Supramolecular platinum complexes for cancer therapy

The rise of supramolecular chemistry offers new tools to design therapeutics and delivery platforms for biomedical applications. This review aims to highlight the recent developments that harness host-guest interactions and self-assembly to design novel supramolecular Pt complexes as anticancer agents and drug delivery systems. These complexes range from small host-guest structures to large metallosupramolecules and nanoparticles. These supramolecular complexes integrate the biological properties of Pt compounds and novel supramolecular structures, which inspires new designs of anticancer approaches that overcome problems in conventional Pt drugs. Based on the differences in Pt cores and supramolecular structures, this review focuses on five different types of supramolecular Pt complexes, and they include host-guest complexes of the FDA-approved Pt(II) drugs, supramolecular complexes of nonclassical Pt(II) metallodrugs, supramolecular complexes of fatty acid-like Pt(IV) prodrugs, self-assembled nanotherapeutics of Pt(IV) prodrugs, and self-assembled Pt-based metallosupramolecules.     

林蛙受精卵的表面收缩波和卵裂起动收缩

林蛙受精卵表面的大豆凝集素结合位点没有侧向运动,联在结合位点上的标记物在卵表面位置的改变应该可以反映卵表面运动。本文利用近景摄影测量术和侧向摄影法观测卵表面标记点位置的变化,得到下面的结果:1.卵裂前30—40min,整个卵表面都向预定分裂沟中心移动,表示卵表面在收缩。卵裂前15min左右,沟中心附近的卵表面开始松弛,随之是离沟较远处的卵表面松弛,显示卵表面有一个从预定分裂沟中心向四周传播的收缩波(图2—5)。如果以相邻标记点之间的距离变化作图(图6),则出现两个波,一个是松弛波,一个是收缩波。本文对卵表面究竟出现一个波还是两个波的问题进行了讨论。2.分裂沟中心附近收缩时,高程逐渐下降,基部两侧逐渐加宽(图7和图8);卵松弛时,高程增加,基部收缩。所以卵高程的变化也是从预定分裂沟中心波浪形地向四周传播的。3.卵裂沟出现前3—5 min,预定分裂沟两端开始向沟中心收缩,这是卵裂起动收缩。以后收缩范围逐渐扩大,强度亦增加,但预定分裂沟两侧的卵表面没有向预定分裂沟两端移动。这一结果支持了赤道区收缩的假说。     

Root traits of perennial C4 grasses contribute to cultivar variations in soil chemistry and species patterns in particulate and mineral-associated carbon pool formation

Recent studies have indicated that the C₄ perennial bioenergy crops switchgrass (Panicum virgatum) and big bluestem (Andropogon gerardii) accumulate significant amounts of soil carbon (C) owing to their extensive root systems. Soil C accumulation is likely driven by inter- and intraspecific variability in plant traits, but the mechanisms that underpin this variability remain unresolved. In this study we evaluated how inter- and intraspecific variation in root traits of cultivars from switchgrass (Cave-in-Rock, Kanlow, Southlow) and big bluestem (Bonanza, Southlow, Suther) affected the associations of soil C accumulation across soil fractions using stable isotope techniques. Our experimental field site was established in June 2008 at Fermilab in Batavia, IL. In 2018, soil cores were collected (30 cm depth) from all cultivars. We measured root biomass, root diameter, specific root length, bulk soil C, C associated with coarse particulate organic matter (CPOM) and fine particulate organic matter plus silt- and clay-sized fractions, and characterized organic matter chemical class composition in soil using high-resolution Fourier-transform ion cyclotron resonance mass spectrometry. C₄ species were established on soils that supported C₃ grassland for 36 years before planting, which allowed us to use differences in the natural abundance of stable C isotopes to quantify C₄ plant-derived C. We found that big bluestem had 36.9% higher C₄ plant-derived C compared to switchgrass in the CPOM fraction in the 0–10 cm depth, while switchgrass had 60.7% higher C₄ plant-derived C compared to big bluestem in the clay fraction in the 10–20 cm depth. Our findings suggest that the large root system in big bluestem helps increase POM-C formation quickly, while switchgrass root structure and chemistry build a mineral-bound clay C pool through time. Thus, both species and cultivar selection can help improve bioenergy management to maximize soil carbon gains and lower CO₂ emissions.     

Increase of atmospheric CO2 promotes phytoplankton productivity

It is usually thought that unlike terrestrial plants, phytoplankton will not show a significant response to an increase of atmospheric CO₂. Here we suggest that this view may be biased by a neglect of the effects of carbon (C) assimilation on the pH and the dissociation of the C species. We show that under eutrophic conditions, productivity may double as a result of doubling of the atmospheric CO₂ concentration. Although in practice productivity increase will usually be less, we still predict a productivity increase of up to 40% in marine species with a low affinity for bicarbonate. In eutrophic freshwater systems doubling of atmospheric CO₂ may result in an increase of the productivity of more than 50%. Freshwaters with low alkalinity appeared to be very sensitive to atmospheric CO₂ elevation. Our results suggest that the aquatic C sink may increase more than expected, and that nuisance phytoplankton blooms may be aggravated at elevated atmospheric CO₂ concentrations.     

