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The intimate relationships of the older population have seldom been analyzed from a sociological perspective. This study provides novel information on what is desired in a partner after the age of 50 in Spain. The academic debate on this topic has been limited. Therefore, the contribution of this article is mainly an exploration of the empirical data. The database used is the Spanish General Social Survey prepared by the Sociological Research Center. The results indicate that personality is the most valued factor, followed by values and physical appearance. The variables with the greatest explanatory power in the estimated multinomial logit model are age, sex, level of education and cohabitation status. Educational homogamy appears among those with higher levels of education, with men more interested in physical appearance and women more interested in values and education. These last two characteristics are also more highly valued among those who are older. [ABSTRACT FROM AUTHOR]

Introduction The addition of ultrasound-guided percutaneous cryoanalgesia (PCr) for pain management after pectus excavatum (PE) surgery offers a new and advantageous approach. Our aim is to describe our experience with PCr applied on the same day, 24 hours, and 48 hours prior to PE surgery. Material and Methods Prospective pilot study in patients undergoing ultrasound-guided PCr (2019–2022) was divided into three groups: PCr on the same day of surgery (PCrSD), PCr 24 hours before (PCr24), and PCr 48 hours before (PCr48). We describe the application of technique and data obtained by comparing the three groups. Results We present 42 patients (25 PCrSD, 11 PCr24, 6 PCr48). PCr24 had a shorter procedure duration than PCrSD (65.8 vs. 91.2 minute; p = 0.048). Related to analgesia, PCr24 and PCr48 showed lower opioid consumption than PCrSD in PCA volume (48.5 and 49.6 vs. 75.1 mL; p = 0.015) and PCA time (23.3 and 23.8 vs. 34.3 hours; p = 0.01). Degree of pain (VAS scale) on the day of surgery and on the second postoperative day was lower in PCr24 and PCr48 than in PCrSD (4 and 2 vs. 5; p = 0.012; 0 and 1 vs. 2; p = 0.01, respectively) as well as shorter hospital stay (3 and 3.5 vs. 5 days; p = 0.021). In addition, PCr24 showed lower opioid consumption and hospital stay than PCr48 (p > 0.05). The greatest savings in hospital costs were obtained in the PCr24 group. Conclusion PCr48 and PCr24 prior to PE surgery offers lower opioid consumption, less pain and shorter hospital stay than PCrSD. PCr24 is comparable to PCr48, but seems to show advantages and simpler logistics for the patient and the hospital. [ABSTRACT FROM AUTHOR]

The narrative about swimmers in Subacuática, by Melina Pogorelsky; El interior afuera, by María Lobo, and Sodio, by Jorge Consiglio, rethink the relationship between the experience of water and the practice of writing often analyzed in studies on regionalism and other literatures of the natural. The difference is that these aquatic spaces are swimming pools located in an urban environment. If writing occurs in relation to place, space and material; its form and process change along with the spatial conditions and characteristics. The question that guides the analysis of the three swimming novels is about the narrative that the motion in and with the water of the pool produces. On the one hand, what stories the swimmers tell about the material experience of the body in water. On the other, how the bodily intersection between "closed water" and swimmers affects the materiality of writing. In a preliminary way, it can be established that, just as the body in water is the place of a transformation or a passage, writing is modified in search of ways to account for the experience of the fluid. [ABSTRACT FROM AUTHOR]

Introduction:  In recent years, pain protocols for pectus excavatum (PE) have incorporated cryoanalgesia through thoracoscopic approach. Since 2019, ultrasound-guided percutaneous cryoanalgesia (PCr) has been applied at our institution, either on the same day as the Nuss procedure or 48 hours before surgery. We carried out a preliminary retrospective review of patients with PE in whom PCr prior to surgery was performed at our institution between 2019 and 2021.Materials and Methods:  Two groups were evaluated: PCr on the same day (PCrSD) and PCr 48 hours before surgery (PCr48). Despite PCr, patients were treated with "patient-controlled analgesia" (PCA) with opioids for at least 24 hours, switching to conventional intravenous analgesia and oral analgesia in the following days. Demographic, clinical-radiological variables, PCA opioid use, pain grade according to the visual analog scale (VAS), and length of stay (LOS) were compared between the groups. A total of 20 patients were included (12 with PCrSD and 8 with PCr48), without significant differences in demographics or clinical-radiological variables. The overall median time of PCr was 65 minutes (55-127), with no differences between the groups.Results:  PCr48 group presented with significantly lower median number of hours of continuous PCA (24 vs. 32 hours; p = 0.031), lower median number of rescue boluses (11 vs. 18; p = 0.042), lower median VAS in the early postoperative hours (2 vs. 5.5; p = 0.043), and lower median LOS (3.5 vs. 5 days).Conclusion:  PCr performed 48 hours prior to surgery is more effective in terms of PCA requirements, VAS, and LOS when compared with cryoanalgesia on the same day. [ABSTRACT FROM AUTHOR]

The ability to understand and predict ambident reactivity is key to the rational design of organic syntheses. An approach to understand trends in ambident reactivity is the hard and soft acids and bases (HSAB) principle. The recent controversy over the general validity of this principle prompted us to investigate the competing gas‐phase SN2 reaction channels of archetypal ambident nucleophiles CN−, OCN−, and SCN− with CH3Cl (SN2@C) and SiH3Cl (SN2@Si), using DFT calculations. Our combined analyses highlight the inability of the HSAB principle to correctly predict the reactivity trends of these simple, model reactions. Instead, we have successfully traced reactivity trends to the canonical orbital‐interaction mechanism and the resulting nucleophile–substrate interaction energy. The HOMO–LUMO orbital interactions set the trend in both SN2@C and SN2@Si reactions. We provide simple rules for predicting the ambident reactivity of nucleophiles based on our Kohn–Sham molecular orbital analysis. [ABSTRACT FROM AUTHOR]

