Charge-Transfer Salts of 6,6-Dicyanopentafulvenes: From Topology to Charge Separation in Solution.

6,6-Dicyanopentafulvene derivatives and metallocenes with redox potentials appropriate for forming their radical anions form highly persistent donor-acceptor salts. The charge-transfer salts of 2,3,4,5-tetraphenyl-6,6-dicyanofulvene with cobaltocene (1⋅Cp2 Co) and 2,3,4,5-tetrakis(triisopropylsilyl)-6,6-dicyanofulvene with decamethylferrocene (2⋅Fc*) have been prepared. The X-ray structures of the two salts, formed as black plates, were obtained and are discussed herein. Compared with neutral dicyanopentafulvenes, the chromophores in the metallocene salts show substantial changes in bond lengths and torsional angles in the solid state. EPR, NMR, and optical spectroscopy, as well as superconducting quantum interference device (SQUID) measurements, reveal that charge-separation in the crystalline states and in frozen and fluid solutions depends on subtle differences of redox potentials, geometry, and on ion pairing. Whereas 1⋅Cp2 Co reveals paramagnetic character in the crystalline state and in solution, compound 2⋅Fc* shows a delicate balance between para- and diamagnetism, depending on the temperature and solvent characteristics.

Ambient-Pressure Synthesis of Two New Vanadium-Based Calcium Ferrite-Type Compounds: NaV1.25Ti0.75O4 and NaVSnO4.

Two new CaFe2O4-type compounds NaV1.25Ti0.75O4 (1) and NaVSnO4 (2) have been prepared at ambient pressure and temperatures < 800 °C. This contrasts with the parent material NaV2O4 which is synthesized at 6 GPa and 1300 °C. The lattice parameters are a = 9.1500(4) Å, b = 2.9399(3) Å, and c = 10.6568(5) Å for 1 and a = 9.3083(6) Å, b = 3.0708(2) Å, and c = 10.9194(5) Å for 2 (space group Pnma). Structure refinement against neutron powder diffraction data reveals that V/Ti and V/Sn are disordered over two octahedral sites. Both materials are characterized by a magnetic transition near 150 K below which the Curie moment is reduced from a value consistent with V(3+) [0.75 emu molV(-1) K(-1) for 1 and 0.58 emu molV(-1) K(-1) for 2] to 0.23 emu molV(-1) K(-1) for 1 and 0.30 emu molV(-1) K(-1) for 2, signaling a 70-50% reduction in the paramagnetic moment. The Weiss temperature (θ) is reduced from -285 (1) and -138 K (2) to values close to 0 K, suggesting that the remaining spins are dilute and weakly interacting. Heat capacity measurements reveal a gradual loss of magnetic entropy between 2 and 150 K, consistent with short-range bulk magnetic ordering. In addition, heat capacity and magnetic susceptibility measurements reveal a number of weak magnetic transitions below 6 K involving both antiferromagnetic and ferromagnetic components.

Cutaneous gamma/delta T-cell lymphoma.

Only 40 cases of primary cutaneous gamma/delta T-cell lymphoma (GD-TCL) have been described. GD-TCL was included as a provisional entity in the WHO-EORTC classification of cutaneous lymphomas in 2005. GD-TCL often failed to respond to polychemotherapy and radiation therapy and have a poor prognosis with a mean survival of only 15 months. We present a patient treated with surgery, immunomodulatory therapy, and polychemotherapy. He then received hematopoietic stem cell transplantation and has been in complete remission since. Allogeneic stem cell transplantation appears to be a promising therapeutic option for aggressive and generally fatal lymphomas like GD-TCL.

Detection of spirochetal micro-organisms by focus-floating microscopy in necrobiotic xanthogranuloma.

