Gallium (III) Complexes Based on Aminobisphenolate Ligands: Extremely High Active ROP-Initiators from Well-Known and Easily Accessible Compounds

We report herein the synthesis and full characterizations of the first examples of gallium complexes based on “privileged” aminobisphenolate ligands which are easily available. These complexes turned out to be extremely active in the ring-opening polymerization of ε-caprolactone even at room temperature and highly active in the ROP of L-lactide. The combination of factors such as the easy availability of these compounds and the supposedly low toxicity, together with the extremely high activity in ROP, allows us to consider these compounds as suitable for use on an industrial scale for the synthesis of biodegradable polymers for biomedical applications.     

Declines in Reproductive Condition of Male Largemouth Bass (Micropterus salmoides) Following Seasonal Exposure to Estrogenic Endocrine-Disrupting Compounds

Reproductive abnormalities, that could lead to possible effects at the population level, have been observed in wild fish throughout the United States, with high prevalence in largemouth bass (LMB; Micropterus salmoides) and smallmouth bass (Micropterus dolomieu). Estrone (E1) and atrazine (ATR) are common environmental contaminants often associated with agricultural land use. 17alpha-ethinylestradiol (EE2) is a contaminant associated with wastewater treatment effluent, and a representative, well-studied estrogen commonly used for fish toxicity testing. Our objective was to assess whether early gonad recrudescence in adult fish was a period of sensitivity for alterations in reproductive condition and function. Adult male LMB were exposed from post-spawning to early gonad recrudescence to either a mixture of E1 (47.9 ng/L) + ATR (5.4 µg/L), or EE2 (2.4 ng/L) in outdoor experimental ponds. Gonad samples were collected from fish just prior to the start of exposure (July), at the end of the exposure period (December), the following spring just prior to spawning (April), and post spawning (May). Gonadosomatic index (GSI) was significantly reduced in E1 + ATR-exposed and EE2-exposed males compared to control at every post-exposure time point. Reduced sperm count and sperm motility were observed in the mixture treatment (E1 + ATR) compared to the control. Sperm motility was also reduced in the EE2 treatment. These data together indicate that estrogenic endocrine-disrupting compounds can lessen the reproductive condition of adult male LMB, and that effects of exposure during early gonad recrudescence can persist at least through the subsequent spawning cycle.     

Unexpected Interacting Effects of Physical (Radiation) and Chemical (Bisphenol A) Treatments on Male Reproductive Functions in Mice

For decades, numerous chemical pollutants have been described to interfere with endogenous hormone metabolism/signaling altering reproductive functions. Among these endocrine disrupting substances, Bisphenol A (BPA), a widely used compound, is known to negatively impact germ and somatic cells in the testis. Physical agents, such as ionizing radiation, were also described to perturb spermatogenesis. Despite the fact that we are constantly exposed to numerous environmental chemical and physical compounds, very few studies explore the impact of combined exposure to chemical and physical pollutants on reproductive health. The aim of this study was to describe the impact of fetal co-exposure to BPA and IR on testicular function in mice. We exposed pregnant mice to 10 µM BPA (corresponding to 0.5 mg/kg/day) in drinking water from 10.5 dpc until birth, and we irradiated mice with 0.2 Gy (γ-ray, RAD) at 12.5 days post-conception. Co-exposure to BPA and γ-ray induces DNA damage in fetal germ cells in an additive manner, leading to a long-lasting decrease in germ cell abundance. We also observed significant alteration of adult steroidogenesis by RAD exposure independently of the BPA exposure. This is illustrated by the downregulation of steroidogenic genes and the decrease of the number of adult Leydig cells. As a consequence, courtship behavior is modified, and male ultrasonic vocalizations associated with courtship decreased. In conclusion, this study provides evidence for the importance of broadening the concept of endocrine disruptors to include physical agents, leading to a reevaluation of risk management and regulatory decisions.     

