Recent progress in the development of organometallics for the treatment of cancer

From their early successes in medicine, organometallic compounds continue to attract interest as potential chemotherapeutics to treat a range of diseases. Here, we show from recent literature selected largely from the last two years that organometallics offer unique opportunities in medicine and, increasingly, a mechanistic-based approach is applied to their development, which has not always been the case.     

Vegetation damage in the vicinity of an aluminum smelter in Brazil

A primary aluminum smelter, which is responsible for releasing fluoride and other pollutants to atmosphere, is located at the vicinities of rocky field ecosystem in Brazil. We aimed to evaluate the biological effects of the smelter emissions using Spondias dulcis as a bioindicator organism. Evaluations of rainwater quality, atmospheric oxidants and toxicity visual symptomatology were performed in 4 different sites. We also collected leaflets with and without visual toxicity symptoms for anatomical studies under light and scanning electron microscopes, histochemistry, X-ray microanalysis, and fluoride quantification. The fluoride detected on leaves was present in plants at all studied sites, principally at Site 1 (park entrance) and less detected at Site 3 (forest area). However, the fluoride quantity was not the main cause of damage, but the large amount of oxidants which was detected at the atmosphere. This amount of oxidants was increased with the distance from the emission source. It was noticed two types of visual symptoms on the leaflets: a darkening at the adaxial face and a wide brownish necrosis. The anatomical studies showed three damage patterns: superficial necrosis, reaching just the palisade and spongy parenchyma, deep necrosis, reaching the entire mesophyll and a punctual necrosis perceived only at the central veins. With scanning electron microscopy it was detected a turgor loss and a flattening of the cell's external periclinal wall. In the areas where the damage was more noticeable, there was an erosion of the epicuticular wax that lead to delayering, resulting on the epidermis rupture and internal tissue exposure. S. dulcis showed visual symptoms after few days of exposure, which culminated in structural alterations, thus indicating that these pollutants are impacting this important vegetation type from a rocky field ecosystem.     

Recent developments in bioorthogonal chemistry and the orthogonality within

The emergence of bioorthogonal reactions has greatly advanced research in the fields of biology and medicine. They are not only valuable for labeling, tracking, and understanding biomolecules within living organisms, but also important for constructing advanced bioengineering and drug delivery systems. As the systems studied are increasingly complex, the simultaneous use of multiple bioorthogonal reactions is equally desirable. In this review, we take a look at the different bioorthogonal reactions that have recently been developed, the methods of cellular incorporation and the strategies to create orthogonality within the bioorthogonal landscape.     

Alpha particle chemistry. On the formation of stable complexes between He2+ and other simple species: implications for atmospheric and interstellar chemistry

The possibility that stable complexes may be formed between alpha particles (He²⁺) and small molecules is investigated using QCISD quantum mechanical calculations. Implications for their presence in the terrestrial atmosphere and/or in interstellar space are discussed. Figure Optimized structure of a stable H₂OHe²⁺ complex     

Concentration and transport of dissolved and suspended substances in the Orinoco River

