Parity Violation Energy Difference Calculation of Atropisomers.

Enantiomers have a different energy due to the parity violation effects. Up to now, these effects are difficult to calculate and their final effect on the choice of one enantiomer in the homochirality issue is still a matter of debate. Nevertheless, many scientists support the role of this tiny energy difference in the triggering of homochirality. In this work, we studied the energy difference in atropisomers, a class of stereoisomers in which the chirality is given by the block of rotation around one bond. Atropisomers might have a low energy barrier for the interconversion and this is interesting for the equilibration of the two enantiomers and the choice of the most stable enantiomer. Moreover, structures might be extended like in the case of polymers or crystals having helical framework and thus giving an additive effect on the parity violation energy of the whole structure. The parity violation energy difference here is discussed with the correlation on the general structure of the final molecule giving a qualitative model to predict the sign of local contributions of atoms.

Changes in genotoxic stress response, ribogenesis and PAP (3'-phosphoadenosine 5'-phosphate) levels are associated with loss of desiccation tolerance in overprimed Medicago truncatula seeds.

Re-establishment of desiccation tolerance is essential for the survival of germinated seeds facing water deficit in the soil. The molecular and ultrastructural features of desiccation tolerance maintenance and loss within the nuclear compartment are not fully resolved. In the present study, the impact of desiccation-induced genotoxic stress on nucleolar ultrastructure and ribogenesis was explored along the rehydration-dehydration cycle applied in standard seed vigorization protocols. Primed and overprimed Medicago truncatula seeds, obtained through hydropriming followed by desiccation (dry-back), were analysed. In contrast to desiccation-tolerant primed seeds, overprimed seeds enter irreversible germination and do not survive dry-back. Reactive oxygen species, DNA damage and expression profiles of antioxidant/DNA Damage Response genes were measured, as main hallmarks of the seed response to desiccation stress. Nuclear ultrastructural features were also investigated. Overprimed seeds subjected to dry-back revealed altered rRNA accumulation profiles and up-regulation of genes involved in ribogenesis control. The signal molecule PAP (3'-phosphoadenosine 5'-phosphate) accumulated during dry-back only in primed seeds, as a distinctive feature of desiccation tolerance. The presented results show the molecular and ultrastructural landscapes of the seed desiccation response, including substantial changes in nuclear organization.

Carbon dioxide photoreduction in prebiotic environments.

The reduction of carbon dioxide is one of the hottest topics due to the concern of global warming. Carbon dioxide reduction is also an essential step for life's origins as photoautotrophs arose soon after Earth formation. Both the topics are of high general interest, and possibly, there could be a fruitful cross-fertilization of the two fields. Herein, we selected and collected papers related to photoreduction of carbon dioxide using compounds easily available on the Earth and considered of prebiotic relevance. This work might be useful also to scientists interested in carbon dioxide photoreduction and/or to have an overview of the techniques available.

Physiological and molecular aspects of seed longevity: exploring intra-species variation in eight Pisum sativum L. accessions.

Conservation of plant genetic diversity is fundamental for crop improvement, increasing agricultural production and sustainability, especially in the face of climatic changes. Although seed longevity is essential for the management of seed banks, few studies have, so far, addressed differences in this trait among the accessions of a single species. Eight Pisum sativum L. (pea) accessions were investigated to study the impact of long-term (approximately 20 years) storage, aiming to reveal contrasting seed longevity and clarify the causes for these differences. The outstanding seed longevity observed in the G4 accession provided a unique experimental system. To characterize the biochemical and physical status of stored seeds, reactive oxygen species, lipid peroxidation, tocopherols, free proline and reducing sugars were measured. Thermoanalytical measurements (thermogravimetry and differential scanning calorimetry) and transmission electron microscopy combined with immunohistochemical analysis were performed. The long-lived G4 seeds neither consumed tocopherols during storage nor showed free proline accumulation, as a deterioration hallmark, whereas reducing sugars were not affected. Thermal decomposition suggested a biomass composition compatible with the presence of low molecular weight molecules. Expansion of heterochromatic areas and reduced occurrence of γH2AX foci were highlighted in the nucleus of G4 seeds. The longevity of G4 seeds correlates with the occurrence of a reducing cellular environment and a nuclear ultrastructure favourable to genome stability. This work brings novelty to the study of within-species variations in seed longevity, underlining the relevance of multidisciplinary approaches in seed longevity research.

