909 research outputs found

    Novel Synthesis and Structures of Tris-Annelated Benzene Donors for the Electron-Density Elucidation of the Classical Mills−Nixon Effect

    Get PDF
    A versatile method for the high-yield synthesis of various tris-, bis-, and mono-annelated benzenes (as well as cyclooctatetraene) is based on the Pd-catalyzed coupling of three (or four) ethylenic units comprised of α,β-dibromoalkenes and α‘-alkenyl Grignard reagentsall carried out in a single pot. The particular application to tris(bicyclopentyl)-annelated benzene yields the syn isomer 1s in high purity; X-ray diffraction analysis confirms the aromatic bond alternation relevant to the Mills−Nixon effect. Most importantly, the efficient synthesis of 1s crystals of extraordinary quality allows us (for the first time) to make precise electron-density measurements of the “banana-type” distortion and the ellipticity (π-character) of the various aromatic C−C bondssufficient to identify the electronic origin of the classical Mills−Nixon effect. The unique electron-donor properties of tris-annelated benzenes also relate to their highly reversible one-electron oxidation potentials even in nonpolar solvents

    Preparation and Structures of Crystalline Aromatic Cation-Radical Salts. Triethyloxonium Hexachloroantimonate as a Novel (One-Electron) Oxidant

    Get PDF
    Triethyloxonium hexachloroantimonate [Et3O+SbCl6-] is a selective oxidant of aromatic donors (ArH), and it allows the facile preparation and isolation of crystalline paramagnetic salts [ArH+•, SbCl6-] for the X-ray structure determination of various aromatic cation radicals. The mechanistic relationship between the Meerwein salt [Et3O+SbCl6-] and the pure Lewis acid oxidant SbCl5 is based on a prior ethyl transfer from oxygen to chlorine within the ion pair

    Disproportionation and Structural Changes of Tetraarylethylene Donors upon Successive Oxidation to Cation Radicals and to Dications

    Get PDF
    The stepwise (one-electron) chemical oxidation of the tetraphenylethylene donor and its substituted analogues (D) can be carried out by electron exchange with aromatic cations or antimony(V) oxidants to selectively afford the cation radical (D+•) initially and then the dication (D2+). The ready interchange of the latter establishes the facile disproportionation (i.e., 2D+• ⇌ D2+ + D) that was originally examined by only transient electrochemical techniques. The successful isolations of the crystalline salts of the tetraanisylethylene cation radical (1+•) as well as the tetraanisylethylene dication (12+) allow X-ray diffraction analysis (for the first time) to quantify the serial changes in the molecular structure upon successive oxidations. Five structural parameters (d, l, θ, φ, and q) are identified as quantitative measures of changes in bond (CαCβ, Cαanisyl) lengths, dihedral (CαCβ)/torsional (anisyl) angles, and quinoidal (anisyl) distortion attendant upon the removal of first one-electron and then another electron from the tetraanisylethylene framework. The linear variation of all five parameters in Chart 3 point to a strongly coupled relaxation of tetraanisylethylene (involving simultaneous changes of d, l, θ, φ, and q) to a severely twisted dication. Most noteworthy is the structure of the cation radical 1+• with d, l, θ, φ, and q values that are exactly one-half those of the dication. The complex molecular changes accompanying the transformation:  D → D+• → D2+ bear directly on the donor properties and the disproportionation processes of various tetraarylethylenes

    ROLE OF VARMAM THERAPY IN KUMBAVATHAM MANAGEMENT

    Get PDF
    ABSTRACTIntroduction: Siddha medicine, one among the ancient indigenous medical systems of India, has a repository of classical formulations as internalmedication and various other unique techniques/therapies as external usage. Varmam is one among such therapies used to treat multiple ailments,especially related to musculoskeletal and neurological deficits. Sometimes, varmam therapy is used along with internal medications and externalapplications as well.Objective: Adhesive capsulitis or periarthritis may be correlated with kumbavatham which is one of the vatha diseases mentioned in the Siddhaliterature Yugi Vaithya Chinthamani. Kumbavatham is one of the most common rheumatological problems in old age group, especially those indiabetic participants. It is the most common long-term complication next to osteoarthritis in diabetes mellitus patients.Methods: The present intervention was done in kumbavatham patients who volunteered to undergo the varmam therapy with regular outpatientdepartment medications, and the results were presented. The effect of varmam therapy on kumbavatham was assessed in accordance with shoulderpain and disability index.Result and Conclusion: The result of the current study concludes that the varmam therapy might be useful in the management of kumbavathamdiseases and thus improves the quality of life of the patients.Keywords: Kumbavatham, Adhesive capsulitis, Varmam therapy, Diabetes mellitus, Siddha

    Pharmacoeconomics of allergic rhinitis drugs treatment in tertiary care hospital

    Get PDF
    Background: Allergic rhinitis also called hay fever; it is a very common in India. Harmless exposing substances cause an allergic reaction. Allergic rhinitis is of the two types, one is the seasonal occurred with the change of seasons, second is the perennial means any time during the year.Methods: This was a cross-sectional study to determine the cost analysis allergic rhinitis drugs used in treatment of ENT OPD in a tertiary care teaching hospital, Kamothe, Navi Mumbai. The patients were interviewed; prescriptions were analyzed number of medicines prescribed.Results: Incidence of polypharmacy two drugs per prescriptions were prescribed 140 and three drugs per prescriptions 60. In the total number of 200 prescriptions, the cost of 43 prescriptions were in between 251-300 Indian rupees and 18 prescriptions were 301-350 Indian rupees. Patient knowledge about the drug use in this study, out of 200 pts 37% of allergic rhinitis patients knew the correct dosage of the prescribed drugs while 63% were not aware.Conclusions: Majority of the participants drugs were prescribed two to three drugs, per prescription cost was high because all the drugs prescribed by brand name and no drugs were prescribed by generic name. Improvement in knowledge about generic medicines is important factor to prefer generic medicine. Reduction in cost of drug will improve compliance

    Mining Association Rule Summarization Techniques to prognosis Diabetic unknown patterns

    Get PDF
    Early detection of patients with lifted danger of creating diabetes mellitus is basic to the enhanced counteractive action and general clinical management of these patients. Data mining now-a-days assumes a critical part in expectation of diseases in human services industry. Data mining is the way toward choosing, investigating, and displaying a lot of data to find obscure examples or connections helpful to the data examiner. Therapeutic data mining has risen perfect with potential for investigating concealed examples from the data sets of medicinal area. These examples can be used for quick and better clinical basic leadership for preventive and suggestive medicine. However crude medicinal data are accessible generally appropriated, heterogeneous in nature and voluminous for common handling. Data mining and Statistics can altogether work better towards finding shrouded examples and structures in data. In this paper, two noteworthy Data Mining strategies v.i.z., FP-Growth and Apriori have been utilized for application to diabetes dataset and association rules are being created by both of these calculations
    • …
    corecore