2-hydroxybenzophenone-controlled self-assembly of enneanuclear lanthanide(III) hydroxo coordination clusters with an “hourglass”-like topology

Enneanuclear lanthanide(III) hydroxo coordination clusters with an “hourglass”- or “sandglass”-like topology have been synthesized via 2-hydroxybenzophenone-controlled hydrolysis of the metal ions in ethanol; the Eu^III₉ complex displays an intense red, metal-centered emission in the solid state at room temperature which is achieved by an indirect process (antenna effect).     

A Polymorphism at the 3′-UTR Region of the Aromatase Gene Is Associated with the Efficacy of the Aromatase Inhibitor,Anastrozole, in Metastatic Breast Carcinoma

Estrogen-related genes and the fat mass and obesity-associated (FTO) gene play a critical role in estrogen metabolism, and those polymorphisms are associated with a poor prognosis in breast cancer. However, little is known about the association between these polymorphisms and the efficacy of anastrozole. The aim was to investigate the impact of the genetic polymorphisms, CYP19A1, 17-β-HSD-1 and FTO, on the response to anastrozole in metastatic breast carcinoma (MBC) and to evaluate the impact of those polymorphisms on various clinicopathologic features. Two-hundred seventy-two women with hormone receptor-positive MBC treated with anastrozole were identified retrospectively. DNA was extracted from peripheral blood and genotyped for five variants in three candidate genes. Time to progression was improved in patients carrying the variant alleles of rs4646 when compared to patients with the wild-type allele (16.40 months versus 13.52 months; p = 0.049). The rs4646 variant alleles were significantly associated with longer overall survival (37.3 months versus 31.6 months; p = 0.007). This relationship was not observed with the rs10046, rs2830, rs9926298 and rs9939609 polymorphisms. The findings of this study indicate that rs4646 polymorphism in the CYP19A1 gene may serve as a prognostic maker of the response to anastrozole in patients with MBC who are treated with anastrozole.     

Is LRP2 Involved in Leptin Transport over the Blood-Brain Barrier and Development of Obesity?

The mechanisms underlying the transport of leptin into the brain are still largely unclear. While the leptin receptor has been implicated in the transport process, recent evidence has suggested an additional role of LRP2 (megalin). To evaluate the function of LRP2 for leptin transport across the blood-brain barrier (BBB), we developed a novel leptin-luciferase fusion protein (pLG), which stimulated leptin signaling and was transported in an in vitro BBB model based on porcine endothelial cells. The LRP inhibitor RAP did not affect leptin transport, arguing against a role of LRP2. In line with this, the selective deletion of LRP2 in brain endothelial cells and epithelial cells of the choroid plexus did not influence bodyweight, body composition, food intake, or energy expenditure of mice. These findings suggest that LRP2 at the BBB is not involved in the transport of leptin into the brain, nor in the development of obesity as has previously been described.     

Study of the Effect of Fluorine Atom(s) on Fluoromethylated Imines in the Tandem Mannich–Michael-type Reaction

Differences in chemical behavior between non-fluorinated and fluorinated methylimines in the tandem Mannich–Michael-type reaction are described based on NMR and computational studies.     

Reaction Pathways for the Enzymatic Degradation of Poly(Ethylene Terephthalate): What Characterizes an Efficient PET-Hydrolase?

Bioprocessing of polyester waste has emerged as a promising tool in the quest for a cyclic plastic economy. One key step is the enzymatic breakdown of the polymer, and this entails a complicated pathway with substrates, intermediates, and products of variable size and solubility. We have elucidated this pathway for poly(ethylene terephthalate) (PET) and four enzymes. Specifically, we combined different kinetic measurements and a novel stochastic model and found that the ability to hydrolyze internal bonds in the polymer (endo-lytic activity) was a key parameter for overall enzyme performance. Endo-lytic activity promoted the release of soluble PET fragments with two or three aromatic rings, which, in turn, were broken down with remarkable efficiency (k_cat/K_M values of about 10⁵ M⁻¹s⁻¹) in the aqueous bulk. This meant that approximatly 70 % of the final, monoaromatic products were formed via soluble di- or tri-aromatic intermediates.     

Reaction of α-tocopherol in heated bulk phase in the presence of methyl linoleate (13S)-hydroperoxide or methyl linoleate

α-Tocopherol and methyl (9Z, 11E)-(S)-13-hydroperoxy-9, 11-octadecadienoate (13-MeLOOH) were allowed to stand at 100°C in bulk phase. The products were isolated and identified as methyl 13-hydroxyoctadecadienoate (1), stereoisomers of methyl 9,11,13-octadecatrienoate (2), methyl 13-oxo-9, 11-octadecadienoate (3), epoxy dimers of methyl linoleate with an ether bond (4), a mixture of methyl (E)-12, 13-epoxy-9-(α-tocopheroxy)-10-octadecenoates and methyl (E)-12, 13-epoxy-9-(α-tocopheroxy)-11-(α-tocopheroxy)-9-octadecenoates (5), a mixture of methyl 9-(α-tocopheroxy)-10,12-octadecadienoates and methyl 13-(α-tocopheroxy)-9, 11-octadecadienoates (6), α-tocopherol spirodiene dimer (7), and α-tocopherol trimer (8). α-Tocopherol and 13-MeLOOH were dissolved in methyl myristate, and the thermal decomposition rate and the distributions of reaction products formed from α-tocopherol and 13-MeLOOH were analyzed. α-Tocopherol disappeared during the first 20 min, and the main products of α-tocopherol were 5 and 6 with the accumulation of 1–4 which were the products of 13-MeLOOH. The results indicate that the alkyl and alkoxyl radicals from the thermal decomposition of 13-MeLOOH could be trapped by α-tocopherol to produce 5 and 6. The reaction products of α-tocopherol during the thermal oxidation of methyl linoleate were compounds 6 and 7. Since the radical flux during the autoxidation might be low, the excess α-tocopheroxyl radical reacted with each other to form 7.     

