidence of [2+2] photocycloadditions taking place between EHMC and MA. This work demonstrates how a clear insight into the photophysics and photochemistry of UV filters, as well as the interactions between them, can inform formulation design to predict sunscreen performance. Full article

Chromium plating has excellent corrosion resistance and is widely used in industry. However, it also has a high environmental load. As an alternative, electric Ni-W plating is attracting attention. However, it is not widely used because the stress is high and the film is prone to cracks. Furthermore, although it is necessary to thicken the film to improve the corrosion resistance, there are also problems that the current efficiency is low and the plating time is long. Therefore, we investigate a film with high corrosion resistance by using the jet-flow plating method that enables plating at a high current density. Our results show that the jet-flow plating enables plating of 50 µm, and high corrosion resistance is obtained by randomly generating fine cracks in the film at 20 A·dm⁻². We also found that the stress changed depending on the current density and shape of the crack also changed. Full article

Colorimetric gas detectors have been widely applied in many fields such as environmental sciences, industrial hygiene, process control, forensic science and indoor air quality monitoring. They have a history of about 100 years and include devices such as gas detector tubes and paper-based gas detectors. The sensitivity and selectivity of the colorimetric gas detector are relatively high compared to other types of gas detectors such as semiconductor, catalytic combustion and electrochemical gas detectors. Detection of gas concentration can be performed by the naked eye in some colorimetric gas detectors. These methods do not require an electrical power source and are simple, so they are suitable for field operations. This review introduces the history and provides a general overview of the development in the research of colorimetric gas detectors. Recently, the sensitivity and selectivity of colorimetric gas detectors have improved. New materials such as enzymes or particles with a large surface area have been utilized to improve selectivity and sensitivity. Moreover, new gas detectors without toxic materials have been developed to reduce the environmental load. At present, there is a rapid development of IoT sensors in many industrial fields, which might extend the applications of colorimetric gas detectors in the near future. Full article