Host-guest complexation of phthalimide-derived strigolactone mimics with cyclodextrins. Application in agriculture against parasitic weeds.

Parasitic weeds are noxious plants that damage crops of economic relevance, especially in Mediterranean and African countries. The strategy of suicidal germination was proposed to deal with this plague by using seed germination inducers that work as a pre-emergence herbicide and reduce the parasitic seed load before sowing. N-Substituted phthalimides with a furanone ring were found to be efficient in inducing the germination of Phelipanche ramosa and Orobanche cumana, two of the most problematic parasitic weeds of crops. However, the solubility of these compounds in water is low. A strategy for enhancing their aqueous solubility is the synthesis of host-guest complexes with cyclodextrins. Three bioactive phthalimide-lactones (PL01, PL04, and PL07) were selected and studied to form complexes of increased water solubility with α-, ß-, HP-ß-, and γ-cyclodextrin. The complexes obtained by the coprecipitation method, with increased aqueous solubility (up to 3.8 times), were studied for their bioactivity and they showed similar or slightly higher bioactivity than free phthalimide-lactones, even without the addition of organic solvents. A theoretical study using semiempirical calculations of molecular models including a solvation system confirmed the physicochemical empirical results. These results demonstrated that cyclodextrins can be used to improve the physicochemical and biological properties of parasitic seed germination inducers.

Optimization through a Box-Behnken Experimental Design of the Microwave-Assisted Extraction of the Psychoactive Compounds in Hallucinogenic Fungi (Psylocibe cubensis).

Hallucinogenic fungi, mainly those from the Psilocybe genus, are being increasingly consumed even though there is no control on their culture conditions. Due to the therapeutic potential as antidepressants and anxiolytics of the alkaloids that they produce (psilocin and psilocybin), some form of control on their production would be highly recommended. Prior to identifying their optimal culture condition, a methodology that allows their study is required. Microwave-assisted extraction method (MAE) is a technique that has proven its efficiency to extract different compounds from solid matrices. For this reason, this study intends to optimize a MAE method to extract the alkaloids found in Psylocibe cubensis. A surface-response Box-Behnken design has been employed to optimize such extraction method and significantly reduce time and other resources in the extraction process. Based on the Box-Behnken design, 50 °C temperature, 60% methanol as extraction solvent, 0.6 g:10 mL sample mass:solvent ratio and 5 min extraction time, were established as optimal conditions. These mild conditions, combined with a rapid and efficient UHPLC analysis result in a practical and economical methodology for the extraction of psilocin and psilocybin from Psylocibe cubensis.

An Analysis of Biomechanical Parameters in OTP Police Physical Intervention Techniques for Occupational Risk Prevention.

(1) Background: a set of ergonomic parameters that are relevant for risk assessment methods for the prevention of occupational risks, such as REBA or NIOSH, have been measured by means of inertial sensors that allow capturing the movements of the human body. These methods base their assessment on a number of postural and dynamic parameters. In the case of police physical intervention techniques, trunk, legs, arms, forearms and wrists angles, joint contact force and sheer force at the L5-Pelvic junction, asymmetry (angle and factor), and muscle power are the more relevant parameters to be considered. (2) Method: The data have been collected by means of a motion capture suit equipped with 19 inertial sensors. The large amount of data and the 3-dimensional plots have been managed by a powerful software package specific for ergonomic analysis. The police physical intervention technique used was OTP. (3) Results: Five ergonomic parameters in a traditional police physical intervention technique have been analyzed. REBA scores and ergonomic metrics have been recorded and discussed with some prevention risk limits from the literature. (4) Conclusions: the usage of inertial sensors to capture the movements in OTPs provides a new and quite an efficient viewpoint for occupational risk research studies.

A Methodology Based on FT-IR Data Combined with Random Forest Model to Generate Spectralprints for the Characterization of High-Quality Vinegars.

Sherry wine vinegar is a Spanish gourmet product under Protected Designation of Origin (PDO). Before a vinegar can be labeled as Sherry vinegar, the product must meet certain requirements as established by its PDO, which, in this case, means that it has been produced following the traditional solera and criadera ageing system. The quality of the vinegar is determined by many factors such as the raw material, the acetification process or the aging system. For this reason, mainly producers, but also consumers, would benefit from the employment of effective analytical tools that allow precisely determining the origin and quality of vinegar. In the present study, a total of 48 Sherry vinegar samples manufactured from three different starting wines (Palomino Fino, Moscatel, and Pedro Ximénez wine) were analyzed by Fourier-transform infrared (FT-IR) spectroscopy. The spectroscopic data were combined with unsupervised exploratory techniques such as hierarchical cluster analysis (HCA) and principal component analysis (PCA), as well as other nonparametric supervised techniques, namely, support vector machine (SVM) and random forest (RF), for the characterization of the samples. The HCA and PCA results present a clear grouping trend of the vinegar samples according to their raw materials. SVM in combination with leave-one-out cross-validation (LOOCV) successfully classified 100% of the samples, according to the type of wine used for their production. The RF method allowed selecting the most important variables to develop the characteristic fingerprint ("spectralprint") of the vinegar samples according to their starting wine. Furthermore, the RF model reached 100% accuracy for both LOOCV and out-of-bag (OOB) sets.

