It is generally accepted that adjacent guanine residues in DNA are the primary target for platinum antitumor drugs and that differences in the conformations of the Pt-DNA adducts can play a role in ...their antitumor activity. In this study, we investigated the effect of the carrier ligand cis-1,3-diaminocyclohexane (cis-1,3-DACH) upon formation, stability, and stereochemistry of the (cis-1,3-DACH)PtG2 and (cis-1,3-DACH)Pt(d(GpG)) adducts (G = 9-EthlyGuanine, guanosine, 5′- and 3′-guanosine monophosphate; d(GpG) = deoxyguanosil(3′-5′)deoxyguanosine). A peculiar feature of the cis-1,3-DACH carrier ligand is the steric bulk of the diamine, which is asymmetric with respect to the Pt-coordination plane. The (cis-1,3-DACH)Pt(5′GMP)2 and (cis-1,3-DACH)Pt(3′GMP)2 adducts show preference for the ΛHT and ∆HT conformations, respectively (HT stands for Head-to-Tail). Moreover, the increased intensity of the circular dichroism signals in the cis-1,3-DACH derivatives with respect to the analogous cis-(NH3)2 species could be a consequence of the greater bite angle of the cis-1,3-DACH carrier ligand with respect to cis-(NH3)2. Finally, the (cis-1,3-DACH)Pt(d(GpG)) adduct is present in two isomeric forms, each one giving a pair of H8 resonances linked by a NOE cross peak. The two isomers were formed in comparable amounts and had a dominance of the HH conformer but with some contribution of the ΔHT conformer which is related to the HH conformer by having the 3′-G base flipped with respect to the 5′-G residue.
Aims
Climate change imposes adaptation of viticulture in risk areas, such as the Mediterranean. Mycorrhization is a valid tool to reduce the impact of the expected temperature/drought increase. Aim ...of this work was to test the effects of mycorrhization on grapevine vegetative growth, element composition of soil/leaves, and microbiota of bulk soil/rhizosphere/endorhiza, in the field, under exacerbated summer stress conditions obtained by planting the rootstocks in June.
Methods
118 rooted cuttings of 1103-Paulsen (
Vitis berlandieri
×
Vitis rupestris
) were planted in Salento (Apulia, Southern Italy); about half of them were mycorrhized. Leaf Area Index, shoot growth and survival rate were monitored across two growing seasons. Leaf/shoot weight, chemical analysis of 25 elements, and 16S rRNA gene metabarcoding of bulk soil/rhizosphere/endorhiza were performed on subsamples.
Results
Mycorrhized plants showed significantly higher survival rate and growth, and accumulated significantly higher amounts of 18 elements. 27 endorhizal OTUs (representing ~20% of total sequences) were differently distributed (20 OTUs more abundant in mycorrhized plants); in the rhizosphere, instead, 12 OTUs (~2.5% of total sequences) were differently distributed. A few Actinobacterial OTUs were enriched by mycorrhization in the root endosphere; the same OTUs were the most correlated with the chemical elements, suggesting a role in element dynamics. These OTUs were not hub taxa of the co-occurrence network.
Conclusions
This work shed light onto the interactions between mycorrhiza and microbiome, in the context of plant element dynamics, which is useful to identify potential target candidates for biotechnological applications, thus moving towards a more sustainable, ecosystem-based viticulture.
A new 2-amino imidazole derivative, 5-(4-chlorophenyl)-N,1-di-o-tolyl-1H-imidazole-2-amine (3), has been synthesized using a green approach. The reaction was conducted in a ChCl (cholinium ...chloride)/urea eutectic mixture, which is a nature-inspired and environmentally friendly reaction medium. The proposed reaction mechanism involves the preliminary regioselective alkylation of the Nsp2 of guanidine (2), followed by an intramolecular condensation between the carbonyl moiety and the secondary N′sp3. Finally, a tautomerization/aromatization step furnished the final product (3). Notably, 2-amino imidazole (3) could be isolated in high yield (91%), just by filtration from the DES/water mixture and subsequent crystallization; the remaining ChCl/urea could be recycled, after water removal, for four consecutive reactions without any significant drop in the (3) yield. The product has been fully characterized by 1H, 13C, 2D 1H-13C HSQC, and 2D 1H-13C HMBC NMR; FT-IR spectroscopy; and EI-MS spectrometry.