双官能团化合物—乙醇胺及其类似物的选择磷（膦）酰化反应

本文主要评述了双官能团化合物——乙醇胺及其类似物的选择磷(膦)酰化反应和反应机理,并详细讨论了磷(膦,次膦)酰化产物的合成、物理化学性质和波谱特征。     

毒死蜱对雄性大鼠生精功能的影响

探讨毒死蜱(chlorpyifos,CPF)对雄性大鼠生殖功能的影响.选择6周龄雄性SD大鼠按体重随机分成4组,每组10只.灌胃给予CPF,剂量为0(对照组)、0.82、2.45、7.35 mg/(kg·d).于染毒8周后,观察大鼠体重、睾丸和附睾重量及脏器系数、精子畸形率、精子计数、活动精子百分率,光镜病理学检查;检测睾丸组织匀浆的乳酸脱氢酶(LDH)、酸性磷酸酶(ACP)、碱性磷酸酶(AKP)、γ-谷氨酰转移酶(γ-GT)的活性.与对照组比较,随CPF染毒剂量的增加,体重显著下降(P＜O.05),染毒组睾丸重量显著升高(P＜0.05),7.35 mg/kg染毒组附睾重量显著升高(P＜0.05),各自脏器系数均显著升高(P＜0.05).与对照组比较,7.35 mg/kg染毒组的附睾精子数及附睾精子活力显著降低,LDH和AKP的活性受到明显抑制(P＜0.05).2.45、7.35 mg/kg染毒组的ACP活力较对照组显著降低,精子畸形率显著升高(P＜0.05).3个染毒组γ-GT活性较对照组增加,差异显著(P＜0.05).CPF可对机体产生明显的毒性作用,主要靶器官为睾丸,对大鼠精子形成和成熟过程有损伤作用,有雄性生殖毒性.     

Carbamate Pesticides: Shedding Light on Their Impact on the Male Reproductive System

Carbamates are widely used and known around the world as pesticides in spite of also having medical applications. This class of chemicals is classified as acetylcholinesterase inhibitors, blocking acetylcholine hydrolyzation in a reversible manner. Their lack of species selectivity and their reported high toxicity can induce, upon exposure, adverse outcomes in male fertility that may lead to infertility. In addition, they are also considered endocrine-disrupting chemicals and can interfere with the hypothalamic–pituitary–testicular axis, essential for the normal function of the male reproductive system, thus being able to provoke male reproductive dysfunctions. Although the molecular mechanisms are not fully understood, various signaling pathways, such as those mediated by acetylcholine or kisspeptin, are affected by exposure to carbamates, thus compromising steroidogenesis and spermatogenesis. Over the last decades, several studies, both in vitro and in vivo, have reported a myriad of negative effects of carbamates on the male reproductive system. In this review, an up-to-date overview of the impact of carbamates on the male reproductive system is discussed, with an emphasis on the role of these compounds on acetylcholine regulation and the male endocrine system.     

Volatile Compounds from the Forehead Region of Male White-Tailed Deer (Odocoileus virginianus)

Secretions produced by sebaceous and apocrine glands of cervids may be important in identifying individuals, establishing dominance, and signaling sexual readiness. The secretions from these glands are transferred to the hair for both lubrication and scent communication via forehead rubbing. We collected hair samples from the forehead and back of 10 male white-tailed deer (Odocoileus virginianus) of various ages and analyzed them with gas chromatography–mass spectrometry to determine age-related differences. Fifty-seven compounds were identified, including alkanes, arenes, aldehydes, ketones, aliphatic alcohols, terpenes, terpene alcohols, and phenols. Although forehead apocrine glands of dominant deer become more active during the breeding season, we found that concentrations of eight compounds found on the forehead hair were higher in subordinate deer, while only one was higher in dominant deer. Subordinate deer may have higher concentrations of these compounds because they rub less frequently than dominant deer. Additionally, only five forehead hair volatiles differed in concentration from those taken from the back hair. This seems to indicate that an increase in forehead glandular activity may take place concurrently with an increase in general integumentary glandular activity. The variation in hair volatiles among individuals also may be indicative of an individual-specific odor that could aid in identification.     