This study analyzes the complementarity of foreign technology acquired under license agreements, technology embedded in machinery and equipment and increase in a company’s productive capacity. We use panel data on Brazilian manufacturing companies from the World Bank Surveys. We used the random effects models, estimated by maximum likelihood. The results indicate that foreign technology, embedded technology and increase of productive capacity have a positive and significant impact on labor productivity. The complementarity test reveals that the relationship between the two technologies analyzed is conditionally substitutive and that the relationship between each of these technologies and increase of productive capacity is conditionally complementary. [ABSTRACT FROM AUTHOR]

Alkaline earth metal amides (AeN′′2: Ae=Ca, Sr, Ba, N′′=N(SiMe3)2) catalyze alkene hydrogenation (80–120 °C, 1–6 bar H2, 1–10 mol % cat.), with the activity increasing with metal size. Various activated C=C bonds (styrene, p‐MeO‐styrene, α‐Me‐styrene, Ph2C=CH2, trans‐stilbene, cyclohexadiene, 1‐Ph‐cyclohexene), semi‐activated C=C bonds (Me3SiCH=CH2, norbornadiene), or non‐activated (isolated) C=C bonds (norbornene, 4‐vinylcyclohexene, 1‐hexene) could be reduced. The results show that neutral Ca or Ba catalysts are active in the challenging hydrogenation of isolated double bonds. For activated alkenes (e.g. styrene), polymerization is fully suppressed due to fast protonation of the highly reactive benzyl intermediate by N′′H (formed in the catalyst initiation). Using cyclohexadiene as the H source, the first Ae metal catalyzed H‐transfer hydrogenation is reported. DFT calculations on styrene hydrogenation using CaN′′2 show that styrene oligomerization competes with styrene hydrogenation. Calculations also show that protonation of the benzylcalcium intermediate with N′′H is a low‐energy escape route, thus avoiding oligomerization. Keep it simple: The widely used, easily accessible, alkaline earth metal amides M(NR2)2 (M=Ca, Sr, Ba, R=SiMe3) are highly active alkene hydrogenation catalysts. Alkene oligomerization is fully suppressed by trapping the reactive intermediate with R2NH. A first example of Group 2 metal hydrogen transfer catalysis is given. [ABSTRACT FROM AUTHOR]

Alkaline earth metal amides (AeN′′2: Ae=Ca, Sr, Ba, N′′=N(SiMe3)2) catalyze alkene hydrogenation (80–120 °C, 1–6 bar H2, 1–10 mol % cat.), with the activity increasing with metal size. Various activated C=C bonds (styrene, p‐MeO‐styrene, α‐Me‐styrene, Ph2C=CH2, trans‐stilbene, cyclohexadiene, 1‐Ph‐cyclohexene), semi‐activated C=C bonds (Me3SiCH=CH2, norbornadiene), or non‐activated (isolated) C=C bonds (norbornene, 4‐vinylcyclohexene, 1‐hexene) could be reduced. The results show that neutral Ca or Ba catalysts are active in the challenging hydrogenation of isolated double bonds. For activated alkenes (e.g. styrene), polymerization is fully suppressed due to fast protonation of the highly reactive benzyl intermediate by N′′H (formed in the catalyst initiation). Using cyclohexadiene as the H source, the first Ae metal catalyzed H‐transfer hydrogenation is reported. DFT calculations on styrene hydrogenation using CaN′′2 show that styrene oligomerization competes with styrene hydrogenation. Calculations also show that protonation of the benzylcalcium intermediate with N′′H is a low‐energy escape route, thus avoiding oligomerization. [ABSTRACT FROM AUTHOR]

The reduction of N,C,N-chelated antimony(III) chlorides [C6H3-2,6-(CH=NR)2]SbCl2 (R=Ph ( 1), tBu ( 2), Dip ( 3); Dip=2,6- iPr2C6H3) with an appropriate amount of KC8 or Li[AlH4] resulted in the formation of rare examples of monomeric stibinidenes [C6H3-2,6-(CH=NR)2]Sb (R=Ph ( 4), tBu ( 5), Dip ( 6)). Similarly, the reduction of compounds 1 or 2 by two equivalents of K[B( sBu)3H] led to the stibinidenes 4 and 5. In contrast, the analogous reaction of compound 3 resulted in the formation of an unprecedented stibinidene [C6H3-2-(CH=NR)-6-(CH2NHR)]Sb ( 7) (R=Dip), in which the hydrogen atoms that come from the K[B( sBu)3H] are incorporated into the ligand backbone. To gain further insight into this intriguing reactivity with K[B( sBu)3H] and to assess the influence of the substitution at both the antimony atom and pendant substituents, we prepared compounds [C6H3-2-(CH=NDip)]Sb(Ph)Cl ( 8) and [C6H2-2-(CH=NDip)-4,6-( tBu)2]SbCl2 ( 9). The treatment of compound 8 with K[B( sBu)3H] smoothly led to the 1-Ph-2-Dip-1 H-2,1-benzazastibole ( 11), whereas the reaction of compound 9 with K[B( sBu)3H] resulted in either tBu-substituted 1-Cl-2-Dip-1 H-2,1-benzazastibole ( 13) or the formation of unprecedented Sb−Sb dimer bis(2-Dip-1 H-2,1-benzazastibole) ( 12) depending on the reaction stoichiometry. The miscellaneous reactivity of antimony(III) precursors with reducing agents together with the structure and bonding of the resulting products has also been investigated from a theoretical point of view. [ABSTRACT FROM AUTHOR]

This study analyzes the relationship between labor productivity, radical innovation, incremental innovation, embodied technology in machinery and equipment, utilization of production capacity and training. The data used are from Spanish companies, manufacturing and services, and have been collected by the Business Environment and Enterprise Performance Survey (BEEPS). The technique used to estimate the coefficients of the model is the ordinary least square regression, since the dependent variable (labor productivity) is continuous. The results indicate that radical innovation and training have a significant positive impact on labor productivity. The influence of embodied technology is also significant, but of negative sign. Finally, note that the companies that export and larger achieve higher levels of productivity. The findings of this study have implications for responsible for economic policy. Spanish policy makers should promote and subsidize the purchase of machinery and equipment more efficient for companies that achieve lower levels of productivity, and subsidize the training of workers in the management of these new equipments. They must also promote and subsidize the development of activities high in R&D for companies that achieve high levels of productivity, to increase their performance in radical innovation. The promotion and subsidization of training programs related to R&D is also essential in this type of companies, especially in a scenario characterized by an intense and rapid technological change. [ABSTRACT FROM AUTHOR]