The Orinoco River, which is hydrologically unregulated and has a minimally disturbed watershed, was sampled quantitatively over a four-year interval. In conjunction with the sampling, a method was developed for quantifying statistical uncertainty in the estimates of annual transport. The discharge-weighted mean concentration of total suspended solids in the Orinoco River is 80 mg/l, which corresponds to total annual transport of 90 × 10⁶ t/y, or, expressed per unit of watershed area, 960 kg/ha/y, of which 96% is inorganic. The mean for dissolved solids is 34 mg/l, of which 25 mg/l is inorganic. The total transport of inorganic material, with a small allowance for bedload, is 128 × 10⁶ t/y, which corresponds to an erosion rate of 4 cm/1000 y. Concentrations of dissolved and suspended constituents derived from rock weathering are very low because of dilution from high runoff (1190 mm/y), coverage of the southern part of the drainage by shield rock, and minimal watershed disturbance. Seasonal patterns in dissolved and suspended constituents are repeated with a high degree of consistency from one year to the next. For most variables, relationships between transport and discharge are described adequately by a power function. There are three categories of response to changing discharge: purging (exponent > 1: soluble organic fractions and all particulate fractions), dilution (exponent 0–1: major ionic solids and silicon), and conservation (exponent < 0: nitrate, interannual). Variability across seasons and across years is highest for the particulate constituents, but within this group variability is lower for the organic than for the inorganic components. Major ions that originate primarily from the atmosphere have a higher seasonal variability than major ions that originate primarily from weathering. Potassium and soluble silicon have the lowest variabilities. Variability is much lower across years than across seasons for most constituents. Because of high runoff per unit area, the Orinoco drainage has a high specific transport of organic carbon (72 kg/ha/y, 6.8 × 10⁶ t/y, 1.6% of global river transport), even though the concentrations of organic carbon in the river are not exceptionally high (mean, 4.4 mg/l dissolved, 1.4 mg/l particulate). Concentrations of ammonium (35 μg/l as N) and of nitrate (80 μg/l as N) are high given the undisturbed nature of the watershed and the high amount of runoff. The high transport rate for total nitrogen (5.7 kg/ha/y, 0.54 × 10⁶ t/y, l.5% of global river transport) can be sustained only by high rates of nitrogen fixation within the watershed. Concentrations of soluble phosphorus are within the range expected for undisturbed river systems (20 μg/l), but concentrations of particulate phosphorus are low because the amounts of particulate matter are small and the phosphorus per unit weight of suspended matter is low. Phosphorus transport (0.75 kg/ha/y) can be accounted for easily by weathering of the parent material, even within the Guayana Shield, where weathering rates are lowest. Biological modification of nutrient and carbon fractions during transit along the main stem are minimal.     

Effective production of the biodiesel additive STBE by a continuous flow process

A new fuel additive, namely solketal tert-butyl ether (STBE), was developed and optimized under continuous flow conditions using a Corning? Advanced-Flow? glass reactor. STBE was obtained in two steps from glycerol, a renewable building-block produced in large amount in the processing of biodiesel. The advantages of the highly engineered Corning glass reactor included high mixing and heat-exchange efficiency, chemical resistance under corrosive flow conditions and a small hold-up. A robust, continuous, green and safe industrial-scale process is described.     

"Click"化学在药物发现中的应用

“click”化学是最近几年发展起来的一种新技术,它在药物发现的许多方面均有着广泛的应用:快速合成小分子化合物库并从中筛选先导化合物、进行靶标导向的活性小分子合成以及在生物耦联技术等方面的应用。     

Denitrification,Nitrificastion and Nitrogen Fixation in Sublittoral Sediments of the South China Sea

Measurements of denitrification, nitrification and nitrogen fixation rates were made alongside with measuring of chemical and physical properties in sublittoral sediments of the South China Sea near the coast of Vietnam. Studied sediments were suboxic (Eh was positive as a rule), had 0.18–1.5 % of organic carbon, 0.004–0.135 % of total nitrogen and 3-12 % of total iron. The numbers of denitrifying and nitrate-reducing bacteria were as high as millions and hundreds of millions cells per gram wet weight of sediment matter, respectively. The processes of nitrification and denitrification were not spearated spacely. The nitrification was measured in both superficial layer and in a 10-cm sediment column. There were indirect evidences suggesting possibility of anaerobic ammonium oxidation. Denitrification was detectable in the sediments from two sites of sampling; maximal value was 86.2 μmoles N m⁻²h⁻¹. The denitrification potential determined at 1 mM nitrate decreased regularly from the upper to lower layers. Its values in the different sediments ranged from 134 to 532 μmoles N m⁻²h⁻¹. Nitrogen fixation (from 4.8 to 86μmoles N m⁻²h⁻¹) was close to that found in similar sediments in temperate waters in summer, and was not a significant source of nitrogen. It was comparable with diffusion of ammonium from sedimnts.     

