Predrag Petrović

The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’

Reliable thermochemical measurements and theoretical predictions for reactions involving large transition metal complexes in which long-range intramolecular London dispersion interactions contribute significantly to their stabilization are still a challenge, particularly for reactions in solution. As an illustrative and chemically important example, two reactions are investigated where a large dipalladium complex is quenched by bulky phosphane ligands (triphenylphosphane and tricyclohexylphosphane). Reaction enthalpies and Gibbs free energies were measured by isotherm titration calorimetry (ITC) and theoretically ‘back-corrected’ to yield 0 K gas-phase reaction energies (ΔE). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source of error in theoretical thermochemistry protocols. The (‘back-corrected’) experimental reaction energies were used to benchmark (dispersion-corrected) density functional and wave function theory methods. Particularly, we investigated whether the atom-pairwise D3 dispersion correction is also accurate for transition metal chemistry, and how accurately recently developed local coupled-cluster methods describe the important long-range electron correlation contributions. Both, modern dispersion-corrected density functions (e.g., PW6B95-D3(BJ) or B3LYP-NL), as well as the now possible DLPNO-CCSD(T) calculations, are within the ‘experimental’ gas phase reference value. The remaining uncertainties of 2–3 kcal mol−1 can be essentially attributed to the solvation models. Hence, the future for accurate theoretical thermochemistry of large transition metal reactions in solution is very promising.

The surgical anatomy of the perforating branches of the anterior choroidal artery.

BACKGROUND The available information about certain microanatomic features of the AChA perforators is incomplete. Precise knowledge of these vessels is necessary to understand the consequences of their occlusion and to safely operate in their region. METHODS The AChA perforators were microdissected and examined under the stereoscopic microscope in 10 vascular casts and in 20 hemispheres injected with india ink or radiopaque substance. RESULTS The perforating branches ranged in number from 2 to 9 (mean, 4.6) and in diameter between 90 microm and 600 microm (mean, 317 microm). The most proximal perforator arose 3.2 mm on average caudal to the AChA origin. The most distal (capsulothalamic) perforator varied in size from 200 microm to 610 microm (mean, 431 microm). One or more of the perforators always originated from the AChA (100%), but some of them also from the uncal (33.3%) or parahippocampal branch (10%) of the AChA, either as individual vessels only (70%) or from common trunks (30%). The perforators gave off the peduncular (20%), optic (23.3%), or uncal side branches (26.7%). CONCLUSIONS Our findings concerning the origin, position, number, size, branching, penetration site, and relationships of the AChA perforators gave the anatomic basis for safe operations in patients with AChA aneurysms or mediobasal limbic epilepsy.

Antioxidants of Edible Mushrooms

Oxidative stress caused by an imbalanced metabolism and an excess of reactive oxygen species (ROS) lead to a range of health disorders in humans. Our endogenous antioxidant defense mechanisms and our dietary intake of antioxidants potentially regulate our oxidative homeostasis. Numerous synthetic antioxidants can effectively improve defense mechanisms, but because of their adverse toxic effects under certain conditions, preference is given to natural compounds. Consequently, the requirements for natural, alternative sources of antioxidant foods identified in edible mushrooms, as well as the mechanistic action involved in their antioxidant properties, have increased rapidly. Chemical composition and antioxidant potential of mushrooms have been intensively studied. Edible mushrooms might be used directly in enhancement of antioxidant defenses through dietary supplementation to reduce the level of oxidative stress. Wild or cultivated, they have been related to significant antioxidant properties due to their bioactive compounds, such as polyphenols, polysaccharides, vitamins, carotenoids and minerals. Antioxidant and health benefits, observed in edible mushrooms, seem an additional reason for their traditional use as a popular delicacy food. This review discusses the consumption of edible mushrooms as a powerful instrument in maintaining health, longevity and life quality.

Anatomy of the cavernous sinus region

The cavernous region was examined in 20 fetuses, injected with Micropaque, and in 5 adults. The lateral wall of the cavernous region in fetuses was noticed to have four layers. The superficial membrane represents the dural sheath. The second membrane of dense connective tissue involves the trochlear nerve. The third layer, formed by loose connective tissue, involves the oculomotor nerve, and the ophthalmic and maxillary division. The fourth layer, which represents the lateral wall of the cavernous sinus, involves the abducent nerve. The meningohypophyseal trunk can be complete or incomplete. The inferolateral trunk and its branches were found to supply the cavernous portions of the mentioned cranial nerves. The obtained data make the anatomic basis for neurosurgical operations in the cavernous region.

The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils

A series of iridacycles bearing π-bonded moieties of variable electron-withdrawing capabilities were tested for their ability to promote water oxidation catalysis (WOC) in the presence of high loading in a sacrificial oxidant, under conditions chosen for optimal dioxygen production. This report shows that none of these complexes performs differently than monometallic iridacycles and that the π-bonded moiety does not affect the overall rate of O(2) production. Furthermore, it is shown that cucurbituril macrocycles significantly inhibit the production of dioxygen independently of the nature of the Cp*Ir(III)-based catalyst used to perform WOC. Theoretical first-principles based DFT-D3 investigations including a complete treatment of solvation with COSMO and COSMO-RS treatments supported by ITC analyses suggest that concealment of the catalyst by curcurbit[7]uril could occur by non-covalent interaction of the Cp*Ir moiety in the hydrophobic pocket of the cavitand. For other cavitands of smaller inner cavity diameter, inclusion may not be the main mode of inhibition. Assuming the intervention of the putative Ir(IV)-oxyl biradical of a Cp*Ir(IV)(O)(H(2)O)(2) species like suggested by many authors, inhibition of WOC by inclusion would probably result from unfavourable coulombic interactions between water and the inclusion complex.

