Two Glass Transitions Associated to Different Dynamic Disorders in the Nematic Glassy State of a Non-Symmetric Liquid Crystal Dimer Dopped with gamma-Alumina Nanoparticles

In the present work, the nematic glassy state of the non-symmetric LC dimer -(4-cyanobiphenyl-4-yloxy)--(1-pyrenimine-benzylidene-4-oxy) undecane is studied by means of calorimetric and dielectric measurements. The most striking result of the work is the presence of two different glass transition temperatures: one due to the freezing of the flip-flop motions of the bulkier unit of the dimer and the other, at a lower temperature, related to the freezing of the flip-flop and precessional motions of the cyanobiphenyl unit. This result shows the fact that glass transition is the consequence of the freezing of one or more coupled dynamic disorders and not of the disordered phase itself. In order to avoid crystallization when the bulk sample is cooled down, the LC dimer has been confined via the dispersion of -alumina nanoparticles, in several concentrations.

Triel Bonds, pi-Hole-pi-Electrons Interactions in Complexes of Boron and Aluminium Trihalides and Trihydrides with Acetylene and Ethylene

MP2/aug-cc-pVTZ calculations were performed on complexes of aluminium and boron trihydrides and trihalides with acetylene and ethylene. These complexes are linked through triel bonds where the triel center (B or Al) is characterized by the Lewis acid properties through its -hole region while -electrons of C2H2 or C2H4 molecule play the role of the Lewis base. Some of these interactions possess characteristics of covalent bonds, i.e., the Al--electrons links as well as the interaction in the BH3-C2H2 complex. The triel--electrons interactions are classified sometimes as the 3c-2e bonds. In the case of boron trihydrides, these interactions are often the preliminary stages of the hydroboration reaction. The Quantum Theory of Atoms in Molecules as well as the Natural Bond Orbitals approach are applied here to characterize the -hole--electrons interactions.

Sphingomyelinase D/Ceramide 1-Phosphate in Cell Survival and Inflammation

Sphingolipids are major constituents of biological membranes of eukaryotic cells. Many studies have shown that sphingomyelin (SM) is a major phospholipid in cell bilayers and is mainly localized to the plasma membrane of cells, where it serves both as a building block for cell architecture and as a precursor of bioactive sphingolipids. In particular, upregulation of (C-type) sphingomyelinases will produce ceramide, which regulates many physiological functions including apoptosis, senescence, or cell differentiation. Interestingly, the venom of some arthropodes including spiders of the genus Loxosceles, or the toxins of some bacteria such as Corynebacterium tuberculosis, or Vibrio damsela possess high levels of D-type sphingomyelinase (SMase D). This enzyme catalyzes the hydrolysis of SM to yield ceramide 1-phosphate (C1P), which promotes cell growth and survival and is a potent pro-inflammatory agent in different cell types. In particular, C1P stimulates cytosolic phospholipase A2 leading to arachidonic acid release and the subsequent formation of eicosanoids, actions that are all associated to the promotion of inflammation. In addition, C1P potently stimulates macrophage migration, which has also been associated to inflammatory responses. Interestingly, this action required the interaction of C1P with a specific plasma membrane receptor, whereas accumulation of intracellular C1P failed to stimulate chemotaxis. The C1P receptor is coupled to Gi proteins and activates of the PI3K/Akt and MEK/ERK1-2 pathways upon ligation with C1P. The proposed review will address novel aspects on the control of inflammatory responses by C1P and will highlight the molecular mechanisms whereby C1P exerts these actions.

Photorelease of Pyridyl Esters in Organometallic Ru(II) Arene Complexes

New Ru(II) arene complexes of formula [((6)-p-cym)Ru(N-N)(X)](2+) (where p-cym = para-cymene, N-N = 2,2'-bipyrimidine (bpm) or 2,2'-bipyridine (bpy) and X = m/p-COOMe-Py, 1-4) were synthesised and characterized, including the molecular structure of complexes [((6)-p-cym)Ru(bpy)(m-COOMe-Py)](2+) (3) and [((6)-p-cym)Ru(bpy)(p-COOMe-Py)](2+) (4) by single-crystal X-ray diffraction. Complexes 1-4 are stable in the dark in aqueous solution over 48 h and photolysis studies indicate that they can photodissociate the monodentate m/p-COOMe-Py ligands selectively with yields lower than 1%. DFT and TD-DFT calculations (B3LYP/LanL2DZ/6-31G**) performed on singlet and triplet states pinpoint a low-energy triplet state as the reactive state responsible for the selective dissociation of the monodentate pyridyl ligands.

