Co-crystallisation as a modular approach to the discovery of spin-crossover materials

Herein we present co-crystallisation as a strategy for materials discovery in the field of switchable spin crossover (SCO) systems. Using [Fe(3-bpp)₂]·2A (where 3-bpp = 2,6-bis(pyrazol-3-yl)pyridine, A = BF₄⁻/PF₆⁻) as a starting point, a total of 11 new cocrystals have been synthesised with five different dipyridyl coformers. Eight of these systems show spin crossover behaviour, and all show dramatically different switching properties from the parent complex. The cocrystals have been studied by variable temperature single-crystal X-ray diffraction and SQUID magnetometry to develop structure–property relationships. The supramolecular architecture of the cocrystals depends on the properties of the coformer. With linear, rigid coformer molecules leading to 1D supramolecular hydrogen-bonded chains, while flexible coformers form 2D sheets and bent coformers yield 3D network structures. The SCO behaviour of the cocrystals can be modified through changing the coformer and thus co-crystallisation presents a rapid, facile and highly modular tool for the discovery of new switchable materials. The wider applicability of this strategy to the design of hybrid multifunctional materials is also discussed.

The switching behaviour of spin crossover cocrystals can be modified through changing the coformer and thus co-crystallisation presents a rapid, facile and highly modular tool for the discovery of new switchable materials.     

Study of Blood Porphyrin Spectral Profile for Diagnosis of Chronic Renal Failure

The progression to end-stage renal failure is independent of the initial pathogenic mechanism. Metabolic acidosis is a common consequence of chronic renal failure that results from inadequate ammonium excretion and decreased tubular bicarbonate reabsorption. Protoporphyrin IX (PpIX) is the immediate metabolic precursor of the heme molecule. The purpose of this study was to evaluate the levels of erythrocytes protoporphyrin IX at an animal model during progressive renal disease. A total of 36 eight-week-old male Wistar rats were divided into six groups: Normal, 4 and 8 weeks after 5/6 nephrectomy (NX). Renal function was evaluated by creatinine clearance and plasma creatinine levels. The autofluorescence of erythrocytes porphyrin of healthy and NX rats was analyzed using fluorescence spectroscopy. Emission spectra were obtained by exciting the samples at 405 nm. Significant differences between normal and NX rats autofluorescence shape occurred in the 600–700 nm spectral region. A correlation was observed between emission band intensity at 635 nm and progression of renal disease.     

Unusually Facile Thermal Homodienyl‐[1,5]‐Hydrogen Shift Reactions in Photochemically Generated Vinyl Aziridines

A range of photochemically generated tri‐ and tetracyclic vinyl aziridines have been found to undergo a general and surprisingly low temperature ring opening through a [1,5]‐hydrogen shift reaction. The rate of the process was found to be highly dependent on the structure and substitution around the azirdine ring and the alkene terminus, with some substrates being observed to undergo ring opening at temperatures as low as 25 °C. The rigid nature of these polycyclic systems precludes a conformational explanation of these rate differences, and an Eyring study confirmed a negligible entropic barrier to the reaction. However, the Eyring plots for two different aziridines systems showed a significant difference in their enthalpies of activation. It is therefore believed that the levels of aziridine ring strain, as well as electronic effects, are the dominant factors in this sequence.     

Synthesis of 2H-1-benzopyrans via palladacycles with a metal-bonded stereogenic carbon

[reaction: see text] Stable oxapalladacycles have been prepared and converted into a series of highly functionalized 2H-1-benzopyrans via regioselective insertion of activated alkynes.     

Measurement of B0-B-0 flavor oscillations in hadronic B0 decays

Flavor oscillations of neutral B mesons have been studied in e+e- annihilation data collected with the BABAR detector at center-of-mass energies near the upsilon(4S) resonance. The data sample used for this purpose consists of events in which one B0 meson is reconstructed in a hadronic decay mode, while the flavor of the recoiling B0 is determined with a tagging algorithm that exploits the correlation between the flavor of the heavy quark and the charges of its decay products. From the time development of the observed mixed and unmixed final states, we determine the B0-B-0 oscillation frequency deltamd to be 0.516+/-0.016(stat)+/-0.010(syst) ps-1.     

Measurement of B --> K*gamma branching fractions and charge asymmetries

The branching fractions of the exclusive decays B0-->K(*0)gamma and B+-->K(*+)gamma are measured from a sample of (22.74+/-0.36)x10(6) BB decays collected with the BABAR detector at the PEP-II asymmetric e(+)e(-) collider. We find B (B0-->K(*0)gamma) = [4.23+/-0.40(stat)+/-0.22(syst)]x10(-5), B(B+-->K(*+)gamma) = [3.83+/-0.62(stat)+/-0.22(syst)]x10(-5) and constrain the CP-violating charge asymmetry to be -0.170K(*)gamma)<0.082 at 90% C.L.     

Urological malignancies and the proteomic-genomic interface

The urological malignancies, renal, bladder and prostate cancer, account for approximately 16% of all cancer cases. Unfortunately 5-year survival rates are relatively poor, largely a result of many cases not being diagnosed before the tumour has metastasised. There is a clear need for the identification of markers which will allow earlier detection of disease, and predict prognosis and response to therapy. In addition, they may be of use as therapeutic targets. Current advances in molecular biology are allowing the identification of a number of tumour-associated changes which could be of clinical use in the future. However, with the rapid technological advances being made in the field of proteomics, this approach could be integrated with genomics providing a complementary alternative, overcoming disparities between mRNA levels and protein production, and additionally allowing the identification of tumour-associated post-translational modifications. These approaches have already been used to identify novel genes and other cancer-related changes involved in the pathogenesis of urological malignancies. This review describes current progress in the genomic and proteomic study of urological malignancies, and highlights the potential of using proteomic technologies in the study of this group of diseases.     

On nonlinear nuclear operators

A class of operators is introduced and referred to as nonlinear nuclear operators. As in the case of linear nuclear operators this class of nonlinear operators is defined by means of a tensor product of two topological vector spaces. It is then shown that, as in the linear case, a series representation of the operator is valid. The deviation of the nonlinear theory from the linear case is discussed and an example in the framework of generalized stochastic processes is given.     

Are adobe walls optimal phase-shift filters?

The adobe house construction gives an automatic, air conditioning effect because the rooms tend to be cool at midday and warm at night. Presumably this is brought about by the walls acting as a heat filter so that there is nearly a 12-hour phase lag. This raises the question of how to optimize the adobe phenomenon by a suitable design of the walls. In this study it is supposed possible to make the walls of layered construction with layers having different thermal resistivity. Such a layered wall can be modeled electrically as a ladder filter of capacitors and resistors. The input to the ladder is a sinusoidal voltage. Then the following question arises: If the filter capacitors have given values, how should the resistors be chosen so that the output voltage has a given phase lag but least attenuation? It is found possible to answer this question by use of a special variational principle. Applying this analysis to building construction shows how to maximize oscillation of interior temperature with a phase lag of a prescribed number of hours.