Stabilization of expansive soils with biomass bottom ashes for an eco-efficient construction.

Green philosophy is gaining popularity worldwide. Recycling materials from building demolitions, reutilizing by-products from industrial facilities and exploring the potential uses of waste during a second life cycle are the objectives of this philosophy. In the present article, bottom ashes from electric power generation plants using biofuel combustion were evaluated to verify their potential use as expansive clay stabilizers. Two objectives are pursued: (1) finding a new use for waste that is typically landfilled despite its great potential arising from its technical properties and (2) improving the mechanical properties and reducing the expansive nature of the expansive clays identified during the construction of a motorway. Based on this framework, the present study demonstrated the potential of biomass bottom ashes to stabilize expansive clays. The optimum dosage to improve the properties of clays was determined based on performance parameters, such as plasticity, free swelling or soil collapse. Afterwards, the contaminating potential of ashes was evaluated, being classified as hazardous waste. However, the stabilized mixtures were classified as inert products, thus guaranteeing the environmental feasibility of their use. Finally, the technical application of the stabilized clays as filling materials for embankments and subgrade for light traffic roads was proved. Graphical abstract.

Optimization of a Novel Method Based on Ultrasound-Assisted Extraction for the Quantification of Anthocyanins and Total Phenolic Compounds in Blueberry Samples (Vaccinium corymbosum L.).

In recent years, consumers' preference for fruits such as blueberry has increased noticeably. This fact is probably related to their bioactive components such as anthocyanins, phenolic compounds, vitamins, minerals, and tannins that have been found in blueberries by the latest research studies. Both total anthocyanins (TA) and total phenolic compounds (TPC) are known for their multiple beneficial effects on our health, due to their anti-inflammatory, anti-oxidant, and anti-cancer properties. This is the reason why the development of new methodologies for the quality control analysis of raw materials or derived products from blueberry has a great relevance. Two ultrasound-assisted extraction methods (UAE) have been optimized for the quantification of TA and TPC in blueberry samples. The six variables to be optimized were: solvent composition, temperature, amplitude, cycle, extraction solvent pH, and sample/solvent ratio using response surface methodology. The optimized methods have proven to be suitable for the extraction of the TPC and TA with good precision (repeatability and intermediate precision) (coefficient of variation (CV) < 5%) and potentially for application in commercial samples. This fact, together with the multiple advantages of UAE, makes these methods a good alternative to be used in quality control analysis by both industries and laboratories.

Complete Real-Scale Application of Recycled Aggregates in a Port Loading Platform in Huelva, Spain.

The application of recycled aggregates (RA) from construction and demolition waste and crushed concrete blocks is a very important challenge for the coming years from the environmental point of view, in order to reduce the exploitation of natural resources. In Spain, the use of these recycled materials in the construction of road bases and sub-bases is growing significantly. However, presently, there are few studies focused on the properties and behavior of RA in civil works such as road sections or seaport platforms. In this work, two types of RA were studied and used in a complete real-scale application. Firstly, recycled concrete aggregates (RCA) were applied in the granular base layer under bituminous superficial layers, and secondly mixed recycled aggregates (MRA) which contain a mix of ceramic, asphalt, and concrete particles were applied in the granular subbase layer, under the base layer made with RCA. Both RA were applied in a port loading platform in Huelva, applying a 100% recycling rate. This civil engineering work complied with the technical requirements of the current Spanish legislation required for the use of conventional aggregates. The environmental benefits of this work have been very relevant, and it should encourage the application of MRA and RCA in civil engineering works such as port platforms in a much more extended way. This is the first and documented real-scale application of RA to completely build the base and sub-base of a platform in the Huelva Port, Spain, replacing 100% of natural aggregates with recycled ones.

A Legal and Forensic Medicine Approach to Police Physical Intervention Techniques in High-Risk Situations.