Novel Unsymmetrical Ru(III) and Mixed-valence Ru(III)/Ru(II) Dinuclear Compounds Related to the Antimetastatic Ru(III) Drug NAMI-A

In this paper we report the stepwise preparation and the characterization of new unsymmetrical monoanionic Ru(III) dinuclear compounds, [NH(4)][{trans-RuCl(4)(Me(2)SO-S)}(mu-L){mer-RuCl(3)(Me(2)SO-S)(Me(2)SO-O)}] (L = pyz (1), pym (2)). By a similar synthetic approach we also prepared new mixed-valence Ru(III)/Ru(II) dinuclear compounds of formula [NH(4)][{trans-RuCl(4)(Me(2)SO-S)}(mu-pyz){cis,cis,cis-RuCl(2)(Me(2)SO-S)(2)(CO)}] (L = pyrazine (pyz, 3), pyrimidine (pym, 4)). Moreover, we describe the chemical behavior of compounds 1-4 in physiological solution, also after complete reduction (with ascorbic acid) to the corresponding Ru(II)/Ru(II) species. Overall, the chemical behavior of 1 and 2 after reduction resembles that of the corresponding dianionic and neutral dinuclear species, [{trans-RuCl(3)(Me(2)SO-S)}(2)(mu-L)](2-)and [{mer-RuCl(3)(Me(2)SO-S)(Me(2)SO-O)}(2) (mu-L)]. On the other hand, the mixed-valence dinuclear compounds 3 and 4, owing to the great inertness of the cis,cis,cis-RuCl(2)(Me(2)SO-S)(2)(CO)(1/2mu-L) fragment, behave substantially like the mononuclear species [trans-RuCl(4)(Me(2)SO-S)(L)](-) in which the terminally bonded L ligand can be considered as bearing a bulky substituent on the other N atom.     

Effects of a Hindered Amine Stabilizer (HAS) on radiolytic and thermal stability of poly(methyl methacrylate)

Commercial Poly(methyl methacrylate) (PMMA) containing Tinuvin 622, a Hindered Amine Stabilizer (HAS), in 0.3% (wt/wt) concentration was investigated. The samples were irradiated with gamma radiation (⁶⁰Co) at room temperature in air. The viscosity‐average molecular weight (M_v) was analyzed by viscosity technique. Both control PMMA (without HAS) and PMMA + 622 (with HAS) showed a decrease in molecular weight with the increase in dose, reflecting the random scissions that occurred in the main chain. The G value (scissions/100 eV of energy transferred to the system) was also obtained by viscosity analysis. G value results showed that the addition of Tinuvin 622 into the PMMA matrix significantly decreased the number of scissions/100 eV at dose range of 0–60 kGy. Analysis of infrared spectra showed a decrease in the carbonyl index (CI) in irradiated samples. However the CI decrease was found lower for PMMA + 622 than for control PMMA sample. Thermogravimetric analysis (TGA) revealed that maximum decomposition temperature of additive PMMA is 42°C higher than control PMMA for unirradiated system. On the other hand this difference is not significant in irradiated systems at 60‐kGy irradiation dose. The activation energy of the thermal degradation of PMMA was 165 kJ/mol, this activation energy increased 60 kJ/mol when Tinuvin 622 was added to PMMA matrix. Therefore Tinuvin 622 is a suitable radiostabilizing agent for commercial PMMA in a 0–60 kGy dose interval. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of Solid Phosphate Compounds of Ti(III) and Ti(IV)

Several new methods for the synthesis of TiPO₄ are described. Crystalline phosphate compounds containing boron and titanium in a single III or mixed (III, IV) oxidation states have been synthesized and identified by X-ray diffraction. An additional family of phosphate compounds containing only Ti(III, IV) has also been synthesized and identified. All the compounds exhibit attractive colors, e.g., bright green, blue, purple, and black, and are stable at room temperature in air and in boiling water.     

Preparation and Properties of Monodispersed Colloidal Particles of Lanthanide Compounds: III, Yttrium(III) and Mixed Yttrium(III)/Cerium(III) Systems

Colloidal dispersions of uniform spherical particles of yttrium basic carbonate and rodlike particles of yttrium ammine carbonate were prepared by aging at elevated temperatures yttrium salt solutions in the presence of urea. Different composition and morphology were achieved by altering the aging temperature and time. Coprecipitation in mixed solutions of yttrium(III) and cerium(III) salts under similar experimental conditions yielded composite spherical particles of basic carbonate. The content of the two metals in the solids followed closely the initial composition of the reacting solutions. On calcination all prepared solids converted to their corresponding oxides while retaining their particle morphology. The so-prepared powders were characterized by various techniques.     

