Fluoride Abstraction Induced by Tris(pentafluoroethyl)difluorophosphorane: A Convenient Way to Synthesize Cationic N-Heterocyclic Carbene- and Cyclic (Alkyl)(amino)carbene-Ligated Copper Alkyne and Arene Complexes.

We herein report the convenient synthesis of different N-heterocyclic carbene (NHC)- and cyclic (alkyl)(amino)carbene (cAAC)-ligated copper cations using the weakly coordinating tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C2F5)3PF3]-). The reaction of the fluorido complexes [(carbene)CuF] (carbene = NHC, cAACMe) 2a-2f and the tris(pentafluoroethyl)difluorophosphorane (C2F5)3PF2 in the presence of alkynes or arenes led to fluoride transfer from Cu to the phosphorane with formation of the cationic transition metal complexes [(carbene)Cu(L)]+ and the weakly coordinating counteranion [(C2F5)3PF3]- (FAP). Using this method, the complexes [(IDipp)Cu(L)]+FAP- (IDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolin-2-ylidene; L = PhC≡CPh, 4d; PhC≡CMe, 5d), [(cAACMe)Cu(L)]+FAP- (cAACMe = 1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene; L = PhC≡CPh, 4f; PhC≡CMe, 5f), [(SIDipp)Cu(C6Me6)]+FAP- (6e), (SIDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolidine-2-ylidene), and [(cAACMe)Cu(C6Me6)]+FAP- (6f) have been synthesized and characterized. The complexes [(IDipp)Cu(C6Me6)]+FAP- (6d) and [(cAACMe)Cu(C6Me6)]+FAP- (6f) have been used as catalysts for the copper(I)-catalyzed cycloaddition of benzyl azide to terminal alkynes.

Hyperfiltration can be detected by transcutaneous assessment of glomerular filtration rate in diabetic obese mice.

We addressed if hyperfiltration can be assessed transcutaneously in male diabetic obese mice (BTBRob/ob) at 12 and 24 wk and how this relates to glomerular parameters indicative for hyperfiltration. Transcutaneous assessment of FITC-Sinistrin clearance [transcutaneous assessment of glomerular filtration rate (tGFR)] was compared against classical plasma clearance. Kidney from SV620C-01-PEI perfused mice were harvested at 24 wk and processed for tissue clearing and classical histology. Perfusion patterns of glomerular capillaries, glomerular size, and vasodilation of the afferent arterioles were assessed. Although at 12 wk FITC-Sinistrin half-life (t1/2) for both tGFR and plasma clearance suggested hyperfiltration, this was not significant anymore at 24 wk. In kidneys of diabetic mice the diameter of the afferent arteriole was significantly larger and positively correlated with glomerular size. Glomerular perfusion pattern in these mice was heterogeneous ranging from non- to well-perfused glomeruli. Nonperfused glomerular areas displayed a strong periodic acid-Schiff's (PAS) positive staining. Collectively our data demonstrate that tGFR is a valid method to detect hyperfiltration. Hyperfiltration occurs early in BTBRob/ob mice and disappears with disease progression as a consequence of a reduced filtration surface. It remains to be assessed if tGFR is also a valid method in diabetic mice with severely compromised renal function.NEW & NOTEWORTHY tGFR measurement is a relatively new method to assess kidney function in conscious rodents, which can be repeated multiple times in the same animal to track the course of the disease and/or the effect of potential treatments. Since the literature was inconclusive on the suitability of this technique in obese mice, we validated it for the first time against classical plasma clearance in the commonly used BTBRob/ob mouse model.

Influence of carnosine and carnosinase-1 on diabetes-induced afferent arteriole vasodilation: implications for glomerular hemodynamics.

