Co-Tetraphenylporphyrin (co-TPP) in TM-TPP (TM = Fe, Co, Ni, Cu, and Zn) series: a new optical material under DFT.

A detailed investigation of the structure, electronic, spectroscopic, and optical properties of a series of transition metal-doped tetraphenylporphyrins (TM-TPP; TM = Fe, Co, Ni, Cu and Zn) is performed under density functional framework. The structure and stability of tetraphenylporphyrin (TPP) and TM-TPPs are understood with HOMO-LUMO gap, chemical hardness, and binding energies of the transition metals to the compound. Optical properties of TPP and TM-TPP series are assessed with relevant optical absorption spectra. A couple of visible active compounds, viz. Co-TPP and Ni-TPP, are reported for the first time for future opto-electronic applications. To gain insight on the possible synthesis of these compounds, we have analyzed frontier molecular orbitals (FMOs) as well as infra-red spectra. Graphical abstract Optical absorption spectra of TPP and TM-TPPs, and infrared spectra of TPP merged with Co-TPP.

Magnetic moment and local moment alignment in anionic and/or oxidized Fe(n) clusters.

First principles studies on the ground state structure, binding energy, spin multiplicity, and the noncollinearity of local spin moments in Fe(n) and Fe(n) (-) clusters and their oxides, viz., Fe(n)O(2) and Fe(n)O(2) (-) have been carried out within a density functional formalism. The ground states of Fe(n) and Fe(n) (-) clusters have collinear spins with a magnetic moment of around 3.0 micro(B) per atom. The O(2) molecule is found to be dissociatively absorbed and its most significant effect on spin occurs in Fe(2), where Fe(2)O(2) and Fe(2)O(2) (-) show antiferromagnetic and noncollinear spin arrangements, respectively. The calculated adiabatic electron affinity and the vertical transitions from the anion to the neutral species are found to be in good agreement with the available negative ion photodetachment spectra, providing support to the calculated ground states including the noncollinear ones.

Multiphilic descriptor for chemical reactivity and selectivity.

In line with the local philicity concept proposed by Chattaraj et al. (Chattaraj, P. K.; Maiti, B.; Sarkar, U. J. Phys. Chem. A. 2003, 107, 4973) and a dual descriptor derived by Morell, Grand and Toro-Labbé, (J. Phys. Chem. A 2005, 109, 205), we propose a multiphilic descriptor. It is defined as the difference between nucleophilic (omega(k)+) and electrophilic (omega(k)-) condensed philicity functions. This descriptor is capable of simultaneously explaining the nucleophilicity and electrophilicity of the given atomic sites in the molecule. Variation of these quantities along the path of a soft reaction is also analyzed. Predictive ability of this descriptor has been successfully tested on the selected systems and reactions. Corresponding force profiles are also analyzed in some representative cases. Also, to study the intra- and intermolecular reactivities another related descriptor, namely, the nucleophilicity excess (Deltaomega(g)-/+) for a nucleophile over the electrophilicity in it, has been defined and tested on all-metal aromatic compounds.

An atom counting strategy towards analyzing the biological activity of sex hormones.

A simple and effective molecular descriptor, viz., the number of atoms in a molecule (N(A)) is made use of in the development of the quantitative structure-activity relationship (QSAR). A series of testosterone derivatives with various biological activities and estrogen derivatives with the activities in terms of relative binding affinity (RBA) are considered to find out the potential of N(A) in predicting the activities of those molecules. It is heartening to note that N(A) along with the electrophilicity index (omega) is capable of explaining the biological activities of the male and female hormones.

Analyzing toxicity through electrophilicity.