Electrolytic Behaviour of Some Chlorothallate(III) Compounds in ethanol solution

Raman spectroscopic and conductivity studies show that pyridinium derivatives of the TlCl₅^2⊖, TlCl₆^3⊖ and Tl₂Cl₉^3⊖ species dissociate in ethanol solution to yield the TlCl₄^⊖ ion, but the [(C₂H₅)₄N]₂TlCl₅ salt does not dissociate further and behaves like a 2:1 electrolyte.     

Synthesis of Olefin‐Oxazoline Ligands (OlefOx) by Rhodium(III)‐Catalyzed Oxidative Olefination

The rhodium(III)‐catalyzed oxidative olefination of 2‐aryloxazolines is described and has been employed for the synthesis of olefin‐oxazoline ligands (OlefOx). The highly modular synthesis starting from readily available 2‐aryloxazolines can be performed under an atmosphere of air as the terminal oxidant with catalytic amounts of copper(II)‐acetate.     

Effects of Fe(III) on floc characteristics of activated sludge

The effects of Fe(III) on floc characteristics of activated sludge were investigated in nine parallel sequencing batch reactors (SBRs). The results showed that Fe(III) improved the quality of organic matters in the effluent of reactors. Concentrations of Fe(III) up to 23.8 mg dm^?3 decreased suspended solids and turbidity in effluent but overdosage resulted in deterioration of these parameters. Activated sludge floc size measurements indicated that Fe(III) led to a shift in the size distribution from large to small flocs. Concentrations of Fe(III) less than 23.8mg dm^?3 did not significantly change the proportion of larger flocs, but overdosage of Fe(III) markedly decreased the fraction of larger flocs and produced a large number of smaller flocs, which may be responsible for the deterioration of effluent suspended solids and turbidity. Scanning electronic microscopic (SEM) observation suggested high Fe(III) concentrations lead to significant changes in floc morphology and reduction of filamentous microorganisms available for the formation of large aggregates. Copyright © 2005 Society of Chemical Industry     

Asymmetric Epoxidation of Chromenes Using Manganese(III) Complexes with Novel Chiral Salen-like Schiff Base Ligands

Abstract  

Three novel chiral salen-like schiff base ligands and their Mn(III) complexes containing different amino acid unit have been synthesized and characterized. Asymmetric epoxidation reactions show these complexes are effective catalysts for the chromenes with buffer NaOCl as terminal oxidant and pyridine N-oxide as co-catalyst in the presence of ionic liquid. Good-to -excellent enantioselectivity and acceptable yields can be obtained under optimum reaction conditions. Catalyst 4c gives the highest ee (95%) for 6-chloro-2,2-dimethylchromene among these catalytic performances. Furthermore, compared the enantioselectivity of catalyst 4c with the other two catalysts 4a and 4b, the positive experimental results suggest that the steric effect of the ligands plays an important role in the asymmetric catalysis.     

Identification and Variation of Volatile Compounds in Sternal Gland Secretions of Male Koalas (Phascolarctos cinereus)

The content of the sternal gland secretion from four male koalas (Phascolarctos cinereus) was analyzed using gas chromatography–mass spectrometry. Volatile fatty acids, aldehydes, ketones, mono- and sesquiterpenes were identified, together with various volatile nitriles and oximes, some of which had not previously been described from any mammalian skin gland. Benzyl cyanide and phenylacetaldehyde oxime were identified as major components of the secretions, together with smaller amounts of the novel 3-methylthiopropanal oxime. The relative abundance of the identified compounds was highly variable between individuals and the scent composition was found to be partly determined by the scent of surrounding conspecifics. Principal component analysis revealed a high similarity between related individuals.     