Dysregulation in glomerular hemodynamics favors hyperfiltration in diabetic kidney disease (DKD). Although carnosine supplementation ameliorates features of DKD, its effect on glomerular vasoregulation is not known. We assessed the influence of carnosine and carnosinase-1 (CN1) on afferent glomerular arteriole vasodilation and its association with glomerular size, hypertrophy, and nephrin expression in diabetic BTBRob/ob mice. Two cohorts of mice including appropriate controls were studied: i.e., diabetic mice that received oral carnosine supplementation (cohort 1) and human (h)CN1 transgenic (TG) diabetic mice (cohort 2). The lumen area ratio (LAR) of the afferent arterioles and glomerular parameters were measured by conventional histology. Three-dimensional analysis using a tissue clearing strategy was also used. In both cohorts, LAR was significantly larger in diabetic BTBRob/ob versus nondiabetic BTBRwt/ob mice (0.41 ± 0.05 vs. 0.26 ± 0.07, P < 0.0001 and 0.42 ± 0.06 vs. 0.29 ± 0.04, P < 0.0001) and associated with glomerular size (cohort 1: r = 0.55, P = 0.001 and cohort 2: r = 0.89, P < 0.0001). LAR was partially normalized by oral carnosine supplementation (0.34 ± 0.05 vs. 0.41 ± 0.05, P = 0.004) but did not differ between hCN1 TG and wild-type BTBRob/ob mice. In hCN1 TG mice, serum CN1 concentrations correlated with LAR (r = 0.90, P = 0.006). Diabetic mice displayed decreased nephrin expression and increased glomerular hypertrophy. This was not significantly different in hCN1 TG BTBRob/ob mice (P = 0.06 and P = 0.08, respectively). In conclusion, carnosine and CN1 may affect intraglomerular pressure in an opposing manner through the regulation of afferent arteriolar tone. This study corroborates previous findings on the role of carnosine in the progression of DKD.NEW & NOTEWORTHY Dysregulation in glomerular hemodynamics favors hyperfiltration in diabetic kidney disease (DKD). Although carnosine supplementation ameliorates features of DKD, its effect on glomerular vasoregulation is not known. We assessed the influence of carnosine and carnosinase-1 (CN1) on afferent glomerular arteriole vasodilation and its association with glomerular size, hypertrophy, and nephrin expression in diabetic BTBRob/ob mice. Our results provide evidence that carnosine feeding and CN1 overexpression likely affect intraglomerular pressure through vasoregulation of the afferent arteriole.

Explicit spatial modeling at the pore scale unravels the interplay of soil organic carbon storage and structure dynamics.

The structure of soil aggregates plays an important role for the turnover of particulate organic matter (POM) and vice versa. Analytical approaches usually do not disentangle the continuous re-organization of soil aggregates, caught between disintegration and assemblage. This led to a lack of understanding of the mechanistic relationship between aggregation and organic matter dynamics in soils. In this study, we took advantage of a process-based mechanistic model that describes the interaction between the dynamic (re-)arrangement of soil aggregates, based on dynamic image analysis data of wet-sieved aggregates, to analyze the turnover of POM, and simultaneous soil surface interactions in a spatially and temporally explicit way. Our novel modeling approach enabled us to unravel the temporal development of aggregate sizes, organic carbon (OC) turnover of POM, and surface coverage as affected by soil texture, POM input, and POM decomposition rate comparing a low and high clay soil (18% and 33% clay content). Our results reveal the importance of the dynamic re-arrangement of soil structure on POM-related turnover of OC in soils. Firstly, aggregation was largely determined by the POM input fostering aggregates through additional gluing joints outweighing soil texture at lower decomposition rate, whereas at higher decomposition rate, soil texture had a higher influence leading to larger aggregates in the high clay soil. Secondly, the POM storage increased with clay content, showing that surface interactions may delay the turnover of OC into CO2 . Thirdly, we observed a structural priming effect in which the increased input of POM induced increased structural re-arrangement stimulating the mineralization of old POM. This work highlights that the dynamic re-arrangement of soil aggregates has important implications for OC turnover and is driven by underlying surface interactions where temporary gluing spots stabilize larger aggregates.

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry.