The reaction of stibinidene and bismuthinidene ArM [where Ar=C6H3-2,6-(CH=N tBu)2; M=Sb ( 1), Bi ( 2)] with transition metal (TM) carbonyls Co2(CO)8 and Mn2(CO)10 produced unprecedented ionic complexes [(ArM)2Co(CO)3]+[Co(CO)4]− and [(ArM)2Mn(CO)4]+[Mn(CO)5]− [where M=Sb ( 3, 5), Bi ( 4, 6)]. The pnictinidenes 1 and 2 behaved as two-electron donors in this set of compounds. Besides the M→TM bonds, the topological analysis also revealed a number of secondary interactions contributing to the stabilization of cationic parts of titled complexes. [ABSTRACT FROM AUTHOR]

This research investigates individual expectations of economic support from different sources: partner, family, friends and formal help. Using data from the International Social Survey Programme (ISSP) the study compares Norway, as representative of the Scandinavian model, and Spain, as representative of the Mediterranean model. The findings confirm that family plays a more important role as a source of economic support in Spain while formal help is far more important in Norway. Moreover, gender and life course have a significant impact on expectations of economic support in both countries, although the differences do not go in the same direction. Women expect more financial support from their partners than men do in Norway, while Spanish women tend to rely more on support from their families. Regarding life course, although expectations of economic support from the family are higher for young and older people in both countries, the life-cycle effect is stronger in Spain. [ABSTRACT FROM AUTHOR]

The heretofore unpredictable behavior of [26] and [28]hexaphyrins upon metalation has been elucidated through quantum chemical calculations. It is demonstrated that the molecular topology of Group 10 and Group 11 metal complexes of hexaphyrins depends on sensitive interplay between the intrinsic ligand strain and the metal-ligand interaction strength. As such, the aromaticity of the ligand and effective charge of the metal are revealed as key factors determining the binding mode and the preference for Möbius or Hückel structures. These findings offer a new perspective to rationalize experimental observations for metalated hexaphyrins. More importantly, the proposed guidelines could be useful for designing novel complexes of hexaphyrins, such as a hitherto unknown Möbius [26]hexaphyrin complex. [ABSTRACT FROM AUTHOR]

The reduction of N,C,N-chelated bismuth chlorides [C6H3-2,6-(CHNR)2]BiCl2 [where R= tBu ( 1), 2′,6′-Me2C6H3 ( 2), or 4′-Me2NC6H4 ( 3)] or N,C-chelated analogues [C6H2-2-(CHN-2′,6′- iPr2C6H3)-4,6-( tBu)2]BiCl2 ( 4) and [C6H2-2-(CH2NEt2)-4,6-( tBu)2]BiCl2 ( 5) is reported. Reduction of compounds 1- 3 gave monomeric N,C,N-chelated bismuthinidenes [C6H3-2,6-(CHNR)2]Bi [where R= tBu ( 6), 2′,6′-Me2C6H3 ( 7) or 4′-Me2NC6H4 ( 8)]. Similarly, the reduction of 4 led to the isolation of the compound [C6H2-2-(CHN-2′,6′- iPr2C6H3)-4,6-( tBu)2]Bi ( 9) as an unprecedented two-coordinated bismuthinidene that has been structurally characterized. In contrast, the dibismuthene {[C6H2-2-(CH2NEt2)-4,6-( tBu)2]Bi}2 ( 10) was obtained by the reduction of 5. Compounds 6- 10 were characterized by using 1H and 13C NMR spectroscopy and their structures, except for 7, were determined with the help of single-crystal X-ray diffraction analysis. It is clear that the structure of the reduced products (bismuthinidene versus dibismuthene) is ligand-dependent and particularly influenced by the strength of the N→Bi intramolecular interaction(s). Therefore, a theoretical survey describing the bonding situation in the studied compounds and related bismuth(I) systems is included. Importantly, we found that the C3NBi chelating ring in the two-coordinated bismuthinidene 9 exhibits significant aromatic character by delocalization of the bismuth lone pair. [ABSTRACT FROM AUTHOR]

Enteromyxum scophthalmi is a myxozoan parasite that causes severe parasitic diseases in cultured turbot affecting mainly the intestine of the host. It is characterized by producing acute enteritis, starvation and eventually death. Current diagnosis of E. scopthalmi use traditional techniques, based on the identification of the morphology of the parasite. These techniques take extended time to be carried out and do not favour the adoption of control measure at turbot farms and require the sacrifice of fish. This study develops a fast real-time PCR molecular tool for the detection of E. scophthalmi in infected farmed turbot. This methodology is applicable for routine controls on the farm at every stage of the parasite infection. Results of the study demonstrate the robustness, specificity, efficiency and reliability of the technique. In addition, this study also provides a non-invasive procedure of sampling through swaps. This allows control, prevention and diagnosis of the parasite infection at turbot farms while maintaining the welfare of the cultivated fish and avoiding sacrifice of the fish sampled. [ABSTRACT FROM AUTHOR]

The increasing maturity of information technologies (IT) in hospitals and their infrastructure development is improving the quality and efficiency of healthcare services. In these circumstances, an investigation of the diffusion of IT in this context would provide some insight into adopters’ behaviours and further the diffusion of IT in the near future. The purpose of this paper is to conduct an investigation of the diffusion of IT’s innovations in hospitals. Technology acceptance model and innovation diffusion theory have been applied in this research trying to find factors that permit an effective discrimination between early and late adopters. The differences in characteristics between these two categories are assessed and implications based on the research findings are discussed. [ABSTRACT FROM PUBLISHER]

The article presents case study of a 28-year-old man immigrant who was admitted to a hospital for progressive thickening of the scrotum and prepuce that he suffered a tank-related injury. The patient then underwent medical examination which revealed paraffinoma, a secondary sclerosing lipogranuloma in his penile and scrotal. The article also discusses the etiology and treatment of paraffinoma among patients.