Background: The physical intervention techniques (PITs) typically used by the police in troublesome situations are examined in terms of injuring potential depending on whether they target a body zone of high, medium or low vulnerability. Based on legal and forensic considerations, and principles of congruence, opportunity and proportionality, a need exists to favor opponent locking and arrest techniques targeting non-vulnerable zones to minimize the risk of severe damage. Methods: A search of the training manuals for the different kind of law of enforcement officers was carried out. Revision of injuries was available from electronic databases of academic o medical journals. Results: Three different locking and arrest PITs based on operational tactical procedures (OTP) that avoid zones of high or medium vulnerability are proposed. The new techniques use blocking, diverting and grabbing of the upper and lower limbs, followed by dislocation and locking of the same targets. Conclusions: The damaging potential of such PITs was assessed in terms of anatomical region and most were found to have a high risk of severe damage. The alternative PITs proposed here, which rely on OTP, improve in legal and forensic medical terms on existing choices and dramatically reduce the risk of injuring arrestees.

Recommendations for the management of construction and demolition waste in treatment plants.

The construction and demolition waste is one of the heaviest and most voluminous waste streams generated in the European Union. It comprises approximately one third of the waste generated. Recycling this stream waste will provide ecological and sustainable benefits. The recycled aggregates from the construction and demolition waste are beginning to be used in civil construction, as substitutes for natural aggregates. The possible applications of recycled aggregates in the infrastructure construction projects will mainly depend on the quality of the recycled aggregates. This will be determined by the nature and the origin of the construction and demolition waste, and the treatment system used. It requires a comprehensive response by part of the processing agents, mainly construction and demolition companies, and above all public administrations. This work proposes recommendations for the handling of the construction and demolition waste, both in the demolition and in the treatment plants. A quality control system is suggested too.

Evaluation of the police operational tactical procedures for reducing officer injuries resulting from physical interventions in problematic arrests. The case of the Municipal Police of Cádiz (Spain).

OBJECTIVES: This paper describes some operational tactical procedures (OTP) and discusses the results of a 14-year-long study, spanning the period 2003-2016, conducted by the Municipal Police of Cádiz, Spain, which comprised 3 time periods: 2003-2006, when the officers were trained in traditional policing procedures; 2007-2013, when the officers were taught an innovative set of OTP in the form of a basic set of self-defense and arrest mechanisms, different from the traditional policing procedures that rely on martial arts and combat sports; and finally 2014-2016, when the OTP training was discontinued. The aim of this study was to improve policing and reduce officer injuries resulting from interventions in controversial or violent situations, such as problematic arrests. MATERIAL AND METHODS: The study involved 162 police officers and commanders of the Municipal Police of Cádiz, who were in street duty for their first time. There were 8 females and 154 males aged 24-55 years. Three OTP stages are shown as examples. RESULTS: Based on the analysis of "training hours" and "physical interventions in problematic arrests," the results were: 1) the number of sick leaves in the police was identical according to the number of arrests, and 2) data on sick leaves show remarkable differences among the 3 periods under analysis. CONCLUSIONS: The OTP-based training substantially reduced officer sick leaves. The overall reduction in sick leaves in the period 2007-2013 was observed that cannot be ascribed to a decrease in criminal acts, and hence in police physical interventions. Int J Occup Med Environ Health. 2020;33(1):35-43.

OTP-PRL: an app for occupational risk prevention in policing activities.

BACKGROUND: The rapid progress in information and communication technologies has promoted the development of smartphone applications (apps) for a wide variety of purposes including workplace safety. However, no specific apps for occupational risk prevention in the police domain seemingly exist as yet. In this work, an app running under the iOS and Android operating systems was developed to help police officers become acquainted with policing-related occupational risks and to prevent their damaging consequences. RESULTS: The proposed app, which uses an iterative user-centered design to avoid occupational risks in policing activities, was assessed for performance by a group of users and experts through a System Usability Scale (SUS) questionnaire. The mean overall score for the questionnaire was 82.3. The app has backend support to facilitate continual improvement through contributions from users and administrators. A field test revealed increased awareness of policing occupational risks after using the app in many users. CONCLUSIONS: A novel product that covers the needs of ORP requirements of police officers has been developed.

Long-term leaching and mechanical behaviour at recycled aggregate with different gypsum contents.

