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Abstract Background Migraine is a chronic neurologic disease that can severely affect the patient's quality of life. Although in recent years many randomised studies have been carried out to investigate the effectiveness of acupuncture as a treatment for migraine, it remains a controversial issue. Our aim is to determine whether acupuncture, applied under real conditions of clinical practice in the area of primary healthcare, is more effective than conventional treatment. Methods/Design The design consists of a pragmatic multi-centre, three-armed randomised controlled trial, complemented with an economic evaluation of the results achieved, comparing the effectiveness of verum acupuncture with sham acupuncture, and with a control group receiving normal care only. Patients eligible for inclusion will be those presenting in general practice with migraine and for whom their General Practitioner (GP) is considering referral for acupuncture. Sampling will be by consecutive selection, and by randomised allocation to the three branches of the study, in a centralised way following a 1:1:1 distribution (verum acupuncture; sham acupuncture; conventional treatment). Secondly, one patient in three will be randomly selected from each of the acupuncture (verum or sham) groups for a brain perfusion study (by single photon emission tomography). The treatment with verum acupuncture will consist of 8 treatment sessions, once a week, at points selected individually by the acupuncturist. The sham acupuncture group will receive 8 sessions, one per week, with treatment being applied at non-acupuncture points in the dorsal and lumbar regions, using the minimal puncture technique. The control group will be given conventional treatment, as will the other two groups. Discussion This trial will contribute to available evidence on acupuncture for the treatment of migraine. The primary endpoint is the difference in the number of days with migraine among the three groups, between the baseline period (the 4 weeks prior to the start of treatment) and the period from weeks 9 to 12. As a secondary aspect, we shall record the index of laterality and the percentage of change in the mean count per pixel in each region of interest measured by the brain perfusion tomography, performed on a subsample of the patients within the real and sham acupuncture groups. Trial registration Current Controlled Trials ISRCTN98703707.

Herein, we report the synthesis of a new family of extremely efficient TADF three-coordinated gold(I) emitters based on the chelating and bridging abilities of the 1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz) ligand and the neutral gold(I) [AuR] fragments (R = C6F5 (1), C6Cl2F3 (2), C6Cl5 (3)). Their emission energies appear in the orange range of the spectrum. The quantum yields of the emissions are directly related to the electronegativity of the perhalophenyl groups bonded to the metal center, even when they are not directly involved in the orbitals responsible for the luminescence. DFT and TD-DFT calculations suggest that the symmetry of the solid-state structures facilitates the coupling of the transition dipole moments, which leads to a drastic increase in their quantum yields as the electronic accepting abilities of the perhalophenyl groups decreases. [ABSTRACT FROM AUTHOR]

The reactivity of the heterometallic polynuclear complexes [{Au(R)2}2Cu2(MeCN)2]n (R=C6F5, C6Cl5) with the thioether crowns 1,4,7‐trithiacyclononane (L1, [12]aneS3), 1,4,8,11‐tetrathiacyclododecane (L2, [14]aneS4), 1,4,7,10,13,16,19,22‐octathiacyclotetracosane (L3, [24]aneS8), and the quinoline functionalized pendant arm derivatives of the 12‐membered mixed‐donor macrocycles 1‐aza‐,4,7,10‐trithiacyclododecane ([12]aneNS3) and 1,7‐diaza‐4,10‐dithiacyclododecane ([12]aneN2S2), L4 and L5, respectively, was investigated in THF solution. While with L4 and L5 only ionic compounds of general formulation [Cu(L)][Au(R)2] were isolated and structurally characterized (none of them featuring Au⋅⋅⋅Cu interactions), with L1‐L3, beside similar ionic compounds, some heteronuclear complexes of general formulation [{Au(R)2}{Cu(L)}] and featuring Au⋅⋅⋅Cu interactions were also obtained. All of them display rather unusual non‐classical C−H⋅⋅⋅Au hydrogen interactions. The complexes display in the solid state different optical properties related to their structures, which have been studied experimentally and theoretically via TD‐DFT calculations. In particular, all compounds of the type [{Au(R)2}{Cu(L)}] featuring Au⋅⋅⋅Cu metallophilic interactions display luminescence in the solid state both at room temperature (RT) and at 77 K. On the contrary, ionic compounds of general formulation [Cu(L)][Au(R)2], except [Cu(L4)][Au(C6F5)2], are not luminescent. [ABSTRACT FROM AUTHOR]

The reaction among [Au2Ag2(C6F5)4(OEt2)2]n, PbCl2 and terpyridine leads to the polymeric complex [{Au(C6F5)2}2{Pb(terpy)}]n (1). Its crystal structure reveals potential voids close to the lead centres large enough to hold different molecules. The availability of these free sites allows complex 1 to act as a VOC sensor. Thus, when 1 is exposed to different solvent vapours such as acetonitrile, toluene or THF, variations in its solid appearance and its photophysical properties are observed as a consequence of the formation of the new polymorphs [{Au(C6F5)2}2{Pb(terpy)(CH3CN)2}]n (2), [{Au(C6F5)2}2{Pb(terpy)}]n·Tol (3) and [{Au(C6F5)2}2{Pb(terpy)(THF)}]n·THF (4). Each polymorph displays a different emission energy depending on its structure and the presence of metallophilic interactions. In addition, the reversible solvent molecule exchange allows the tuning of the luminescence emissions in the greenish yellow–red range. DFT and TD-DFT calculations were performed to explain the origin of the luminescence of all these complexes. [ABSTRACT FROM AUTHOR]

New luminescent heterometallopolymers [(Au‐C6F5)m(AgOSO2CF3)n (PVP)] with different Au:Ag molar ratios were synthesized. The luminescent emissions of these polymers are strongly dependent on the temperature, excitation wavelengths, and the Au(I):Ag(I) molar ratio. The incorporation of a precise amount of Ag(I) atoms in the backbone of [(Au‐C6F5)m(PVP)] metallopolymer allows a controlled tuning of the emission energy in the green‐blue range. [ABSTRACT FROM AUTHOR]