Synthesis of heterobimetallic gold(i) ferrocenyl-substituted 1,2,3-triazol-5-ylidene complexes as potential anticancer agents.

1,2,3-Triazol-5-ylidene (trz) complexes of gold(i) containing a ferrocenyl substituent on the C4-position of the trz ring were synthesized to yield the neutral heterobimetallic gold(i) trz chlorido (2), gold(i) trz phenyl (3), and the cationic gold(i) trz triphenylphospine (5) complexes. In order to compare the effect of silver(i) as central metal vs. gold(i), [Ag(trz)2]+ (4) was also prepared, while variation of the C4-1,2,3-triazol-5-ylidene substituent from a ferrocenyl to a phenyl group was done to prepare the monometallic analogue of 5, namely the cationic Au(i) trz triphenylphosphine complex 6. The complexes were characterised with spectroscopic and electrochemical methods, and the single crystal X-ray structures of 2-6 were determined. NMR stability studies of 5 as a representative example of the series of complexes were performed to confirm the stability of the complexes in the solvent dimethylsulfoxide and in aqueous solution. The anti-cancer potential of 5 was evaluated against the lung cancer cell lines A549 and H1975, and the human embryonic kidney cell line (HEK-293) was used as a non-cancer model. IC50 values of 0.89, 0.23 and 5.43 µM, respectively, were obtained for A549, H1975 and HEK-293, respectively, indicating the activity and selectivity of 5 for cancer cells. Fluorescence microscopy experiments as a preliminary mode-of-action study evidenced an apoptotic cell death mechanism rather than necrotic cell death.

Ruthenium(II) Polypyridyl Complexes Coordinated Directly to the Pyrrole Backbone of π-Extended Boron Dipyrromethene (Bodipy) Dyes: Synthesis, Characterization, and Spectroscopic and Electrochemical Properties.

A series of new Bodipy dyes incorporating the π-extended isoquino[5,6-c]pyrrole have been synthesized and characterized. The dyes display intense Bodipy (π-π*) transitions and emissions with high quantum efficiencies. Spectroscopic, electrochemical, and theoretical calculations are used to give insight into the frontier orbitals. Coordination of {Ru(bpy)2Cl}+ subunits to the peripheral isoquinol nitrogen atoms of the Bodipy dyes leads to three new bis-Ru(II)-polypyridyl-Bodipy complexes with the Ru(II) centers in direct contact with the dipyrrin core. Spectroscopic studies of the complexes reveal the traditional metal to ligand charge transfer (MLCT) transitions associated with Ru(dπ) to bpy(π*) transitions. However, a more intense transition above 600 nm is also observed. This transition is independent of the meso-substituents of the dipyrrin and is shifted to lower energy by as much as 25 nm compared to that of the Bodipy dyes without the Ru(II) subunits. Spectroscopic, electrochemical, and spectroelectrochemical studies suggest that the Bodipy π-orbitals are destabilized by coordination of the Ru(II) moieties. All three Ru2-Bodipy complexes show the ability to generate singlet oxygen when irradiated within the photodynamic therapy window (600-850 nm) as evidenced by singlet oxygen trapping experiments.

Antimicrobial Properties of Tris(homoleptic) Ruthenium(II) 2-Pyridyl-1,2,3-triazole "Click" Complexes against Pathogenic Bacteria, Including Methicillin-Resistant Staphylococcus aureus (MRSA).

A series of tris(homoleptic) ruthenium(II) complexes of 2-(1-R-1H-1,2,3-triazol-4-yl)pyridine "click" ligands (R-pytri) with various aliphatic (R = butyl, hexyl, octyl, dodecyl, and hexdecyl) and aromatic (R = phenyl and benzyl) substituents was synthesized in good yields (52%-66%). The [Ru(R-pytri)3]2+(X-)2 complexes (where X- = PF6- or Cl-) were characterized by elemental analysis, high-resolution electrospray ionization mass spectrometry (HR-ESI-MS), 1H and 13C nuclear magnetic resonance (NMR) and infrared (IR) spectroscopies, and the molecular structures of six of the compounds confirmed by X-ray crystallography. 1H NMR analysis showed that the as-synthesized materials were a statistical mixture of the mer- and fac-[Ru(R-pytri)3]2+ complexes. These diastereomers were separated using column chromatography. The electronic structures of the mer- and fac-[Ru(R-pytri)3]2+ complexes were examined using ultraviolet-visible (UV-Vis) spectroscopy and cyclic and differential pulse voltammetry. The family of R-pytri ligands and the corresponding mer- and fac-[Ru(R-pytri)3]2+ complexes were tested for antimicrobial activity in vitro against both Staphylococcus aureus and Escherichia coli bacteria. Agar-based disk diffusion assays indicated that two of the [Ru(R-pytri)3](X)2 complexes (where X = PF6- and R = hexyl or octyl) displayed good antimicrobial activity against Gram-positive S. aureus and no activity against Gram-negative E. coli at the concentrations tested. The most active [Ru(R-pytri)3]2+ complexes ([Ru(hexpytri)3]2+ and Ru(octpytri)3]2+) were converted to the water-soluble chloride salts and screened for their activity against a wider range of pathogenic bacteria. As with the preliminary screen, the complexes showed good activity against a variety of Gram-positive strains (minimum inhibitory concentration (MIC) = 1-8 µg/mL) but were less effective against Gram-negative bacteria (MIC = 16-128 µg/mL). Most interestingly, in some cases, the ruthenium(II) "click" complexes proved more active (MIC = 4-8 µg/mL) than the gentamicin control (MIC = 16 µg/mL) against two strains of methicillin-resistant S. aureus (MRSA) (MR 4393 and MR 4549). Transmission electron microscopy (TEM) experiments and propidium iodide assays suggested that the main mode of action for the ruthenium(II) R-pytri complexes was cell wall/cytoplasmic membrane disruption. Cytotoxicity experiments on human dermal keratinocyte and Vero (African green monkey kidney epithelial) cell lines suggested that the complexes were only modestly cytotoxic at concentrations well above the MIC values.