Quantitative Structure-Activity Relationship (QSAR) Studies on the Toxic Effects of Nitroaromatic Compounds (NACs): A Systematic Review

Nitroaromatic compounds (NACs) are ubiquitous in the environment due to their extensive industrial applications. The recalcitrance of NACs causes their arduous degradation, subsequently bringing about potential threats to human health and environmental safety. The problem of how to effectively predict the toxicity of NACs has drawn public concern over time. Quantitative structure–activity relationship (QSAR) is introduced as a cost-effective tool to quantitatively predict the toxicity of toxicants. Both OECD (Organization for Economic Co-operation and Development) and REACH (Registration, Evaluation and Authorization of Chemicals) legislation have promoted the use of QSAR as it can significantly reduce living animal testing. Although numerous QSAR studies have been conducted to evaluate the toxicity of NACs, systematic reviews related to the QSAR modeling of NACs toxicity are less reported. The purpose of this review is to provide a thorough summary of recent QSAR studies on the toxic effects of NACs according to the corresponding classes of toxic response endpoints.     

Interaction of Ruthenium(II)-dipyridophenazine Complexes with CT-DNA: Effects of the Polythioether Ancillary Ligands

The complexes [Ru([9]aneS(3))(dppz)Cl]Cl 1 and [Ru([12]aneS(4))(dppz)]Cl(2)2 ([9]aneS(3) = 1,4,7- trithiaciclononane and [12]aneS(4) = 1,4,7,10-tetrathiaciclododecane) were synthesised and fully characterised. These complexes belong to a small family of dipyridophenazine complexes with non-polypyridyl ancillary ligands . Interaction studies of these complexes with CT-DNA (UV/Vis titrations, steady-state emission and thermal denaturation) revealed their high affinity for DNA . Intercalation constants determined by UV/Vis titrations are of the same order of magnitude (10(6)) as other dppz metallointercalators, namely [Ru(II)(bpy)(2)dppz]S(2+). Differences between l and2 were identified by steady-state emission and thermal denaturation studies . Emission results are in accordance with structural data, which indicate how geometric distortions and different donor and/or acceptor ligand abilities affect luminescence. The possibility of noncovalent interactions between ancillary ligands and nucleobases by van der Waals contacts and H-bridges is discussed . Furthermore, complex l undergoes aquation under intra-cellular conditions and an equilibrium with the aquated form l' is attained . This behaviour may increase the diversity of available interaction modes.     

Effects of Virgin Olive Oil on Blood Pressure and Renal Aminopeptidase Activities in Male Wistar Rats

High saturated fat diets have been associated with the development of obesity and hypertension, along with other pathologies related to the metabolic syndrome. In contrast, the Mediterranean diet, characterized by its high content of monounsaturated fatty acids, has been proposed as a dietary factor capable of positively regulating cardiovascular function. These effects have been linked to changes in the local renal renin angiotensin system (RAS) and the activity of the sympathetic nervous system. The main goal of this study was to analyze the role of two dietary fat sources on aminopeptidases activities involved in local kidney RAS. Male Wistar rats (six months old) were fed during 24 weeks with three different diets: the standard diet (S), the standard diet supplemented with virgin olive oil (20%) (VOO), or the standard diet enriched with butter (20%) plus cholesterol (0.1%) (Bch). Kidney samples were separated in medulla and cortex for aminopeptidase activities (AP) assay. Urine samples were collected for routine analysis by chemical tests. Aminopeptidase activities were determined by fluorometric methods in soluble (sol) and membrane-bound (mb) fractions of renal tissue, using arylamide derivatives as substrates. After the experimental period, the systolic blood pressure (SBP) values were similar in standard and VOO animals, and significantly lower than in the Bch group. At the same time, a significant increase in GluAP and IRAP activities were found in renal medulla of Bch animals. However, in VOO group the increase of GluAP activity in renal medulla was lower, while AspAP activity decreased in the renal cortex. Furthermore, the VOO diet also affected other aminopeptidase activities, such as TyrAP and pGluAP, related to the regulation of the sympathetic nervous system and the metabolic rate. These results support the beneficial effect of VOO in the regulation of SBP through changes in local AP activities of the kidney.