The preparation of the novel carbon-rich iron-
and ruthenium-containing tetraynes 3 and 5
from
HC⋮CC6H4C⋮CSiiPr3
(2), via catalyzed CC coupling
and ruthenium−vinylidene activation, is described.
Their desilylated products 4 and 6, which
possess two
π-conjugated “rod”-shaped arms and C⋮CH hands,
have
been used as monomers for access to novel mixed
d6/d8
metal containing rigid and flexible units (7 and
8) or
unidimensional (9) oligomers.
Addition reaction of the malonate-based second-generation ferrocene-containing liquid-crystalline dendrimer 16 to [60]fullerene led to the title compound 1. Molecule 1 showed good solubility
in common organic solvents and good thermal stability. Examination of its mesomorphic properties
revealed the presence of an enantiotropic smectic A phase, which was identified by polarized optical
microscopy from the observation of typical focal−conic and homeotropic textures. The dendritic addend
16 exhibited similar properties as those of the fullerene-based dendrimer. The results described in this
report open the way to the elaboration of fullerene-containing liquid-crystalline macromolecules.
Grafting of a ferrocene-containing liquid-crystalline malonate derivative to C60 led to the mixed fullerene-ferrocene material 1 which gave rise to a smectic A phase. Cholesterol was used as liquid-crystalline promoter. X-ray diffraction experiments and volumetric measurements indicated that 1 is organized in double layered structures. The corresponding supramolecular organization within the mesomorphic lamellar phase is characterized by a microsegregation of the different units (ferrocene, fullerene, and cholesterol) in distinct sublayers. In such a smectic A phase, C60 imposes the arrangement of the other molecular moieties. Photophysical studies revealed that electron transfer occurs from the donor ferrocene to the electron accepting fullerene. The formation of a long-lived radical pair, with lifetimes of the order of several hundred nanoseconds, was confirmed by time-resolved spectrometry, especially in the near infrared region, in which the radical anion of the fullerene moiety displays its characteristic fingerprint absorption.
Behavioral and psychologic symptoms of dementia (BPSD) are common manifestations in mid- and late-stage Alzheimer's disease (AD). Traditional treatments for BPSD are neuroleptics and sedatives, which are not devoid of serious adverse effects. A number of studies show beneficial effects in the treatment of BPSD with acetylcholinesterase inhibitors (AChEI). The present study aimed to evaluate the effect of donepezil (using the generic drug Memorit) as monotherapy for AD patients suffering from BPSD. Twenty-eight consecutive patients followed at the Memory Outpatient Clinic and Psychogeriatric Department of the Abarbanel Mental Health Center were treated with donepezil for 6 months. Starting dose was 5 mg daily during the first 4 weeks and continuation with 10 mg daily thereafter. Treatment effects were evaluated using the Mini Mental State Examination (MMSE), the Neuro-Psychiatric Inventory (NPI), and the Clinical Global Impression of Change Scale (CGIC) caregiver version. Twenty-four of 28 patients completed the study. Of these, five patients needed additional rescue neuroleptic treatment due to incomplete response. The mean dose of donepezil was 9.10 mg/day (median 10 mg/day). The overall NPI improved significantly from 33.4 to 21.2 (p = 0.008). The mean CGIC at study's end was 3.0 (mild improvement). The cognitive scores did not change significantly. When compared to the patients who completed the study, patients who discontinued had higher mean scores on the irritability and agitation subscales of the NPI, they were older, and they had longer disease duration and lower MMSE mean scores. Three adverse events were recorded: one syncope causing a toe phalanx fracture and gastrointestinal complaints that resolved over time in two additional patients. Acetylcholinesterase inhibitors should be considered for the treatment of BPSD before neuroleptic treatment is instituted in AD patients with low levels of irritability and agitation.
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