The toxicological structure-activity relationships are investigated using conceptual DFT based descriptors like global and local electrophilicities. In the present work the usefulness of electrophilicity in predicting toxicity of several polyaromatic hydrocarbons (PAH) is assessed. The toxicity is expressed through biological activity data (pIC50) defined as molar concentration of those chemicals necessary to displace 50% of radiolabeled tetrachlorodibenzo-p-dioxin (TCDD) from the arylhydrocarbon (Ah) receptor. The experimental toxicity values (pIC50) for the electron acceptor toxin like polychlorinated dibenzofurans (PCDF) are taken as dependent variables and the DFT based global descriptor electrophilicity index (omega) is taken as independent variable in the training set. The same model is then tested on a test set of polychlorinated biphenyls (PCB). A good correlation is obtained which vindicates the importance of these descriptors in the QSAR studies on toxins. These toxins act as electron acceptors in the presence of biomolecules whereas aliphatic amines behave as electron donors some of which are also taken into account for the present work. The toxicity values of the aliphatic amines in terms of the 50% inhibitory growth concentration (IGC50) towards ciliate fresh-water protozoa Tetrahymena pyriformis are considered. Since there is no global nucleophilicity we apply local nucleophilicity (omegamax+) as the descriptor in this case of training set. The same regression model is then applied to a test set of amino alcohols. Although the correlation is very good the statistical analysis reflects some cross validation problem. As a further check the amines and amino alcohols are used together to form both the training and the test sets to provide good correlation. It is demonstrated that the toxicity of several toxins (both electron donors and acceptors) in the gas and solution phases can be adequately explained in terms of global and local electrophilicities. Amount of charge transfer between the toxin and the biosystem, simulated as nucleic acid bases and DNA base pairs, indicates the importance of charge transfer in the observed toxicity. The major strength of the present analysis vis-à-vis the existing ones rests on the fact that it requires only one descriptor having a direct relationship with toxicity to provide a better correlation. Importance of using the information from both the toxin and the biosystem is also analyzed.

Careful scrutiny of the philicity concept.

The philicity concept [J. Phys. Chem. A 2003, 107, 4973] is put in proper perspective. In the present work we analyze different physicochemical problems using philicity. It provides satisfactory results in all such cases. We also compare the relative electro(nucleo)philicity with philicity to show that philicity is better than relative electro(nucleo)philicity when the intermolecular reactivity trends are considered and there is hardly any preference of one above the other as far as the intramolecular reactivities are concerned. On the contrary, the philicity concept has some advantages over the other concept.

Electrophilicity as a possible descriptor for toxicity prediction.

Electrophilicity is one of the cardinal chemical reactivity descriptors successfully employed in various molecular reactivity studies within a structure-activity relationship parlance. The applications of this quantity in the modeling of toxicological properties have inspired us to perform a more exhaustive study in order to test and/or to validate the application of electrophilicity in assessing its chemical and toxicological potential. For this reason the toxicity of a large data set of molecules comprising 252 aliphatic compounds on the Tetrahymena pyriformis is studied. A quantitative structure-activity relationship analysis enabled us to model toxicity in terms of global and local electrophilicities, which provide a reasonably good prediction of aliphatic toxicity. It is heartening to note that the global and local electrophilicity values together can explain the toxicity of a large variety of aliphatic compounds nicely without resorting to any other descriptor or other microscopic/macroscopic physicochemical properties as is the situation in all other QSAR studies.

Stability and reactivity of all-metal aromatic and antiaromatic systems in light of the principles of maximum hardness and minimum polarizability.

It is demonstrated that among various possible isomers of all-metal aromatic compounds such as Al(4)(2-) and their complexes the most stable isomer with the minimum energy is the hardest and the least polarizable. A similar situation is observed for different isomers of all-metal antiaromatic compounds such as Al(4)(4-) and their complexes. It is shown that linear Al(4)(4-) is energetically more stable than its cyclic isomer. The reaction energies associated with the complexation processes highlight the stability of those complexes. The difference in energy, hardness, and polarizability between a cyclic molecule and its linear counterpart convincingly shows that an aromatic molecule exhibits negative changes in energy and polarizability but positive changes in hardness as expected from the principles of minimum energy, minimum polarizability, and maximum hardness. Although the aromaticity of Al(4)(2-) is unequivocally established through this study, the antiaromaticity picture in the case of Al(4)(4-) is shown to be poorly understood;however, the present analysis sheds light on this controversy.

Electrophilicity index as a possible descriptor of biological activity.

The purpose of this study is to probe the suitability of DFT based chemical reactivity parameter, electrophilicity index as a possible biological activity descriptor in the development of QSAR. Testosterone derivatives with activity described in terms of various biological activity parameters and the estrogen derivatives by relative binding affinity (RBA) values have been selected as model systems. The implications for the ability of electrophilicity to describe the biological activities are discussed. From the results it is possible to observe that electrophilicity index may be suitable to effectively describe the biological activity.

Growth plate forces in the adolescent human knee: a radiographic and mechanical study of epiphyseal staples.