Noncovalent interactions involving aromatic rings, such as π-stacking and CH/π interactions, are central to many areas of modern chemistry. However, recent studies proved that aromaticity is not required for stacking interactions, since similar interaction energies were computed for several aromatic and aliphatic dimers. Herein, the nature and origin of π/π, σ/σ, and σ/π dispersion interactions has been investigated by using dispersion-corrected density functional theory, energy decomposition analysis, and the recently developed noncovalent interaction (NCI) method. Our analysis shows that π/π and σ/σ stacking interactions are equally important for the benzene and cyclohexane dimers, explaining why both compounds have similar boiling points. Also, similar dispersion forces are found in the benzene⋅⋅⋅methane and cyclohexane⋅⋅⋅methane complexes. However, for systems larger than naphthalene, there are enhanced stacking interactions in the aromatic dimers adopting a parallel-displaced configuration compared to the analogous saturated systems. Although dispersion plays a decisive role in stabilizing all the complexes, the origin of the π/π, σ/σ, and σ/π interactions is different. The NCI method reveals that the dispersion interactions between the hydrogen atoms are responsible for the surprisingly strong aliphatic interactions. Moreover, whereas σ/σ and σ/π interactions are local, the π/π stacking are inherently delocalized, which give rise to a non-additive effect. These new types of dispersion interactions between saturated groups can be exploited in the rational design of novel carbon materials. [ABSTRACT FROM AUTHOR]

meso-Substituted pentaphyrins(1.1.1.1.1) were unexpectedly isolated as N-fused species under Rothemund-type conditions. The reaction mechanism is unknown at present, but the first example of a nonfused [22]pentaphyrin was reported in 2012. Here, the conformational preferences and N-fusion reaction of [22]- and [24]pentaphyrins have been investigated using density functional calculations, together with their aromaticity-molecular topology relationships. Two global minima are found for the unsubstituted [22]pentaphyrin corresponding to T0 and T04,D Hückel structures. Möbius transition states are located in the interconversion pathways with activation barriers of 27 kcal mol-1. Conversely, [24]pentaphyrin is able to switch between Hückel and Möbius conformers with very low activation barriers. However, nonfused [24]pentaphyrins are unstable and spontaneously undergo an N-fusion reaction driven by the strain release. On the contrary, nonfused [22]pentaphyrins could be isolated if a T04,D conformation is adopted. Importantly, conformational control of pentaphyrins can be achieved by meso-substituents. Two stable conformations (T04,D and T04,D) are found for the nonfused [22]pentaphyrin, which are delicately balanced by the number of substituents. The T04,D conformation is preferred by fully meso-aryl pentaphyrins, which is converted to the N-fused species. Interestingly, the removal of one aryl group prevents the N-fusion reaction, providing stable aromatic nonfused [22]pentaphyrins in excellent agreement with the experimental results. [ABSTRACT FROM AUTHOR]

The switching of topology between 'figure-eight', Möbius, and untwisted conformations in [32]heptaphyrins(1.1.1.1.1.1.1) has been investigated by using density functional theory calculations. Such a change is achieved by variation of one internal dihedral angle and, if properly controlled, can provide access to molecular switches with unique optical and magnetic properties. In this work, we have explored different conformational control methods, such as solvent, protonation and meso substituents. Despite its antiaromatic character, most of the [32]heptaphyrins (R=H, CH3, CF3, Ph, C6F5) adopt a figure-eight conformation in the neutral state, owing to their more-effective hydrogen-bonding interactions. The aromatic Möbius topology is only preferred with dichlorophenyl groups, which minimize the steric hindrance that arises from the bulky chlorine atoms. The conformational equilibrium is sensitive to the solvent, so polar solvents, such as DMSO, further stabilize the Möbius conformation. Protonation induces a conformational change into the Möbius topology, irrespective of the meso-aryl groups. In the triprotonated species, the conformational switch is blocked and a non-twisted conformer becomes much more stable than the figure-eight conformation. We have shown that the relative energies of the protonated [32]heptaphyrins are dominated by aromaticity. Importantly, this topology switching induces a dramatic change in the magnetic properties and reactivity of the macrocycles, as revealed by several energetic, magnetic, structural, and reactivity indices of aromaticity. [ABSTRACT FROM AUTHOR]

Microalgae are the main component of first tropic level in aquatic food chain; it is for this reason that they are used as food in aquaculture. Also due to its biotechnological potential properties, they are used in the production of diverse components, dyes, antioxidants, enzymes, emulsifiers, etc. The extended ways of microalgae applications require physiologically and genetically stable cultures as well as correctly identified organisms to guarantee reproducibility and reliability. But the variety of species and the morphological similarity between some of them make difficult the identification of some microalgae. The use of molecular markers has supplied a very useful tool for identification of microalgae in fast mode, such as in classification. The present study has worked on the molecular characterization of main species of microalgae used in aquaculture in base of the molecular markers 18S rRNA and 16S rRNA. Microalgae DNA has been amplified and sequenced, and the resultant sequences were analyzed and reflected in phylogenetic trees. The phylogenetic analyses obtained reflect as both molecular markers allow to differentiate the main genus used in aquaculture. [ABSTRACT FROM AUTHOR]

Recently, hexaphyrins have emerged as a promising class of π-conjugated molecules that display a range of interesting electronic, optical, and conformational properties, including the formation of stable Möbius aromatic systems. Besides the Möbius topology, hexaphyrins can adopt a variety of conformations with Hückel and twisted Hückel topologies, which can be interconverted under certain conditions. To determine the optimum conditions for viable Möbius topologies, the conformational preferences of [26]- and [28]hexaphyrins and the dynamic interconversion between the Möbius and Hückel topologies were investigated by density functional calculations. In the absence of meso substituents, [26]hexaphyrin prefers a planar dumbbell conformation, strongly aromatic and relatively strain free. The Möbius topology is highly improbable: the most stable tautomer is 33 kcal mol−1 higher in energy than the global minimum. On the other hand, the Möbius conformer of [28]hexaphyrin is only 6.5 kcal mol−1 higher in energy than the most stable dumbbell conformation. This marked difference is due to aromatic stabilization in the Möbius 4 n electron macrocycle as opposed to antiaromatic destabilization in the 4 n+2 electron system, as revealed by several energetic, magnetic, structural, and reactivity indices of aromaticity. For [28]hexaphyrins, the computed activation barrier for interconversion between the Möbius aromatic and Hückel antiaromatic conformers ranges from 7.2 to 10.2 kcal mol−1, in very good agreement with the available experimental data. The conformation of the hexaphyrin macrocycle is strongly dependent on oxidation state and solvent, and this feature creates a promising platform for the development of molecular switches. [ABSTRACT FROM AUTHOR]