BACKGROUND: Necrobiotic xanthogranuloma (NXG) is a rare histiocytic disorder of unknown origin. OBJECTIVE: We conducted an investigation of skin biopsy specimens from 7 patients with NXG for the presence of Borrelia by focus-floating microscopy. METHODS: Focus-floating microscopy is a recently described, modified immunohistochemical technique in which the sections of a slide are simultaneously scanned both horizontally and vertically. Focus-floating microscopy is more sensitive for the detection of micro-organisms than polymerase chain reaction. RESULTS: Borrelia could be detected as single, paired, or clusters of spirochetes in 6 cases of NXG whereas two cases investigated with a Borrelia-specific polymerase chain reaction (23s-RNA) remained negative. LIMITATIONS: Limited biopsy material in each patient prohibited a more detailed study of the life history of cutaneous lesions in NXG. CONCLUSIONS: The detection of this micro-organism in NXG points to a specific involvement of B burgdorferi or other similar strains in the development of or as a trigger of this disease.

Vasoactive Therapy in Systemic Sclerosis: Real-life Therapeutic Practice in More Than 3000 Patients.

OBJECTIVE: Vasculopathy is a key factor in the pathophysiology of systemic sclerosis (SSc) and the main cause for Raynaud phenomenon (RP), digital ulcers (DU), and/or pulmonary arterial hypertension (PAH). It is so far unknown how patients with SSc are treated with vasoactive agents in daily practice. To determine to which extent patients with SSc were treated with different vasoactive agents, we used data from the German Network for Systemic Scleroderma registry. METHODS: The data of 3248 patients with SSc were analyzed. RESULTS: Patients were treated with vasoactive drugs in 61.1% of cases (1984/3248). Of these, 47.6% received calcium channel inhibitors, followed by 34.2% treated with angiotensin-converting enzyme (ACE) inhibitors, 21.1% treated with intravenous (IV) prostanoids, 10.1% with pentoxifylline, 8.8% with angiotensin 1 receptor antagonists (AT1RA), 8.7% with endothelin 1 receptor antagonists (ET1RA), 4.1% with phosphodiesterase type 5 (PDE5) inhibitors, and 5.3% with others. Patients with RP received vasoactive therapy in 63.3% of cases, with DU in 70.1%, and with PAH in 78.2% of cases. Logistic regression analysis revealed that patients with PAH were significantly more often treated with PDE5 inhibitors and ET1RA, and those with DU with ET1RA and IV prostanoids. In addition, 41.8% of patients were treated with ACE inhibitors and/or AT1RA. Patients registered after 2009 received significantly more often ET1RA, AT1RA, and IV prostanoids compared with patients registered prior to 2005. CONCLUSION: These data clearly indicate that many patients with SSc do not yet receive sufficient vasoactive therapy. Further, in recent years, a marked change of treatment regimens can be observed.

New high capacity cathode materials for rechargeable Li-ion batteries: vanadate-borate glasses.

V2O5 based materials are attractive cathode alternatives due to the many oxidation state switches of vanadium bringing about a high theoretical specific capacity. However, significant capacity losses are eminent for crystalline V2O5 phases related to the irreversible phase transformations and/or vanadium dissolution starting from the first discharge cycle. These problems can be circumvented if amorphous or glassy vanadium oxide phases are employed. Here, we demonstrate vanadate-borate glasses as high capacity cathode materials for rechargeable Li-ion batteries for the first time. The composite electrodes of V2O5 - LiBO(2) glass with reduced graphite oxide (RGO) deliver specific energies around 1000 Wh/kg and retain high specific capacities in the range of ~ 300 mAh/g for the first 100 cycles. V2O5 - LiBO(2) glasses are considered as promising cathode materials for rechargeable Li-ion batteries fabricated through rather simple and cost-efficient methods.

Circumscribed palmar or plantar hypokeratosis: two cases of a recently described entity of unknown origin.

Circumscribed palmar or plantar hypokeratosis is a new entity recently described by Perez et al in 2002. It seems to be underdiagnosed or clinically it is often misdiagnosed as Bowen's disease or porokeratosis. Obviously the number of case reports of circumscribed palmar or plantar hypokeratosis has increased since the first publication by Perez et al.The histopathological hallmarks of this condition are a stair-like configuration with an abrupt thinning of the stratum corneum from uninvolved to involved skin with a central hypokeratotic area. There are no atypical keratinocytes or cornoid lamellation. We describe two new patients with circumscribed palmar hypokeratosis. In one case there were additional histopathological features including the loss of granular cell layer in the center of the lesion and an overlying compact thin parakeratotic layer.