The purpose of this study was to quantify the forces produced by the growth plates of the adolescent human proximal tibia and distal femur. The postoperative deformations of staples used to treat genu valgum were correlated with similar staple deformations produced by mechanical testing. Staple deformation was measured in sequential radiographs of 35 knees in 20 patients. Mechanical tests were performed on new staples to determine the force necessary to bend the staples to the observed displacements. Based on deformation at final examination, the static equivalent loads exerted at the joint centerline by the growth plates of the proximal tibia and distal femur were 0.5 kN per physis. The estimated corresponding stress was 1 MPa. These results indicated that successful lower limb hemiepiphysiodesis suppressed a longitudinally directed, centrally applied compressive force on the order of body weight.

Complications of surgery of the foot and ankle in hereditary neurologic disorders.

The hereditary motor and sensory neuropathies are one of a group of hereditary neurologic disorders. Patients with these disorders initially may present with a deformity of the feet and toes. Complications in the treatment of these deformities can be minimized by a proper diagnosis, identifying the components of the deformity, and selecting the appropriate procedure(s). Correcting the muscle imbalance and the deformity will be necessary in most patients and most patients will require a combination of surgical procedures.

Osteomyelitis of the patella.

Osteomyelitis of the patella is an uncommon infection that is primarily a disease of childhood. The diagnosis frequently is delayed because of its rarity and variable presentation, which may be acute with systemic signs or insidious with mild local signs. The diagnosis should be considered in patients with persistent peripatellar pain and swelling, cellulitis, septic prepatellar bursitis, and septic arthritis of the knee that does not respond to standard treatment. Treatment is identical to the treatment of osteomyelitis at other locations. The outcome is favorable in the child regarding range of motion and activity, although there may be persistent changes radiographically.

Endoscopic pelvic osteotomy for the treatment of hip dysplasia.

Adolescent and adult hip dysplasia can be surgically treated by rotating the acetabulum into a better weight-supporting position; however, open pelvic osteotomies are among the most invasive of all pediatric orthopaedic procedures. Endoscopic pelvic osteotomy offers the theoretical advantages of magnified visualization of the bone cuts, minimized surgical dissection, and rapid postoperative recovery. The technique of endoscopically assisted triple innominate osteotomy requires the combination of endoscopic skills and facility with more standard surgical approaches.

Developmental expression of intracellular targets of cGMP in rat visual cortex and alteration with dark rearing.

We describe the temporal pattern of mRNA expression of some of the molecular components of the NO/cGMP second messenger system in the developing rat visual cortex and the effect of dark rearing on their expression levels using semiquantitative RT-PCR. mRNA expression for these molecules was altered by dark rearing in one of three ways: (1) no change--rod, olfactory, and cone/testis CNG channels, nonselective cation channels gated by cyclic nucleotides and highly permeable to Ca2+; (2) decrease--cyclic nucleotide phosphodiesterases which regulate cyclic nucleotide levels, and soluble guanylyl cyclase, the key synthetic enzyme producing cGMP and potently activated by nitric oxide; and (3) increase--cGMP kinase 1, a key enzyme activated by cGMP to phosphorylate a variety of intracellular proteins including cytoskeletal elements. These data suggest important and distinct roles for the cGMP system in both early and late developmental events in the rat visual cortex.

The effect of surgical timing on the perioperative complications of treatment of supracondylar humeral fractures in children.

BACKGROUND: The purpose of this study was to evaluate the perioperative complication rates associated with early surgical treatment (eight hours or less following injury) and delayed surgical treatment (more than eight hours following injury) of displaced supracondylar humeral fractures in children. METHODS: Fifty-two patients had early surgical treatment and 146 patients had delayed surgical treatment of a displaced supracondylar humeral fracture. The perioperative complication rates of the two groups were compared with the use of bivariate and multivariate statistical methods. RESULTS: There was no significant difference between the two groups with respect to the need for conversion to formal open reduction and internal fixation (p = 0.56), pin-track infection (p = 0.12), or iatrogenic nerve injury (p = 0.72). No compartment syndromes occurred in either group. Power analysis revealed that our study had an 86% power to detect a 20% difference between the two groups if one existed. CONCLUSIONS: We were unable to identify any significant difference, with regard to perioperative complication rates, between early and delayed treatment of displaced supracondylar humeral fractures. Within the parameters outlined in our study, we think that the timing of surgical intervention can be either early or delayed as deemed appropriate by the surgeon.

Limited magnetic resonance imaging examination after surgical reduction of developmental dysplasia of the hip.

