Amygdala functional connectivity in borderline personality disorder.

Borderline personality disorder (BPD) is characterised by structural and functional brain alterations. Yet, there is little data on functional connectivity (FC) across different levels of brain networks and parameters. In this study, we applied a multi-level approach to analyse abnormal functional connectivity. We analysed resting-state functional magnetic resonance imaging (fMRI) data sets of 69 subjects: 17 female BPD patients and 51 age-matched psychiatrically healthy female controls. fMRI was analysed using CONN toolbox including: a) seed-based FC analysis of amygdala connectivity, b) independent component analysis (ICA) based network analysis of intra- and inter-network FC of selected resting-state networks (DMN, SN, FPN), as well as c) graph-theory based measures of network-level characteristics. We show group-level seed FC differences with higher amygdala to contralateral (superior) occipital cortex connectivity in BPD, which correlated with schema-therapy derived measures of symptoms/traits across the entire cohort. While there was no significant group effect on DMN, SN, or FPN intra-network or inter-network FC, we show a significant group difference for local efficiency and cluster coefficient for a DMN-linked cerebellum cluster. Our findings demonstrate BPD-linked changes in FC across multiple levels of observation, which supports a multi-level analysis for future studies to consider different aspects of functional connectome alterations.

Triplet Energy Transfer Mechanism in Copper Photocatalytic N- and O-Methylation.

Methylation reactions are chemically simple but challenging to perform under mild and non-toxic conditions. A photochemical energy transfer strategy was merged with copper catalysis to enable fast reaction times of minutes and broad applicability to N-heterocycles, (hetero-)aromatic carboxylic acids, and drug-like molecules in high yields and good functional group tolerance. Detailed mechanistic investigations, using kinetic analysis, aprotic MS, UV/Vis, and luminescence quenching experiments revealed a triplet-triplet energy transfer mechanism between hypervalent iodine(III) reagents and readily available photosensitizers.

The Effects of Salinity on the Anatomy and Gene Expression Patterns in Leaflets of Tomato cv. Micro-Tom.

Salinity is a form of abiotic stress that impacts growth and development in several economically relevant crops and is a top-ranking threat to agriculture, considering the average rise in the sea level caused by global warming. Tomato is moderately sensitive to salinity and shows adaptive mechanisms to this abiotic stressor. A case study on the dwarf tomato model Micro-Tom is here presented in which the response to salt stress (NaCl 200 mM) was investigated to shed light on the changes occurring at the expression level in genes involved in cell wall-related processes, phenylpropanoid pathway, stress response, volatiles' emission and secondary metabolites' production. In particular, the response was analyzed by sampling older/younger leaflets positioned at different stem heights (top and bottom of the stem) and locations along the rachis (terminal and lateral) with the goal of identifying the most responsive one(s). Tomato plants cv. Micro-Tom responded to increasing concentrations of NaCl (0-100-200-400 mM) by reducing the leaf biomass, stem diameter and height. Microscopy revealed stronger effects on leaves sampled at the bottom and the expression analysis identified clusters of genes expressed preferentially in older or younger leaflets. Stress-related genes displayed a stronger induction in lateral leaflets sampled at the bottom. In conclusion, in tomato cv. Micro-Tom subjected to salt stress, the bottom leaflets showed stronger stress signs and response, while top leaflets were less impacted by the abiotic stressor and had an increased expression of cell wall-related genes involved in expansion.

The influence of the formal replacement of thiophenes by stannoles in terthiophene and sexithiophene on the optoelectronic properties and electrochemical behavior.

Polystannoles with thienyl co-monomers are in many ways similar to polythiophenes, but they display much reduced band gaps. However, their polymerization processes are not well researched. Thiophene can be oxidatively electropolymerized, but as stannoles are organometallic, the fundamental question arises whether their inclusion in a conjugated backbone can protect them sufficiently to be able to perform an oxidative electropolymerization. As well-defined oligothiophenes can be used as models to understand the optical and electronic properties of polythiophenes, we transposed this concept on stannole containing polymers; therefore we synthesized a monomeric 1 and dimeric thiophene-flanked stannole 2 and investigated their optoelectronic properties comparatively including polystannoles and the corresponding oligothiophenes in our analysis. With respect to monomer 1, a significantly redshifted absorption (λmax = 510 nm, Δ = 93 nm) and a small optical band gap (Eg,opt(2) = 2.13 eV), close to the bandgap of polymeric stannoles, was observed. In comparison to oligothiophenes, these thienyl-flanked stannoles exhibited a redshift in absorption and emission as well as a lower oxidation potential. Despite these differences, they showed an oligothiophene-like electrochemical behavior. Stannole 1 and the dimer 2 were subjected to an electropolymerization process. This process was investigated in detail by spectroelectrochemical methods which showed that radical cation species were formed in situ but readily decomposed. Nevertheless, under the milder multiscan cyclovoltammetric conditions, electropolymerization occurred as shown by cyclovoltammetry.