Effects of ammonium sulphate application on the chemistry of bulk soil,rhizosphere, fine roots and fine-root distribution in a Picea abies (L.) karst. stand

The effect of ammonium sulphate application on the bulk and rhizosphere soil chemistry, elemental concentration of living fine roots (<2 mm in diameter), amounts of living and dead fine roots, root length density and specific root length density were investigated in a 28 year old Norway spruce stand in SW Sweden. The treatments started in 1988. Core samples of the LFH layer and mineral soil layers were sampled in control (C) and ammonium sulphate (NS) treatment plots in 1988, 1989 and 1990. Soil pH and NO₃-S and SO₄-S, Al, Ca, Mg, Mn and K concentrations were measured for both the bulk soil and rhizosphere soil.The pH-values of the bulk and rhizosphere soil decreased in 1989 and 1990 in NS plots compared to control plots, while the SO₄-S concentration increased. The Ca, Mg and K concentration increased in the NS treatment in almost all layers in the bulk and the rhizosphere soil. Ammonium ions may have replaced these elements in the soil organic matter. The NS treatment reduced Mg concentration in fine roots in all layers in 1990. The Al concentrations in the rhizosphere and bulk soil were higher in NS plots in all layers, except at 0–10 cm depth, both in 1989 and 1990. The Al content of living fine roots was higher in NS plots than C plots but the differences were not significant. The NS addition did not affect the P and K contents of fine roots in any soil layer, but the S concentrations of fine roots were significantly higher in NS plots in 1989 and 1990. The fine root necromass was higher in NS than in C in 1990, in the LFH layer, indicating a gradual decrease in the vitality of the fine roots. It was suggested that the NS treatment resulted in displacement of Mg and K from exchange sites in the LFH layer leading to leaching of these cations to the mineral soil. Further application of ammonium sulphate may damage the fine roots and consequently adversely affect the water and nutrient uptake of root systems.     

Phosphoryl amino acids: Common origin for nucleic acids and protein

A series of compounds (DAP-AA) composed of an amino acid (AA) and a dialkyl phosphoryl group (DAP) is the basic elements of life chemistry. Self-catalysis of DAP-AA gives the self-assembly oligopeptides, even in aqueous medium at 38°C. The oligo-nucleotides could also be assembled from nucleosides' phosphorylation by DAP-AA. DAP-AA acts as the energy source as well as the phosphoryl donor for the synthesis of nuclic Acids and protein. A general expression for the self assembly system is proposed.     

Interaction of chlorpromazine with phospholipid membranes

The interaction of chlorpromazine (CPZ) with artificial membranes (egg-yolk phosphatidylcholine liposomes) has been studied. Measurements of the surface electric potential, which is modified in the presence of the ionized form of the drug, were obtained by electron paramagnetic resonance spectroscopy (EPR) using a positively charged amphiphilic spin-probe. This probe partitions between the aqueous and lipidic phases depending on the surface potential and on the structural state of the membrane. The surface potential was measured as a function of drug concentration in the range where the spectral line-shapes are not affected by the incorporation of the drug. From these experimental results and through an appropriate formalism we obtain information on the binding of the drug to the lipid bilayer and on the ionization of the drug in the lipidic phase. Correspondence to: C. Anteneodo     

Strategies for the identification and purification of ligands for orphan biomolecules

The isolation of related genes with evolutionary conserved motifs by the application ofpolymerase chain reaction-based molecular biology techniques, or from database searchingstrategies, has facilitated the identification of new members of protein families. Many of theseprotein molecules will be involved in protein–protein interactions (e.g. growth factors,receptors, adhesion molecules), since such interactions are intrinsic to virtually every cellularprocess. However, the precise biological function and specific binding partners of these novelproteins are frequently unknown, hence they are known as orphan molecules.Complementary technologies are required for the identification of the specific ligands orreceptors for these and other orphan proteins (e.g., antibodies raised against crude biologicalextracts or whole cells). We describe herein several alternative strategies for the identification,purification and characterisation of orphan peptide and protein molecules, specifically thesynergistic use of micropreparative HPLC and biosensor techniques.     

Detection and minimization of H-phosphonate side reaction during phosphopeptide synthesis by a post-assembly global phosphorylation strategy

Summary In the course of solid-phase synthesis of phosphopeptides by a post-assembly global phosphorylation strategy, the corresponding H-phosphonate peptides form as byproducts. We describe model studies to investigate this side reaction as a function of reaction conditions, and use this information to develop conditions that minimize the problem, i.e., use of dibenzyl N,N-di-isopropyl phosphoramidite for phosphitylation, followed immediately by oxidation with anhydrous tert-butyl hydroperoxide in dry tetrahydrofuran under argon, and final acidolytic cleavage.This work was taken in part from the Ph.D. Theses of E.A. Ottinger (1994) and Q. Xu (1996), University of Minnesota, Minneapolis, MN, U.S.A. Preliminary presentations of portions of this work were made at the Twenty-Second European Peptide Symposium, Interlaken, Switzerland, September 13–19, 1992, see Ref. 1, at the 14th American Peptide Symposium, Columbus, OH, U.S.A., June 18–23, 1995, and at the Fourth International Symposium on Solid Phase Synthesis & Combinatorial Chemical Libraries, Edinburgh, Scotland, U.K., September 12–16, 1995, see Ref. 2. The title side reaction was first discussed for tyrosine (see Refs 1 and 3), but all of the mechanism studies discussed herein are for serine and threonine.Amino acid symbols denote the l-configuration, and abbreviations for amino acids and peptides follow rules of the IUPAC-IUB Commission of Biochemical Nomenclature [J. Biol. Chem., 247 (1972) 977].