The main goal of this article is to understand social support models in Spain from the perspective of an individual facing a situation of need, whether domestic, economic or emotional. The data used come from the 2001 ‘Social Networks II’ survey of the International Social Survey Programme (ISSP). The study shows clear family-oriented models of preference, primarily between the closest members of the nuclear family of origin. The partner is especially important when domestic and emotional help are required, but parents come first when the need is economic. People’s behaviour also shows both traces of the more recent process of individuation in western society and differences based on the variables studied. The explanatory variables par excellence are gender, age, marital status and geographical distance. [ABSTRACT FROM PUBLISHER]

Abstract: Trichinella are a group of widely distributed parasites which have acquired high social relevance due to their involvement in foodborne infections caused by consumption of raw or undercooked food. A TaqMan®-LNA probe Real-time PCR assay targeting the 5S rRNA was developed allowing the simultaneous detection of the 10 species and 3 genotypes of Trichinella present in meat tissues. The detection limit employing dilutions of genomic DNA was 2 pg and the determination of the detection limt in terms of ppm was 1 ppm. The main novelty of this work lies in the fact that it can assure the absence of 10 species and 3 genotypes of Trichinella in an only assay. The proposed methodology is rapid, robust, highly sensitive and readily adaptable in routine molecular diagnostic laboratories, and can be employed as molecular screening method in order to assess the food security. [Copyright &y& Elsevier]

From the microinformation of the "survey on technological innovation 1998-2000" a database is constructed by the manufacturing Spanish companies that realize activities of innovation. Subsequently, by testing Pearson Chi-square and Mann-Whitney, test whether the size of companies influences the participation of innovative manufacturing companies in the systems of public support for innovation as well as the address of that conditioning. In this regard, the contrasts made indicate that the variable size is related to the variable public funding, and which are the larger companies which benefit most from public support for innovation. [ABSTRACT FROM AUTHOR]

Aromaticity is an essential concept in chemistry, invented to account for the stability, reactivity, molecular structure, and properties of many organic and inorganic compounds. In recent years, numerous methods to quantify aromaticity based on the energetic, magnetic, structural, and electronic properties of molecules have been proposed but none of them is universal. The inability of establishing a universal scale of aromaticity based on a single parameter is due to the multidimensional character of this phenomenon. Consequently, aromaticity analyses should be carried out by employing a set of aromaticity descriptors on the basis of different physical manifestations of aromaticity. Here, we report a universal scale of aromaticity for π-organic compounds based on the Euclidean distance between neurons in a self-organizing map. The most widely used aromaticity indicators have been used as molecular descriptors, and so our approach provides the first scale of aromaticity which contains the energetic, magnetic, and structural aspects of this property. The method is applicable to a wide variety of unsaturated organic compounds and allows quantification of both aromaticity and antiaromaticity. Additionally, the position of a compound on the bidimensional map determinates immediately the following: (a) the group (aromatic, nonaromatic, or antiaromatic) to which the system belongs, (b) their degree of π-electronic delocalization, and (c) the similarity in aromaticity/antiaromaticity between different compounds. This new scale of aromaticity is able to indicate the expected order of aromaticity of analogues of fulvene and heptafulvene, heteroaromatic species, substituted benzenes, and functionalized cyclopentadienyl compounds. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 [ABSTRACT FROM AUTHOR]

A thorough experimental and computational study of derivatives of (3-sec-butyl-2,3-dihydroisoqui-nolin-4-ylidene)acetic acid was performed. Some of these compounds are calpain inhibitors and could be useful as therapeutic agents, since this enzyme is a Ca2+-dependent cysteine protease involved in a wide variety of metabolic and physiological processes, whose over-activation is associated to several pathological conditions. To gain a better understanding of the structure-activity relationships, a structural analysis was carried out with ¹H and 13C NMR spectroscopy and DFT calculations together with the X-ray diffraction data of three compounds. The solid state structures showed that the crystal packing as well as the intermolecular interactions depend on the substituent nature of the COOR group. Also, the reactivity of the exocyclic double bond was theoretically evaluated, finding that the more reactive compound is the most potent inhibitor of calpain (IC50 = 25 nM). [ABSTRACT FROM AUTHOR]

Abstract: In mammals, glucosensing neurons reside in brain areas known to play a critical regulatory role in energy homeostasis and neuroendocrine function. In fish, although no glucosensing neurons have been characterized to date, glucokinase (GCK; the main glucosensing marker in mammals) activity and expression were found in hypothalamus and hindbrain of rainbow trout where they related to food intake regulation and glucose homeostasis. However, there are no available studies in literature regarding GCK distribution in brain areas as well as the cell types expressing that protein. In the present study we hypothesize that, as occurs in mammals, GCK would be localized where glucosensing areas have been described. In this sense, we have found GCK immunoreactivity in several areas of trout hypothalamus, of which some of them are related to glucose metabolism, energy homeostasis and food intake, including the lateral hypothalamus, anterior tuberal nucleus, posterior tuberal nucleus and lateral tuberal nucleus. On the other hand, GCK immunoreactivity was also observed in other areas where the glucosensor system is probably functional, such as the preoptic area and the oculomotor nucleus. Therefore, in this study using immunoreactive techniques, we have demonstrated in those specific areas of the rainbow trout brain previously described as glucosensor the presence of GCK in different cell types. [Copyright &y& Elsevier]