Catalytic Oxygenation of Hydrocarbons by Mono-µ-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear CuI /CuII Peroxo Complexes.

One of the challenges of catalysis is the transformation of inert C-H bonds to useful products. Copper-containing monooxygenases play an important role in this regard. Here we show that low-temperature oxygenation of dinuclear copper(I) complexes leads to unusual tetranuclear, mixed-valent µ4 -peroxo [CuI /CuII ]2 complexes. These Cu4 O2 intermediates promote irreversible and thermally activated O-O bond homolysis, generating Cu2 O complexes that catalyze strongly exergonic H-atom abstraction from hydrocarbons, coupled to O-transfer. The Cu2 O species can also be produced with N2 O, demonstrating their capability for small-molecule activation. The binding and cleavage of O2 leading to the primary Cu4 O2 intermediate and the Cu2 O complexes, respectively, is elucidated with a range of solution spectroscopic methods and mass spectrometry. The unique reactivities of these species establish an unprecedented, 100 % atom-economic scenario for the catalytic, copper-mediated monooxygenation of organic substrates, employing both O-atoms of O2 .

A Review on the Beneficial Role of Silicon against Salinity in Non-Accumulator Crops: Tomato as a Model.

Salinity is an abiotic stress that affects agriculture by severely impacting crop growth and, consequently, final yield. Considering that sea levels rise at an alarming rate of >3 mm per year, it is clear that salt stress constitutes a top-ranking threat to agriculture. Among the economically important crops that are sensitive to high salinity is tomato (Solanum lycopersicum L.), a cultivar that is more affected by salt stress than its wild counterparts. A strong body of evidence in the literature has proven the beneficial role of the quasi-essential metalloid silicon (Si), which increases the vigor and protects plants against (a)biotic stresses. This protection is realized by precipitating in the cell walls as opaline silica that constitutes a mechanical barrier to the entry of phytopathogens. With respect to Si accumulation, tomato is classified as a non-accumulator (an excluder), similarly to other members of the nightshade family, such as tobacco. Despite the low capacity of accumulating Si, when supplied to tomato plants, the metalloid improves growth under (a)biotic stress conditions, e.g., by enhancing the yield of fruits or by improving vegetative growth through the modulation of physiological parameters. In light of the benefits of Si in crop protection, the available literature data on the effects of this metalloid in mitigating salt stress in tomato are reviewed with a perspective on its use as a biostimulant, boosting the production of fruits as well as their post-harvest stability.

Synthesis and crystal structure of (E)-1,2-bis-[2-(methyl-sulfan-yl)phen-yl]diazene.

The title compound, C14H14N2S2, was obtained by transmetallation of 2,2'-bis-(tri-methyl-stann-yl)azo-benzene with methyl lithium, and subsequent quenching with dimethyl di-sulfide. The asymmetric unit comprises two half-mol-ecules, the other halves being completed by inversion symmetry at the midpoint of the azo group. The two mol-ecules show only slight differences with respect to N=N, S-N and aromatic C=C bonds or angles. Hirshfeld surface analysis reveals that except for one weak H⋯S inter-action, inter-molecular inter-actions are dominated by van der Waals forces only.

Synthesis, Structure, Thermal Behavior and cis/trans Isomerization of 2,2'-(EMe3)2 (E = C, Si, Ge, Sn) Substituted Azobenzenes.

The synthesis of a series of 2,2'-bis(trimethyltetrel) azobenzenes is reported, evaluating the different synthetic approaches that different group 14 element substituents individually require. The synthetic access to the carbon substituted congener is very different from the heavier tetrels, in that the key step is the formation of the N=N bond in azobenzene, rather than the azobenzene-C bond. Sn could be introduced with a cross-coupling route, whereas the Si and Ge congeners were prepared by a stannylation-lithiation-electrophilic quenching sequence. Iodo-lithium exchange was also a possible route to obtain the dilithiated species, which can be attributed to the chelating effect of the nitrogen atoms. However, the organo-lead species could not be obtained via these routes. The resulting structures were fully characterized (NMR, FTIR, HRMS and XRD). Furthermore, their thermal properties (TGA and DSC) and their photoswitching behavior in solution (UV-VIS & NMR experiments) were investigated and compared for the different tetrels (C, Si, Ge, Sn).