Trends in Summer Chemistry Linked to Productivity in Lakes Recovering from Acid Deposition in the Adirondack Region of New York

The US Environmental Protection Agency established the Adirondack Effects Assessment Program (AEAP) to evaluate and monitor the status of biological communities in lakes in the Adirondack region of New York that have been adversely affected by acid deposition. This program includes chemical analysis of 30 lakes, sampled two to three times each summer. Results of trends analysis for lake chemistry and chlorophyll a (chlor a) are presented for 1994 to 2003, and a general comparison is made with recent results of the Adirondack Long-Term Monitoring (ALTM) Program, which included chemical analysis of all but two of these lakes (plus an additional 24 lakes) monthly, year-round for 1992–2004. Increases in pH were found in 25 of the 30 AEAP lakes (P < 0.05) and increases in acid-neutralizing capacity (ANC) were found in 12 of the 30 lakes (P < 0.05). Concentrations of both SO ₄ ²⁻ and Mg²⁺ decreased in 11 lakes (P < 0.05), whereas concentrations of NO ₃ ⁻ decreased in 20 lakes (P < 0.05). Concentrations of NH ₄ ⁺ decreased in 10 lakes at a significance level of P < 0.05 and in three other lakes based on P < 0.1. Concentrations of inorganic and organic monomeric aluminum generally were below the reporting limit of 1.5 μmol L⁻¹, but decreases were detected in four and five lakes, respectively (P < 0.1). Concentrations of chlor a increased in seven lakes at a significance level of P < 0.05 and two lakes at a significance level of P < 0.1. A significant inverse correlation was also found between chlor a and NO ₃ ⁻ concentrations in nine lakes at a significance level of P < 0.05 and two lakes at a significance level of P < 0.1. Results of AEAP analysis of lake chemistry were similar to those of the ALTM Program, although decreases in SO ₄ ²⁻ concentrations were more evident in the year-round ALTM record. Overall, the results suggest (a) a degree of chemical recovery from acidification during the summer, (b) an increase in phytoplankton productivity, and (c) a decreasing trend in NO ₃ ⁻ concentrations resulting from the increased productivity.     

On the relative stabilities of the alkali cations 222 cryptates in the gas phase and in water-methanol solution

The relative stabilities of the alkali [M ⊂ 222]⁺ cryptates (M = Na, K, Rb and Cs) in the gas phase and in solution (80:20 v/v methanol:water mixture) at 298 K, are computed using a combination of ab initio quantum-chemical calculations (HF/6-31G and MP2/6-31+G*//HF/6-31+G*) and explicit-solvent Monte Carlo free-energy simulations. The results suggest that the relative stabilities of the cryptates in solution are due to a combination of steric effects (compression of large ions within the cryptand cavity), electronic effects (delocalization of the ionic charge onto the cryptand atoms) and solvent effects (dominantly the ionic dessolvation penalty). Thus, the relative stabilities in solution cannot be rationalized solely on the basis of a simple match or mismatch between the ionic radius and the cryptand cavity size as has been suggested previously. For example, although the [K ⊂ 222]⁺ cryptate is found to be the most stable in solution, in agreement with experimental data, it is the [Na ⊂ 222]⁺ cryptate that is the most stable in the gas phase. The present results provide further support to the notion that the solvent in which supramolecules are dissolved plays a key role in modulating molecular recognition processes. Figure Alkali cryptates [M ⊂ 222]+ (M = Na, K, Rb and Cs) relative stabilities in gas and methanol:water solution: solvent effects and molecular recognition

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Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The role of rock weathering in the phosphorus budget of terrestrial watersheds

