Synthesis, Characterization, and Reactivity Studies of New Cyclam-Based Y(III) Complexes.

[(Bn2Cyclam)Y(N(SiMe3)2)] was prepared by reaction of H2Bn2Cyclam with Y[N(SiMe3)2]3. The protonation of the macrocycle ligand in [(Bn2Cyclam)Y(N(SiMe3)2)] is observed upon reaction with [HNMe3][BPh4] leading to the formation of [(HBn2Cyclam)Y(N(SiMe3)2)][BPh4]. DFT analysis of [(Bn2Cyclam)Y(N(SiMe3)2)] showed that the HOMO is located on the anionic nitrogen atoms of the cyclam ring indicating that protonation follows orbital control. Addition of H2Bn2Cyclam and H2(3,5-tBu2Bn)2Cyclam to a 1:3 mixture of YCl3 and LiCH2SiMe3 in THF resulted in the formation of [((C6H4CH2)BnCyclam)Y(THF)(µ-Cl)Li(THF)2] and [Y{(η3-3,5-tBu2Bn)2Cyclam}Li(THF)], respectively. The reaction of H23,5-tBu2Bn2Cyclam with Y(CH2SiMe3)3(THF)2 was studied and monitored by a temperature variation NMR experiment revealing the formation of [(3,5-tBu2Bn2Cyclam)Y(CH2SiMe3)]. Preliminary catalytic assays have shown that [Y{(η3-3,5-tBu2Bn)2Cyclam}Li(THF)] is a very efficient catalyst for the intramolecular hydroamination of 2,2-diphenyl-pent-4-enylamine.

Mobile and wearable technologies for the analysis of Ten Meter Walk Test: A concise systematic review.

Physical issues started to receive more attention due to the sedentary lifestyle prevalent in modern culture. The Ten Meter Walk Test allows measuring the person's capacity to walk along 10 m and analyzing the advancement of various medical procedures for ailments, including stroke. This systematic review is related to the use of mobile or wearable devices to measure physical parameters while administering the Ten Meter Walk Test for the analysis of the performance of the test. We applied the PRISMA methodology for searching the papers related to the Ten Meter Walk Test. Natural Language Processing (NLP) algorithms were used to automate the screening process. Various papers published in two decades from multiple scientific databases, including IEEE Xplore, Elsevier, Springer, EMBASE, SCOPUS, Multidisciplinary Digital Publishing Institute (MDPI), and PubMed Central were analyzed, focusing on various diseases, devices, features, and methods. The study reveals that chronometer and accelerometer sensors measuring spatiotemporal features are the most pertinent in the Gait characterization of most diseases. Likewise, all studies emphasized the close relation between the quality of the sensor's data obtained and the system's ultimate accuracy. In other words, calibration procedures are needed because of the body part where the sensor is worn and the type of sensor. In addition, using ambient sensors providing kinematic and kinetic features in conjunction with wearable sensors and consistently acquiring walking signals can enhance the system's performance. The most common weaknesses in the analyzed studies are the sample size and the unavailability of continuous monitoring devices for measuring the Ten Meter Walk Test.

Are Health Information Systems Ready for the Digital Transformation in Portugal? Challenges and Future Perspectives.

PURPOSE: This study aimed to reflect on the challenges of Health Information Systems in Portugal at a time when technologies enable the creation of new approaches and models for care provision, as well as to identify scenarios that may characterize this practice in the future. DESIGN/METHODOLOGY/APPROACH: A guiding research model was created based on an empirical study that was conducted using a qualitative method that integrated content analysis of strategic documents and semi-structured interviews with a sample of fourteen key actors in the health sector. FINDINGS: Results pointed to the existence of emerging technologies that may promote the development of Health Information Systems oriented to "health and well-being" in a preventive model logic and reinforce the social and management implications. ORIGINALITY/VALUE: The originality of this work resided in the empirical study carried out, which allowed us to analyze how the various actors look at the present and the future of Health Information Systems. There is also a lack of studies addressing this subject. RESEARCH LIMITATIONS/IMPLICATIONS: The main limitations resulted from a low, although representative, number of interviews and the fact that the interviews took place before the pandemic, so the digital transformation that was promoted was not reflected. Managerial implications and social implications: The study highlighted the need for greater commitment from decision makers, managers, healthcare providers, and citizens toward achieving improved digital literacy and health. Decision makers and managers must also agree on strategies to accelerate existing strategic plans and avoid their implementation at different paces.

