The influence of pseudohalide ligands on the SIM behaviour of four-coordinate benzylimidazole-containing cobalt(ii) complexes.

Three, mononuclear complexes of the formula [Co(bmim)2(SCN)2] (1), [Co(bmim)2(NCO)2] (2) and [Co(bmim)2(N3)2] (3) [bmim = 1-benzyl-2-methylimidazole] were prepared and structurally analyzed by single-crystal X-ray crystallography. The cobalt(ii) ions in 1-3 are tetrahedrally coordinated with two bmim molecules and two pseudohalide anions. The angular distortion parameter δ was calculated and the SHAPE program (based on the CShM concept) was used for 1-3 to estimate the angular distortion from an ideal tetrahedron. The molecules of 1-3 are effectively separated, and the values of the shortest distance of cobalt-cobalt are 8.442(6) and 6.774(8) Å for 1, 10.349(8) and 10.716(8) Å for 2 and 6.778(1) and 9.232(1) Å for 3. Direct current (dc) magnetic susceptibility measurements on the crushed crystals of 1-3 were carried out in the temperature range 1.9-295 K. The variable-temperature magnetic data of 1-3 mainly obey the zero-field splitting effect (D) of the 4A2 ground term of the tetrahedral cobalt(ii) complexes (2D being the energy gap between the |±1/2 and |±3/2 levels of the spin). The analysis of their magnetic data through the Hamiltonian H = D[S2z - S(S + 1)/3] + E(Sx2 - Sy2) + gßHS led to the following best-fit parameters: g = 2.29, D = -7.5 cm-1 and E/D = 0.106 (1), g = 2.28, D = + 6.3 cm-1 and E/D = 0.007 (2) and g = 2.36, D = + 6.7 cm-1 and E/D = 0.090 (3). The signs of D for 1-3 were confirmed by Q-band EPR spectra on powdered samples in the temperature range 4.0-20 K. Field-induced SIM behaviour was observed for 1-3 below 4.0 K, and the frequency-dependent maxima of χ''M were observed for 1 and only incipient signals of χ''M occurred for 2 and 3. The values of the exponential factor (τ0) and activation energy (Ea) for 1-3 which were obtained from the Arrhenius plot suggest a single relaxation process characteristic of an Orbach mechanism.

Synthesis, crystal structure and magnetic properties of H2tppz[ReCl6] and [Cu(bpzm)2(µ-Cl)ReCl3(µ-ox)Cu(bpzm)2(µ-ox)ReCl3(µ-Cl)]n.

Two new Re(iv) compounds of formulae H2tppz[ReCl6] (1) and [Cu(bpzm)2(µ-Cl)ReCl3(µ-ox)Cu(bpzm)2(µ-ox)ReCl3(µ-Cl)]n (2) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine and bpzm = bis(pyrazolyl-1-yl)methane] have been prepared and their crystal structures determined by X-ray diffraction on single crystals. Compound 1 is a mononuclear species whose structure consists of octahedral hexachlororhenate(iv) anions and diprotonated H2tppz(2+) cations which are arranged in the unit cell as alternating anionic and cationic layers, held together by electrostatic forces. The structure of 2 is made up of alternating [Cu(1)(bpzm)2](2+) and [(ox)ReCl3(µ-Cl)Cu(2)(bpzm)2(µ-Cl)ReCl3(ox)](2-) entities interlinked by oxalate bridges to afford a neutral heterobimetallic chain. The oxalate group adopts the didentate (at Re)/monodentate (at Cu) bridging mode. The magnetic behavior of 1 and 2 has been investigated over the temperature range 1.9-295 K. 1 is a magnetically diluted Re(iv) complex, the relatively large value of the zero-field splitting of the ground level [D = -15.8(2) cm(-1)] accounting for the variation of χMT in the low temperature range. Weak intrachain ferromagnetic interactions between Re(iv) and Cu(ii) through oxalate (J1 = +0.15 cm(-1)) and single chloro (J2 = +4.9 cm(-1)) bridges occur in 2 which are obscured by the large zero-field splitting of the Re(iv) ion (DRe = 42 cm(-1)). In addition, interchain antiferromagnetic interactions are also involved in 2 which are responsible for the metamagnetic behavior observed, the value of the critical dc magnetic field (Hc) being 20 kOe.

A Neanderthal lower molar from Stajnia Cave, Poland.