Geometries of stacking interactions between phenanthroline ligands in crystal structures of square-planar metal complexes

Stacking interactions of phenanthroline square-planar complexes in crystal structures were studied by analyzing data from the Cambridge Structural Database. In most of the crystal structures, two phenanthroline complexes were oriented “head to tail.” Phenanthroline complexes show a wide range of overlap geometries in stacking interactions, while short metal–metal distances were not observed. Stacking chains with alternating overlaps were the predominant type of packing in the crystal structures.

Carbon-hydrogen bond activation by a titanium neopentylidene complex

Abstract The titanium neopentylidene complex (PNP)Ti=CHtBu(CH2tBu), PNP=N[2-PiPr2-4-methylphenyl]2−, can activate both sp2 and sp3 C–H bonds under mild conditions. In this work, we studied the reaction mechanism of this complex with benzene and methane using modern density functional theory, specifically the ωB97XD functional which contains long-range exchange and dispersion corrections. The mechanism of the reaction is similar to that computed previously in the literature, but we describe a new conformer that is both more stable and kinetically more reactive. The four-step mechanism is very similar for both benzene and methane. However, the highest energy barriers differ; for methane, it is the last step, which elucidates the inertness of that reactant. In addition, the hydrogen exchange between alkyl and alkylidene ligands in methane’s product was studied by two different mechanisms: tautomerization to form (PNP)TiCHtBu(=CH2) and reverse C–H activation to form (PNP)Ti≡CtBu(CH3). The feasibility of the tautomerization, through a preliminary, accessible isomerization, suggests that these systems can be used to explore the reactivity of terminal methylidenes. Finally, methodological considerations are also discussed, as the importance of including the dispersion in the density functionals was determined by comparing several functionals. This comparison has shown that the dispersion is critical for accurate modeling, especially in the stability of the unsaturated intermediate; this has been neglected in previous studies.

Total quality index of Agaricus bisporus mushrooms packed in modified atmosphere

BACKGROUND The aim of this study was to develop a total quality index and examine the effects of modified atmosphere packaging (MAP) on the quality of Agaricus bisporus mushrooms stored for 22 days at 4 °C. Mushrooms were packaged under three MAPs: high nitrogen packaging (HNP), low carbon dioxide packaging (LCP) and low oxygen packaging (LOP). Passive MAP with air inside initially was used as the atmosphere treatment (AIR). RESULTS This research revealed two phases in quality deterioration of A. bisporus mushrooms. During the first week, most of the quality parameters were not statistically different. Thereafter, odor intensities were stronger for all four types of packaging. Color difference and browning index values showed significantly lower color changes for AIR and LOP compared with HNP and LCP mushrooms. CONCLUSION The best total quality index was calculated for LOP, followed by LCP and AIR. The findings of this study are useful with respect to examining two-component MAPs, separating the limiting factors (O2 and CO2 ) and evaluating quality deterioration effects and the total quality index of A. bisporus mushrooms.

Methane Activations by Titanium Neopentylidene Complexes: Electronic Resilience and Steric Control

The titanium neopentylidene complex (PNP)Ti═CHtBu(CH2tBu) (PNP = N[2-PiPr2-4-methylphenyl]2-) is capable of activating both sp2 and sp3 C-H bonds under mild conditions. In addition to methane C-H activation, competition between the initial hydrogen abstraction reaction to form the methane activation product and the tautomerization reaction of this product to form a terminal methylidene was also explored. Several modifications of the PNP and CHtBu ligands were explored to determine the effect of these changes on C-H bond activation. In general, on the one hand, the modifications involving electronic effects have small and inconsistent influence on the stability of the intermediates and products and on the reaction barriers. On the other hand, the use of bulky groups in the ligands favors the methane activation process. By replacing the iPr groups in the PNP ligand with tBu groups, both methane activation and tautomerization reactions become more energetically favorable than in the unmodified complex. On the one hand, the largest acceleration of the methane C-H activation occurs when tBu groups in the phosphine are combined with an extra CH2 linker between the aromatic ring and the phosphine. On the other hand, replacing the nitrogen in the PNP ligand by phosphorus results in lower barriers for the tautomerization reaction and the stabilization of the product of the tautomerization although it remains slightly less stable than product of methane C-H activation. While several ligand modifications related to the electronic effects were examined, it is interesting that most of them did not make a significant change on the barriers for either reaction, indicating a significant resilience of this titanium complex, which could be used to enhance the practical aspects of the complex without a significant loss of its activity.

Unexpected Importance of Aromatic–Aliphatic and Aliphatic Side Chain–Backbone Interactions in the Stability of Amyloids

The role of aromatic and nonaromatic amino acids in amyloid formation has been elucidated by calculating interaction energies between β-sheets in amyloid model systems using density functional theory (B3LYP-D3/6-31G*). The model systems were based on experimental crystal structures of two types of amyloids: (1) with aromatic amino acids, and (2) without aromatic amino acids. Data show that these two types of amyloids have similar interaction energies, supporting experimental findings that aromatic amino acids are not essential for amyloid formation. However, different factors contribute to the stability of these two types of amyloids. In the former, the presence of aromatic amino acids significantly contributes to the strength of interactions between side chains; interactions between aromatic and aliphatic side chains are the strongest, followed by aromatic-aromatic interactions, while aliphatic-aliphatic interactions are the weakest. In the latter, that is, the amyloids without aromatic residues, stability is provided by interactions of aliphatic side chains with the backbone and, in some cases, by hydrogen bonds.