Computational Study of the Stability of Natural Amino Acid isomers.

The secular debate on the origin of life on our planet represents one of the open challenges for the scientific community. In this endeavour, chemistry has a pivotal role in disclosing novel scenarios that allow us to understand how the formation of simple organic molecules would be possible in the early primitive geological ages of Earth. Amino acids play a crucial role in biological processes. They are known to be formed in experiments simulating primitive conditions and were found in meteoric samples retrieved throughout the years. Understanding their formation is a key step for prebiotic chemistry. Following this reasoning, we performed a computational investigation over 100'000 structural isomers of natural amino acids. The results we have found suggest that natural amino acids are among the most thermodynamically stable structures and, therefore, one of the most probable ones to be synthesised among their possible isomers.

Metabolic and gene expression hallmarks of seed germination uncovered by sodium butyrate in Medicago truncatula.

Because high-quality seeds are essential for successful crop production in challenging environments, understanding the molecular bases of seed vigour will lead to advances in seed technology. Histone deacetylase inhibitors, promoting histone hyperacetylation, are used as tools to explore aspects still uncovered of the abiotic stress response in plants. The aim of this work was to investigate novel signatures of seed germination in Medicago truncatula, using the histone deacetylase inhibitor sodium butyrate (NaB) as stress agent. NaB-treated and untreated seeds collected at 2 and 8 hr of imbibition and at the radicle protrusion stage underwent molecular phenotyping and nontargeted metabolome profiling. Quantitative enrichment analysis revealed the influence of NaB on seed nucleotide, amino acid, lipid, and carbohydrate metabolism. Up-regulation of antioxidant and polyamine biosynthesis genes occurred in response to NaB. DNA damage evidenced in NaB-treated seeds correlated with up-regulation of base-excision repair genes. Changes in N1 -methyladenosine and N1 -methylguanine were associated with up-regulation of MtALKBH1 (alkylation repair homolog) gene. N2 ,N2 -dimethylguanosine and 5-methylcytidine, tRNA modifications involved in the post-transcriptional regulation of DNA damage response, were also accumulated in NaB-treated seeds at the radicle protrusion stage. The observed changes in seed metabolism can provide novel potential metabolic hallmarks of germination.

Role of solute-solvent hydrogen bonds on the ground state and the excited state proton transfer in 3-hydroxyflavone. A systematic spectrophotometric study.

A detailed account on the photophysics of 3-hydroxyflavone (3HF) in 27 organic solvents is reported. Dual fluorescence of neutral 3HF was observed in protic, polar, and weakly polar solvents, endowed with sufficiently high hydrogen bond accepting and/or donating capabilities. Ground-state solvent-induced 3HF deprotonation was reported in 14 cases. 3HF anion photophysics was investigated, and the deprotonation constant Kdep calculated. Previously reported models (based on solute-solvent intermolecular hydrogen bonds) to explain solvent effects on Excited-State Intramolecular Proton Transfer (ESIPT) and on solvent-induced deprotonation have been re-examined and improved in order to rationalize the observed photophysical behaviour in all the studied solvents. Hydrogen bond donor acidity and hydrogen bond acceptor basicity are shown to be key parameters. The results are discussed in the framework of the use of 3HF as an environment-sensitive fluorescent sensor in several research fields, and as a model system in the study of ESIPT reactions. Solvent effects on 3HF reactivity are also discussed, as the role of the surrounding media on the chemistry of flavonols is an emerging topic in natural product research.

Self-Assembly of Pseudorotaxane Structures from a Dicopper(II) Molecular Cage and Dicarboxylate Axles.

