Synthesis and Supramolecular Structure of a (5-(3-(1H-tetrazol-5-yl)phenyl)-1H-tetrazole) Cobalt Complex

The reaction of CoCl2·6H2O with m-BDTH2 (1,3-benzeneditetrazol-5-yl) leads to [Co(C8H6N8)2(H2O)2(CH3CN)2]Cl2 (1). Both tetrazolic groups remain protonated existing in a 1H tautomeric form. A trifurcated chlorine atom and stacking interactions assemble compound 1 into a three-dimensional network

An undecanuclear ferrimagnetic Cu9Dy2 SMM achieved through ligand fine-tuning

We describe the concept of increasing the nuclearity of a previously reported high-spin Cu5Gd2 core using a “fine tuning” ligand approach. Thus two Cu9Ln2 coordination clusters, with Ln = Dy (1), Gd(2) were synthesized with the Gd compound having a ground spin state of 17/2 and the Dy analogue showing SMM behavior in zero field

Tetranuclear CuII2DyIII2 coordination cluster as Suzuki (C–C) coupling reaction promoter

The air stable and high yielding tetranuclear coordination cluster [CuII2DyIII2L4(NO3)2(CH3CN)2]·2(CH3CN) promotes the Suzuki coupling reaction of phenylboronic acid with substituted aryl halides in environmentally benign conditions

Systematic studies of hexanuclear {MIII4LnIII2} complexes (M = Fe, Ga; Ln = Er, Ho): structures, magnetic properties and SMM behavior

Four isostructural MIII4LnIII2 coordination clusters, [M4Ln2(μ3-OH)2(nbdea)4(C6H5COO)8]•MeCN (M = Fe, Ln = Er (1); M = Ga, Ln = Er (2); M = Fe, Ln = Ho (3); M = Ga, Ln = Ho (4)) have been synthesized and characterized. Single-crystal X-ray diffraction and X-ray powder diffraction studies revealed that all four compounds crystallize isomorphously to each other, and to the previously reported MIII4DyIII2 (M = Fe or Ga) and FeIII4YIII2 analogues. DC magnetic susceptibility measurements for compounds 1-4, taken in combination with those for the FeIII4YIII2 analogue, indicated that the interactions between ErIII ions are weakly ferromagnetic and the FeIII-ErIII interactions are very weakly antiferromagnetic, while the HoIII-HoIII and FeIII-HoIII interactions are both negligible. By comparison, for the FeIII4DyIII2 analogue, the DyIII-DyIII interactions are antiferromagnetic while the FeIII-DyIII are ferromagnetic. Both Er analogues 1 and 2 display single-molecule magnet (SMM) behavior with the effective energy barrier Ueff increasing from 12.8 K (for Fe4Er2 1) to 53.5 K (for Ga4Er2 2), indicating that the very weak 3d-4f interaction enhances the QTM effect

SMM behaviour and magnetocaloric effect in heterometallic 3d-4f coordination clusters with high azide : metal ratios

We present the synthesis and characterization of heterometallic compounds with a very large azide to metal ratio and fascinating magnetic properties

Stepwise investigation of the influences of steric groups versus counter ions to target Cu/Dy complexes

From an investigation of varying the steric bulk of a flexible ligand, we have produced a family of structures using similar reaction conditions. Even small changes from a hydrogen atom to a methyl to an ethyl group on the ligand influences the structural outcome, which can also be steered by the nature of the metal source. We employed Schiff base ligands by combining o-vanillin and three different 2-amino-1,3-propandiol units, leading to H3L1 (R=hydrogen), H3L2 (R=methyl) and H3L3 (R=ethyl). The differing nuclearities of the three clusters, 1 to 3, originate mainly from the steric influence, while this effect is not seen in complex 4 to 6, where the general butterfly motif is maintained. We present here the synthesis, crystal structures and magnetic properties of six new CuII-LnIII complexes, providing valuable insight into future synthetic directions. The topological part includes a table of all CuII-DyIII complexes with nuclearities higher than four and their topological motif. The investigation of the magnetic behaviors reveal that all six complexes show frequency dependent signals in the out-of phase ac susceptibility, which is indicative for SMM behavior

Varying the dimensionality of Cu(II)-based coordination polymers through solvent influence

This work reports the synthesis and structure of a large porous zeotype network observed within compound (1) using {Cu2(piv)4} as the linking unit (piv = pivalate). The slow in-situ formation of the hmt ligand (hexamethylenetetramine) appears to be key in generating a µ4-briding mode of the hmt-node. Attempts to improve the low yield of compound (1) using different solvent layer diffusion methods resulted in the µ3-hmt complexes (2) and (3). Both compounds exhibit a 3D network of two intertwined chiral networks. Strong hydrogen bonding present in (3) leads to the formation of intertwined DNA-like double-helix structures. The use of bulky solvents in the synthesis of compound (4) leads to the structure crystallizing solvent-free. The packing of (4) is dominated by energy minimization which is achieved when the 1D-“cylinders” pack into the closest possible arrangement. This work highlights the potential for solvent controlled synthesis of extended copper-hmt systems