Abstract: Sequential treatment of a (3-substituted-1-thioxo-1,2,3,4-tetrahydroisoquinolin-4-ylidene)acetic acid with thionyl chloride and a nucleophile did not give the expected ester or amide, but a derivative of 2-(3-substituted-1-chloroisoquinolin-4-yl)acetic acid, constituting a simple procedure for the synthesis of functionalized 1-chloroisoquinolines, which can be useful synthetic intermediates. The different reactivity between lactams and thiolactams has been computationally modelled. The activity as calpain inhibitors of both thiolactams and chloroisoquinoline has been measured, finding that some of these compounds are inhibitors in the micromolar range. [Copyright &y& Elsevier]

Abstract: We studied the distribution of calretinin immunoreactivity (CR-ir) in the rostral and intermediate levels of the spinal cord of lampreys from embryonic to adult periods. CR-ir was first observed at hatching in motoneurons and primary sensory neurons of the spinal cord, the dorsal cells. During the prolarval period two new cell types showed CR-ir: ganglion cells and interneurons. Motoneurons, dorsal cells, and ganglion cells were strongly positive, whereas interneurons were weakly stained in late prolarvae. The intensity of CR-ir in these four types of cells changed during the larval period. Increase of CR-expression was found in interneurons but a decrease in dorsal cells and in ganglion cells. These changes were more evident in premetamorphic larvae. Postmetamorphic lampreys showed almost no CR-ir in dorsal cells. In adult lampreys, the interneurons showed the highest CR-ir, whereas motoneurons were more weakly stained than in earlier stages of development. Moreover, in adults the dorsal cells and the ganglion cells showed no CR-ir. The present study shows that CR-ir changes during lamprey spinal cord development in different types of neurons, sometimes in opposite ways. This plasticity of CR-expression may indicate different needs from subsets of lamprey spinal cord cells involved in the different locomotor behaviors along its life cycle. [Copyright &y& Elsevier]

It has been accepted that aryl hydrocarbon receptor (AhR) ligands are compounds with two or more aromatic rings in a coplanar conformation. Although general agreement exists that carbaryl is able to activate the AhR, it has been proposed that such activation could occur through alternative pathways without ligand binding. This idea was supported by studies showing a planar conformation of carbaryl as unlikely. The objective of the present work was to clarify the process of AhR activation by carbaryl. In rat H4IIE cells permanently transfected with a luciferase gene under the indirect control of AhR, incubation with carbaryl led to an increase of luminescence. Ligand binding to the AhR was studied by means of a cell-free in vitro system in which the activation of AhR can occur only by ligand binding. In this system, exposure to carbaryl also led to activation of AhR. These results were similar to those obtained with the AhR model ligand β-naphthoflavone, although this compound exhibited higher potency than carbaryl in both assays. By means of computational modeling (molecular mechanics and quantum chemical calculations), the structural characteristics and electrostatic properties of carbaryl were described in detail, and it was observed that the substituent at C-1 and the naphthyl ring were not coplanar. Assuming that carbaryl would interact with the AhR through a hydrogen bond, this interaction was studied computationally using hydrogen fluoride as a model H-bond donor. Under this situation, the stabilization energy of the carbaryl molecule would permit it to adopt a planar conformation. These results are in accordance with the mechanism traditionally accepted for AhR activation: Binding of ligands in a planar conformation. [ABSTRACT FROM AUTHOR]

With the objective to understand structural features responsible for the biological activity, novel nonelectrophilic biphenyl derivatives and peptide-biphenyl hybrids have been synthesized and evaluated as calpain I inhibitors. The preliminary results indicate that the presence of additional aromatic rings (besides the biphenyl system) makes these compounds potent calpain inhibitors with IC50 values in the nanomolar range. [Copyright &y& Elsevier]

Inverse sandwich complexes of Yb and Sm stabilized by a bulky β‐diketiminate (BDI) ligand have been prepared: (BDI)Ln(η6,η6‐C6H6)Ln(BDI); Ln=lanthanide. Coordinated benzene ligands can be neutral, di‐anionic or, often controversially discussed, even tetra‐anionic. The formal charge on benzene is correlated to assignment of the metal oxidation state which generally poses a problem. Herein, we take advantage of the structural similarities found when comparing CaII with YbII, and SrII with SmII complexes. In this work, we found an excellent overlap of the Ca/Yb inverse sandwich structures but a striking difference for the Sr/Sm pair. The much shorter Sm−N and Sm‐C6H6 distances are strong evidence for a SmIII‐benzene−4‐SmIII assignment. This was further supported by NMR spectroscopy, magnetic susceptibility, reactivity and comprehensive computational investigation. [ABSTRACT FROM AUTHOR]

Inverse sandwich complexes of Yb and Sm stabilized by a bulky β‐diketiminate (BDI) ligand have been prepared: (BDI)Ln(η6,η6‐C6H6)Ln(BDI); Ln=lanthanide. Coordinated benzene ligands can be neutral, di‐anionic or, often controversially discussed, even tetra‐anionic. The formal charge on benzene is correlated to assignment of the metal oxidation state which generally poses a problem. Herein, we take advantage of the structural similarities found when comparing CaII with YbII, and SrII with SmII complexes. In this work, we found an excellent overlap of the Ca/Yb inverse sandwich structures but a striking difference for the Sr/Sm pair. The much shorter Sm−N and Sm‐C6H6 distances are strong evidence for a SmIII‐benzene−4‐SmIII assignment. This was further supported by NMR spectroscopy, magnetic susceptibility, reactivity and comprehensive computational investigation. [ABSTRACT FROM AUTHOR]

Recent advances in alkaline earth (Ae) metal hydrogenation catalysis have broadened the spectrum of potential catalysts to include candidates from the main group, providing a sustainable alternative to the commonly used transition metals. Although Ae-amides have already been demonstrated to catalyze hydrogenation of imines and alkenes, a lucid understanding of how different metal/ligand combinations influence the catalytic activity is yet to be established. In this article, we use linear scaling relationships and molecular volcano plots to assess the potential of the Ae metal-based catalysts for the hydrogenation of alkenes. By analyzing combinations of eight metals (mono-, bi-, tri-, and tetravalent) and seven ligands, we delineate the impact of metal-ligand interplay on the hydrogenation activity. Our findings highlight that the catalytic activity is majorly determined by the charge and the size of the metal ions. While bivalent Ae metal cations delicately regulate the binding and the release of the reactants and the products, respectively, providing the right balance for this reaction, ligands play only a minor role in determining their catalytic activity. We show how volcano plots can be utilized for the rapid screening of prospective Ae catalysts to establish a guideline to achieve maximum activity in facilitating the hydrogenation process. [ABSTRACT FROM AUTHOR]