Effects of temperature on the fitness of the alfalfa weevil (Hypera postica).

BACKGROUND: Temperature directly influences the survival, development and reproduction of insects and limits their biological activity. The alfalfa weevil (Hypera postica Gyllenhal) is a destructive pest of alfalfa crops in Spain and in most of the alfalfa production countries. The knowledge of how temperature affects the fitness of this pest can be used to predict its activity in current or forecasted environmental conditions and to develop more accurate control strategies. RESULTS: We evaluated the fitness of alfalfa weevil at eight constant temperatures (8-36 °C) at 4 °C intervals by using life tables and models for the description of temperature-dependent development rates. We found that most of the parameters we studied were temperature dependent. Development was observed at all temperatures. However, postembryonic survival was optimal at 16 °C but very low at 36 °C. Adults did not reproduce at 8, 32 or 36 °C. The highest fecundity and net reproductive rate were observed at 20 °C, but the highest intrinsic rate of increase occurred at 24 °C. We predicted the phenology of the pest based on the heat needed for development, the cumulative degree days from the beginning of October to the end of May, and the day length in the study region. CONCLUSION: Our prediction was validated using field data reporting the first occurrence of larval instars and adults, revealing that no more than two generations are possible within an annual cycle. In a hypothetical case where average monthly temperatures increase by 1-2 °C, the number of generations would not change. © 2022 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

The Influence of Planting Periods on Herbivore and Natural Enemy Abundance on Yellow Sticky Traps in Bt Maize Fields.

Knowledge of the insect densities during crop development is necessary for adopting appropriate measures for the control of insect pests and minimizing yield losses. Within integrated pest management programs, crop rotation has been carried out in recent years, but this current trend delays the planting period for Bt maize. The small amount of available information regarding the influence of sowing Bt maize early or late on the seasonal abundance of herbivores prompted us to study these aspects in two current common planting periods in northeastern Spain in 52 maize fields over three consecutive years. We sampled the fields planted on different dates with sticky yellow traps. Our results show that only the abundances of herbivore thrips, other than Frankliniella occidentalis, and Syrphidae were significantly different between the two planting periods. Moreover, when we performed yearly analyses, we found significant effects of the planting period on Coccinellidae and Chrysopidae in 2015 and on Aeolothrips sp. in 2016 and 2017. In most of the taxa, the abundance peaks in earlier growth stages, which is related to pollination (before or during). Only the abundances of Stethorus punctillum and Syrphidae peak later in the season. In addition, F. occidentalis, aphids, Syrphidae, and Coccinellidae registered higher abundance in fields sown in the late planting period. These results highlight the effects of sowing in different planting periods on insect dynamics in Bt maize and can be used to identify the abundance of certain pests and natural enemies in specific phenological stages of maize, which may allow producers to adopt better-integrated management and thus avoid reaching the level of economic damage.

Effects of Temperature and Relative Humidity on the Embryonic Development of Hypera postica Gyllenhal (Col.: Curculionidae).

The combined effect of the temperature and relative humidity on the survival and development time of the eggs of Spanish populations of the weevil Hypera postica, a key pest of alfalfa around the world, was evaluated under laboratory conditions. The experimental temperatures ranged from 8 to 36 °C, in 4 °C increments. Three relative humidity ranges were defined: high, medium, and low. Eggs of the alfalfa weevil successfully developed until larval emergence at all of the 24 conditions tested. However, the temperature and relative humidity affected the survival of the eggs. The egg developmental time decreased as the temperature increased from 8 to 32 °C, and the longest time was recorded at a low relative humidity (RH). The relationship between the development rate and temperature fit well to the lineal model for relative humidity. The minimum development threshold (T0) and the thermal requirement for egg development (K) ranged between 3 and 4 °C and 209 and 246 degree-days, respectively. According to these values and the occurrence of eggs and larvae (in winter) and adults (in autumn) in field samplings, the period of oviposition was determined. The results of the study contribute to better understanding the annual cycle and phenology of H. postica in the Iberian Peninsula and southern Europe.

