Effect of π-electron conjugation length on the solvent-dependent S1 lifetime of peridinin

Peridinin exhibits an anomalous solvent dependence of its S₁ excited state lifetime attributed to the presence of an intramolecular charge transfer (ICT) state. The nature of this state has yet to be elucidated. Ultrafast time-resolved optical spectroscopy has been performed on a synthetic analog, C₃₅-peridinin, having one less conjugated double bond than peridinin. The data reveal the lifetime decreases from 1.5 ns in n-hexane to 9.2 ps in methanol, an order of magnitude larger than peridinin. This is the strongest solvent dependence on the lifetime of an S₁ state of a carotenoid yet reported. The data support the view that the S₁ and ICT states are strongly coupled.     

Orbit-orbit relativistic corrections to the pure vibrational non-Born-Oppenheimer energies of H(2)

We report the derivation of the orbit-orbit relativistic correction for calculating pure vibrational states of diatomic molecular systems with sigma electrons within the framework that does not assume the Born-Oppenheimer (BO) approximation. The correction is calculated as the expectation value of the orbit-orbit interaction operator with the non-BO wave function expressed in terms of explicitly correlated Gaussian functions multiplied by even powers of the internuclear distance. With that we can now calculate the complete relativistic correction of the order of alpha(2) (where alpha=1/c). The new algorithm is applied to determine the full set of the rotationless vibrational levels and the corresponding transition frequencies of the H(2) molecule. The results are compared with the previous calculations, as well as with the frequencies obtained from the experimental spectra. The comparison shows the need to include corrections higher than second order in alpha to further improve the agreement between the theory and the experiment.     

Heat capacities of the mixtures of ionic liquids with methanol at temperatures from 283.15 K to 323.15 K

The molar isobaric heat capacities of (methanol + 1-hexyl-3-methylimidazolium tetrafluoroborate) and (methanol + 1-methyl-3-octylimidazolium tetrafluoroborate) mixtures have been determined over the temperature range from 283.15 K to 323.15 K within the whole composition range. The excess molar heat capacities of investigated mixtures have been fitted to the Redlich–Kister equation at several selected temperatures. Positive deviations from the additivity of molar heat capacities have been observed in both examined systems. The results obtained have been discussed in terms of molecular interactions in binary mixtures.     

Protein structure prediction: combining de novo modeling with sparse experimental data

Routine structure prediction of new folds is still a challenging task for computational biology. The challenge is not only in the proper determination of overall fold but also in building models of acceptable resolution, useful for modeling the drug interactions and protein-protein complexes. In this work we propose and test a comprehensive approach to protein structure modeling supported by sparse, and relatively easy to obtain, experimental data. We focus on chemical shift-based restraints from NMR, although other sparse restraints could be easily included. In particular, we demonstrate that combining the typical NMR software with artificial intelligence-based prediction of secondary structure enhances significantly the accuracy of the restraints for molecular modeling. The computational procedure is based on the reduced representation approach implemented in the CABS modeling software, which proved to be a versatile tool for protein structure prediction during the CASP (CASP stands for critical assessment of techniques for protein structure prediction) experiments (see http://predictioncenter/CASP6/org). The method is successfully tested on a small set of representative globular proteins of different size and topology, including the two CASP6 targets, for which the required NMR data already exist. The method is implemented in a semi-automated pipeline applicable to a large scale structural annotation of genomic data. Here, we limit the computations to relatively small set. This enabled, without a loss of generality, a detailed discussion of various factors determining accuracy of the proposed approach to the protein structure prediction.     

Effect of Physiological Concentrations of Vitamin C on the Inhibitation of Hydroxyl Radical Induced Light Emission from Fe2+-EGTA-H2O2 and Fe3+-EGTA-H2O2 Systems In Vitro

Ascorbic acid (AA) has antioxidant properties. However, in the presence of Fe²⁺/Fe³⁺ ions and H₂O₂, it may behave as a pro-oxidant by accelerating and enhancing the formation of hydroxyl radicals (^•OH). Therefore, in this study we evaluated the effect of AA at concentrations of 1 to 200 µmol/L on ^•OH-induced light emission (at a pH of 7.4 and temperature of 37 °C) from 92.6 µmol/L Fe²⁺—185.2 µmol/L EGTA (ethylene glycol-bis (β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid)—2.6 mmol/L H₂O₂, and 92.6 µmol/L Fe³⁺—185.2 µmol/L EGTA—2.6 mmol/L H₂O₂ systems. Dehydroascorbic acid (DHAA) at the same range of concentrations served as the reference compound. Light emission was measured with multitube luminometer (AutoLumat Plus LB 953) for 120 s after automatic injection of H₂O₂. AA at concentrations of 1 to 50 µmol/L and of 1 to 75 µmol/L completely inhibited light emission from Fe²⁺-EGTA-H₂O₂ and Fe³⁺-EGTA-H₂O₂, respectively. Concentrations of 100 and 200 µmol/L did not affect chemiluminescence of Fe³⁺-EGTA-H₂O₂ but tended to increase light emission from Fe²⁺-EGTA-H₂O₂. DHAA at concentrations of 1 to 100 µmol/L had no effect on chemiluminescence of both systems. These results indicate that AA at physiological concentrations exhibits strong antioxidant activity in the presence of chelated iron and H₂O₂.     