In this work, we employed for the first time a dinuclear bis[tris(2-aminoethyl)amine] cryptate to obtain the self-assembly of pseudorotaxane structures in an aqueous solution. The goal was achieved by exploiting the well-known affinity of the dicopper azacryptate with diphenyl spacers for the terephthalate anion. In particular, a series of molecular threads were synthesized by appending either alkyl or polyoxyethylene chains on both sides of the terephthalate benzene ring. The obtained dicarboxylic acids were precipitated as sodium salts, and their affinity toward the dicopper azacryptate was determined in a methanol/water mixture (pH 7). Experimental investigations showed that the chains' length and nature have a small impact on the 1:1 binding constants, whose values range between 4.98 and 5.18 log units. Computational studies indicated that the molecular axle is threaded through the azacryptate cavity, with the terephthalate group wedged between the two copper ions, coordinating both of them in the apical position (the one that, in the free azacryptate, is occupied by a water molecule). Compared to the inclusion complex with the plain terephthalate anion, a slight strain was found in the pseudorotaxane structure, induced by the inner chain of the thread inside the cavity. These results may be of great interest in all of the fields of science and technology in which host-guest recognition and molecular cages are applied.

Silica-supported pyrolyzed lignin for solid-phase extraction of rare earth elements from fresh and sea waters followed by ICP-MS detection.

Silica-supported pyrolyzed lignin (pLG@silica) was investigated as a solid sorbent for the pre-concentration of rare earth elements (REE) from natural waters followed by inductively coupled plasma mass spectrometry (ICP-MS) analysis. The carbon-based material was easily prepared by pyrolytic treatment of lignin at 600 °C after its adsorption onto silica micro-particles. pLG@silica was characterized by scanning electron microscopy (SEM), surface area measurements (BET method), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), point of zero charge measurement, and X-ray photoelectron spectroscopy (XPS). The as-prepared material (50 mg) was tested as fixed-bed sorbent for the solid-phase extraction (SPE) of tap, river, and sea water samples spiked with REE in the 10-150 ng L-1 range, followed by ICP-MS analysis. A quantitative adsorption was observed for all REE with recoveries in the range of 72-118%. A suitable inter-day precision (RSDs 5-12%, n = 3) was obtained. Sample volumes up to 250 mL provided enrichment factors up to 100. The method detection and quantification limits (MDLs and MQLs) were in the range of 0.4-0.6 ng L-1 and 1-2 ng L-1, respectively. The batch-to-batch reproducibility was verified on four pLG@silica independent preparations. As remarkable advantages, pLG@silica proved to be of easy preparation using a waste material, inexpensive, and reusable for at least 20 SPE cycles.

Characterization of phenolic pellets for ESR dosimetry in photon beam radiotherapy.

This work deals with the dosimetric features of a particular phenolic compound (IRGANOX 1076®) for dosimetry of clinical photon beams by using electron spin resonance (ESR) spectroscopy. After the optimization of the ESR readout parameters (namely modulation amplitude and microwave power) to maximise the signal without excessive spectrum distortions, basic dosimetric properties of laboratory-made phenolic dosimeters in pellet form, such as reproducibility, dose-response, sensitivity, linearity and dose rate dependence were investigated. The dosimeters were tested by measuring the depth dose profile of a 6 MV photon beam. A satisfactory intra-batch reproducibility of the ESR signal of the manufactured dosimeters was obtained. The ESR signal proved to increase linearly with increasing dose in the investigated dose range 1-13 Gy. The presence of an intrinsic background signal limits the minimum detectable dose to a value of approximately 0.6 Gy. Reliable and accurate assessment of the dose was achieved, independently of the dose rate. Such characteristics, together with the fact that IRGANOX 1076® is almost tissue-equivalent, and the stability of the ESR signal, make these dosimeters promising materials for ESR dosimetric applications in radiotherapy.

Photochemistry of N-Arylsulfonimides: An Easily Available Class of Nonionic Photoacid Generators (PAGs).

The photochemical behavior of differently substituted N-arylsulfonimides was investigated. Homolysis of the S-N bond took place as the exclusive path from the singlet state to afford both N-arylsulfonamides and photo-Fries adducts, the amount of which depended on reaction conditions and aromatic substituents. Sulfinic and sulfonic acids were released upon irradiation under deaerated and oxygenated conditions, respectively. The nature of the excited states and intermediates involved were proved by laser flash photolysis and EPR experiments. These results highlighted the potential of such compounds as nonionic photoacid generators able to photorelease up to two equivalents of a strong acid for each mole of substrate.

Formation of Hexamethylenetetramine (HMT) from HCHO and NH3--Relevance to Prebiotic Chemistry and B3LYP Consideration.