Patients with Schizophrenia Do Not Demonstrate Worse Outcome After Sleeve Gastrectomy: a Short-Term Cohort Study.

PURPOSE: The aim of this study was to compare surgical and psychiatric outcome and weight loss in schizophrenia patients with mentally healthy patients after sleeve gastrectomy. MATERIALS AND METHODS: A cohort study design was selected, comprising patients with schizophrenia with mentally healthy patients who underwent sleeve gastrectomy and were adherent to a follow-up at least 12 months after surgery. RESULTS: Seven schizophrenia (5 male, 2 female) and 59 (12 male, 47 female) mentally healthy patients were included in this study. A laparoscopic sleeve gastrectomy was performed safely in all 66 patients. The calculated excess weight loss (%EWL) showed no significant differences in both groups and reached 51.68 ± 15.84% for schizophrenia group and 60.68 ± 19.95% for mentally healthy group at 24-month follow-up (p = 0.33). The decrease in the HbA1c levels within 2 years after sleeve gastrectomy was similar in both groups (p = 0.79, 0.88, 0.82, 0.73 for surgery time, time of 6-, 12-, and 24-month follow-up respectively). The psychiatric status of the patients of the schizophrenia group was stable in all cases and no exacerbation of psychiatric symptoms was observed during time of follow-up. Furthermore, an overall significant improvement of the self-estimated mood and satisfaction was observed in both groups (Manova: f = 1.26, p < 0.0001). CONCLUSIONS: The results 2 years after sleeve gastrectomy in stable patients with schizophrenia and after an adequate psychological evaluation were encouraging and comparable to the outcome in mentally healthy patients.

Tuning the Optoelectronic Properties of Stannoles by the Judicious Choice of the Organic Substituents.

Stannoles are organometallic rings in which the heteroatom is involved in a form of conjugation that is called σ*-π* conjugation. Only very little is known about how the substituents on the Sn atom or substituents on the stannole ring determine the optoelectronic properties of these heterocycles. In this work, this question has been studied experimentally and theoretically. Calculations of optimized equilibrium geometries, energy gaps between the highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs), and of the absorption spectra of a wide range of compounds were performed. The computational data showed that the substituents on the Sn atom influence the optoelectronic properties to a lower extent than the substituents in the 2 and 5 positions of the ring. These substituents in the 2 and 5 positions of the stannole ring can also have a strong influence on the overall planarity of the structure, in which mesomeric effects can play a substantial role only if the structure is planar. Thus, only structures with a planar backbone are of interest in the context of tuning the optoelectronic properties. These were selected for the experimental studies. On the basis of this information, a series of six novel stannoles was synthesized by the formation of a zirconium intermediate and subsequent transmetalation to obtain the tin compound. The calculated electronic HOMO-LUMO energy gaps varied between 2.94 and 2.68 eV. The measured absorption maxima were located between 415 and 448 nm compared to theoretically calculated values ranging from 447 nm (2.77 eV) to 482 nm (2.57 eV). In addition to these optical measurements, cyclic voltammetry data could be obtained, which show two reversible oxidation processes for three of the six stannoles. With this study, it could be demonstrated how the judicious choice of the substituents can lead to large and predictable bathochromic shifts in the absorption spectra.

How do patients with diabetes report their comorbidities? Comparison with administrative data.

AIMS: Patients with diabetes are probably often unaware of their comorbidities. We estimated agreement between self-reported comorbidities and administrative data. METHODS: In a random sample of 464 diabetes patients, data from a questionnaire asking about the presence of 14 comorbidities closely related to diabetes were individually linked with statutory health insurance data. RESULTS: Specificities were >97%, except cardiac insufficiency (94.5%), eye diseases (93.8%), peripheral arterial disease (92.6%), hypertension (90.9%), and peripheral neuropathy (85.8%). Sensitivities were <60%, except amputation (100%), hypertension (83.1%), and myocardial infarction (67.2%). A few positive predictive values were >90% (hypertension, myocardial infarction, and eye disease), and six were below 70%. Six negative predictive values were >90%, and two <70% (hypertension and eye disease). Total agreement was between 42.7% (eye disease) and 100% (dialysis and amputation). Overall, substantial agreement was observed for three morbidities (kappa 0.61-0.80: hypertension, myocardial infarction, and amputation). Moderate agreement (kappa 0.41-0.60) was estimated for angina pectoris, heart failure, stroke, peripheral neuropathy, and kidney disease. Factors associated with agreement were the number of comorbidities, diabetes duration, age, sex, and education. CONCLUSIONS: Myocardial infarction and amputation were well reported by patients as comorbidities; eye diseases and foot ulceration rather poorly, particularly in older, male, or less educated patients. Patient information needs improving.