Fluoride abstraction from different types of transition metal fluoride complexes [Ln MF] (M=Ti, Ni, Cu) by the Lewis acid tris(pentafluoroethyl)difluorophosphorane (C2 F5 )3 PF2 to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C2 F5 )3 PF3 ]- ) is reported. (C2 F5 )3 PF2 reacted with trans-[Ni(iPr2 Im)2 (ArF )F] (iPr2 Im=1,3-diisopropylimidazolin-2-ylidene; ArF =C6 F5 , 1 a; 4-CF3 -C6 F4 , 1 b; 4-C6 F5 -C6 F4 , 1 c) through fluoride transfer to form the complex salts trans-[Ni(iPr2 Im)2 (solv)(ArF )]FAP (2 a-c[solv]; solv=Et2 O, CH2 Cl2 , THF) depending on the reaction medium. In the presence of stronger Lewis bases such as carbenes or PPh3 , solvent coordination was suppressed and the complexes trans-[Ni(iPr2 Im)2 (PPh3 )(C6 F5 )]FAP (trans-2 a[PPh3 ]) and cis-[Ni(iPr2 Im)2 (Dipp2 Im)(C6 F5 )]FAP (cis-2 a[Dipp2 Im]) (Dipp2 Im=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were isolated. Fluoride abstraction from [(Dipp2 Im)CuF] (3) in CH2 Cl2 or 1,2-difluorobenzene led to the isolation of [{(Dipp2 Im)Cu}2 ]2+ 2 FAP- (4). Subsequent reaction of 4 with PPh3 and different carbenes resulted in the complexes [(Dipp2 Im)Cu(LB)]FAP (5 a-e, LB=Lewis base). In the presence of C6 Me6 , fluoride transfer afforded [(Dipp2 Im)Cu(C6 Me6 )]FAP (5 f), which serves as a source of [(Dipp2 Im)Cu)]+ . Fluoride abstraction of [Cp2 TiF2 ] (7) resulted in the formation of dinuclear [FCp2 Ti(µ-F)TiCp2 F]FAP (8) (Cp=η5 -C5 H5 ) with one terminal fluoride ligand at each titanium atom and an additional bridging fluoride ligand.

The influence of anodal transcranial direct current stimulation over the right auditory cortex on interference effects in memory for melodies.

The study investigates how transcranial direct current stimulation (tDCS) over the auditory cortex (AC) modulates memory for melodies under different noise conditions, whilst also considering cumulative disruptive interference effects. Forty-one participants completed a continuous recognition melody task, as well as a visual control task, which included four noise conditions for which noise was either present only during encoding (N-C), only during retrieval (C-N), during both (N-N) or not at all (C-C) and completed the tasks after receiving anodal or sham tDCS over the right AC. The results of the sham session replicate previous findings by revealing that memory for melodies is worse when noise in added to the encoding phase (N-C) whereas the N-N condition shows good performance, highlighting a context effect, and that cumulative disruptive interference is not present in memory for melodies except in the N-C condition. After anodal stimulation the memory pattern differs such as that memory performance is best in the C-C condition and furthermore the cumulative disruptive interference effect in the N-C condition is diminished. In sum, the study highlights the involvement of the right AC for memory for melodies and the results indicate an association of the AC for creating context effects.

Diagnosis and treatment of isolated snoring-open questions and areas for future research.

STUDY OBJECTIVES: Snoring is a common phenomenon which is generated by vibration of soft tissue of the upper airway during sleep. Due to the high incidence of isolated snoring and the substantial burden for the patient and the bed partner, a thorough examination and appropriate therapy are required. Many recommendations for the treatment of isolated snoring are either not evidence-based or are derived from recommendations for the management of obstructive sleep apnea. Therefore, the aim of this study is the identification and description of open questions in the diagnosis and treatment of isolated snoring and the illustration of areas for further research. METHODS: In the context of the development of the new version of the German guideline "Diagnosis and treatment of isolated snoring in adults," a multidisciplinary team of experts performed a systematic literature search on the relevant medical data and rated the current evidence regarding the key diagnostic and therapeutic measures for snoring. RESULTS: The systematic literature review identified 2293 articles. As a major inclusion criterion, only studies on primary snoring based on objective sleep medical assessment were selected. After screening and evaluation, 33 full-text articles remained for further analysis. Based on these articles, open questions and areas for future research were identified for this review. CONCLUSION: Several major gaps in the literature on the diagnosis and treatment of isolated snoring were identified. For the majority of diagnostic and therapeutic measures for snoring, high-level scientific evidence is still lacking.