Despite its importance in the prebiotic and biochemical fields, a complete theoretical study of the formation of hexamethylenetetramine (HMT) starting from its precursors ammonia and formaldehyde has not received due considerations in the literature with regard to the thermodynamic feasibility of many of the mechanistically proposed intermediates in its formation. Most of the studies in this area have been mostly concerned with the initial steps of the reaction between formaldehyde and ammonia, while poor attention is dedicated to successive steps. In this article, different results from published literature were critically considered and the most probable hypothesis regarding the mechanism of HMT formation is discussed on the basis of B3LYP calculations of free energies.

Chiral nanostructuring of multivalent macrocycles in solution and on surfaces.

We describe the design and synthesis of a novel functionality-rich, homochiral macrocycle, possessing the overall molecular D2 symmetry, in which multivalency is introduced into the covalent framework by means of four suitably positioned pyridine moieties. The macrocycle synthesis is carried out with functionalized, enantiopure 1,1'-binaphthyl synthons as the source of chirality by means of a room temperature esterification reaction as the cyclization procedure. Upon addition of Pd(2+), coordination of the pyridine moieties occurs both intra and intermolecularly, to afford chiral ordered mono and dimeric macrocycles or multimeric aggregates depending on the solvents and conditions used. The metal binding event takes place in combination with a significant macrocyclic conformational rearrangement detected by circular dichroism spectroscopy. When in combination with a third component (C60), the macrocycle-Pd(2+) hybrid undergoes surface-confined nanostructuring into chiral nanofibres.

Sunlight-promoted photocatalytic hydrogen gas evolution from water-suspended cellulose: a systematic study.

This work presents a systematic study of cellulose (CLS) as a sacrificial biomass for photocatalytic H2 evolution from water. The idea is indeed to couple a largely available and not expensive biomass, and water, with a renewable energy like solar radiation. An aqueous CLS suspension irradiated either at 366 nm (UV-A) or under sunlight in the presence of Pt/TiO2 behaves as a H2 evolving system. The effects of irradiation time, catalyst and CLS concentrations, pH and water salinity are studied. Addition of CLS to the sample significantly improved H2 evolution from water splitting, with yields up to ten fold higher than those observed in neat water. The mechanism of the photocatalytic process relies on the TiO2-mediated CLS hydrolysis, under irradiation. The polysaccharide depolymerisation generates water-soluble species and intermediates, among them 5-hydroxymethylfurfural (HMF) was identified. These intermediates are readily oxidized following the glucose photoreforming, thus enhancing water hydrogen ion reduction to give gas-phase H2. The formation of "colored" by-products from HMF self-polymerization involves a sort of "in situ dye sensitization" that allows an effective photoreaction even under solar light. The procedure is evaluated and successfully extended on cellulosic biomasses, i.e. rice husk and alfalfa (Medicago sativa) stems, not previously investigated for this application.

MicroRNAs potentially targeting DDR-related genes are differentially expressed upon exposure to γ-rays during seed germination in wheat.

DNA damage response (DDR), a complex network of cellular pathways that cooperate to sense and repair DNA lesions, is regulated by several mechanisms, including microRNAs. As small, single-stranded RNA molecules, miRNAs post-transcriptionally regulate their target genes by mRNA cleavage or translation inhibition. Knowledge regarding miRNAs influence on DDR-associated genes is still scanty in plants. In this work, an in silico analysis was performed to identify putative miRNAs that could target DDR sensors, signal transducers and effector genes in wheat. Selected putative miRNA-gene pairs were tested in an experimental system where seeds from two wheat mutant lines were irradiated with 50 Gy and 300 Gy gamma(γ)-rays. To evaluate the effect of the treatments on wheat germination, phenotypic and molecular (DNA damage, ROS accumulation, gene/miRNA expression profile) analyses have been carried out. The results showed that in dry seeds ROS accumulated immediately after irradiation and decayed soon after while the negative impact on seedling growth was supported by enhanced accumulation of DNA damage. When a qRT-PCR analysis was performed, the selected miRNAs and DDR-related genes were differentially modulated by the γ-rays treatments in a dose-, time- and genotype-dependent manner. A significant negative correlation was observed between the expression of tae-miR5086 and the RAD50 gene, involved in double-strand break sensing and homologous recombination repair, one of the main processes that repairs DNA breaks induced by γ-rays. The results hereby reported can be relevant for wheat breeding programs and screening of the radiation response and tolerance of novel wheat varieties.