The primary aim of this study was to conduct a taxonomic assessment of the second of three isolated human teeth found in the Stajnia Cave (north of the Carpathians, Poland) in 2008. The specimen was located near a human tooth (S5000), which was identified by Urbanowski et al. (2010) as a Neanderthal permanent upper molar. Both of these teeth were excavated from the D2 layer, which belongs to the D stratigraphic complex comprising the archaeological assemblage associated with the Micoquian tradition. An Ursus spelaeus bone and Mammuthus primigenius tooth that were also excavated from the D2 layer were dated to >49,000 years BP (by AMS (14)C) and 52.9 ka BP (by U-Th), respectively. The sediment overlying stratigraphic complex D was dated to 45.9 ka BP by the OSL method. The S4300 tooth is a lower first or second permanent molar belonging to an individual other than that who once possessed the S5000 tooth. The S4300 tooth exhibits a combination of traits typical of Neanderthal lower molars, including a mid-trigonid crest, large anterior fovea, taurodontism and subvertical grooves on the interproximal face, indicating that this tooth belonged to a Neanderthal individual. The S4300 tooth from Stajnia Cave is one of the oldest human remains found in Poland.

Novel endomorphin-2 analogs with mu-opioid receptor antagonist activity.

A series of position 4-substituted endomorphin-2 (Tyr-Pro-Phe-Phe-NH2) analogs containing 3-(1-naphthyl)-alanine (1-Nal) or 3-(2-naphthyl)-alanine (2-Nal) in L- or D-configuration, was synthesized. The opioid activity profiles of these peptides were determined in the mu-opioid receptor representative binding assay and in the Guinea-Pig Ileum assay/Mouse Vas Deferens assay (GPI/MVD) bioassays in vitro, as well as in the mouse hot-plate test of analgesia in vivo. In the binding assay the affinity of all new analogs for the mu-opioid receptor was reduced compared with endomorphin-2. The two most potent analogs were [D-1-Nal(4)]- and [D-2-Nal4]endomorphin-2, with IC50 values 14 +/- 1.25 and 19 +/- 2.1 nM, respectively, compared with 1.9 +/- 0.21 nM for endomorphin-2. In the GPI assay these analogs were found to be weak antagonists and they were inactive in the MVD assay. The in vitro GPI assay results were in agreement with those obtained in the in vivo hot-plate test. Antinociception induced by endomorphin-2 was reversed by concomitant intracerebroventricula (i.c.v.) administration of [D-1-Nal4]- and [D-2-Nal4]-endomorphin-2, indicating that these analogs were mu-opioid antagonists. Their antagonist activity was compared with that of naloxone. At a dose 5 microg per animal naloxone almost completely inhibited antinociceptive action of endomorphin-2, while [D-1-Nal4]endomorphin-2 in about 46%.

Structure-property relationships of a tetrapyrrolidinyl PNP-lariat ether and its complexes with potassium, sodium, and silver cations.

Spectral properties of the tetrapyrrolidinyl PNP-lariat ether, L, and its complexes with K+, Na+, and Ag+ were investigated. Crystal structures of L and its complex with potassium iodide [KL]I were determined. Protonation constants of the ligand and formation constants of its complexes with Ag+, K+, and Na+ in aqueous solutions were determined. 1H NMR, 31P NMR, FTIR, and ESIMS spectra as well as potentiometric measurements indicate that complexation of Ag+ involves participation of the polyether oxygen donors and the endocyclic nitrogen atom of the cyclophosphazene ring. On the other hand, for complexation of K+ and Na+, only polyether oxygen atoms are involved. The latter conclusion is confirmed in the solid-state structure of the [KL]I complex.

Neurology in ancient faces.

BACKGROUND: Clinical paleoneurology is almost non-existent, but recognition of neurological diseases in ancient people might be possible by scrutinising portraits apparently representing people as they appeared in life. METHODS: About 200 mummy portraits painted in colour at the beginning of the first millennium were examined. Thirty two skulls excavated at Hawara in the Fayum (northern Egypt), where most of the portraits were found were measured, and nine caliper measures on each side of the skulls were taken. The right/left ratios were statistically analyzed by analysis of variance (ANOVA). One skull was subjected to 3D CT scanning and transilluminated. RESULTS: Two patients were found with progressive facial hemiatrophy (Parry-Romberg syndrome), three with deviations of the visual axes (tropia) and one with oval pupils (corectopia). CONCLUSIONS: Clinical paleoneurology is possible in the absence of a living nervous system. The patients probably had focal epilepsy, hemiplegic migraine, and autonomic nervous system dysfunction.

The incidence of osteo-arthritis of the temporomandibular joint in various cultures.

Three hundred and forty-eight cranial remains from Bronze and Iron Age British, Romano-British, Anglo-Saxon, Eastern Coast Australian aborigines, Medieval Christian Norse, Medieval Scarborough, 17--20th century British and German cultures, were examined for the presence of osteoarthritis in the temporomandibular joints. Cultures exposed to more stringent living conditions and with well-worn teeth had about twice the incidence of osteo-arthritis as the more sophisticated cultures. In general, loss of either molar support or occlusal imbalance were potent aetiological factors in this disease.