Live-Attenuated Influenza Vaccine Induces Tonsillar Follicular T Helper Cell Responses That Correlate With Antibody Induction.

BACKGROUND: Influenza remains a major threat to public health. Live-attenuated influenza vaccines (LAIV) have been shown to be effective, particularly in children. Follicular T helper (TFH) cells provide B-cell help and are crucial for generating long-term humoral immunity. However the role of TFH cells in LAIV-induced immune responses is unknown. METHODS: We collected tonsils, plasma, and saliva samples from children and adults receiving LAIV prior to tonsillectomy. We measured influenza-specific TFH-cell responses after LAIV by flow cytometry and immunohistochemistry. Systemic and local antibody responses were analysed by hemagglutination inhibition assay and enzyme-linked immunosorbent assay. RESULTS: We report that LAIV induced early (3-7 days post-vaccination) activation of tonsillar follicles and influenza-specific TFH-cell (CXCR5+CD57+CD4+ T cell) responses in children, and to a lesser extent in adults. Serological analyses showed that LAIV elicited rapid (day 14) and long-term (up to 1 year post-vaccination) antibody responses (hemagglutination inhibition, influenza-specific IgG) in children, but not adults. There was an inverse correlation between pre-existing influenza-specific salivary IgA concentrations and tonsillar TFH-cell responses, and a positive correlation between tonsillar TFH-cell and systemic IgG induction after LAIV. CONCLUSIONS: Our data, taken together, demonstrate an important role of tonsillar TFH cells in LAIV-induced immunity in humans.

Upper airway stimulation for obstructive sleep apnea-Can radiological position monitoring predict tongue motion one year after implantation?

BACKGROUND: Tongue motion patterns (TMP) can influence the outcome of upper airway stimulation (UAS) in the treatment of obstructive sleep apnea (OSA). As a postoperative control, the cuff position of the stimulation lead is monitored via X­ray imaging. A multidimensional X­ray assessment system was established and the association between these positional assessments and TMP was investigated 1 year after implantation. MATERIAL AND METHODS: The study on TMP and the X­ray assessments were carried out at a German ear nose and throat clinic as an implantation center. The TMPs were assessed under bipolar electrode configuration and were categorized according to the currently available literature as right-sided protrusion (RP), left-sided protrusion (LP), bilateral protrusion (BP) and mixed activation (MA). The X­ray assessment was carried out in five dimensions: the position relative to the mandible and hyoid, cuff steepness in the lateral view of the neck, the cuff position based on the single electrode, and the lead connection to the cuff in the anterior-posterior view. The analyses were performed by three raters with different medical backgrounds and knowledge regarding TMP. RESULTS: In approximately 60% of patients, the apnea-hypopnea index was reduced to below 15/h 1 year after implantation. The most common TMPs were RP and BP (82.9%). The interrater variability of the X­ray assessment was good except for one category. Furthermore, no relevant associations were found apart from the correlation between a favorable TMP and the cuff position with respect to the lateral position of the stimulation cable. CONCLUSION: Despite good interrater variability and convenient usage of the suggested X­ray assessment system, this approach did not enable the identification of any associations by which a TM and, therefore, a possible straightforward or complicated treatment pathway could be predicted. Attention should possibly be paid to a rotation of the cuff during implantation with a lateral position of the stimulation lead.

[Upper Airway Stimulation for obstructive sleep apnea-Can radiological position monitoring predict tongue motion one year after implantation? German version]. / Die obere Atemwegsstimulation bei obstruktiver Schlafapnoe ­ Kann die radiologische Lage des Stimulation-Cuff die Zungenbewegung vorhersagen?