The drive to develop maximal atom‐efficient catalysts coupled to the continuous striving for more sustainable reactions has led to an ever‐increasing interest in single‐atom catalysis. Based on a periodic conceptual density functional theory (cDFT) approach, fundamental insights into the reactivity and adsorption of single late transition metal atoms supported on a fully hydroxylated amorphous silica surface have been acquired. In particular, this investigation revealed that the influence of van der Waals dispersion forces is especially significant for a silver (98 %) or gold (78 %) atom, whereas the oxophilicity of the Group 8–10 transition metals plays a major role in the interaction strength of these atoms on the irreducible SiO2 support. The adsorption energies for the less‐electronegative row 4 elements (Fe, Co, Ni) ranged from −1.40 to −1.92 eV, whereas for the heavier row 5 and 6 metals, with the exception of Pd, these values are between −2.20 and −2.92 eV. The deviating behavior of Pd can be attributed to a fully filled d‐shell and, hence, the absence of the hybridization effects. Through a systematic analysis of cDFT descriptors determined by using three different theoretical schemes, the Fermi weighted density of states approach was identified as the most suitable for describing the reactivity of the studied systems. The main advantage of this scheme is the fact that it is not influenced by fictitious Coulomb interactions between successive, charged reciprocal cells. Moreover, the contribution of the energy levels to the reactivity is simultaneously scaled based on their position relative to the Fermi level. Finally, the obtained Fermi weighted density of states reactivity trends show a good agreement with the chemical characteristics of the investigated metal atoms as well as the experimental data. [ABSTRACT FROM AUTHOR]

A hitherto unexplored class of molecules for molecular force probe applications are expanded porphyrins. This work proves that mechanical force is an effective stimulus to trigger the interconversion between Hückel and Möbius topologies in [28]hexaphyrin, making these expanded porphyrins suitable to act as conformational mechanophores operating at mild (sub‐1 nN) force conditions. A straightforward approach based on distance matrices is proposed for the selection of pulling scenarios that promote either the planar Hückel topology or the three lowest lying Möbius topologies. This approach is supported by quantum mechanochemical calculations. Force distribution analyses reveal that [28]hexaphyrin selectively allocates the external mechanical energy to molecular regions that trigger Hückel–Möbius interconversions, explaining why certain pulling scenarios favor the Hückel two‐sided topology and others favor Möbius single‐sided topologies. The meso‐substitution pattern on [28]hexaphyrin determines whether the energy difference between the different topologies can be overcome by mechanical activation. [ABSTRACT FROM AUTHOR]

Nowadays, an active research topic is the connection between Clar's rule, aromaticity, and magnetic properties of polycyclic benzenoid hydrocarbons. In the present work, we employ a meticulous magnetically induced current density analysis to define the net current flowing through any cyclic circuit, connecting it to aromaticity based on the ring current concept. Our investigation reveals that the analyzed polycyclic systems display a prominent global ring current, contrasting with subdued semi‐local and local ring currents. These patterns align with Clar's aromatic π‐sextets only in cases where migrating π‐sextet structures are invoked. The results of this study will enrich our comprehension of aromaticity and magnetic behavior in such systems, offering significant insights into coexisting ring current circuits in these systems. [ABSTRACT FROM AUTHOR]

Molecular switches, in which a stimulus induces a large and reversible change in molecular properties, are of significant interest in the domain of photonics. Due to their commutable redox states with distinct nonlinear optical (NLO) properties, hexaphyrins have emerged as a novel platform for multistate switches in nanoelectronics. In this study, we employ an inverse design algorithm to find functionalized 26R→28R redox switches with maximal β H R S contrast. We focus on the role of core modifications, since a synergistic effect with meso-substitutions was recently found for the 30R-based switch. In contrast to these findings, the inverse design optima and subsequent database analysis of 26R-based switches confirm that core modifications are generally not favored when high NLO contrasts are targeted. Moreover, while push–pull combinations enhance the NLO contrast for both redox switches, they prefer a different arrangement in terms of electron-donating and electron-withdrawing functional groups. Finally, we aim at designing a three-state 26R→28R→ 30R switch with a similar NLO response for both ON states. Even though our best-performing three-state switch follows the design rules of the 30R-based component, our chemical compound space plots show that well-performing three-state switches can be found in regions shared by high-responsive 26R and 30R structures. [ABSTRACT FROM AUTHOR]

Multifunctional triple color photoluminescent (PL) nitrogen–boron doped carbon quantum dots (CQDs) with high quantum yield (QY) of 58% are fabricated by one step femtosecond pulsed laser irradiation of a single precursor (2‐aminopyrimidine‐5‐boronic acid) in solution. In situ generated non‐linear and linear emissions are used to monitor CQDs formation which results in enhanced second harmonic generation, two photon absorption (2PA), and linear fluorescence; implying triple mode emission. These CQDs present blue, green, and possible red color rendering which are mostly independent to the respective excitation wavelengths (λ) with large stokes shift of 100 nm. Solid‐state photoluminescence with QY of 46% is achieved by incorporating CQDs into thin transparent nanoporous silica (pSiO2) films (thickness 50 µm) to form a CQDs‐pSiO2 composite which exhibits reverse saturable absorption at λ = 800 nm with 2PA coefficient and excited state absorption cross‐section of 4.94 × 10−10 m W−1 and 6.23 × 10−17 cm2, respectively. CQDs‐pSiO2 is also sensitive to glucose concentration down to 1.0 mg dL−1 in a wide linear range up to 100 mg dL−1. This work therefore demonstrates facile, controllable, and up‐scalable bottom‐up fabrication of CQDs forming multifunctional solid‐state CQDs‐pSiO2 with proven application in optical limiting and glucose sensing. [ABSTRACT FROM AUTHOR]