Residual soils (saprolites) developed on crystalline rocks appear to form by an essentially isovolumetric process (i.e. without dilation or compaction). Isovolumetric geochemical analysis of a suite of saprolite samples developed on a common parent rock can be used to estimate the relative rates of long-term losses of P and Si during weathering. Using the export of dissolved Si in rivers as a weathering index, one can then estimate the rate of P release due to chemical weathering by means of the P-Si loss ratio in saprolite. For three basins where data are available (Liberty Hill, SC; Amazon River, Brazil: Rio Negro, Brazil) estimated P weathering release rates are 163, 457, and 242 moles P km^–2 yr^–1 respectively. These compare to precipitation inputs of 684, 700 and 630 moles P km^–2 yr^–1 and total river exports of 256, 4490 and 820 moles P km^–2 yr^–1, respectively. The Rio Negro shows a near perfect balance between the input of P via precipitation and chemical weathering and the riverine output of dissolved and suspended P. This system, however, raised the unsolved problem of the source that supports the atmospheric P input.     

Comparison of spatial variation in otolith chemistry of two fish species and relationships with water chemistry and otolith growth

Spatial variation in the chemistry (Mg, Mn, Sr and Ba) of recently deposited otolith material (last 20–30 days of life) was compared between two demersal fish species; snapper Pagrus auratus (Sparidae) and sand flathead Platycephalus bassensis (Platycephalidae), that were collected simultaneously at 12 sites across three bays in Victoria, south-eastern Australia. Otolith chemistry was also compared with ambient water chemistry and among three sampling positions adjacent to the proximal otolith margin. For both species, variation in otolith chemistry among bays was significant for Ba, Mn and Sr; however, differences among bays were only similar between species for Ba and Mn. Only Ba showed significant variation at the site level. Across the 12 sites, mean otolith Ba levels were significantly positively correlated between species. Further, although incorporation rates differed, mean ambient Ba levels for both species were positively correlated with ambient Ba levels. Spatial variation in multi-element otolith chemistry was also broadly similar between species and with multi-element water chemistry. Partition coefficients clearly indicated species-specific incorporation of elements into otoliths. Mg and Mn were consistently higher in snapper than sand flathead otoliths (mean ±s .d ., Mg snapper 22·1 ± 3·8 and sand flathead 9·9 ± 1·5 μg g⁻¹, Mn snapper 4·4 ± 2·6 and sand flathead 0·5 ± 0·3 μg g⁻¹), Sr was generally higher in sand flathead otoliths (sand flathead 1570 ± 235 and snapper 1346 ± 104 μg g⁻¹) and Ba was generally higher in snapper otoliths (snapper 12·1 ± 12·8 and sand flathead 1·8 ± 1·4 μg g⁻¹). For both species, Mg and Mn were higher in the faster accreting regions of the otolith margin, Sr was lower in the slower accreting region and Ba showed negligible variation among the three sampling regions. This pattern was consistent with the higher Mg and Mn, and generally lower Sr observed in the faster accreting snapper otoliths. It is hypothesized that the differences between species in the incorporation of these elements may be at least partly related to differences in metabolic and otolith accretion rate. Although rates of elemental incorporation into otoliths appear species specific, for elements such as Ba where incorporation appears consistently related to ambient concentrations, spatial variation in otolith chemistry should show similarity among co-occurring species.     