BACKGROUND: Tongue motion patterns (TMP) can influence the outcome of upper airway stimulation (UAS) in the treatment of obstructive sleep apnea (OSA). As a postoperative control the cuff position of the stimulation lead is monitored via X­ray imaging. A multidimensional X­ray assessment system was established and the association between these positional assessments and TMP was investigated 1 year after implantation. MATERIAL AND METHODS: The study on TMP and the X­ray assessments were carried out at a German ear nose and throat clinic as an implantation center. The TMPs were assessed under bipolar electrode configuration and were categorized according to the currently available literature as right-sided protrusion (RP), left-sided protrusion (LP), bilateral protrusion (BP) and mixed activation (MA). The X­ray assessment was carried out in five dimensions: the position relative to the mandible and hyoid, cuff steepness in the lateral view of the neck, the cuff position based on the single electrode and the lead connection to the cuff in the anterior-posterior view. The analyses were performed by three raters with different medical backgrounds and knowledge regarding TMP. RESULTS: In approximately 60% of the patients the apnea-hypopnea index was reduced to below 15/h, 1 year after implantation. The most common TMPs were RP and BP (82.9%). The interrater variability of the X­ray assessment was good except for one category. Furthermore, no relevant associations were found apart from the correlation between a favorable TMP and the cuff position with respect to the lateral position of the stimulation cable. CONCLUSION: Despite good interrater variability and convenient usage of the suggested X­ray assessment system, this approach did not enable the identification of any associations, by which a TM and therefore a possible straightforward or complicated treatment pathway could be predicted. Attention should possibly be paid to a rotation of the cuff during implantation with a lateral position of the stimulation lead.

Rapid soil formation after glacial retreat shaped by spatial patterns of organic matter accrual in microaggregates.

Global change contributes to the retreat of glaciers at unprecedented rates. The deglaciation facilitates biogeochemical processes on glacial deposits with initiating soil formation as an important driver of evolving ecosystems. The underlying mechanisms of soil formation and the association of soil organic matter (SOM) with mineral particles remain unclear, although further insights are critical to understand carbon sequestration in soils. We investigated the microspatial arrangement of SOM coatings at intact soil microaggregate structures during various stages of ecosystem development from 15 to >700 years after deglaciation in the proglacial environment of the Damma glacier (Switzerland). The functionally important clay-sized fraction (<2 µm) was separated into two density fractions with different amounts of organo-mineral associations: light (1.6-2.2 g/cm3 ) and heavy (>2.2 g/cm3 ). To quantify how SOM extends across the surface of mineral particles (coverage) and whether SOM coatings are distributed in fragmented or connected patterns (connectivity), we developed an image analysis protocol based on nanoscale secondary ion mass spectrometry (NanoSIMS). We classified SOM and mineral areas depending on the 16 O- , 12 C- , and 12 C14 N- distributions. With increasing time after glacial retreat, the microspatial coverage and connectivity of SOM increased rapidly. The rapid soil formation led to a succession of patchy distributed to more connected SOM coatings on soil microaggregates. The maximum coverage of 55% at >700 years suggests direct evidence for SOM sequestration being decoupled from the mineral surface, as it was not completely masked by SOM and retained its functionality as an ion exchange site. The chemical composition of SOM coatings showed a rapid change toward a higher CN:C ratio already at 75 years after glacial retreat, which was associated with microbial succession patterns reflecting high N assimilation. Our results demonstrate that rapid SOM sequestration drives the microspatial succession of SOM coatings in soils, a process that can stabilize SOM for the long term.

Long-run in operando NMR to investigate the evolution and degradation of battery cells.