Triptycene-based diiron(II) mesocates: spin-crossover in solution.

Triptycene-based diiron(II) and dizinc(II) mesocates were obtained using a novel rigid ligand with two pyridylbenzimidazole chelating units fused into the triptycene scaffold. Studies on the diiron(II) assembly in solution showed that the complex undergoes thermal-induced one-step spin-crossover with T1/2 at 243 K (Evans method).

Innovative chitin-glucan based material obtained from mycelium of wood decay fungal strains.

Fungi are an alternative source to animal-based chitin. In fungi, chitin fibrils are strongly interconnected and bound with glucans that justify the unique matrix. The present study aimed to extract chitin and glucans from the mycelium of several wood decay fungal strains in order to obtain flexible materials and to check correlations between chitin content and the mechanical properties of these materials. Five strains were chosen in consideration of their different cell wall chemical composition (high content of α-glucans, ß-glucans or chitin) to evaluate how these differences could influence the mechanical and chemical characteristics of the material. The fungal strains were cultivated in liquid-submerged dynamic fermentation (both flasks and bioreactor). Chitin and glucans were crosslinked with acetic acid and plasticized with glycerol to obtain flexible sheets. Abortiporus biennis, Fomitopsis iberica and Stereum hirsutum strains were found to adapt to produce material with adequate flexibility. The obtained materials were characterized by Thermogravimetric analysis (TGA) for the understanding of the material composition. The material obtained from each species was mechanically tested in terms of tear strength, elongation at break, and Young's modulus.

Knockout of pgdS and ggt genes improves γ-PGA yield in B. subtilis.

One of the emerging biopolymers that are currently under active investigation is bacterial poly(γ-glutamic acid) (γ-PGA). However, before its full industrial exploitation, a substantial increase in microbial productivity is required. γ-PGA obtained from the Bacillus subtilis laboratory strain 168 offers the advantage of a producer characterized by a well defined genetic framework and simple manipulation techniques. In this strain, the knockout of genes for the major γ-PGA degrading enzymes, pgdS and ggt, leads to a considerable improvement in polymer yield, which attains levels analogous to the top wild γ-PGA producer strains. This study highlights the convenience of using the laboratory strain of B. subtilis over wild isolates in designing strain improvement strategies aimed at increasing γ-PGA productivity.

Radiation-induced grafting of carbon nanotubes on HPLC silica microspheres: theoretical and practical aspects.

Multi-walled carbon nanotubes (MWCNTs) were grafted for the first time by γ-radiation onto silica microspheres in the presence of polybutadiene (PB) as the linking agent, obtaining a novel hybrid material with chromatographic properties, with an alternative approach to the existing procedures. The synthesis involves the one-pot γ-radiation-induced grafting of MWCNTs onto silica microspheres in the presence of PB as a linking agent. PB also serves as a coating layer of the silica particles, to which MWCNTs are anchored through stable chemical bonds formed via radical chain reaction with the polymer. The product (MWCNT-PB-modified silica) resulted in MWCNT bundles interlaying the silica particles which acted as a support and as a spacer. This new material highlights the unquestionable properties of CNTs also when grafted in a composite, thus allowing the disposition of a more robust material whose properties are still related to the nanotube structure. The grafting was confirmed by Raman spectroscopy. The surface area, determined by BET isotherms, resulted in 132 m(2) g(-1), about 34% lower than that of pure silica, pointing to the cross-linking effect of PB in the silica matrix. The evaluation of MWCNT-PB-modified silica as a LC stationary phase was performed by separation of aromatics, with satisfactory resolution and reproducibility, while structural selectivity was proved by isomer separation. A good resolution was obtained also for acid/basic compounds as barbiturates. A comparison with a commercial C18 sorbent highlighted the advantage in using the CNT column for separating aromatic hydrocarbons. Control experiments on the PB-coated silica column proved the key role of MWCNTs in the chromatographic performance.