Construction and demolition recycling is regarded as an essential subject in the EU, as the target established by its policies to 2020 ratio is far from being achieved. The use of materials recycled from such waste has been widely deemed a contribution to the sustainability of the construction sector. Gypsum is one the limiting components of recycled aggregates used as a base layer in road construction. The aim of this research was to analyse the effect on mechanical properties, leaching behaviour and dimensional changes at long term in recycled aggregates with different gypsum contents. Load bearing capacity was conducted by California bearing ratio on prepared samples. Moreover, the compressive strength was conducted on samples prepared with a 3% cement addition. Both tests were studied long term. Dimensional changes were studied through swelling in California bearing ratio test mould under the modified Proctor conditions for 1 year and using an oedometer device for 5 months. Furthermore, environmental risk assessment was performed, classifying the material with gypsum addition as non-hazardous, given that sulphate anion was above the inert limit. Good mechanical behaviour in the long term and no significant dimensional changes were found regardless of gypsum content.

FT-IR, Vis spectroscopy, color and multivariate analysis for the control of ageing processes in distinctive Spanish wines.

During the ageing period, diverse physicochemical changes occur affecting the quality of the final product. For this reason, it is important to study and optimize this step. Fourier transform infrared (FT-IR) and UV-visible (UV-Vis) spectroscopic techniques combined with multivariate analysis were used to obtain regression models to correlate both spectroscopic data and chromatic parameters with the ageing level of high quality Sherry wines. Three spectral ranges were obtained that contain the highest variance: two different fingerprint ranges in FT-IR (1100-2000 cm-1 and 2300-2999 cm-1) and one range in the visible region (380-450 nm). The regression model has enabled full differentiation between the seven levels of ageing in the wine explored. A good linear regression fit (R2 above 0.95) was obtained regardless of the ranges used. The results demonstrate that both spectroscopic techniques can be used to optimize the ageing process in a simple and fast way.

An Electronic Nose Based Method for the Discrimination of Weathered Petroleum-Derived Products.

In recent years pollution due to hydrocarbon spills has increased markedly as a result of the numerous advances in technologies and industrial processes. Anthropogenic activities (accidental or illegal) are responsible for most of these incidents. In some cases, the spills are not detected at the moment they occur and the contaminants are subjected to different degradation phenomena that may change the chemical composition of the hydrocarbon over time. An incorrect or ineffective identification of the spill could lead to significant consequences, bearing in mind that most spills are hazardous to the environment. In the present work the capacity of the analytical technique based on the Electronic Nose (eNose) combined with chemometrics in the identification and discrimination of different weathered petroleum-derived products (PDPs) was studied. Different volumes (40 μL and 80 μL) of PDPs (gasoline, diesel, and paraffin) were poured onto different supports (wood, cork, paper, and cotton sheet) and subjected to a natural weathering process by evaporation for one month. The porosity of the support was also studied. The application of linear discriminant analysis allowed the full discrimination of the samples according to the presence/absence of PDP and a 97.7% of correct discrimination of the different PDPs regardless of the weathering time, support or volume used. The results show that the system is capable of detecting and discriminating the presence of petroleum-derived products in any of the situations studied.

Risk assessment by percolation leaching tests of extensive green roofs with fine fraction of mixed recycled aggregates from construction and demolition waste.

Extensive green roofs are urban construction systems that provide thermal regulation and sound proofing for the buildings involved, in addition to providing an urban heat island mitigation or water retention. On the other hand, policies towards reduction of energy consumption, a circular economy and sustainability are core in the European Union. Motivated by this, an experimental study was carried out to evaluate the environmental risk assessment according to release levels of polluting elements on leachates of different green roof substrate mixtures based on recycled aggregates from construction and demolition waste through (i) the performance in laboratory of two procedures: compliance and percolation tests and (ii) an upscaled experimental leaching test for long-term on-site prediction. Four plots were built on a building roof and covered with autochthonous Mediterranean plants in Córdoba, South of Spain. As growing substrate, four mixtures were used of a commercial growing substrate with different proportions of a fine mixed recycled aggregate ranging from 0 to 75% by volume. The results show that these mixtures were classified as non-hazardous materials according to legal limits of the Landfill Directive 2003/33/CE. The release levels registered in extensive green roofs were lower compared to the laboratory test data. This shows how laboratory conditions can overestimate the potential pollutant effect of these materials compared to actual conditions.

Study of the Weathering Process of Gasoline by eNose.

In a fire investigation the rapid detection of the presence of ignitable liquids like gasoline is of great importance as it allows appropriate treatment of the remains, the identification of prevention methods and detects the possible presence of an arsonist. In some cases, analysts cannot access the fire scene in the first few hours due to the dangers involved in the situation and, as a consequence, phenomena such as weathering start. Ignitable liquid weathering is an evaporation process that results in an increase in the abundance of non-volatile compounds relative to volatile compounds, and this process changes the chemical composition. In the present work, the weathering of samples of gasoline at different times (from 0 h to a month) has been studied using an electronic nose (eNose). The influence of the volume used (40 µL and 80 µL) and the type of support (cork, wood, paper and cotton sheet) has been studied. Chemometric tools have been used with the aim of ascertaining the weathering time for which the developed method is capable of detecting the presence of gasoline. The eNose was able to discriminate samples of weathered gasoline. The support used for the samples did not seem to have an influence on the detection and the system.

