Angela Tuzi

Diplopimarane, a 20-nor-ent-pimarane produced by the oak pathogen Diplodia quercivora.

In this study a new 20-nor-ent-pimarane, named diplopimarane, was isolated together with sphaeropsidins A (9) and C (10), and (+)-epiepoformin (11) from organic crude extracts of Diplodia quercivora, a recently described oak pathogen originally found on declining Quercus canariensis trees in Tunisia. Diplopimarane was characterized as (1S,2R)-2,8,8-trimethyl-2-vinyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-1,9,10-triol by spectroscopic, X-ray, optical, and chemical methods. It exhibited a wide range of activities including remarkable phytotoxicity on nonhost plants such as tomato cuttings, moderate antifungal activity against important plant pathogens, and moderate zootoxicity against Artemia salina. Its derivatives (2-4 and 6) were also tested for their phytotoxic and zootoxic activities. All these derivatives proved to be active against A. salina at 200 μg/mL, while 2 and 6 were also active on tomato cuttings. The other secondary metabolites (9, 10, and 11) herein reported for D. quercivora exhibited phytotoxic, antifungal, and zootoxic activity. This is the first report on the secondary metabolites secreted in vitro by this oak pathogen that could be key components of its adaptative strategies.

Chenopodolin: A Phytotoxic Unrearranged ent-Pimaradiene Diterpene Produced by Phoma chenopodicola, a Fungal Pathogen for Chenopodium album Biocontrol

A new phytotoxic unrearranged ent-pimaradiene diterpene, named chenopodolin, was isolated from the liquid culture of Phoma chenopodicola, a fungal pathogen proposed for the biological control of Chenopodium album, a common worldwide weed of arable crops such as sugar beet and maize. The structure of chenopodolin was established by spectroscopic, X-ray, and chemical methods as (1S,2S,3S,4S,5S,9R,10S,12S,13S)-1,12-acetoxy-2,3-hydroxy-6-oxopimara-7(8),15-dien-18-oic acid 2,18-lactone. At a concentration of 2 mg/mL, the toxin caused necrotic lesions on Mercurialis annua, Cirsium arvense, and Setaria viride. Five derivatives were prepared by chemical modification of chenopodolin functionalities, and some structure-activity relationships are discussed.

New NLO active cyclopalladated chromophores in main-chain polymers

Abstract Four new OH-functionalized orthopalladated complexes bearing an electron-donor and an acceptor group in a trans -like arrangement with respect to the metal have been prepared and characterized. The ligands are Schiff bases, bound as C,N- or N,O-chelating moieties. Four new polyesters were obtained by polycondensation from the monomeric complexes and pentyloxyterephthaloyl chloride. Two “model” complexes, each one related to one monomer, were also synthetized, in order to obtain further and more detailed characterization data, and in particular to perform measurements of μβ .

A series of compounds forming polar crystals and showing single-crystal-to-single-crystal transitions between polar phases

Condensation of 4-hydroxybenzohydrazide with a variety of non-chiral aliphatic ketones, methylethylketone, acetone, cyclohexanone and cyclobutanone, affords imine compounds crystallizing in polar space groups (Pna21 or Cc). For all the compounds synthesized, the crystal structure was determined by single crystal X-ray analysis and second harmonic generation experiments were performed on powder samples. The imine obtained using acetone shows solid state polymorphism with unusual behaviour; three different crystal phases have been identified (phases I, II and III), all having the same polar space group Pna21, and the transitions from I to II and from III to II are topotactic, i.e. single-crystal-to-single-crystal. During the irreversible transition from phase I to II, the polar axis undergoes a strong compression (about 15%) and single crystals of the parent phase are violently shattered into single crystal fragments of the new phase, while in the reversible transition from phase III to II, the polar axis expands (about 14%) and the integrity of single crystals is preserved.

Structure and Electronic Properties of Extended Chromophores for Applications in Second-Order Nonlinear Optics

A structural and theoretical analysis of new 2-[(4-phenylazo)phenyl] benzoxazole chromophores of potential interest in the field of second-order nonlinear optics is presented. Computations predict comparatively high hyperpolarizabilities for most of the compounds in their equilibrium nuclear configuration, with a significant dependence upon some conformational degrees of freedom and independence upon some others. This behavior is rationalized in the frame of the two-level model and sheds light on the conjugation pattern of these new chromophores.

Strong and Anomalous Thermal Expansion Precedes the Thermosalient Effect in Dynamic Molecular Crystals.

The ability of thermosalient solids, organic analogues of inorganic martensites, to move by rapid mechanical reconfiguration or ballistic event remains visually appealing and potentially useful, yet mechanistically elusive phenomenon. Here, with a material that undergoes both thermosalient and non-thermosalient phase transitions, we demonstrate that the thermosalient effect is preceded by anomalous thermal expansion of the unit cell. The crystal explosion occurs as sudden release of the latent strain accumulated during the anisotropic, exceedingly strong expansion of the unit cell with αa = 225.9 × 10−6 K−1, αb = 238.8 × 10−6 K−1 and αc = −290.0 × 10−6 K−1, the latter being the largest negative thermal expansivity observed for an organic compound thus far. The results point out to the occurence of the thermosalient effect in phase transitions as means to identify new molecular materials with strong positive and/or negative thermal expansion which prior to this work could only be discovered serendipitously.