Six platinum(IV) compounds derived from an oxaliplatin analogue containing the unsaturated cyclic diamine
-1,2-diamino-4-cyclohexene (DACHEX), in place of the 1,2-diaminocyclohexane, and a range of ...axial ligands, were synthesized and characterized. The derivatives with at least one axial chlorido ligand demonstrated solvent-assisted photoreduction. The electrochemical redox behavior was investigated by cyclic voltammetry; all compounds showed reduction potentials suitable for activation in vivo. X-ray photoelectron spectroscopy (XPS) data indicated an X-ray-induced surface reduction of the Pt(IV) substrates, which correlates with the reduction potentials measured by cyclic voltammetry. The cytotoxic activity was assessed in vitro on a panel of human cancer cell lines, also including oxaliplatin-resistant cancer cells, and compared with that of the reference compounds cisplatin and oxaliplatin; all IC
values were remarkably lower than those elicited by cisplatin and somewhat lower than those of oxaliplatin. Compared to the other Pt(IV) compounds of the series, the bis-benzoate derivative was by far (5-8 times) the most cytotoxic showing that low reduction potential and high lipophilicity are essential for good cytotoxicity. Interestingly, all the complexes proved to be more active than cisplatin and oxaliplatin even in three-dimensional spheroids of A431 human cervical cancer cells.
Heavy metals (HMs) are released into the environment by many human activities and persist in water even after remediation. The efficient filtration of solubilized HMs is extremely difficult. ...Phytoremediation appears a convenient tool to remove HMs from polluted water, but it is limited by the choice of plants able to adapt to filtration of polluted water in terms of space and physiological needs. Biomasses are often preferred. Aquatic moss biomasses, thanks to gametophyte characteristics, can act as live filtering material. The potential for phytoremediation of Hypnales aquatic mosses has been poorly investigated compared to aquatic macrophytes. Their potential is usually indicated as a tool for bioindication and environmental monitoring more than for pollutant removal. When phytoremediation has been considered, insufficient attention has been paid to the adaptability of biomasses to different needs. In this study the heavy metal uptake of moss
grown in two different light conditions, was tested with high concentrations of elements such as Pb, Cd, Zn, Cu, As, and Cr. This moss produces dense mats with few culture needs. The experimental design confirmed the capacity of the moss to accumulate HMs accordingly to their physiology and then demonstrated that a significant proportion of HMs was accumulated within a few hours. In addition to the biosorption effect, an evident contribution of the active simplistic mass can be evidenced. These reports of HM accumulation within short time intervals, show how this moss is particularly suitable as an adaptable bio-filter, representing a new opportunity for water eco-sustainable remediation.
SYP51 and 52 are the two members of the SYP5 Qc-SNARE gene family in
. These two proteins, besides their high level of sequence identity (85%), have shown to have differential functional specificity ...and possess a different interactome. Here we describe a unique and specific interaction of SYP51 with an ER aquaporin, AtNIP1;1 (also known as NLM1) indicated to be able to transport arsenite As(III) and previously localized on PM. In the present work we investigate in detail such localization
and characterize the interaction with SYP51. We suggest that this interaction may reveal a new mechanism regulating tonoplast invagination and recycling. We propose this interaction to be part of a regulatory mechanism associated with direct membrane transport from ER to tonoplast and Golgi mediated vesicle trafficking. We also demonstrate that NIP1;1 is important for plant tolerance to arsenite but does not alter its uptake or translocation. To explain such phenomenon the hypothesis that SYP51/NIP1;1 interaction modifies ER and vacuole ability to accumulate arsenite is discussed.
In order to evaluate the local environmental risk deriving from coal transport and burning, 30 soil samples were collected along the coal conveyor belt and around the coal-burning power plant ...Federico II of Brindisi (Apulia, southern Italy). Since soil pollution of metals and metalloids is measured not only by their total concentration but also by evaluating their mobility and availability, arsenic sequential extraction, leaching test and speciation analysis were performed. The analytical results showed that the most abundant As amount was contained in the final residue of the sequential extraction procedure, the so-called occluded As, embedded in rock formations such as sulphides. Moreover speciation chemical analysis showed that As(V) was by far the most abundant species, whereas As(III), which represents the most soluble and available species, was only a very small fraction. No arsenic organic species were detected in the soil samples.