To improve the lifetime of lithium-ion batteries, a detailed understanding of the degradation mechanisms is essential. Nuclear magnetic resonance (NMR) is able to unravel the reversible as well as irreversible transient changes of composition, shape and morphology in a battery cell. Using a newly developed cylindrical battery container free of metallic components in combination with a numerically optimized saddle coil, in operando NMR investigations of battery cells over hundreds of charge/discharge cycles are presented. Alternating with NMR data acquisition, electrochemical impedance spectra (EIS) can be recorded, which enables correlative analysis of the two techniques. Long-run in operando NMR measurements on a Li metal vs. graphite cell reveal the formation and evolution of mossy and dendritic Li microstructures over a period of 1000 h, which illustrates the capabilities of NMR to identify dendrite mitigation strategies in cells operated under realistic conditions.

Complete concentric collapse at the soft palate in sleep endoscopy: what change is possible after UPPP in patients with CPAP failure?

PURPOSE: The aim of this work was to assess whether uvulopalatopharyngoplasty in patients with failure for positive airway pressure not only reduces the degree of obstructive sleep apnea but also to determine as well if it changes the collapse pattern of the soft palate and thereby fulfills the qualifications for implementing upper airway stimulation (UAS) as an adjunctive solution. METHOD: Fifteen patients with intolerance for positive airway pressure were included in this retrospective cohort study. Polygraphy and drug-induced sleep endoscopy were used in order to evaluate the reduction of the apnea-hypopnea index (AHI), as well as the change of collapse pattern at the soft palate level before and about 3 months after uvulopalatopharyngoplasty and tonsillectomy (TE-UPPP). RESULTS: In 93% of the patients, a postoperative change of the initially complete concentric palatal collapse pattern could be found during drug-induced sleep endoscopy. In one patient, no obstruction at all was seen at the soft palatal level. Only one patient still presented with a complete concentric collapse at velum level. AHI decreased from mean 34.7 events per hour to 20.2/h and oxygen desaturation index from 25.3 events per hour to 16.1/h. CONCLUSION: Patients seeking for positive airway pressure alternatives could not only benefit from reduction of AHI by TE-UPPP postoperatively; additionally, by changing the collapse pattern at the soft palate, they might also fulfill criteria for upper airway stimulation (UAS) in case of persistent OSA of at least moderate degree.

Patient-reported outcome: results of the multicenter German post-market study.

PURPOSE: Upper airway stimulation (UAS) is an alternative second-line treatment option for patients with obstructive sleep apnea (OSA). In our substudy of a previous multicentre study of patients implanted with UAS, we focused on patient-related outcomes like Epworth Sleepiness Scale (ESS), the Functional Outcomes of Sleep Questionnaire (FOSQ), snoring and personal satisfaction 6 and 12 months after the implantation. METHODS: 60 patients, who were initially non-adherent to CPAP and implanted with UAS, were included in a prospective multicentre study. Data were collected preoperative, 6 and 12 months after implantation regarding FOSQ, ESS, snoring, and their experience with the UAS device. RESULTS: Besides relevant Apnoea-Hypopnea Index (AHI) reduction, we saw significant improvements in ESS (p < 0.001), FOSQ (p < 0.001) and snoring under UAS therapy. A strong correlation between AHI results postoperative and the personal satisfaction of the patients after implantation was found as well as between usage results and AHI compared to the preoperative results. CONCLUSION: The more the patients benefit from UAS according to their self-reported outcome, the higher is the therapy use.

[Sleep endoscopy and complete concentric collapse in CPAP failure]. / Schlafendoskopie und komplett konzentrischer Weichgaumenkollaps bei CPAP-Nutzungsproblemen.

INTRODUCTION: First-line treatment for patients with obstructive sleep apnea (OSA) is continuous positive airway pressure (CPAP) therapy. However, many patients cannot use CPAP sufficiently. With drug-induced endoscopy (DISE), it is possible to assess the collapse pattern in the upper airway. The aim of this work was to evaluate a collective of patients with CPAP usage problems using DISE, in order to evaluate their usage problems and therapy recommendations. METHODS: Over a period of 5 years, all patients with an apnea-hypopnea index (AHI) of at least 15/h were retrospectively evaluated using DISE. The recommended treatment options were then analyzed. RESULTS: Data analysis of 210 patients showed that about two thirds reported mask problems as the cause of non-adherence to CPAP. A complete concentric collapse (CCC) could be excluded in 75%. These patients had a lower AHI and more frequent tonsillectomy (TE) than patients with CCC. Double the number of patients with a body mass index (BMI) > 35 kg/m2 had a CCC compared to those with a BMI < 35 kg/m2. Among patients with similar BMI and AHI, CCC was twice as likely to be found in patients without TE. CONCLUSION: The course of treatment recommended for OSA often differs, depending on CCC, BMI > 35 kg/m2, and previous TE.