CoII Cryptates Convert CO2 into CO and CH4 under Visible Light.

Three CoII octaazacryptates, with different substituents on the aromatic rings (Br, NO2 , CCH), were synthesised and characterised. These and the already published non-substituted cryptate catalysed CO2 photoreduction to CO and CH4 under blue visible light at room temperature. Although CO was observed after short irradiation times and a large range of catalyst concentrations, CH4 was only observed after longer irradiation periods, such as 30 h, but with a small catalyst concentration (25 nm). Experiments with 13 C labelled CO2 showed that CO is formed and reacts further when the reaction time is long. The CCH catalyst is deactivated faster than the others and the more efficient catalyst for CH4 production is the one with Br. This reactivity trend was explained by an energy decomposition analysis based on DFT calculations.

Cooperative Metal-Ligand Hydroamination Catalysis Supported by C-H Activation in Cyclam Zr(IV) Complexes.

Complexes of the type (R2Cyclam)ZrCl2 (where R = CH2═C(H)CH2 (All), CH2═C(Me)CH2 (MeAll), and PhCH2 (Bn)) react with suitable Grignard reagents to produce the corresponding alkyl derivatives (R2Cyclam)ZrR'2 (R' = Me, CH2Ph). Thermally induced double metalation of the pending arms of the cyclam ligand led to the formation of complexes ((CH═C(H)CH2)2Cyclam)Zr, 14, ((CH═C(Me)CH2)2Cyclam)Zr, 15, or ((C6H4CH2)2Cyclam)Zr, 16. These reactions proceed through C(sp2)-H bond activation and R'H elimination and convert the original dianionic tetracoordinated cyclam-based ligands in tetraanionic hexacoordinated ligands that establish two new Zr-C bonds. The cleavage of the Zr-C bonds may be readily achieved by treatment of the bis( ortho-metalated) species 16 with protic substrates ( tert-butanol, phenol, thiophenol, aniline, benzophenone hydrazone, pyrazole, and N, N'-diphenylhydrazine), to give rise to (Bn2Cyclam)ZrX2 complexes (X = OtBu, OPh, SPh, NHPh, NHNCPh2, C3H3N2, N, N'-PhNNPh). In catalytic conditions, complexes (All2Cyclam)Zr(NMe2)2, 14, 15, or 16 convert 2,2-diphenyl-pent-4-enylamine to 2-methyl-4,4-diphenylpyrrolidine with 100% selectivity and conversion values varying between 61 and 88% in 4.5 h, at 115 °C. Complexes 14 and 15, which display metalated allyl and methallyl pending groups on the cyclam ring, are the most active species (1.7 < TOF < 2.0 h-1). The mechanism of this reaction was studied by density functional theory that revealed two competitive paths, one proceeding through an imido intermediate and another that occurs via an amido ligand. Both cases represent cooperative mechanisms with active participation of the cyclam, as proton exchange between the coordinated substrate and the ligand side arm with reversible C-H activation is a crucial feature of the mechanism.

Prey Acceptability and Preference of Oenopia conglobata (Coleoptera: Coccinellidae), a Candidate for Biological Control in Urban Green Areas.

Oenopia conglobata is one of the most common ladybird species in urban green areas of the Mediterranean region. We have obtained data about its prey acceptability and prey preferences. In a laboratory experiment, we investigated the acceptability of seven aphid and one psyllid species as prey for this coccinellid: the aphids Chaitophorus populeti, Aphis gossypii, Aphis craccivoraMonelliopsis caryae, Eucallipterus tiliae, Aphis nerii (on white poplar, pomegranate, false acacia, black walnut, lime, and oleander, respectively), and the psyllid Acizziajamatonica on Persian silk tree. These species are abundant in urban green areas in the Mediterranean region. In addition, we tested the acceptability of Rhopalosiphum padi on barley, an aphid species easily reared in the laboratory. We also tested preferences of the predator in cafeteria experiments with three aphid species and one aphid and the psyllid. Adults and larvae of the coccinellid accepted all of the preys offered, except A. nerii, with a clear preference for M. caryae. The predator also showed preference for M. caryae when it was offered in a cafeteria experiment with other aphid species or with the psyllid. The aphid R. padi obtained a good acceptability and could be used for rearing O. conglobata in the laboratory.