Role of the isoflavonoid coumestrol in the constitutive antixenosic properties of “Davis” soybeans against an oligophagous insect,the mexican bean beetle

The antixenosic properties of the isoflavonoid, coumestrol, were tested in dual-choice leaf disk bioassays with the Mexican bean beetle (Epilachna varivestis Mulsant).E. varivestis preferred the methanol-r,reated (solvent-control) disk when the coumestrol concentration was 1.8 or 0.9/leaf disk. No preference was observed between the coumestrol-treated and the solvent-control disks when the coumestrol concentration was higher, at 3.6, or lower, at 0.45g/leaf disk. Coumestrol alone clearly is not responsible for the significant constitutive antixenosic properties of Davis soybeans,Glycine max (L.) Merrill, because the amount of coumestrol in these plants is significantly less than the minimum concentration which was antixenosic in this study. However, it might contribute to a constitutive antixenosis in Davis involving a profile of allelochemicals. A computer-aided densitometer, adapted to measure the leaf disk area, increased the resolution of the leaf area 250 (X)-fold as compared to the standard LI-COR leaf area meter.     

Revisiting the specificity of an α-(1→4)-mannosyltransferase involved in mycobacterial methylmannose polysaccharide biosynthesis

In order to evaluate the proposed biosynthetic pathway for the methylmannose (MMPs) polysaccharides produced by mycobacteria, two homologous series of synthetic α-(1→4)-linked 3-O-methyl-mannopyranosides, one terminated at the non-reducing end by a free mannopyranose residue (unmethylated oligosaccharides; OS) and the other terminated by a 3-O-methyl-mannopyranose residue (methylated OS), were prepared and evaluated as potential acceptors of an α-(1→4)-mannosyltransferase. Using a mycobacterial membrane preparation as the source of the transferase, it was found that unmethylated OS are better substrates for the enzyme compared to the methylated OS of the same length. These results are inconsistent with the proposed MMP biosynthetic pathway, which suggests only methylated OS are acceptors of this transferase. To confirm that the observed activity arose from the desired α-(1→4)-mannosyltransferase, as opposed to other mannosyltransferases present in the membrane preparation, the products resulting from tetrasaccharides 4 (unmethylated OS) and 9 (methylated OS), which only differ in the terminal residue, were further analyzed. MALDI-MS, exo-glycosidase digestion and (1) H NMR spectroscopy were used to evaluate the structures of these reaction products. These experiments revealed that the enzymatic products of both 4 and 9 contain only α-(1→4)-linked mannose residues, confirming the activity of the α-(1→4)-mannosyltransferase. This supports the finding that both methylated and unmethylated OS are acceptors of the enzyme. It was also demonstrated that a homologous series of oligosaccharides with different number of mannose residues were formed from both 4 and 9, as opposed to a single reaction product. These results, again, challenge the previously proposed MMP biosynthetic pathway involving alternating methylation and mannosylation reactions.     

Preparation of Cyclopentanol By Direct Hydration of Cyclopentene( Ⅱ ) ∶Optimization of the Reaction

以正丁醇为溶剂,强酸性阳离子交换树脂Amberlyst36为催化剂,环戊烯为原料,采用直接水合法合成环戊醇.通过考察了反应温度、反应时间、助催化剂的种类、n(水)∶n(环戊烯)、催化剂的用量等关键素对反应的影响,得出适宜的反应条件:以正丁醇为溶剂,在n(环戊烯)∶n(水)为1∶4,催化剂Amberlyst36的用量为体系总质量的9％,反应温度150℃,反应时间2h的条件下,得到环戊烯的转化率为12.42％,环戊醇的选择性为95.78％,并在此条件下考察了催化剂的稳定性,结果表明催化剂性能稳定.     

On the Influence of Additives of Polymer,Sodium Nitrate,and 1-Methyl-2-Pyrrolidone on the Extraction of Thiophene in an n-Hexan–Water System

Theoretical Foundations of Chemical Engineering - The effect of individual and multicomponent additives—water-soluble polymers (polyethylene glycol 400, polypropylene glycol 425, and...     

