Does a Reinforced Kinetic Macrocyclic Effect Exist? The Demetallation in Strong Acid of Copper(II) Complexes with Open and Cyclic Tetramines Containing a Piperazine Fragment

The demetallation in acidic solution of the Cu(II) complexes with open-chain and cyclic tetramines containing a piperazine unit (2 and 3) has been investigated in terms of its kinetic aspects and compared with the behaviour of unsubstituted counterparts (tetramines 1 and 4). The presence of the piperazine fragment slows demetallation of the open-chain-ligand complex owing to the activation barrier associated with the conformational change from boat-to-half-boat; however, it does not affect the demetallation of the macrocyclic complex, which involves the spontaneous boat-to-twist conformational change. Thus, lateral reinforcement of a cyclam-like ligand does not add any further contribution to the typical inertness in demetallation of macrocyclic complexes.     

Determination of creatinine in human serum by short-end injection capillary zone electrophoresis

A new ultra-rapid free-solution capillary zone electrophoresis method to measure serum creatinine is presented. Procedural parameters such as injection mode, concentration and pH of phosphate running buffer and acidic deproteinization of serum samples were investigated. Short-end injection permits a decrease of the analysis time by injecting samples at the outlet end of a silica capillary closest to the detection window, so reducing the migration distance. Thus, when a capillary with an effective length of 10.2 cm and a 40 mmol/L sodium phosphate buffer pH 2.35 was used, the obtained migration time of the creatinine peak was the shortest never described before, about 1.1 min. These conditions give a good reproducibility of the migration times (coefficient of variation, CV% < 0.5) and the peak areas (CV% < 2.8). Intra- and interassay CV were 3.06 and 6.26%, respectively, and analytical recovery was 99.4%. We compared our proposed method to Jaffé colorimetric assay, by measuring serum creatinine in 128 normal subjects. The obtained data were analyzed by the Passing and Bablok regression and Bland-Altman test. Creatinine concentration in healthy subjects was also used to investigate on its relationships with plasma thiols levels.     

Functional MRI using intravascular contrast agents: detrending of the relative cerebrovascular (rCBV) time course

In pharmacological fMRI experiments in animal models, blood pool contrast agents may be used to map cerebral blood volume change as a surrogate for neural activation. When the background signal drift due to contrast agent washout is non-negligible over the duration of the signal changes of interest, time-course detrending is essential for accurate interpretation of the experiment. Detrending approaches based on estimation of the background signal from a baseline period of the time course prior to pharmacological (or functional) challenge were evaluated with the aim of identifying a robust method of estimating the contrast agent washout contribution to the background signal drift. For fMRI studies in the rat, it was found that a constrained fit of a mono-exponential washout model was more accurate than a constant background approximation and unconstrained fits for experiments investigating the functional response to rapid pharmacological challenges such as cocaine and amphetamine. Moreover, the constrained fitting approach allows shorter baseline periods than unconstrained extrapolation, reducing the required duration of the experiment.     

Synthesis and ab-initio XRPD structure of group 12 imidazolato polymers

Two new 3D homoleptic binary imidazolates, Cd(im)2 and Hg(im)2 (Him = imidazole), as well as [Hg(im)]NO3, containing 1D polycations of [Hg(im)]n(n+) formulation, have been prepared and characterized by ab-initio XRPD methods.     

Homolytic vs heterolytic paths in the photochemistry of haloanilines

The photochemistry of 4-haloanilines and 4-halo-N,N-dimethylanilines has been studied in apolar, polar aprotic, and protic solvents. Photophysical and flash photolysis experiments show that the reaction proceeds in any case from the triplet state. It is rather unreactive in apolar media, the highest value being Phi = 0.05 for the iodoanilines in cyclohexane. Changing the solvent has little effect for iodoanilines and for the poorly reacting bromo analogue, while it leads to a variation of over 2 orders of magnitude in the quantum yield for the chloro and fluoro derivatives. The triplets have been characterized at the UB3LYP/6-31G(d) level of theory, evidencing a deformation and an elongation (except for C-F) of the C-X bond. Homolytic fragmentation is in every case endothermic, but calculations in acetonitrile solution show that heterolytic cleavage of C-Cl and C-Br is exothermic. Experimentally, the occurrence of heterolytic fragmentation has been monitored through selective trapping of the resulting phenyl cation by allyltrimethylsilane. Heterolytic dechlorination occurs efficiently in polar media (e.g., Phi = 0.77 in MeCN), while debromination remains ineffective due to the short lifetime of the triplet. Heterolytic defluorination is efficient only in protic solvents (Phi = 0.48 in MeOH), in accord with calculations showing that in the presence of an ancillary molecule of water fragmentation is exothermic due to the formation of the strong H-F bond. The energy profile for both homo- and heterolytic dissociation paths has been mapped along the reaction coordinates in the gas phase and in acetonitrile. The conditions determining the efficiency and mode of dehalogenation have been defined. This is significant for devising synthetic methods via photogenerated phenyl cations and for rationalizing the photodegradation of halogenated aromatic pollutants and the phototoxic effect of some fluorinated drugs.     

A sharp bound for the degree of proper monomial mappings between balls

The authors prove that a proper monomial holomorphic mapping from the two-ball to the N-ball has degree at most 2N-3, and that this result is sharp. The authors first show that certain group-invariant polynomials (related to Lucas polynomials) achieve the bound. To establish the bound the authors introduce a graph-theoretic approach that requires determining the number of sinks in a directed graph associated with the quotient polynomial. The proof also relies on a result of the first author that expresses all proper polynomial holomorphic mappings between balls in terms of tensor products.     

4-Iodo-2-methyl-5-nitro­aniline exhibits neither strong hydrogen bonding nor intermolecular I⃛nitro interactions

In the title compound, C₇H₇IN₂O₂, the O atoms of the nitro group are disordered over two sets of sites and there is evidence that the intramolecular I⃛nitro interaction is repulsive. In the crystal structure, there are neither strong hydrogen bonds, nor intermolecular I⃛nitro interactions, nor aromatic π–π-stacking interactions.