The Environmental, Social, Governance, and Financial Performance Effects on Companies that Adopt the United Nations Global Compact

This paper aims to investigate companies' environmental, social, governance (ESG), and financial implications of their commitment to the United Nations Global Compact (UNGC). The focus is placed on companies operating in the three countries with the highest number of UNGC participants: Spain, France, and Japan. The results clearly reveal that adoption of the UNGC often requires an organizational change that fosters stakeholder engagement, ultimately resulting in improvements in companies' ESG performance. Additionally, the results reveal that ESG performance has a significant impact on financial performance for companies that adopted the principles of the UNGC. These findings provide both non-financial and financial incentives to companies to commit to this voluntary corporate social responsibility (CSR) initiative, which will have important implications on companies' strategic management policies that aim to foster sustainable businesses and community development. Finally, the linkages between the UNGC-committed companies' ESG and financial performance may be influenced by geographical spread, mainly due to the appearance of differences in the institutional, societal, and cultural settings.

Piper and Vismia Species from Colombian Amazonia Differentially Affect Cell Proliferation of Hepatocarcinoma Cells

There is an increasing interest to identify plant-derived natural products with antitumor activities. In this work, we have studied the effects of aqueous leaf extracts from Amazonian Vismia and Piper species on human hepatocarcinoma cell toxicity. Results showed that, depending on the cell type, the plants displayed differential effects; thus, Vismia baccifera induced the selective killing of HepG2, while increasing cell growth of PLC-PRF and SK-HEP-1. In contrast, these two last cell lines were sensitive to the toxicity by Piper krukoffii and Piper putumayoense, while the Piperaceae did not affect HepG2 growth. All the extracts induced cytotoxicity to rat hepatoma McA-RH7777, but were innocuous (V. baccifera at concentrations < 75 mu g/mL) or even protected cells from basal death (P. putumayoense) in primary cultures of rat hepatocytes. In every case, cytotoxicity was accompanied by an intracellular accumulation of reactive oxygen species (ROS). These results provide evidence for the anticancer activities of the studied plants on specific cell lines and suggest that cell killing could be mediated by ROS, thus involving mechanisms independent of the plants free radical scavenging activities. Results also support the use of these extracts of the Vismia and Piper genera with opposite effects as a model system to study the mechanisms of the antitumoral activity against different types of hepatocarcinoma.

Luminescence and Magnetic Properties of Two Three -Dimensional Terbium and Dysprosium MOFs Based on Azobenzene-4,4 '-Dicarboxylic Linker

We report the in situ formation of two novel metal-organic frameworks based on terbium and dysprosium ions using azobenzene-4,4-dicarboxylic acid (H(2)abd) as ligand, synthesized by soft hydrothermal routes. Both materials show isostructural three-dimensional networks with channels along a axis and display intense photoluminescence properties in the solid state at room temperature. Textural properties of the metal-organic frameworks (MOFs) have been fully characterized although no appreciable porosity was obtained. Magnetic properties of these materials were studied, highlighting the dysprosium material displays slightly frequency-dependent out of phase signals when measured under zero external field and under an applied field of 1000 Oe.

Azaspiracid shellfish poisoning: a review on the chemistry, ecology, and toxicology with an emphasis on human health impacts

Azaspiracids (AZA) are polyether marine toxins that accumulate in various shellfish species and have been associated with severe gastrointestinal human intoxications since 1995. This toxin class has since been reported from several countries, including Morocco and much of western Europe. A regulatory limit of 160 μg AZA/kg whole shellfish flesh was established by the EU in order to protect human health; however, in some cases, AZA concentrations far exceed the action level. Herein we discuss recent advances on the chemistry of various AZA analogs, review the ecology of AZAs, including the putative progenitor algal species, collectively interpret the in vitro and in vivo data on the toxicology of AZAs relating to human health issues, and outline the European legislature associated with AZAs.

In utero domoic acid toxicity: a fetal basis to adult disease in the California sea lion (Zalophus californianus)

California sea lions have been a repeated subject of investigation for early life toxicity, which has been documented to occur with increasing frequency from late February through mid-May in association with organochlorine (PCB and DDT) poisoning and infectious disease in the 1970's and domoic acid poisoning in the last decade. The mass early life mortality events result from the concentrated breeding grounds and synchronization of reproduction over a 28 day post partum estrus cycle and 11 month in utero phase. This physiological synchronization is triggered by a decreasing photoperiod of 11.48 h/day that occurs approximately 90 days after conception at the major California breeding grounds. The photoperiod trigger activates implantation of embryos to proceed with development for the next 242 days until birth. Embryonic diapause is a selectable trait thought to optimize timing for food utilization and male migratory patterns; yet from the toxicological perspective presented here also serves to synchronize developmental toxicity of pulsed environmental events such as domoic acid poisoning. Research studies in laboratory animals have defined age-dependent neurotoxic effects during development and windows of susceptibility to domoic acid exposure. This review will evaluate experimental domoic acid neurotoxicity in developing rodents and, aided by comparative allometric projections, will analyze potential prenatal toxicity and exposure susceptibility in the California sea lion. This analysis should provide a useful tool to forecast fetal toxicity and understand the impact of fetal toxicity on adult disease of the California sea lion.