Syntheses and Properties of Tin-Containing Conjugated Heterocycles.

Heterocycles that contain tin atoms can be aromatic in a similar sense to well-known aromatic compounds such as benzene or thiophene, but such examples are rare. However, due to the low-lying σ*-orbitals of the tin-substituent bond in stannoles, they are capable of σ*-π* conjugation in a way that is exclusive to heavier element containing heterocycles. This makes stannoles very interesting alternatives for purely organic heterocycles in material applications, in which optoelectronic properties are of interest. This Concept article will highlight the synthesis, reactivity and physical properties of stannoles and related fluorenostannoles. At first, a brief introduction to different types of tin-containing heterocycles is presented, followed by a discussion on different approaches to prepare stannoles, their reactivity and their physical properties. In addition, the first stannole-containing polymer will be reviewed.

Community-Associated Staphylococcus aureus from Sub-Saharan Africa and Germany: A Cross-Sectional Geographic Correlation Study.

Clonal clusters and gene repertoires of Staphylococcus aureus are essential to understand disease and are well characterized in industrialized countries but poorly analysed in developing regions. The objective of this study was to compare the molecular-epidemiologic profiles of S. aureus isolates from Sub-Saharan Africa and Germany. S. aureus isolates from 600 staphylococcal carriers and 600 patients with community-associated staphylococcal disease were characterized by DNA hybridization, clonal complex (CC) attribution, and principal component (PCA)-based gene repertoire analysis. 73% of all CCs identified representing 77% of the isolates contained in these CCs were predominant in either African or German region. Significant differences between African versus German isolates were found for alleles encoding the accessory gene regulator type, enterotoxins, the Panton-Valentine leukocidin, immune evasion gene cluster, and adhesins. PCA in conjunction with silhouette analysis distinguished nine separable PCA clusters, with five clusters primarily comprising of African and two clusters of German isolates. Significant differences between S. aureus lineages in Africa and Germany may be a clue to explain the apparent difference in disease between tropical/(so-called) developing and temperate/industrialized regions. In low-resource countries further clinical-epidemiologic research is warranted not only for neglected tropical diseases but also for major bacterial infections.

High molecular weight poly(N-methyl-B-vinylazaborine) - a semi-inorganic B-N polystyrene analogue.

We present the synthesis of a B-N analogue of polystyrene, poly(N-methyl-B-vinylazaborine) in high molecular weight (MW = 24.9 kDa). Furthermore, it was possible to prepare a copolymer with the C-C analogue. A thorough comparison between the polymers by NMR spectroscopy, TGA, DSC and GPC showed significant differences between these polymers.

Agreement found between self-reported and health insurance data on physician visits comparing different recall lengths.

OBJECTIVE: To analyze the impact of different recall lengths on agreement between self-reported physician visits and those documented in health insurance data applying an experimental design. STUDY DESIGN AND SETTING: We randomly assigned 432 patients with diabetes to one of two versions of a written survey, each asking about the number of physician visits over a 3- or 6-month recall period. Health insurance data were linked individually. RESULTS: In both groups, the mean number of self-reported physician visits per month was lower than in the insurance data, with a larger difference in the 6-month group (-0.9; 95% CI -1.0, -0.7) than in the 3-month group (-0.5; -0.7; -0.2), difference between the two groups: 0.4 (0.1-0.7; P = 0.009). The percentage of participants with correct reporting was small and did not differ largely between the two groups (6.5% and 9.3%). However, there was more overreporting in the 3-month group (25.6% vs. 11.1%). CONCLUSIONS: Shorter recall periods may produce more accurate results when estimating the mean number of physician visits. However, this may be driven not by a more accurate reporting, but by a higher proportion of respondents that overreported and a lower proportion of respondents that underreported, when compared to the longer reporting period.

Crystal structures of 3,3'-bis-(hy-droxy-dimethylsilan-yl)azo-benzene and 4,4'-bis-(hy-droxy-dimethyl-silane)azo-benzene.