Synthesis, Characterization and Optimum Reaction Conditions of Oligo-N, N′-bis (2-hydroxy-1-naphthalidene) Thiosemicarbazone

The oxidative polycondenzation reaction conditions of N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone (HNTSC) using air oxygen, H₂O₂ and NaOCl were studied in an aqueous alkaline medium between 50–90°C. Oligo-N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone was characterized by ¹H-NMR, FT-IR, UV-Vis, size exclusion chromatography (SEC) and elemental analysis techniques. Solubility testing of oligomer was investigated using organic solvents such as DMF, THF, DMSO, methanol, ethanol, CHCl₃, CCl₄, toluene acetonitrile, ethyl acetate, concentrated H₂SO₄ and an aqueous alkaline solution. Using NaOCl, H₂O₂ and air O₂ oxidants, conversion to oligo-N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone (OHNTSC) of N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone was found to be 85, 80 and 76%, respectively, in an aqueous alkaline medium. According to the SEC analyses, the number-average molecular weight, weight-average molecular weight and polydispersity index values of OHNTSC synthesized were found to be 1050 gmol^–1 1715 gmol^–1 and 1.63, using NaOCl, and 2137, 2957 gmol^–1 and 1.38, using air O₂ and 2155 gmol^–1 4164 gmol^–1 and 1.93, using air H₂O₂, respectively. Also, TG analysis was shown to be unstable of oligo-N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone against thermo-oxidative decomposition. The weight loss of OHNTSC was found to be 97.29% at 900°C.     

Interplay of coordination and hydrogen bonding modes in the self-assembly of the supramolecular network in copper(II) phthalate–trimethoprim complex (0.5:1:1)

Trimethoprim cations forming self complementary hydrogen-bonded DADA arrays interact with the copper–phthalate supramolecular frameworks through extensive hydrogen bonding.     

Mechanistic Exploration of Methionine 274 Acting as a “Switch” of the Selective Pocket Involved in HDAC8 Inhibition: An in Silico Study

The overexpression of histone deacetylase 8 (HDAC8) causes several diseases, and the selective inhibition of HDAC8 has been touted as a promising therapeutic strategy due to its fewer side effects. However, the mechanism of HDAC8 selective inhibition remains unclear. In this study, flexible docking and in silico mutation were used to explore the structural change of methionine (M274) during HDAC8 binding to inhibitors, along with the reason for this change. Meanwhile, steered and conventional molecular dynamics simulations were employed to explore the stability of the structural change. The findings suggest that M274 acts as a “switch” to control the exposure of the HDAC8-selective pocket. The structure of M274 changes from flipped-out to flipped-in only when L-shaped inhibitors bind to HDAC8. This structural change forms a groove that allows these inhibitors to enter the selective pocket. In other HDACs, a leucine residue replaces M274 in situ, and the same structural change is not observed. The findings reveal the mechanism of selective HDAC8 inhibition and provide guidance for the development of novel selective inhibitors.     

Comparison of the Activity of Pd–M (M: Ag,Co, Cu,Fe, Ni,Zn) Bimetallic Electrocatalysts for Oxygen Reduction Reaction

Topics in Catalysis - Carbon-supported 7.5 wt% Pd–2.5 wt% M (M: Ag, Co, Cu, Fe, Ni, Zn) bimetallic catalysts were synthesized via wet impregnation and assessed as...     

Use of Linear Free Energy Relationships (LFERs) to Elucidate the Mechanisms of Reaction of a γ-Methyl-β-alkynyl and an ortho-Substituted Aryl Chloroformate Ester

The specific rates of solvolysis of 2-butyn-1-yl-chloroformate (1) and 2-methoxyphenyl chloroformate (2) are studied at 25.0 °C in a series of binary aqueousorganic mixtures. The rates of reaction obtained are then analyzed using the extended Grunwald-Winstein (G-W) equation and the results are compared to previously published G-W analyses for phenyl chloroformate (3), propargyl chloroformate (4), p-methoxyphenyl choroformate (5), and p-nitrophenyl chloroformate (6). For 1, the results indicate that dual side-by-side addition-elimination and ionization pathways are occurring in some highly ionizing solvents due to the presence of the electron-donating γ-methyl group. For 2, the analyses indicate that the dominant mechanism is a bimolecular one where the formation of a tetrahedral intermediate is rate-determining.     

Comparison of the performance of the LCVM model (an EoS/GE model) and the PHCT EoS (the Perturbed Hard Chain Theory Equation of State) in the prediction of the Vapor–Liquid Equilibria of binary systems containing light gases

The purpose of this work is to compare two models, which are able to perform Vapor–Liquid Equilibrium (VLE) predictions. The first one, the LCVM model, is an EoS/G^E one and it has been successfully applied in the prediction of the VLE behavior of polar and non-polar systems, as well as, systems of dissimilar component size, such as those containing gases with large n-alkanes. The second one is PHCT, an equation of state based on the perturbed hard chain theory. It has also been successfully applied in binary systems of supercritical fluids and non-polar molecules and in systems containing light gases and large n-paraffins. The comparisons results presented in this paper, proved that the two models are comparable, concerning the ability to predict the VLE, as well as, the volumetric behavior of systems with low to medium component size difference (supercritical fluids with non-polar components up to about 10 carbon atoms). However, as the size difference increases, LCVM performs better, especially in the near critical region of such systems.