Increasing chloride concentration causes retention of mercury in melted Arctic snow due to changes in photoreduction kinetics.

Mercury (Hg) in the Arctic is a significant concern due to its bioaccumulative and neurotoxic properties, and the sensitivity of Arctic environments. Previous research has found high levels of Hg in snowpacks with high chloride (Cl-) concentrations. We hypothesised that Cl- would increase Hg retention by decreasing Hg photoreduction to Hg(0) in melted Arctic snow. To test this, changes in Hg photoreduction kinetics in melted Alert, NU snow were quantified with changing Cl- concentration and UV intensity. Snow was collected and melted in Teflon bottles in May 2014, spiked with 0-10µg/g Cl-, and irradiated with 3.52-5.78W·m-2 UV (280-400nm) radiation in a LuzChem photoreactor. Photoreduction rate constants (k) (0.14-0.59hr-1) had positive linear relationships with [Cl-], while photoreduced Hg amounts (Hg(II)red) had negative linear relationships with [Cl-] (1287-64pg in 200g melted snow). Varying UV and [Cl-] both altered Hg(II)red amounts, with more efficient Hg stabilisation by Cl- at higher UV intensity, while k can be predicted by Cl- concentration and/or UV intensity, depending on experimental parameters. Overall, with future projections for greater snowpack Cl- loading, our experimental results suggest that more Hg could be delivered to Arctic aquatic ecosystems by melted snow (smaller Hg(II)red expected), but the Hg in the melted snow that is photoreduced may do so more quickly (larger k expected).

An Investigation of the Symmetric and Asymmetric Cleavage Products in the System Aluminum Trihalide/1-Butylimidazole.

Mixtures of AlX3 (X=Cl, Br) with 1-butylimidazole (BuIm) in various ratios were investigated. The mixtures were characterized by multinuclear (1 H, 27 Al, 13 C, and 15 N) NMR, IR, and Raman spectroscopy and in part by single-crystal X-ray diffraction. Depending on the molar fraction x(AlBr3 ) of the AlBr3 -based mixtures, the cationic aluminum complexes [Al(BuIm)6 ]3+ and [AlBr2 (BuIm)4 ]+ , the neutral adduct [AlBr3 (BuIm)], as well as the anions Br- , [AlBr4 ]- , and [Al2 Br7 ]- could be identified as the products of the symmetric and asymmetric cleavage of dimeric Al2 Br6 . Furthermore, there are hints at the formation of [AlBr2 (BuIm)2 ]+ or related cations. Comparison of the AlBr3 /BuIm system with AlCl3 -based mixtures revealed the influence of the halide: In contrast to AlBr3 , the trication [Al(BuIm)6 ]3+ could not be detected as main product in a 1:6 mixture of AlCl3 and BuIm. Additionally, [AlCl3 (BuIm)] crystallizes from a mixture with x(AlCl3 )=0.60 at room temperature, whereas the corresponding AlBr3 -based mixture remains liquid even at +6 °C. Three AlBr3 -based mixtures are liquid at room temperature, whereas all other mixtures are solids with melting points between 46 and 184 °C. The three liquid mixtures exhibit medium to high viscosities (117 to >1440 mPa s), low conductivities (0.03-0.20 mS cm-1 ), but high densities (1.80-2.21 g cm-3 ). Aluminum could be successfully deposited from one of the neat Lewis acidic mixtures of the AlBr3 -based system.

A Novel Approach to Prenatal Measurement of the Fetal Frontal Lobe Using Three-Dimensional Sonography.