Ciguatera Fish Poisoning: treatment, prevention and management

Ciguatera Fish Poisoning (CFP) is the most frequently reported seafood-toxin illness in the world, and it causes substantial physical and functional impact. It produces a myriad of gastrointestinal, neurologic and/or cardiovascular symptoms which last days to weeks, or even months. Although there are reports of symptom amelioration with some interventions (e.g. IV mannitol), the appropriate treatment for CFP remains unclear to many physicians. We review the literature on the treatments for CFP, including randomized controlled studies and anecdotal reports. The article is intended to clarify treatment options, and provide information about management and prevention of CFP, for emergency room physicians, poison control information providers, other health care providers, and patients.

Immunomodulatory effects of domoic acid differ between In vivo and In vitro exposure in mice

The immunotoxic potential of domoic acid (DA), a well-characterized neurotoxin, has not been fully investigated. Phagocytosis and lymphocyte proliferation were evaluated following in vitro and in vivo exposure to assay direct vs indirect effects. Mice were injected intraperitoneally with a single dose of DA (2.5 µg/g b.w.) and sampled after 12, 24, or 48 hr. In a separate experiment, leukocytes and splenocytes were exposed in vitro to 0, 1, 10, or 100 µM DA. In vivo exposure resulted in a significant increase in monocyte phagocytosis (12-hr), a significant decrease in neutrophil phagocytosis (24-hr), a significant decrease in monocyte phagocytosis (48-hr), and a significant reduction in T-cell mitogen-induced lymphocyte proliferation (24-hr). In vitro exposure significantly reduced neutrophil and monocyte phagocytosis at 1 µM. B- and T-cell mitogen-induced lymphocyte proliferation were both significantly increased at 1 and 10 µM, and significantly decreased at 100 µM. Differences between in vitro and in vivo results suggest that DA may exert its immunotoxic effects both directly and indirectly. Modulation of cytosolic calcium suggests that DA exerts its effects through ionotropic glutamate subtype surface receptors at least on monocytes. This study is the first to identify DA as an immunotoxic chemical in a mammalian species.

复合垂直流构建湿地系统净化水体中的痕量有机物

在稳定运行三年的复合垂直流构建湿地中试系统中进行了水体中痕量有机物的净化研究。进水为东湖茶港附近的湖水。水流方式为下行流 -上行流 ,进水方式采用间歇式 ,间隔为 8h ,水力负荷为 80 0mm3/(mm2 ·d)。采用C18反相SPE柱富集萃取中试系统的进出水及自来水 ,然后对其进行GC/MS分析 ,结果表明 ,东湖水主要为石油烃污染 ,酞酸酯类污染严重 ,自来水中亦存在痕量有机物的污染。复合垂直流构建湿地中试系统的出水比进水中痕量有机物的种类及数量均有所减少 ,说明这种系统有助于水体中痕量有机物的去

界牌河段航道整治工程对白鱀豚和长江江豚影响评价研究

界牌河段航道整治工程于 1994年动工 ,1998年基本结束。为了防止在施工过程中对白豚和长江江豚造成意外伤害 ,并对整治该河段的环境变化对白豚和长江江豚的影响作出评价 ,作者在 1995年至 1999年在界牌河段对白豚和江豚的活动和航道整治前后的情况进行了监测。调查结果表明 ,界牌航道在整治过程中没有对白豚和江豚造成伤害 ,原来碍航严重的界牌航道得到了有效的整治 ,同时也有利于白豚和江豚的活动。

纯公钥模型下对NP语言的高效并发零知识证明系统

提出了一种从3轮公开掷币的对任何NP语言的诚实验证者零知识证明系统到纯公钥模型下4轮f轮最优）对同一语言的具有并发合理性的并发零知识证明系统．该转化方法有如下优点：1）它只引起D（1）（常数个）额外的模指数运算，相比DiCrescenzo等人在ICALP05上提出的需要qn）个额外的模指数运算的转化方法孩系统在效率上有着本质上的提高，而所需的困难性假设不变；2）在离散对数假设下，该转化方法产生一个完美零知识证明系统．注意到DiCrescenzo等人提出的系统只具有计算零知识性质．该转化方法依赖于一个特殊的对承诺中的离散对数的3轮诚实验证者零知识的证明系统．构造了两个基于不同承诺方案的只需要常数个模指数运算的系统这种系统可能有着独立价值．

Lipase-catalyzed synthesis of biodiesel from acid oil in fixed bed reactor

Acid oil, which is a by-product in vegetable oil refining, mainly contains free fatty acids (FFAs) and acylglycerols and is a feedstock for production of biodiesel fuel now. The transesterification of acid oil and methanol to biodiesel was catalyzed by immobilized Candida lipase in fixed bed reactors. The reactant solution was a mixture of acid oil, water, methanol and solvent (hexane) and the main product was biodiesel composed of fatty acid methyl ester (FAME) of which the main component was methyl oleate. The effects of lipase content, solvent content, water content temperature and flow velocity of the reactant on the reaction were analyzed. The experimental results indicate that a maximum FAME content of 90.18% can be obtained in the end product under optimum conditions. Most of the chemical and physical properties of the biodiesel were superior to the standards for 0(#) diesel (GB/T 19147) and biodiesel (DIN V51606 and ASTM D6751).