GATA1-Deficient Dendritic Cells Display Impaired CCL21-Dependent Migration toward Lymph Nodes Due to Reduced Levels of Polysialic Acid.

Dendritic cells (DCs) play a pivotal role in the regulation of the immune response. DC development and activation is finely orchestrated through transcriptional programs. GATA1 transcription factor is required for murine DC development, and data suggest that it might be involved in the fine-tuning of the life span and function of activated DCs. We generated DC-specific Gata1 knockout mice (Gata1-KODC), which presented a 20% reduction of splenic DCs, partially explained by enhanced apoptosis. RNA sequencing analysis revealed a number of deregulated genes involved in cell survival, migration, and function. DC migration toward peripheral lymph nodes was impaired in Gata1-KODC mice. Migration assays performed in vitro showed that this defect was selective for CCL21, but not CCL19. Interestingly, we show that Gata1-KODC DCs have reduced polysialic acid levels on their surface, which is a known determinant for the proper migration of DCs toward CCL21.

IRF8 Transcription Factor Controls Survival and Function of Terminally Differentiated Conventional and Plasmacytoid Dendritic Cells, Respectively.

Interferon regulatory factor-8 (IRF8) has been proposed to be essential for development of monocytes, plasmacytoid dendritic cells (pDCs) and type 1 conventional dendritic cells (cDC1s) and remains highly expressed in differentiated DCs. Transcription factors that are required to maintain the identity of terminally differentiated cells are designated "terminal selectors." Using BM chimeras, conditional Irf8(fl/fl) mice and various promotors to target Cre recombinase to different stages of monocyte and DC development, we have identified IRF8 as a terminal selector of the cDC1 lineage controlling survival. In monocytes, IRF8 was necessary during early but not late development. Complete or late deletion of IRF8 had no effect on pDC development or survival but altered their phenotype and gene-expression profile leading to increased T cell stimulatory function but decreased type 1 interferon production. Thus, IRF8 differentially controls the survival and function of terminally differentiated monocytes, cDC1s, and pDCs.

Farm dust and endotoxin protect against allergy through A20 induction in lung epithelial cells.

Growing up on a dairy farm protects children from allergy, hay fever, and asthma. A mechanism linking exposure to this endotoxin (bacterial lipopolysaccharide)-rich environment with protection has remained elusive. Here we show that chronic exposure to low-dose endotoxin or farm dust protects mice from developing house dust mite (HDM)-induced asthma. Endotoxin reduced epithelial cell cytokines that activate dendritic cells (DCs), thus suppressing type 2 immunity to HDMs. Loss of the ubiquitin-modifying enzyme A20 in lung epithelium abolished the protective effect. A single-nucleotide polymorphism in the gene encoding A20 was associated with allergy and asthma risk in children growing up on farms. Thus, the farming environment protects from allergy by modifying the communication between barrier epithelial cells and DCs through A20 induction.

Mixed infection of Leishmania infantum and Leishmania braziliensis in rodents from endemic urban area of the New World.

BACKGROUND: In Brazil Leishmania braziliensis and L. infantum are the principal species responsible for cutaneous and visceral leishmaniases, respectively. Domestic dogs are the main reservoirs of visceral leishmaniasis, while rodents and marsupials are the main reservoirs for cutaneous leishmaniasis. It has also been suggested that dogs could play a role in transmission of cutaneous leishmaniasis. The identification of the species of Leishmania, the reservoirs, and the vectors involved in each particular transmission cycle is critical for the establishment of control activities. Belo Horizonte has emerged as an endemic region for leishmaniases, however, epidemiological studies assessing the contribution of wild reservoirs to transmission are scarce in the area. The aim of this study was to investigate Leishmania spp. infection in possible reservoirs of an urbanized area. RESULTS: A high rate of infection was found in small mammals (64.9%) and dogs (DG1 30.4% and DG2 48.6%). The presence of L. infantum and L. braziliensis was detected in small mammals and dogs, and mixed infections by both species were detected in rodents which, to the best of our knowledge, is the first description of this phenomenon in an urban area. Additionally, L. amazonensis was detected in the canine samples. CONCLUSION: The possible role of these animals as a source of infection of the vector of each species of Leishmania identified should not be overlooked and should be taken into account in future control activities. The results of mixed infection by L. braziliensis and L. infantum in cosmopolitan rodents as M. musculus and R. rattus, may have important implications in the context of the control of leishmaniasis in urban areas, especially when considering that these rodents live in close relationship with human dwellings, especially those in more precarious conditions.