Upscaling the pollutant emission from mixed recycled aggregates under compaction for civil applications.

In general terms, plant managers of sites producing construction wastes assess materials according to concise, legally recommended leaching tests that do not consider the compaction stage of the materials when they are applied on-site. Thus, the tests do not account for the real on-site physical conditions of the recycled aggregates used in civil works (e.g., roads or embankments). This leads to errors in estimating the pollutant potential of these materials. For that reason, in the present research, an experimental procedure is designed as a leaching test for construction materials under compaction. The aim of this laboratory test (designed specifically for the granular materials used in civil engineering infrastructures) is to evaluate the release of pollutant elements when the recycled aggregate is tested at its commercial grain-size distribution and when the material is compacted under on-site conditions. Two recycled aggregates with different gypsum contents (0.95 and 2.57%) were used in this study. In addition to the designed leaching laboratory test, the conventional compliance leaching test and the Dutch percolation test were performed. The results of the new leaching method were compared with the conventional leaching test results. After analysis, the chromium and sulphate levels obtained from the newly designed test were lower than those obtained from the conventional leaching test, and these were considered more seriously pollutant elements. This result confirms that when the leaching behaviour is evaluated for construction aggregates without density alteration, crushing the aggregate and using only the finest fraction, as is done in the conventional test (which is an unrealistic situation for aggregates that are applied under on-site conditions), the leaching behaviour is not accurately assessed.

Characterization and Differentiation of Petroleum-Derived Products by E-Nose Fingerprints.

Characterization of petroleum-derived products is an area of continuing importance in environmental science, mainly related to fuel spills. In this study, a non-separative analytical method based on E-Nose (Electronic Nose) is presented as a rapid alternative for the characterization of several different petroleum-derived products including gasoline, diesel, aromatic solvents, and ethanol samples, which were poured onto different surfaces (wood, cork, and cotton). The working conditions about the headspace generation were 145 °C and 10 min. Mass spectroscopic data (45-200 m/z) combined with chemometric tools such as hierarchical cluster analysis (HCA), later principal component analysis (PCA), and finally linear discriminant analysis (LDA) allowed for a full discrimination of the samples. A characteristic fingerprint for each product can be used for discrimination or identification. The E-Nose can be considered as a green technique, and it is rapid and easy to use in routine analysis, thus providing a good alternative to currently used methods.

Complexation of sesquiterpene lactones with cyclodextrins: synthesis and effects on their activities on parasitic weeds.

Allelochemicals are safer, more selective and more active alternatives than synthetic agrochemicals for weed control. However, the low solubility of these compounds in aqueous media limits their use as agrochemicals. Herein, we propose the application of α-, ß- and γ-cyclodextrins to improve the physicochemical properties and biological activities of three sesquiterpene lactones: dehydrocostuslactone, costunolide and (-)-α-santonin. Complexation was achieved by kneading and coprecipitation methods. Aqueous solubility was increased in the range 100-4600% and the solubility-phase diagrams suggested that complex formation had been successful. The results of the PM3 semiempirical calculations were consistent with the experimental results. The activities on etiolated wheat coleoptiles, Standard Target Species and parasitic weeds were improved. Cyclodextrins preserved or enhanced the activity of the three sesquiterpene lactones. Free cyclodextrins did not show significant activity and therefore the enhancement in activity was due to complexation. These results are promising for applications in agrochemical design.

Authentication of virgin olive oil by a novel curve resolution approach combined with visible spectroscopy.

Adulteration of olive oil is not only a major economic fraud but can also have major health implications for consumers. In this study, a combination of visible spectroscopy with a novel multivariate curve resolution method (CR), principal component analysis (PCA) and linear discriminant analysis (LDA) is proposed for the authentication of virgin olive oil (VOO) samples. VOOs are well-known products with the typical properties of a two-component system due to the two main groups of compounds that contribute to the visible spectra (chlorophylls and carotenoids). Application of the proposed CR method to VOO samples provided the two pure-component spectra for the aforementioned families of compounds. A correlation study of the real spectra and the resolved component spectra was carried out for different types of oil samples (n=118). LDA using the correlation coefficients as variables to discriminate samples allowed the authentication of 95% of virgin olive oil samples.