The title compounds {systematic names (E)-[diazene-1,2-diylbis(3,1-phenyl-ene)]bis-(di-methyl-silanol) and (E)-[diazene-1,2-diylbis(4,1-phenyl-ene)]bis-(di-methyl-silanol)}, both of the sum formula C16H22N2O2Si2, were obtained by transmetallation of the respective bis-stannylated azo-benzenes with di-chloro-dimethyl-silane and esterification followed by hydrolysis. The asymmetric unit of 3,3'-diazenediylbis[dimeth-yl(phen-yl)silanol] (with the silanol functional group in a meta position) consists of two mol-ecules, of which one occupies a general position, whereas the second is located on a centre of inversion. In 4,4'-diazenediylbis[dimeth-yl(phen-yl)silanol] (with the silanol functional group in a para position) likewise two mol-ecules are present in the asymmetric unit, but in this case both occupy general positions. Differences between all mol-ecules can be found in the torsions about the N=N bond, as well as in the dihedral angles between the benzene rings. In both structures, inter-molecular O-H⋯O hydrogen bonding is observed, leading to the formation of layers parallel to (01-1) for (I) and to chains parallel to the a axis for (II).

The international dimension of drug policy reform in Uruguay.

BACKGROUND: In 2013, Uruguay became the first country in the world to legally regulate cannabis from seed to smoke. A growing body of research addresses drug policy reform in Uruguay. However, existing studies have almost completely elided its international dimension, treating the process as exclusively domestic phenomenon. METHODS: To consider the international dimension of drug policy reform in Uruguay, the paper draws on primary and secondary sources such as existing studies, media reports, official documents, parliamentary debates and interviews with stakeholders and policy analysts from Uruguay and elsewhere. RESULTS: The paper shows that, when, and, how international factors and actors contributed to Uruguay's drug policy reform process. Two ways in which the international dimension manifested itself are identified. First, as drug policy debate around the world changed, the context for reforms in Uruguay evolved. This resulted in a rather mixed international reaction to Uruguay's reform proposal. Second, international actors became directly involved in the process. Drug policy experts informed and legitimated cannabis reform and transnational advocates supported campaigning and mobilisation in Uruguay. CONCLUSION: By unearthing the international dimension of Uruguay's drug policy reform, the paper adds a novel perspective to the study of drug policy reform in the Uruguay.

The gut is not only the target but a source of inflammatory mediators inhibiting gastrointestinal motility during sepsis.

BACKGROUND: Sepsis is a common problem in intensive care patients leading to multi-organ failure and gastrointestinal paralysis. AIM: The aim of the study was to investigate whether the gastrointestinal tract is not only the target but also the source of inflammatory mediators inhibiting gastrointestinal motility. METHODS: Mesenteric lymph was obtained from rats in which a sepsis was induced by lipopolysaccharide (LPS) intraperitoneally. Gastrointestinal motility was recorded following mesenteric lymph- or TNFα infusion into the jugular vein of separate healthy recipient rats using the strain gauge transducer technique. RESULTS: Infusion of sepsis lymph significantly impairs gastric and colonic motility, decreasing the motility-index in the stomach and colon by about 57% and 21% respectively in comparison to baseline motility. Among other inflammatory mediators, TNFα plays an important role in mediating the inhibitory effect of mesenteric lymph on gastrointestinal motility during sepsis. CONCLUSIONS: The gastrointestinal tract is the source and the target of inflammatory mediators released during sepsis causing paralytic ileus.

Laparoscopic resection of a lymphangiomatous cyst of the colon: a case report.

INTRODUCTION: Lymphangiomatous cysts are submucosal masses that are rarely found in the gastrointestinal tract and more often in the neck, oral cavity, and skin. These cysts are benign tumors and mostly clinically silent. Symptoms include abdominal pain, diarrhea, and rectal bleeding. Their pathogenesis remains unclear. CASE PRESENTATION: During a routine ultrasound examination of a Caucasian 25-year-old woman, a structure that raised our suspicions of an ovarian cyst was found. MRI showed a 4.5 cm cystic lesion in the cecal region. Laparoscopic exploration revealed unexpected contact with the ascending colon. The cyst, including its base and of portion of the colon, was resected laparoscopically. The histological examination revealed cystic lymphangioma. CONCLUSION: Lymphangiomatous cysts of the colon are very rare lesions. Although their pathology is benign, the recommended treatment is resection, which can be performed with minimal invasiveness.