The Psymberin Story—Biological Properties and Approaches towards Total and Analogue Syntheses

Psymberin is a marine natural product which has attracted a great deal of interest since its isolation: While the highly cytotoxic compound was detected early on as an ingredient in a marine sponge, it took over a decade and 600 additional samples for the structure to eventually be assigned. In the last eight years fascinating synthetic and biosynthetic investigations have led to a more detailed understanding as well as a new starting point for structure–activity studies towards new antitumor compounds. The Review gives an in‐depth insight into the progress in the field of the marine polyketide psymberin and demonstrates how organic synthesis is influencing neighboring scientific subjects.     

明日叶黄酮类化合物清除羟基自由基活性研究

为了研究明日叶黄酮类化合物对羟基自由基的清除作用,以明日叶（主要取叶片）为原料,用体积分数为65％乙醇提取明日叶总黄酮,测定其总黄酮含量.通过Fenton反应体系产生羟基自由基,利用明日叶提取液中的功能成分黄酮类化合物对羟基自由基的清除作用进行研究.结果表明：明日叶提取物总黄酮质量分数为10.18％,且黄酮类化合物对羟基自由基有较强清除效力,当提取物总黄酮浓度在0.1～1.0 mg/mL范围内,其与清除率呈正相关.明日叶中黄酮类化合物对羟基自由基有较强清除效力,作为天然抗氧化产品开发具有一定价值.     

Total Synthesis of α-Elvucitabine

Total synthesis of α-elvucitabine was achieved in 26% overall yield by a concise nine-step procedure starting from L-lyxose, with trimethylsilyl trifluoromethaneoulfonate (TMSOTf)–mediated stereocontrolled α-N-glycosidation and olefination through Barton–McCombie deoxygenation being the key steps, and the stereochemistry of the product was determined by nuclear Overhauser effect spectroscopy.     

Total Synthesis of Pulchellalactam via an RCM Strategy

Total synthesis of (Z) pulchellalactam, a CD protein tyrosine phosphatase inhibitor, from commercially available methallyl chloride employing ring‐closure metathesis (RCM) as a key step is described.     

Catalytic solid substrate-room temperature phosphorimetry for the determination of trace As(V) based on oxidising reaction between hydrogen peroxide and fullerenol using tween-80 as sensitizer

A new catalytic solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace arsenic(V) has been established. It is based on the fact that fullerenol (F-ol) emitted strong and stable room temperature phosphorescence (RTP) on nitric acid cellulose membrane (NCM) substrate. H₂O₂ could oxidise F-ol to cause the quenching of RTP. As(V) could catalyse H₂O₂ to oxidise F-ol and decrease the RTP signal of F-ol sharply. After adding tween-80 in the system, its ΔI _p enhanced 7.7 times compared with the without-tween-80 levels. Under the optimum conditions, the linear dynamic range of this method was 0.016?11.2 ag spot^?1 with a detection limit (LD) of 9.3 zg spot^?1 (corresponding concentration: 2.3 × 10^?17 g mL^?1). This sensitive, simple and selective method has been successfully applied to the determination of trace As(V) in human hair and tea samples. The reaction mechanism for SS-RTP is also discussed.     

Levels of Pesticide Residues in Food: Evaluation of Data from Total Diet Studies in Italy

Abstract

Total Diet Studies on pesticide residues in foods carried out in Italy in the last two decades are briefly summarized and data are discussed. Health risk assessment is expressed by the ratio total intake/ADI (%ADI ingested) for each compound and by the sum of the percentages of ADI for each compound within the same class of pesticides.

The total dietary intake of chlorinated pesticides, that was almost 100% of ADI in the years 1970-74, decreased down to 10% in the period 1978-84. This trend was confirmed for DDT in recent years, while data on Lindane and Heptachlor seem to be constant.

As regards the organophosphorus pesticides the sum of the percentages of ADI ingested for each compound, extrapolated from recent data (1990-1991) is about 20% and can be regarded as reasonably acceptable because the study included practically all the mainly used compounds.

Only few data are available for some pesticides like dithiocarbamates, especially EBDCs and their derivatives (e.g. ETU), other carbamates (e.g. aldicarb), paraquat etc. Moreover, analytical methods for these compounds should be improved.

The need for a considerable improvement in the number and organization of monitoring structures, in the use of standardized analytical procedures, in good laboratory practice standards and in the realibility of “monitoring protocols” and their homogeneity is evidenced.     

Highly sensitive inhibitory kinetics fluorescence method for determination of arsenic

A new and highly sensitive inhibitory kinetic fluorescence method for the determination of arsenic (III) has been established based on its inhibitory effect on the oxidation reaction of Acridine red (ADR) by KBrO₃ in sulphuric acid medium. The reaction has been followed by measuring the enhancement of fluorescence at 550?nm. It relies on the linear relationship where the change in the fluorescence (ΔF) versus added As(III) amounts in the range of 0–0.450?µg?mL^?1 is plotted, under the optimum conditions. The sensitivity of the proposed method, i.e. the limit of detection, is 2.1?×?10^?2?ng?mL^?1. The method is featured with good accuracy and reproducibility for arsenic (III) determination. This method was successfully applied for the quantitative determination of arsenic (III) in food products samples, and the relative standard deviations and the recoveries were in ranges of 2.31–2.83% and 90.0–107.2%, respectively. A review of recently published catalytic or inhibiting kinetic methods for the determination of arsenic (III) has also been presented for comparison. The mechanism of reaction was studied.     

Synthesis and Biological Activity of 7,8,9‐Trideoxy‐ and 7R DesTHP‐Peloruside A

The stereoselective syntheses of 7,8,9‐trideoxypeloruside A ( 4 ) and a monocyclic peloruside A analogue lacking the entire tetrahydropyran moiety ( 3 ) are described. The syntheses proceeded through the PMB‐ether of an ω‐hydroxy β‐keto aldehyde as a common intermediate which was elaborated into a pair of diastereomeric 1,3‐syn and ‐anti diols by stereoselective Duthaler–Hafner allylations and subsequent 1,3‐syn or anti reduction. One of these isomers was further converted into a tetrahydropyran derivative in a high‐yielding Prins reaction, to provide the precursor for bicyclic analogue 4 . Downstream steps for both syntheses included the substrate‐controlled addition of a vinyl lithium intermediate to an aldehyde, thus connecting the peloruside side chain to C15 (C13) of the macrocyclic core structure in a fully stereoselective fashion. In the case of monocyclic 3 macrocyclization was based on ring‐closing olefin metathesis (RCM), while bicyclic 4 was cyclized through Yamaguchi‐type macrolactonization. The macrolactonization step was surprisingly difficult and was accompanied by extensive cyclic dimer formation. Peloruside A analogues 3 and 4 inhibited the proliferation of human cancer cell lines in vitro with micromolar and sub‐micromolar IC₅₀ values, respectively. The higher potency of 4 highlights the importance of the bicyclic core structure of peloruside A for nM biological activity.