Clinico-radiological profile of indirect neural decompression using cage or auto graft as interbody construct in posterior lumbar interbody fusion in spondylolisthesis: Which is better?

STUDY DESIGN: A prospective clinical study of posterior lumbar interbody fusion in grade I and II degenerative spondylolisthesis was conducted between Mar 2007 and Aug 2008. PURPOSE: The objective was to assess the clinicoradiological profile of structural v/s nonstructural graft on intervertebral disc height and its consequences on the low back pain (LBP) assessed by Visual analog score (VAS) score and oswestry disability index (ODI) . This study involved 28 patients. INCLUSION CRITERIA: Age of 30-70 years, symptomatic patient with disturbed Activities of daily living (ADL), single-level L4/L5 or L5/S1 grade I or grade II degenerative spondylolisthesis. EXCLUSION CRITERIA: Patients with osteoporosis, recent spondylodiscitis, subchondral sclerosis, visual and cognitive impairment and all other types of spondylolisthesis. All the patients underwent short-segment posterior fixation using CD2 or M8 instrumentation, laminectomy discectomy, reduction and distraction of the involved vertebral space. In 53.5% (n = 15) of the patients, snugly fitted local bone chips were used while in 46.4% (n = 13) of the patients, cage was used. Among the cage group, titanium cage was used in nine (32.1%) and PEEK cages were used in four (14.2%) patients. In one patient, a unilateral PEEK cage was used. The mean follow-up period was 24 months. Among the 28 patients, 67.8% (n = 19) were females and 32.14% (n = 9) were males. 68.24% (n = 18) had L4/L5 and 35.71% (n = 10) had L5/S1 spondylolisthesis. 39.28% (n = 11) were of grade I and 60.71% (n = 17) were of grade II spondylolisthesis. CONCLUSIONS: There was a statistically significant correlation (P < 0.012 and P < 0.027) between the change in disc height achieved and the improvement in VAS score in both the graft group and the cage group. The increment in disc height and VAS score was significantly better in the cage group (2 mm ± SD vis-a-vis 7.2 [88%]) than the graft group (1.2 mm ± SD vis-a-vis 5 [62 %]).

Interpenetrating network hydrogel membranes of sodium alginate and poly(vinyl alcohol) for controlled release of prazosin hydrochloride through skin.

Interpenetrating network (IPN) hydrogel membranes of sodium alginate (SA) and poly(vinyl alcohol) (PVA) were prepared by solvent casting method for transdermal delivery of an anti-hypertensive drug, prazosin hydrochloride. The prepared membranes were thin, flexible and smooth. The X-ray diffraction studies indicated the amorphous dispersion of drug in the membranes. Differential scanning calorimetric analysis confirmed the IPN formation and suggests that the membrane stiffness increases with increased concentration of glutaraldehyde (GA) in the membranes. All the membranes were permeable to water vapors depending upon the extent of cross-linking. The in vitro drug release study was performed through excised rat abdominal skin; drug release depends on the concentrations of GA in membranes. The IPN membranes extended drug release up to 24 h, while SA and PVA membranes discharged the drug quickly. The primary skin irritation and skin histopathology study indicated that the prepared IPN membranes were less irritant and safe for skin application.

Supernumerary Fascicle of Abductor digiti minimi Muscle and Compression of Ulnar Nerve and Ulnar Artery: A Case Report / Fascículo Supernumerario del Músculo Abductor del dedo Mínimo y Compresión del Nervio y Arteria Ulnares: Reporte de Caso

The supernumerary fascicles of abductor digiti minimi muscle have been implicated in vascular and nerve compression. During routine dissection of an old male cadaver we observed an anomalous muscle was found to take it's origin from the antebrachial fascia and flexor retinaculum, traversed ulnar canal (Guyon's) superficial to ulnar vessels and nerves to reach the proximal part of abductor digiti minimi. The anomaly is one of a kind. Its course through Guyon's canal could be a cause for Guyon's canal syndrome. It was innervated by the ulnar nerve.

Los fascículos supernumerarios del músculo abductor del dedo mínimo han sido implicados en la compresión neurovascular. Durante una disección de rutina de un cadáver masculino adulto, se observó un músculo anómalo que se originaba en la fascia antebraquial y en el retináculo flexor, atravesaba el canal ulnar, superficial a los vasos y nervio ulnares para llegar a la parte proximal del músculo abductor del dedo mínimo. La anomalía es única en su tipo. Su curso a través del canal ulnar puede causar el síndrome del canal ulnar. El músculo estaba inervado por el nervio ulnar.