Precise synthesis of polymers containing functional end groups by living ring-opening metathesis polymerization (ROMP): Efficient tools for synthesis of block/graft copolymers

This article summarizes recent examples for precise synthesis of (co)polymers containing functional end groups prepared by living ring-opening metathesis polymerization (ROMP) using molybdenum, ruthenium complex catalysts. In particular, this article reviews recent examples for synthesis of amphiphilic block/graft copolymers by adopting transition metal-catalyzed living ROMP technique. Unique characteristics of the living ROMP initiated by the molybdenum alkylidene complexes (so-called Schrock type catalyst), which accomplish precise control of the block segment (hydrophilic and hydrophobic) as well as exclusive introduction of functionalities at the polymer chain end, enable us to provide the synthesis of block copolymers varying different backbones by adopting the “grafting to” or the “grafting from” approach as well as “soluble” star shape polymers with controlled manner. The “grafting through” approach (polymerization of macromonomers) by the repetitive ROMP technique offers precise control of the amphiphilic block segments.     

Identification and Composition of Clasper Scent Gland Components of the Butterfly Heliconius erato and Its Relation to Mimicry

The butterfly Heliconius erato occurs in various mimetic morphs. The male clasper scent gland releases an anti-aphrodisiac pheromone and additionally contains a complex mixture of up to 350 components, varying between individuals. In 114 samples of five different mimicry groups and their hybrids 750 different compounds were detected by gas chromatography/mass spectrometry (GC/MS). Many unknown components occurred, which were identified using their mass spectra, gas chromatography/infrared spectroscopy (GC/IR)-analyses, derivatization, and synthesis. Key compounds proved to be various esters of 3-oxohexan-1-ol and (Z)-3-hexen-1-ol with (S)-2,3-dihydrofarnesoic acid, accompanied by a large variety of other esters with longer terpene acids, fatty acids, and various alcohols. In addition, linear terpenes with up to seven uniformly connected isoprene units occur, e. g. farnesylfarnesol. A large number of the compounds have not been reported before from nature. Discriminant analyses of principal components of the gland contents showed that the iridescent mimicry group differs strongly from the other, mostly also separated, mimicry groups. Comparison with data from other species indicated that Heliconius recruits different biosynthetic pathways in a species-specific manner for semiochemical formation.     

Loliolide,a New Therapeutic Option for Neurological Diseases? In Vitro Neuroprotective and Anti-Inflammatory Activities of a Monoterpenoid Lactone Isolated from Codium tomentosum

Parkinsons Disease (PD) is the second most common neurodegenerative disease worldwide, and is characterized by a progressive degeneration of dopaminergic neurons. Without an effective treatment, it is crucial to find new therapeutic options to fight the neurodegenerative process, which may arise from marine resources. Accordingly, the goal of the present work was to evaluate the ability of the monoterpenoid lactone Loliolide, isolated from the green seaweed Codium tomentosum, to prevent neurological cell death mediated by the neurotoxin 6-hydroxydopamine (6-OHDA) on SH-SY5Y cells and their anti-inflammatory effects in RAW 264.7 macrophages. Loliolide was obtained from the diethyl ether extract, purified through column chromatography and identified by NMR spectroscopy. The neuroprotective effects were evaluated by the MTT method. Cells’ exposure to 6-OHDA in the presence of Loliolide led to an increase of cells’ viability in 40%, and this effect was mediated by mitochondrial protection, reduction of oxidative stress condition and apoptosis, and inhibition of the NF-kB pathway. Additionally, Loliolide also suppressed nitric oxide production and inhibited the production of TNF-α and IL-6 pro-inflammatory cytokines. The results suggest that Loliolide can inspire the development of new neuroprotective therapeutic agents and thus, more detailed studies should be considered to validate its pharmacological potential.     

Multivariate process trajectories for molecular description of MF thermal curing and correlation with hydrolytic stability

During curing of thermosetting resins the technologically relevant properties of binders and coatings develop. However, curing is difficult to monitor due to the multitude of chemical and physical processes taking place. Precise prediction of specific technological properties based on molecular properties is very difficult. In this study, the potential of principal component analysis (PCA) and principal component regression (PCR) in the analysis of Fourier transform infrared (FTIR) spectra is demonstrated using the example of melamine-formaldehyde (MF) resin curing in solid state. FTIR/PCA-based reaction trajectories are used to visualize the influence of temperature on isothermal cure. An FTIR/PCR model for predicting the hydrolysis resistance of cured MF resin from their spectral fingerprints is presented which illustrates the advantages of FTIR/PCR compared to the combination differential scanning calorimetry/isoconversional kinetic analysis. The presented methodology is transferable to the curing reactions of any thermosetting resin and can be applied to model other technologically relevant final properties as well.     

Partitioning,solubility and solubilization of limonene into water or short-chain phosphatidylcholine solutions

Using headspace solid-phase microextraction (HS–SPME), equilibrium distributions could be determined for hydrophobic solutes in closed systems containing vapor and aqueous solution, either in the absence or presence of two short-chain phospholipids, dihexanoyl-phosphatidylcholine (diC₆PC) and diheptanoyl-phosphatidylcholine (diC₇PC). Without phospholipid, HS–SPME with short extraction times was used to measure water–vapor partition coefficients for d-limonene at five temperatures within 15–40°C, with results in good agreement with existing literature. The temperature dependence of yielded the enthalpy of volatilization 34.5 kJ/mol for limonene. At 25°C, solubility values for d-limonene, 1-octanol, and n-decane were obtained using similar measurements above aqueous solutions of various solute concentrations. Short-time HS–SPME extraction of limonene in closed vials containing diC₆PC or diC₇PC micelles was also used to evaluate distributions of solute between vapor, aqueous dissolution, and micelles, for various surfactant concentrations at 15–40°C. Resulting vapor phase concentrations were analyzed using a mass balance and measured values, to obtain micelle–water partition coefficients and critical micelle concentrations. in diC₆PC solutions (1–2 mM⁻¹) weakly increased with temperature, but decreased significantly with increased temperature for diC₇PC micelles (2–4 mM⁻¹). Solubilization in short-chain PC micelles has previously received little attention, and our results show that the extent of partitioning into these diacyl (i.e., two-tailed) lipids is comparable to that for single-tailed anionic or nonionic surfactants.     