Reactions of heteroallenes with cyclam-based Zr(IV) complexes.

This work describes reactions of heteroallenes with diamido-diamine cyclam-based Zr(iv) complexes of the general formula (Bn2Cyclam)ZrX2 (X = O(t)Bu, , O(i)Pr, , SPh, , NH(t)Bu, ) as well as the di-orthometallated species ((C6H4CH2)2Cyclam)Zr, . The reactions of isocyanates or isothiocyanates with , or resulted in the formation of N-bonded ureate or thioureate cyclam complexes upon [2 + 2] cycloaddition of the Zr-Namido bonds of the cyclam to the heteroallene (). DFT calculations showed that κ(2)-N,N'-ureate bonding is favoured over κ(2)-N,O-ureates, which in turn may be formed in reactions with bulky isocyanates as 1-naphthyl isocyanate (NpN[double bond, length as m-dash]C[double bond, length as m-dash]O). The reactions of with N,N'-cyclohexylcarbodiimide (CyN[double bond, length as m-dash]C[double bond, length as m-dash]NCy) and carbon disulfide afforded guanidinate and dithiocarbamate fragments, respectively, appended to one of the nitrogen atoms of the cyclam ligand. These reactions represent a reliable method for the synthesis of asymmetrically N-functionalized cyclams giving rise to C1 symmetry Zr(iv) species by addition of one equivalent of heteroallenes. The reaction of (Bn2Cyclam)Zr(NH(t)Bu)2, , with one equivalent of mesityl isocyanate (MesN[double bond, length as m-dash]C[double bond, length as m-dash]O) also proceeds through insertion, involving one Zr-NH(t)Bu bond. However, it was observed that the reaction of (Bn2Cyclam)Zr(NH(t)Bu)2, , with MesN[double bond, length as m-dash]C[double bond, length as m-dash]O follows a different path if the reaction is carried out at 60 °C. In this case the reaction leads to [2 + 2] addition of the Zr-Ncyclam bond to the isocyanate, with a concomitant occurrence of orthometallation of the one benzyl pending group of the cyclam ring. The reaction of (t)BuN[double bond, length as m-dash]C[double bond, length as m-dash]O with the di-orthometallated complex ((C6H4CH2)2Cyclam)Zr, , also gave a κ(2)-N,N'-ureate fragment, by isocyanate addition to the macrocycle. DFT calculations on these systems were conducted in an attempt to rationalise the reactivity patterns observed.

Innate immune cells in asthma.

Asthma is an inflammatory disease of the airways associated with a T helper (Th)2 response. Such a response in the lungs requires complex interactions between innate cells and structural cells. Dendritic cells (DCs) are pivotal during sensitization to allergens but clearly require epithelium-derived signals to become activated. Epithelial cells also contribute to the activation and the survival of mast cells (MCs), basophils, and eosinophils and group 2 innate lymphoid cells (ILC2s). In turn, these innate cells can activate DCs to sustain Th2 immunity. Here, we review the role played by these different populations of immune cells in the pathogenesis of asthma and how they interact to orchestrate Th2 immunity.

Toward the understanding of radical reactions: experimental and computational studies of titanium(III) diamine bis(phenolate) complexes.