OBJECTIVE: While prenatal 3D ultrasonography results in improved diagnostic accuracy, no data are available on biometric assessment of the fetal frontal lobe. This study was designed to assess feasibility of a standardized approach to biometric measurement of the fetal frontal lobe and to construct frontal lobe growth trajectories throughout gestation. STUDY DESIGN: A sonographic 3D volume set was obtained and measured in 101 patients between 16.1 and 33.7 gestational weeks. Measurements were obtained by two independent raters. To model the relationship between gestational age and each frontal lobe measurement, flexible linear regression models were fit using penalized regression splines. RESULTS: The sample contained an ethnically diverse population (7.9% Native Americans, 45.5% Hispanic/Latina). There was high inter-rater reliability (correlation coefficients: 0.95, 1.0, and 0.87 for frontal lobe length, width, and height; p-values < 0.001). Graphs of the growth trajectories and corresponding percentiles were estimated as a function of gestational age. The estimated rates of frontal lobe growth were 0.096 cm/week, 0.247 cm/week, and 0.111 cm/week for length, width, and height. CONCLUSION: To our knowledge, this is the first study to examine fetal frontal lobe growth trajectories through 3D prenatal ultrasound examination. Such normative data will allow for future prenatal evaluation of a particular disease state by 3D ultrasound imaging.

A Novel Approach to Prenatal Measurement of the Fetal Frontal Lobe Using Three-Dimensional Sonography.

Objective: To assess the feasibility of a standardized approach to biometric measurement of the fetal frontal lobe and to construct frontal lobe growth trajectories throughout gestation. Study Design: A sonographic 3-dimensional (3D) volume set was obtained and measured in 101 patients between 16.1 and 33.7 gestational weeks. Measurements were obtained by 2 independent raters. To model the relationship between gestational age and each frontal lobe measurement, flexible linear regression models were fit using penalized regression splines. Results: The sample contained an ethnically diverse population (7.9% Native Americans, 45.5% Hispanics/Latinas). There was high interrater reliability (correlation coefficients 0.95, 1.0, and 0.87 for frontal lobe length, width, and height; p values <0.001). Graphs of the growth trajectories and corresponding percentiles were estimated as a function of gestational age. The estimated rates of frontal lobe growth were 0.096 cm/week, 0.247 cm/week, and 0.111 cm/week for length, width, and height, respectively. Conclusion: To our knowledge, this is the first study to examine fetal frontal lobe growth trajectories through 3D prenatal ultrasound examination. Such normative data will allow for future prenatal evaluation of a particular disease state by 3D ultrasound imaging.

Supine position and REM dependence in obstructive sleep apnea : Critical model considerations.

BACKGROUND: When considering supine position and REM dependence, many studies refer to the traditional definition in which obstructive sleep apnea (OSA) severity is at least doubled in the corresponding position/sleep stage (Cartwright index). The lack of consideration of the time spent in that particular sleep situation can lead to clinical bias. PATIENTS AND METHODS: Two cohorts of patients with at least moderate OSA were analyzed retrospectively for anthropometric associations and correlations with OSA severity. One group consisted of 48 patients diagnosed using a polygraph, and the other group of 222 patients underwent polysomnography. First, the conventional Cartwright index was used, and a modified index was later applied to integrate the relative time component for REM sleep and the supine position. RESULTS: Less than a fifth of the patients fulfilled the classic conditions for supine position or REM sleep dependency. There were no definitive cut-offs in the classic or modified Cartwright index with regard to daytime sleepiness. Both indices show there was a correlation between OSA severity and being overweight. CONCLUSION: The modified Cartwright index allowed us to identify borderline cases that were characterized by a very low or high amount of time spent in the supine position or REM sleep situation. Therapy effects that could have been biased only by varying amounts of time spent in the supine position could be better controlled for. Future studies will possibly include various other ratios besides the previously accepted 2:1 ratio when different statistical parameters are considered, such as the reduction of OSA severity or therapy adherence.