Purpose. To evaluate medium-term clinical outcomes with XEN® 45 or XEN® 63 Gel Stent (Allergan, Dublin, Ireland) for treatment of primary open angle glaucoma (POAG). Materials and Methods. Retrospective, descriptive, and observational study involving 40 patients implanted with a XEN® 45 Gel Stent and 34 implanted with a XEN® 63 Gel Stent who had undergone POAG surgery and had been followed up and controlled between 12 and 36 months. Results. IOP dropped from 18.02 ± 5.23 mmHg preop to 13.81 ± 1.88, 14.80 ± 2.23, and 14.62 ± 1.90 at 1, 2, and 3 years after surgery (p < 0.001) consecutively with XEN® 45 and from 19.00 ± 6.11 mmHg preop to 15.47 ± 2.45, 14.66 ± 2.45, and 15.46 ± 2.48 at 1, 2, and 3 years after surgery (p < 0.001) with XEN® 63. The number of drugs used by patients to treat their glaucoma decreased after undergoing surgery in both groups. Within the XEN® 45 group, mean changes at 1 year, 2 years, and 3 years amounted to 70%, 74.3%, and 37.5%, respectively, whereas within the XEN® 63 group, the mean reduction was 75%, 79.8%, and 71.9%. When comparing the outcomes for two groups, the differences did not prove to be statistically significant. More than 90% of the procedures included in the study (using either gel-stent device) were completed without any noteworthy complications. Conclusion. POAG surgical procedures with either XEN® 45 or XEN® 63 Gel Stent implantation could be a safe and effective treatment approach. [ABSTRACT FROM AUTHOR]

The alkene transfer hydrogenation (TH) of a variety of alkenes has been achieved with simple AeN′′2 catalysts [Ae=Ca, Sr, Ba; N′′=N(SiMe3)2] using 1,4‐cyclohexadiene (1,4‐CHD) as a H source. Reaction of 1,4‐CHD with AeN′′2 gave benzene, N′′H, and the metal hydride species N′′AeH (or aggregates thereof), which is a catalyst for alkene hydrogenation. BaN′′2 is by far the most active catalyst. Hydrogenation of activated C=C bonds (e.g. styrene) proceeded at room temperature without polymer formation. Unactivated (isolated) C=C bonds (e.g. 1‐hexene) needed a higher temperature (120 °C) but proceeded without double‐bond isomerization. The ligands fully control the course of the catalytic reaction, which can be: 1) alkene TH, 2) 1,4‐CHD dehydrogenation, or 3) alkene polymerization. DFT calculations support formation of a metal hydride species by deprotonation of 1,4‐CHD followed by H transfer. Convenient access to larger quantities of BaN′′2, its high activity and selectivity, and the many advantages of TH make this a simple but attractive procedure for alkene hydrogenation. The hydrogen shuffle: Transfer of hydrogens from 1,4‐cyclohexadiene to a variety of alkenes is catalyzed by simple alkaline‐earth metal amides. The proposed mechanism for this convenient and highly selective transfer hydrogenation is supported by DFT calculations. [ABSTRACT FROM AUTHOR]

The alkene transfer hydrogenation (TH) of a variety of alkenes has been achieved with simple AeN′′2 catalysts [Ae=Ca, Sr, Ba; N′′=N(SiMe3)2] using 1,4‐cyclohexadiene (1,4‐CHD) as a H source. Reaction of 1,4‐CHD with AeN′′2 gave benzene, N′′H, and the metal hydride species N′′AeH (or aggregates thereof), which is a catalyst for alkene hydrogenation. BaN′′2 is by far the most active catalyst. Hydrogenation of activated C=C bonds (e.g. styrene) proceeded at room temperature without polymer formation. Unactivated (isolated) C=C bonds (e.g. 1‐hexene) needed a higher temperature (120 °C) but proceeded without double‐bond isomerization. The ligands fully control the course of the catalytic reaction, which can be: 1) alkene TH, 2) 1,4‐CHD dehydrogenation, or 3) alkene polymerization. DFT calculations support formation of a metal hydride species by deprotonation of 1,4‐CHD followed by H transfer. Convenient access to larger quantities of BaN′′2, its high activity and selectivity, and the many advantages of TH make this a simple but attractive procedure for alkene hydrogenation. [ABSTRACT FROM AUTHOR]

The unpredictable behavior of [26] ‐ and [28]hexaphyrins upon metalation is elucidated by M. Alonso et al. in their Full Paper on page 17631 ff. Quantum chemical calculations demonstrate that the molecular topology of Group 10 and Group 11 metal complexes of hexaphyrins depends on sensitive interplay between the intrinsic ligand strain and the metal – ligand interaction strength. As such, the aromaticity of the ligand and effective charge of the metal are revealed as key factors determining the binding mode and the preference for Möbius or Hückel structures. [ABSTRACT FROM AUTHOR]

Invited for this month′s cover is the Quantum Chemistry group (ALGC) of the Free University of Brussels (VUB). The image depicts an artist's impression of how the metal influences the molecular topology and aromaticity of hexaphyrins. Read the full text of the article at . [ABSTRACT FROM AUTHOR]

Noncovalent interactions involving aromatic rings, such as π ‐ stacking and CH/π interactions, are central to many areas of modern chemistry. In their Full Paper on page 4931 ff., M. Alonso et al. describe their investigations on the nature and origin of π/π, σ/σ and σ/π dispersion interactions by using dispersion ‐ corrected density functional theory, energy decomposition analysis and the noncovalent interaction method. The analysis confirms that π/π and σ/σ stacking interactions are equally important in energy for the benzene and cyclohexane dimers, but different in origin. These new types of dispersion interactions between saturated groups can be exploited in the rational design of novel carbon materials. [ABSTRACT FROM AUTHOR]

Invited for the cover of this issue is the ALGC Quantum Chemistry group of the Free University of Brussels (VUB) in collaboration with the LCT group in Paris. The image depicts how π/π and σ/σ stacking interactions are surprisingly equal in strength for the benzene and cyclohexane dimers, but different in origin, and how π-stacking becomes more important as the size of the dimer increases. Read the full text of the article at . [ABSTRACT FROM AUTHOR]