Metabolomic Reprogramming of C57BL/6-Macrophages during Early Infection with L. amazonensis

Leishmania survival inside macrophages depends on factors that lead to the immune response evasion during the infection. In this context, the metabolic scenario of the host cell–parasite relationship can be crucial to understanding how this parasite can survive inside host cells due to the host’s metabolic pathways reprogramming. In this work, we aimed to analyze metabolic networks of bone marrow-derived macrophages from C57BL/6 mice infected with Leishmania amazonensis wild type (La-WT) or arginase knocked out (La-arg⁻), using the untargeted Capillary Electrophoresis-Mass Spectrometry (CE-MS) approach to assess metabolomic profile. Macrophages showed specific changes in metabolite abundance upon Leishmania infection, as well as in the absence of parasite-arginase. The absence of L. amazonensis-arginase promoted the regulation of both host and parasite urea cycle, glycine and serine metabolism, ammonia recycling, metabolism of arginine, proline, aspartate, glutamate, spermidine, spermine, methylhistidine, and glutathione metabolism. The increased L-arginine, L-citrulline, L-glutamine, oxidized glutathione, S-adenosylmethionine, N-acetylspermidine, trypanothione disulfide, and trypanothione levels were observed in La-WT-infected C57BL/6-macrophage compared to uninfected. The absence of parasite arginase increased L-arginine, argininic acid, and citrulline levels and reduced ornithine, putrescine, S-adenosylmethionine, glutamic acid, proline, N-glutamyl-alanine, glutamyl-arginine, trypanothione disulfide, and trypanothione when compared to La-WT infected macrophage. Moreover, the absence of parasite arginase leads to an increase in NO production levels and a higher infectivity rate at 4 h of infection. The data presented here show a host-dependent regulation of metabolomic profiles of C57BL/6 macrophages compared to the previously observed BALB/c macrophages infected with L. amazonensis, an important fact due to the dual and contrasting macrophage phenotypes of those mice. In addition, the Leishmania-arginase showed interference with the urea cycle, glycine, and glutathione metabolism during host–pathogen interactions.     

Endothelial Colony-Forming Cells Dysfunctions Are Associated with Arterial Hypertension in a Rat Model of Intrauterine Growth Restriction

Infants born after intrauterine growth restriction (IUGR) are at risk of developing arterial hypertension at adulthood. The endothelium plays a major role in the pathogenesis of hypertension. Endothelial colony-forming cells (ECFCs), critical circulating components of the endothelium, are involved in vasculo-and angiogenesis and in endothelium repair. We previously described impaired functionality of ECFCs in cord blood of low-birth-weight newborns. However, whether early ECFC alterations persist thereafter and could be associated with hypertension in individuals born after IUGR remains unknown. A rat model of IUGR was induced by a maternal low-protein diet during gestation versus a control (CTRL) diet. In six-month-old offspring, only IUGR males have increased systolic blood pressure (tail-cuff plethysmography) and microvascular rarefaction (immunofluorescence). ECFCs isolated from bone marrow of IUGR versus CTRL males displayed a decreased proportion of CD31+ versus CD146+ staining on CD45− cells, CD34 expression (flow cytometry, immunofluorescence), reduced proliferation (BrdU incorporation), and an impaired capacity to form capillary-like structures (Matrigel test), associated with an impaired angiogenic profile (immunofluorescence). These dysfunctions were associated with oxidative stress (increased superoxide anion levels (fluorescent dye), decreased superoxide dismutase protein expression, increased DNA damage (immunofluorescence), and stress-induced premature senescence (SIPS; increased beta-galactosidase activity, increased p16^INK4a, and decreased sirtuin-1 protein expression). This study demonstrated an impaired functionality of ECFCs at adulthood associated with arterial hypertension in individuals born after IUGR.     

Legal Frameworks Governing Water in the Middle East and North Africa

For millennia, countries in the Middle East and North Africa (MENA) region have developed laws, regulations and other rules to govern their scarce water. These laws have been updated in recent years. This review of the legal frameworks (including regulations, decrees and other rules) reveals both progress and gaps in managing water quality, water quantity and procedural aspects. Of note, while the general frameworks are usually in place, in many instances the necessary details are lacking to give effect to the goals. However, in some instances the legal frameworks governing water lack certain key principles or approaches. In order to effectively meet the growing demands on their water resources, MENA countries will need to further strengthen and develop their legal frameworks.     

AVO技术在克拉玛依克75井区的应用效果

新疆首次应用ＡＶＯ技术对克拉玛依油田克７５井区的含油气范围进行了预测，其步骤是：首失根据出油气井测井的纵横波资料，建立正演这集模型；然后对实际剖面上储层顶、底界面作油层ＡＶＯ追踪，以检测两者响应是否相同；认证后再捉据此特征沿剖面追踪以确定油水边界，并预测其他可能的含油ＡＶＯ异常带。经钻井、试油资料检验，这项技术在该区的应用效果是比较理想的。