Phomentrioloxin: A Phytotoxic Pentasubstituted Geranylcyclohexentriol Produced by Phomopsis sp., a Potential Mycoherbicide for Carthamus lanatus Biocontrol

A new phytotoxic geranylcyclohexenetriol, named phomentrioloxin, was isolated from the liquid culture of Phomopsis sp., a fungal pathogen proposed for the biological control of Carthamus lanatus, a widespread and troublesome thistle weed belonging to the Asteraceae family causing severe crop and pastures losses in Australia. The structure of phomentrioloxin was established by spectroscopic, X-ray, and chemical methods as (1S,2S,3S,4S)-3-methoxy-6-(7-methyl-3-methylene-oct-6-en-1-ynyl)cyclohex-5-ene-1,2,4-triol. At a concentration of 6.85 mM, the toxin causes the appearance of necrotic spots when applied to leaves of both host and nonhost plants. It also causes growth and chlorophyll content reduction of fronds of Lemna minor and inhibition of tomato rootlet elongation. Finally, in preliminary bioassays, phomentrioloxin did not show any antibacterial, fungicidal, or zootoxic activities.

Permittivity-dependent entropy driven complexation ability of cone and paco tetranitro-calix[4]arene toward para-substituted phenols.

Considering the importance of the polarizability of the rings of calixarenes in the entropy-driven interaction processes, we examined the effect of entropy compensation on the complex formation of cone and partial cone (paco) conformers of tetranitro-calix [4]arene, possessing O-ethyl substituents at the lower rim. Both calixarene conformers were fully characterized including X-ray crystallography. Various para-substituted phenols were used as guest molecules. Photoluminescence (PL) measurements and quantum-chemical (QC) investigations were used. A permittivity dependence of the molecular interactions was obtained in different alcohols as solvents. It was found that the cone conformer of the title calixarene derivative forms stable complexes with all phenols of the p-substituted series. The free enthalpy changes show very high complex stability of cone calixarene with p-nitro and p-chloro-substituted phenols. In the cases of parent phenol, p-cresol and p- tBu-phenol, the stability is significantly lower; however, it slightly increases with the increasing electron density on the aromatic ring of guest molecules. Similarly, the entropy changes are significantly different for these two separated groups: the entropy changes obtained in the former cases are nearly the same, while large differences in the formation entropy were obtained in the latter cases. Both the experimental and theoretical investigations revealed that no considerable interaction exists between phenols and the paco conformer of the title calixarene. It is probably due to the locking of the calixarene cavity by the bent O-ethyl chain.

Sphaeropsidones, phytotoxic dimedone methyl ethers produced by diplodia cupressi : a structure−activity relationship study

Sphaeropsidone and episphaeropsidone are two phytotoxic dimedone methyl ethers produced by Diplodia cupressi, the causal agent of a canker disease of cypress in the Mediterranean area. In this study, eight derivatives obtained by chemical modifications and two natural analogues were assayed for phytotoxic and antifungal activities, and a structure-activity relationship was examined. Each compound was tested on nonhost plants and on five fungal pathogenic species belonging to the genus Phytophthora. The results provide insights into structure-activity relationships within these compounds. It was found that the hydroxy group at C-5, the absolute C-5 configuration, the epoxy group, and the C-2 carbonyl group appear to be structural features important in conferring biological activity. The conversion of sphaeropsidone into the corresponding 1,4-dione derivative led to a compound showing greater antifungal activity than its precursor. This finding could be useful in devising new natural fungicides for practical application in agriculture.

Papyracillic Acid, a Phytotoxic 1,6-Dioxaspiro[4,4]nonene Produced by Ascochyta agropyrina Var. nana, a Potential Mycoherbicide for Elytrigia repens Biocontrol

A strain of Ascochyta agropyrina var. nana was isolated from Elytrigia repens (quack grass), a noxious perennial weed widespread through the cold regions of the northen and southern hemispheres. Papyracillic acid was isolated for the first time from the fungal solid culture and identified using spectroscopic methods, including X-ray diffractometric and CD analysis for the assignment of the relative and absolute stereochemistries. Some key derivatives were prepared and used in a structure-activity relationship study. Tested by leaf disk-puncture assay, papyracillic acid at the concentration of 1 mg/mL was shown to be phytotoxic both for the host plant and a number of nonhost plants of the fungus. Papyracillic acid was active against bacteria (Xanthomonas campestris and Bacillus subtilis) and the fungus Candida tropicalis at 6 microg/disk. Derivatives of papyracillic acid were significantly less active than original toxin. However, the monoacetyl derivative of the toxin did not possess antimicrobial activity but remained highly phytotoxic to quack grass. Hence, papyracillic acid and its analogues have potential as nonselective herbicides of natural origin. Some structure-activity relationship observations for papyracillic acid and its derivatives were also made.