We evaluated the utility of limited magnetic resonance imaging (MRI) after surgical reduction and spica casting for developmental dysplasia of the hip (DDH) with respect to feasibility, time, need for sedation, and charge. Eighteen limited MRI examinations were performed in 10 children (mean age, 9 months) with a 1.5-T magnet. Twenty-eight dysplastic hips were imaged within 4 hours of surgery. Mean imaging time for two sequences was approximately 3 minutes. All examinations were interpretable, although three were degraded by motion. No child required sedation, additional sequences, or repeat study. Two thirds of the dysplastic hips had no proximal femoral ossification center on MRI. A reduced charge was assigned to the examination. We conclude that using limited MRI to confirm intraoperative reduction for DDH is feasible and desirable. The lack of radiation or need for sedation, the reduced charge that reflects the short time needed for imaging, and the superb visualization of nonosseous structures have made it our preferred method to evaluate surgical reduction of DDH.

Traumatic hip dislocation in children. Long-term followup of 42 patients.

To assess the impact of traumatic hip dislocations in the skeletally immature patient, 42 children younger than 16 years of age (average age, 9 years 10 months) who were treated at the authors' institution were studied. Data were collected from charts and radiographs and by completion of questionnaires. The average followup after injury was 10 years 1 month. The majority of dislocations (64%) were attributable to low energy injuries. Ipsilateral fractures about the hip occurred in 17% of patients. Avascular necrosis of the femoral head developed in 12% of patients, with the amount of time spent dislocated being the only statistically proven risk factor. Patients whose reduction was delayed greater than 6 hours had a 20 times higher risk of having avascular necrosis develop compared with patients whose hips were reduced in 6 hours or less. The use of computed tomography for joint asymmetry of 3 mm or greater and omission of bone scan screening were supported by this study. Functional outcomes were very good in this series with 95% of patients suffering mild (usually weather related) or no pain and 95% of patients suffering mild pain (intermittently noticeable) or no limp. A large percentage of the patients (78%) continued to participate in high demand activities such as football, soccer, and basketball.

Latex glove allergy--dilemma for health care workers. An overview.

1. The prevalence of latex allergy in health care workers is estimated to be between 10% and 17%. 2. Reactions from wearing latex gloves can include irritant contact dermatitis, allergic contact dermatitis, and contact urticaria from latex proteins. 3. Individuals with a history of atopy, multiple surgeries early in life (particularly with bladder catheterization), or allergies to certain foods are considered at risk of latex allergy. 4. An early intervention protocol and documentation forms are offered for occupational health nurses faced with assessing potentially latex allergic employees.

Temporal and spatial pattern of expression of cyclic nucleotide-gated channels in developing rat visual cortex.

Cyclic nucleotide-gated channels, ligand-gated and highly permeable to calcium, are good candidates for transducing signals received by migrating cells, growth cones and developing synapses. The level of calcium in growth cones is important for axon guidance. Further, cyclic nucleotides, whose levels can be altered by nitric oxide and other transmitters, are known to alter growth cone motility. We use rat visual cortex as a model in our semi-quantitative RT-PCR and in situ hybridization studies to determine the developmental time course and localization of all three CNG family members (rod, olfactory and cone/testis). We demonstrate that in the cortex, the three channel subtypes are each expressed in a distinct temporal and spatial pattern in only sensorimotor and occipital regions of the cortex. Specifically, the rod and olfactory subtypes are present at the time of migration and rapid dendritic outgrowth, and the cone/testis subtype is highly expressed after eye opening. These results suggest CNG channels may play a role in both early and late events in visual cortical development.

The Jnk1 and Jnk2 protein kinases are required for regional specific apoptosis during early brain development.

The c-Jun NH2-terminal kinase (Jnk) family is implicated in apoptosis, but its function in brain development is unclear. Here, we address this issue using mutant mice lacking different members of the family (Jnk1, Jnk2, and Jnk3). Mice deficient in Jnk1, Jnk2, Jnk3, and Jnk1/Jnk3 or Jnk2/Jnk3 double mutants all survived normally. Compound mutants lacking Jnk1 and Jnk2 genes were embryonic lethal and had severe dysregulation of apoptosis in brain. Specifically, there was a reduction of cell death in the lateral edges of hindbrain prior to neural tube closure. In contrast, increased apoptosis and caspase activation were found in the mutant forebrain, leading to precocious degeneration. These results suggest that Jnk1 and Jnk2 regulate region-specific apoptosis during early brain development.