海河流域61种植物磷元素化学特征及地理分异

海河流域６１种植物磷元素化学特征及地理分异的分析结果表明：滨蒿（Ａｒｔｅｍｉｓｉａｓｃｏｐａｒｉａ）含磷量最高,达０．２１２％,浮萍（Ｌｅｍｎａｍｉｎｏｒ）最低,只有０．０４３％;玉米（Ｚｅａｍａｙｓ）、高粱（Ｓｏｒｇｈｕｍｖｕｌｇａｒｅ）、谷子（Ｐａｎｉｃｕｍｍｉｌｉａｃｅｕｍ）、水稻（Ｏｒｙｚａｓａｔｉｖａ）、小麦（Ｔｒｉｔｉｃｕｍａｅｓｔｉｖｕｍ）、莜麦（Ａｖｅｎａｎｕｄａ）等谷物含磷量＜０．２００％,低于作物正常含量水平,反应了土壤缺磷特点。各类植物含磷量大小为：盐生植物＞天然草本植物＞农作物＞蔬菜＞落叶阔叶树＞灌木半灌木＞果树＞针叶树＞水生植物（Ｐ＜０．０５）。农作物各器官部位以果实含磷量最高达０．２３４％,其次是叶０．１６１％和茎０．１１１％,根最低,只有０．０８４％,这种结果造成土壤有效磷因收获而亏损。不同支流域植物磷的地理分布规律表现为：滹沱河流域＞永定河流域＞漳卫河流域＞潮白河流域＞大清河流域（Ｐ＜０．０５）。土壤中含磷量相对较低,以及盐碱土ｐＨ较高,不利于植物吸收磷,造成植物磷营养元素相对缺乏     

On the basics of carbohydrate-metal chemistry: complexes of palladium(II) with hydroxyaldehyde and -ketone hydrates

In this work, we present novel complexes of hydroxyaldehydes and ketones with palladium(II). The compounds are studied by two-dimensional NMR spectroscopy in solution (COSY, HMQC, HMBC). Glycolaldehyde, d-glyceraldehyde, glyoxal and 2,4-O-ethylidene-d-erythrose were used as aldehydes, d-erythrulose was used as an alpha-hydroxyketone. Although different species are present in solution, only the hydrated forms of the aldehydes can coordinate to the metal centre. These complexes are stable at 4 degrees C in aqueous solution. The crystal structure of a complex formed by mesoxalic acid and palladium(II) is reported and shows coordination by both hydroxy groups of the hydrated ketone.     

24-脱氢胆固醇还原酶基因转基因小鼠血生化指标分析

目的建立全身表达24-脱氢胆固醇还原酶基因（Dhcr24）转基因小鼠动物模型,研究该基因过表达对小鼠代谢的影响。方法RT-PCR法克隆小鼠Dhcr24基因,把该基因插入CMV启动子下游,构建转基因表达载体,通过显微注射法建立Dhcr24转基因小鼠。PCR鉴定Dhcr24转基因小鼠的基因型,RT-PCR和Western Blot检测基因表达水平,血生化检测仪检测转基因小鼠血生化指标的改变。结果建立了2个不同表达水平的Dhcr24转基因小鼠品系,转入的Dhcr24基因在肝和脾组织中的表达高于内源的Dhcr24。血生化检测证实：乳酸脱氢酶（LDH）、总蛋白（TP）、白蛋白（Alb）和血肌酐（SCr）较野生型小鼠明显降低,而高密度脂蛋白胆固醇（HDL-c）和碱性磷酸酶（ALP）较野生型小鼠明显增加,并且Dhcr24转基因雌鼠的体重比野生型小鼠明显降低,均有显著差异。但Dhcr24转基因雄鼠各项指标与野生型小鼠相比没有显著差异。结论成功建立了全身表达Dhcr24转基因小鼠,并证实Dhcr24基因对雌性小鼠的体重和血生化指标,包括LDH,TP,Alb,SCr,HDL-c and ALP具有明显的影响。     

Immunocytochemical localization of the major glycoprotein of epididymal fluid from the cauda in the epithelium of the mouse epididymis