Despite many advantages, digital impressions, when compared to the conventional one, produce contrasting results and their complete substitution is still under debate. This comparative study aims to ...test a way to perform a clinical evaluation of digital impression Accuracy and Trueness with a gypsum check. After calculating the Trueness, Precision, and Accuracy of the digital impressions, a gypsum check was fabricated and screwed on implant abutments. The impression was not considered reliable if the gypsum check fractured during the insertion. The gypsum check test was correlated to a cut-off of 100 µm Trueness. Mean Trueness was 151.19 ± 37.23 µm of the first optical impression and 125.47 ± 41.90 µm of the second optical impression. The Precision mean was 39.76 ± 10.89 µm. The mean Accuracy percentage was 98.69 ± 0.29%. The gypsum checks fractured 10 times on 42 tests, and in any case, the Trueness value was above the 100 µm cut off, with a p = 0.001. A gypsum check screwed onto an implant abutment could be considered a way to perform clinical measurement of Trueness, allowing the clinician to understand if the Trueness value is higher or lower than 100 µm and reflecting the reliability of digital impressions.
Two new Pt(II)-pyrophosphato complexes containing the carrier ligands
-1,3-diaminocyclohexane (
-1,3-DACH) and
-1,2-diamine-4-cyclohexene (1,2-DACHEX), variants of the 1
,2
-diaminocyclohexane ligand ...present in the clinically used Pt-drug oxaliplatin, have been synthesized with the aim of developing new potential antitumor drugs with high bone tropism. The complexes are more stable at physiological pH than in acid conditions, with Na
Pt(pyrophosphato)(
-1,3-DACH) (
) slightly more stable than Pt(dihydrogenpyrophosphato)(1,2-DACHEX) (
). The greater reactivity at acidic pH ensures a greater efficacy at the tumor site. Preliminary NMR studies indicate that
and
react slowly with 5'-GMP (used as a model of nucleic acids), releasing the pyrophosphate ligand and affording the bis 5'-GMP adduct. In vitro cytotoxicity assays performed against a panel of four human cancer cell lines have shown that both compounds are more active than oxaliplatin. Flow cytometry studies on HCT116 cells showed that the pyrophosphato compounds with the non-classical 1,3- and 1,4-diaminocyclohexane ligands (
and
) are the most capable to induce cells' death by apoptosis and necrosis.
A smart nanocarrier system for cancer therapy, based on a recently developed technique for preparing pure nanometric calcium carbonate (CaCO3), was studied. Different approaches were used to obtain ...sustained release of cisplatin: at first, pure CaCO3 nanoparticles were evaluated as carriers, then the nanoparticles were functionalized with polymer or silanes, and finally they were employed as a substrate to build layer by layer (LbL) self-assembled polyelectrolyte nanocapsules. Loading efficiency and release kinetics were measured. The best loadings were obtained with the LbL nanocapsules, allowing for high loading efficiency and the possibility of controlling the release rate of the drug. The behavior of all the carriers was evaluated on four neoplastic cell lines, representative of different types of neoplastic disease, namely MCF-7 (breast cancer), SKOV-3 (ovarian cancer), HeLa (cervical cancer) and CACO-2 (human epithelial colorectal adenocarcinoma). Negligible cytotoxicity of the nanoparticles, functionalized nanoparticles, and nanocapsules was observed in experiments with all cell lines. Nanocapsules were functionalized with fluorescein isothiocyanate (FITC) in order to track their kinetic of internalization and localization in the cell line by confocal laser scanning microscopy (CLSM). The cytotoxicity of the loaded capsules was evaluated, showing cell survival rates close to those expected for non-encapsulated cisplatin at the same nominal concentration.
An efficient polymeric drug delivery system based on novel synthetic nanosized CaCO3 is reported that both efficiently loads the widespread anticancer drug cisplatin and controls its release. Optimal loading results were obtained with layer by layer self-assembled polyelectrolyte nanocapsules, which showed a cytotoxic activity comparable to free cisplatin. Display omitted
•Alginic acid/protamine (ALG/PRM) nanocapsules give loading efficiency and fast uptake.•The fastest uptake of nanocapsules is obtained for the human mammarian MCF-7 cell line.•Nanocapsules' intracellular localization is perinuclear for the four examined cell lines.•Loaded capsules have comparable cytotoxicity to free cisplatin at similar concentrations.
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