Mercury loading within the Selenga River basin and Lake Baikal, Siberia

Mercury (Hg) loading in Lake Baikal, a UNESCO world heritage site, is growing and poses a serious health concern to the lake’s ecosystem due to the ability of Hg to transform into a toxic form, known as methylmercury (MeHg). Monitoring of Hg into Lake Baikal is spatially and temporally sparse, highlighting the need for insights into historic Hg loading. This study reports measurements of Hg concentrations from water collected in August 2013 and 2014 from across Lake Baikal and its main inflow, the Selenga River basin (Russia, Mongolia). We also report historic Hg contamination using sediment cores taken from the south and north basins of Lake Baikal, and a shallow lake in the Selenga Delta. Field measurements from August 2013 and 2014 show high Hg concentrations in the Selenga Delta and river waters, in comparison to pelagic lake waters. Sediment cores from Lake Baikal show that Hg enrichment commenced first in the south basin in the late-19th century, and then in the north basin in the mid-20th century. Hg flux was also 20-fold greater in the south basin compared to the north basin sediments. Hg enrichment was greatest in the Selenga Delta shallow lake (Enrichment Ratio (ER) = 2.3 in 1994 CE), with enrichment occurring in the mid- to late-20th century. Local sources of Hg are predominantly from gold mining along the Selenga River, which have been expanding over the last few decades. More recently, another source is atmospheric deposition from industrial activity in Asia, due to rapid economic growth across the region since the 1980s. As Hg can bioaccumulate and biomagnify through trophic levels to Baikal’s top consumer, the world’s only truly freshwater seal (Pusa sibirica), it is vital that Hg input at Lake Baikal and within its catchment is monitored and controlled

Diagnostic accuracy of cyst fluid amphiregulin in pancreatic cysts

<p>Abstract</p> <p>Background</p> <p>Accurate tests to diagnose adenocarcinoma and high-grade dysplasia among mucinous pancreatic cysts are clinically needed. This study evaluated the diagnostic utility of amphiregulin (AREG) as a pancreatic cyst fluid biomarker to differentiate non-mucinous, benign mucinous, and malignant mucinous cysts.</p> <p>Methods</p> <p>A single-center retrospective study to evaluate AREG levels in pancreatic cyst fluid by ELISA from 33 patients with a histological gold standard was performed.</p> <p>Results</p> <p>Among the cyst fluid samples, the median (IQR) AREG levels for non-mucinous (n = 6), benign mucinous (n = 15), and cancerous cysts (n = 15) were 85 pg/ml (47-168), 63 pg/ml (30-847), and 986 pg/ml (417-3160), respectively. A significant difference between benign mucinous and malignant mucinous cysts was observed (<it>p </it>= 0.025). AREG levels greater than 300 pg/ml possessed a diagnostic accuracy for cancer or high-grade dysplasia of 78% (sensitivity 83%, specificity 73%).</p> <p>Conclusion</p> <p>Cyst fluid AREG levels are significantly higher in cancerous and high-grade dysplastic cysts compared to benign mucinous cysts. Thus AREG exhibits potential clinical utility in the evaluation of pancreatic cysts.</p

Gene expression changes associated with Barrett's esophagus and Barrett's-associated adenocarcinoma cell lines after acid or bile salt exposure

<p>Abstract</p> <p>Background</p> <p>Esophageal reflux and Barrett's esophagus represent two major risk factors for the development of esophageal adenocarcinoma. Previous studies have shown that brief exposure of the Barrett's-associated adenocarcinoma cell line, SEG-1, or primary cultures of Barrett's esophageal tissues to acid or bile results in changes consistent with cell proliferation. In this study, we determined whether similar exposure to acid or bile salts results in gene expression changes that provide insights into malignant transformation.</p> <p>Methods</p> <p>Using previously published methods, Barrett's-associated esophageal adenocarcinoma cell lines and primary cultures of Barrett's esophageal tissue were exposed to short pulses of acid or bile salts followed by incubation in culture media at pH 7.4. A genome-wide assessment of gene expression was then determined for the samples using cDNA microarrays. Subsequent analysis evaluated for statistical differences in gene expression with and without treatment.</p> <p>Results</p> <p>The SEG-1 cell line showed changes in gene expression that was dependent on the length of exposure to pH 3.5. Further analysis using the Gene Ontology, however, showed that representation by genes associated with cell proliferation is not enhanced by acid exposure. The changes in gene expression also did not involve genes known to be differentially expressed in esophageal adenocarcinoma. Similar experiments using short-term primary cultures of Barrett's esophagus also did not result in detectable changes in gene expression with either acid or bile salt exposure.</p> <p>Conclusion</p> <p>Short-term exposure of esophageal adenocarcinoma SEG-1 cells or primary cultures of Barrett's esophagus does not result in gene expression changes that are consistent with enhanced cell proliferation. Thus other model systems are needed that may reflect the impact of acid and bile salt exposure on the esophagus <it>in vivo</it>.</p