Summary The most abundant protein in fluid from the mouse cauda epididymidis, designated CP 27, is a glycoprotein that migrates at approximately 27000 daltons on SDS-polyacrylamide gels. Samples of CP 27 were isolated by preparative gel electrophoresis and were used to raise a guinea-pig polyclonal antiserum, which reacted with a single band on western blots of caudal epididymal fluid. This antiserum was used for immunocytochemical localization of CP 27 in histological sections of mouse epididymis using the peroxidase-antiperoxidase and protein A-gold methods. The most proximal staining with anti-CP 27 was in segment 6 of the distal caput epididymidis, where the lumen and a portion of the supranuclear cytoplasm of principal cells were stained. In contrast, in the distal corpus and cauda epididymidis (segments 8–11), there was pronounced staining of the luminal contents, stereocilia, and scattered cells identified as the light cells of the epididymal epithelium. Although CP 27 was found in the epididymal lumen of all segments distal to segment 6, the intensity of staining appeared to decline distally in the cauda epididymidis. Control sections exposed to pre-immune serum instead of anti-CP 27 showed no reaction. The results suggest that CP 27, the major glycoprotein of cauda epididymal fluid, is synthesized by principal cells of segment 6 of the distal caput epididymidis. CP 27 may be among the substances absorbed from the lumen by the light cells of the distal epididymis.     

Vegetation patterns and nutrient status of two mixed mires in the southern Alps

Abstract. Two mixed-mire complexes in the southern Alps (Italy) were analyzed for vegetation patterns and water and peat chemistry. Six vegetation units were distinguished, representing three phytosociological orders, the Sphagnetalia magellanici, Scheuchzerietalia palustris and Caricetalia fuscae. Boundaries between these units are sharp and marked by difference in calcium concentrations in mire water and pH values. Relatively high Ca concentrations (up to 150 |j.eq/l) were measured at ombrotrophic sites. They mirror similarly high concentrations in precipitation and are probably correlated with dry deposition of calcium-rich particles. Phosphorous appears to be the main differentiating nutrient between the units; no significant differences are found for nitrogen. The vegetation is mainly characterized by the distributional pattern of Caricetalia fuscae species, being restricted to minerotrophic sites.     

Radiation of pollination systems in the Iridaceae of sub-Saharan Africa

BACKGROUND: Seventeen distinct pollination systems are known for genera of sub-Saharan African Iridaceae and recurrent shifts in pollination system have evolved in those with ten or more species. Pollination by long-tongued anthophorine bees foraging for nectar and coincidentally acquiring pollen on some part of their bodies is the inferred ancestral pollination strategy for most genera of the large subfamilies Iridoideae and Crocoideae and may be ancestral for the latter. Derived strategies include pollination by long-proboscid flies, large butterflies, night-flying hovering and settling moths, hopliine beetles and sunbirds. Bee pollination is diverse, with active pollen collection by female bees occurring in several genera, vibratile systems in a few and non-volatile oil as a reward in one species. Long-proboscid fly pollination, which is apparently restricted to southern Africa, includes four separate syndromes using different sets of flies and plant species in different parts of the subcontinent. Small numbers of species use bibionid flies, short-proboscid flies or wasps for their pollination; only about 2 % of species use multiple pollinators and can be described as generalists. SCOPE: Using pollination observations for 375 species and based on repeated patterns of floral attractants and rewards, we infer pollination mechanisms for an additional 610 species. Matching pollination system to phylogeny or what is known about species relationships based on shared derived features, we infer repeated shifts in pollination system in some genera, as frequently as one shift for every five or six species of southern African Babiana or Gladiolus. Specialized systems using pollinators of one pollination group, or even a single pollinator species are the rule in the family. Shifts in pollination system are more frequent in genera of Crocoideae that have bilaterally symmetric flowers and a perianth tube, features that promote adaptive radiation by facilitating precise shifts in pollen placement, in conjunction with changes in flower colour, scent and tube length. CONCLUSIONS: Diversity of pollination systems explains in part the huge species diversity of Iridaceae in sub-Saharan Africa, and permits species packing locally. Pollination shifts are, however, seen as playing a secondary role in speciation by promoting reproductive isolation in peripheral, ecologically distinct populations in areas of diverse topography, climate and soils. Pollination of Iridaceae in Eurasia and the New World, where the family is also well represented, is poorly studied but appears less diverse, although pollination by both pollen- and oil-collecting bees is frequent and bird pollination rare.