Radical reactions of titanium(III) [Ti((tBu2)O2NN')Cl(S)] (S = THF, 1; S = py, 2; (tBu2)O2NN' = Me2N(CH2)2N(CH2-2-O-3,5-(t)Bu2C6H2)2) are described. Reactions with neutral electron acceptors led to metal oxidation to Ti(IV), [Ti((tBu2)O2NN')Cl(TEMPO)] (4) being formed with the TEMPO radical and [Ti((tBu2)O2NN')Cl2] (9) with PhN═NPh. [Ti((tBu2)O2NN')Cl2] was also formed when [Ti((tBu2)O2NN')Cl(S)] was oxidized by [Cp2Fe][BPh4], but the [Cp2Fe][PF6] analogue yielded [Ti((tBu2)O2NN')ClF] (8). The reactions of [Ti((tBu2)O2NN')Cl(S)] with O2 gave [Ti((tBu2)O2NN')Cl]2(µ-O) (3). The DFT calculated Gibbs energy for the above reaction showed it to be exergonic (ΔG298 = -123.6 kcal·mol(-1)). [Ti((tBu2)O2NN')(CH2Ph)(S)] (S = THF, 5; py, 6) are not stable in solution for long periods and in diethyl ether gave 1:1 cocrystals of [Ti((tBu2)O2NN')(CH2Ph)2] (7) and [Ti((tBu2)O2NN')Cl]2(µ-O) (3), most probably resulting from a disproportionation process of titanium(III) followed by oxygen abstraction by the resulting Ti(II) species. The oxidation of [Ti((tBu2)O2NN')(κ(2)-{CH2-2-(NMe2)-C6H4})] (10), which is a Ti(III) benzyl stabilized by the intramolecular coordination of the NMe2 moiety, led to a complex mixture. Recrystallization of this mixture under air led to a 1:1 cocrystal of two coordination isomers of the titanium oxo dimer (3). In one of these isomers, one metal is pentacoordinate and the dimethylamine moiety of the diamine bis(phenolate) ligand is not bonded to the metal, displaying a coordination mode of the ligand never observed before. The other titanium center is distorted octahedral with two cis-phenolate moieties. In the second unit, the coordination of the two ancillary ligands to the titanium centers reveals mutually cis-phenolate groups in one-half of the molecule and trans-coordinated in the other titanium center, keeping a distorted octahedral environment around each titanium.

Conventional and monocyte-derived CD11b(+) dendritic cells initiate and maintain T helper 2 cell-mediated immunity to house dust mite allergen.

Dendritic cells (DCs) are crucial for mounting allergic airway inflammation, but it is unclear which subset of DCs performs this task. By using CD64 and MAR-1 staining, we reliably separated CD11b(+) monocyte-derived DCs (moDCs) from conventional DCs (cDCs) and studied antigen uptake, migration, and presentation assays of lung and lymph node (LN) DCs in response to inhaled house dust mite (HDM). Mainly CD11b(+) cDCs but not CD103(+) cDCs induced T helper 2 (Th2) cell immunity in HDM-specific T cells in vitro and asthma in vivo. Studies in Flt3l(-/-) mice, lacking all cDCs, revealed that moDCs were also sufficient to induce Th2 cell-mediated immunity but only when high-dose HDM was given. The main function of moDCs was the production of proinflammatory chemokines and allergen presentation in the lung during challenge. Thus, we have identified migratory CD11b(+) cDCs as the principal subset inducing Th2 cell-mediated immunity in the LN, whereas moDCs orchestrate allergic inflammation in the lung.

European pharmacy students' experience with virtual patient technology.

OBJECTIVE: To describe how virtual patients are being used to simulate real-life clinical scenarios in undergraduate pharmacy education in Europe. METHODS: One hundred ninety-four participants at the 2011 Congress of the European Pharmaceutical Students Association (EPSA) completed an exploratory cross-sectional survey instrument. RESULTS: Of the 46 universities and 23 countries represented at the EPSA Congress, only 12 students from 6 universities in 6 different countries reported having experience with virtual patient technology. The students were satisfied with the virtual patient technology and considered it more useful as a teaching and learning tool than an assessment tool. Respondents who had not used virtual patient technology expressed support regarding its potential benefits in pharmacy education. French and Dutch students were significantly less interested in virtual patient technology than were their counterparts from other European countries. CONCLUSION: The limited use of virtual patients in pharmacy education in Europe suggests the need for initiatives to increase the use of virtual patient technology and the benefits of computer-assisted learning in pharmacy education.