Assessment of the Effectiveness of Rehabilitation after Total Knee Replacement Surgery Using Sample Entropy and Classical Measures of Body Balance

Exercises in virtual reality (VR) have recently become a popular form of rehabilitation and are reported to be more effective than a standard rehabilitation protocol alone. The aim of this study was to assess the efficacy of adjunct VR training in improving postural control in patients after total knee replacement surgery (TKR). Forty-two patients within 7–14 days of TKR were enrolled and divided into a VR group and a control group (C). The C group underwent standard postoperative rehabilitation. The VR group additionally attended twelve 30-min exercise sessions using the Virtual Balance Clinic prototype system. Balance was assessed on the AMTI plate in bipedal standing with and without visual feedback before and after the four-week rehabilitation. Linear measures and sample entropy of CoP data were analyzed. After four weeks of rehabilitation, a significant reduction in parameters in the sagittal plane and ellipse area was noted while the eyes remained open. Regression analysis showed that sample entropy depended on sex, body weight, visual feedback and age. Based on the sample entropy results, it was concluded that the complexity of the body reaction had not improved. The standing-with-eyes-closed test activates automatic balance mechanisms and offers better possibilities as a diagnostic tool.     

Functions of finite fractional variation and their applications to fractional impulsive equations

We introduce a notion of a function of finite fractional variation and characterize such functions together with their weak σ-additive fractional derivatives. Next, we use these functions to study differential equations of fractional order, containing a σ-additive term—we prove existence and uniqueness of a solution as well as derive a Cauchy formula for the solution. We apply these results to impulsive equations, i.e. equations containing the Dirac measures.     

Nature of the interaction between ammonia derivatives and carbon disulfide. A theoretical investigation

The interactions between NH₃, its methylated and chlorinated derivatives and CS₂ are investigated by ab initio CCSD(T) and density functional BLYP‐D3 methods. The CCSD(T)/aug‐cc‐pVTZ calculated interaction energies of complexes characterized by the S···N chalcogen bonds range between ?1.71 and ?2.78 kcal mol^?1. The S···N bonds are studied by atoms in molecules, natural bond orbital, and noncovalent interaction methods. The lack of correlation between the interaction energies of methylated amines complexes and the electrostatic potential results from the lone pair effect in aliphatic amines. Different structures of CS₂ complexed with ammonia derivatives, stabilized by other than the S···N chalcogen bonds, are also predicted. These structures are characterized by interaction energies ranging between 1.15 and 3.46 kcal mol^?1. The results show that the complexing ability of CS₂ is not very high but this molecule is able to attack the electrophilic or nucleophilic sites of a guest molecule.     

Structure,Physicochemical and Biological Properties of an Aqua (2,2′,2′′‐Nitrilotriacetato)‐oxidovanadium(IV) Salt with 4‐Methylpyridinium Cation

The crystal structure of a nitrilotriacetate (nta) oxidovanadium(IV) salt with 4‐methylpyridinium cation, [4‐Me(Py)H]⁺, of [4‐Me(Py)H][VO(nta)(H₂O)] stoichiometry was determined. The complex comprises a discrete mononuclear [VO(nta)(H₂O)]^– coordination entity that can be rarely found among other known compounds containing nitrilotriacetate oxidovanadium(IV) moieties. The complex was characterized by spectroscopic (IR and EPR) methods, magnetic measurements, and thermogravimetry (TG‐FTIR). The stability of the title compound in aqueous solutions was investigated by using the potentiometric titration method. Furthermore, spectrophotometric (UV/Vis) studies have revealed that the compound is capable to scavenge the superoxide free radicals (O₂ ^{? –}) as well as stable organic radicals i.e. 2,2′‐azinobis(3‐ethylbenzothiazoline‐6 sulfonic acid) cation radical (ABTS^{+ ?} ) and 2,2‐diphenyl‐1‐picrylhydrazyl radical (DPPH ^? ). Finally, biological properties of the complex studied were investigated in relation to its cytoprotective activity against the oxidative damage generated exogenously by using hydrogen peroxide in the HT22 hippocampal neuronal cell line (the MTT assay). Additionally, the biological action of the compound towards two human osteosarcoma HOS and MG‐63 cell lines (the MTT and BrdU tests) as well as the untransformed human osteoblast hFOB 1.19 cell line was tested.     

2-Methylthio-imidazolins: a rare case of different tautomeric forms in solid state and in solution

Structural Chemistry - The synthesis and structure elucidation of two new compounds, 2-(methylthio)-1,3-diazaspiro[4.4]non-2-ene-4-one (1) and 2-(methylthio)-1,3-diazaspiro[4.4]non-2-ene-4-thione...