SEARCH · PubMed Health

Results for “energy optimization”

Explore indexed PubMed citations for clinical trials, systematic reviews and public health research. Read source abstracts and follow each citation to its original PubMed record.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 739 records · Page 41Linked to original sources

PubMed1998

Improved photochemotherapy of malignant cells with daunomycin and the KTP laser.

Laser photochemotherapy of malignancies may become an effective palliative treatment for advanced had and neck cancer using light-sensitive, chemotherapeutic drugs activated in tumors via interstitial laser fiberoptics. Previously, it was reported that cultured human P3 squamous cells incubated 2 hours with daunomycin (Dn) exhibited tenfold enhanced cytotoxicity after exposure to argon laser light at 514 nm. This short-term uptake leads to drug localization in cytoplasmic and membrane sites prior to nuclear accumulation and daunomycin topoisomerase inhibition. In the current study phototoxicity of Dn-sensitized human cancer cells was tested using broad-spectrum white light compared to monochromatic green-wavelength light. Drug uptake and laser energy levels were optimized for maximum synergy. To test light-enhanced chemotherapy in vitro, the kinetics of cell uptake and toxicity of daunomycin was measured at 1, 2, and 5 microg/ml in three human tumor cell lines: P3 squamous-cell carcinoma, M26 melanoma, and TE671 fibrosarcoma. After 2 hr Dn uptake, all cell lines were tested for phototherapy response by exposure to 300- to 900-nm visible light from a xenon lamp or monochromatic 532-nm green light from a KTP laser. When the KTP laser output was varied from 0 to 120 Joules in Dn-sensitized tumor cells, a linear phototherapy response was seen with energy as low as 12 J inducing drug phototoxicity. These results provide evidence that daunomycin cytotoxicity is enhanced when exposed to 532-nm laser illumination in the three tumor types tested and confirm that the response is related to both energy level and drug dose.

Carcinoma, Squamous Cell↗

PubMed2002

Reactive nitrogen and the world: 200 years of change.

This paper examines the impact of food and energy production on the global N cycle by contrasting N flows in the late-19th century with those of the late-20th century. We have a good understanding of the amounts of reactive N created by humans, and the primary points of loss to the environment. However, we have a poor understanding of nitrogen's rate of accumulation in environmental reservoirs, which is problematic because of the cascading effects of accumulated N in the environment. The substantial regional variability in reactive nitrogen creation, its degree of distribution, and the likelihood of increased rates of reactive-N formation (especially in Asia) in the future creates a situation that calls for the development of a Total Reactive Nitrogen Approach that will optimize food and energy production and protect environmental systems.

Agriculture↗

PubMed2001

Packing is a key selection factor in the evolution of protein hydrophobic cores.

The energy derived from optimized van der Waals interactions in closely packed, folded proteins has been proposed to be of similar energetic magnitude to hydrophobicity in stabilizing the native state. If packing is this energetically important, it should influence the evolution of protein core sequences. To test this hypothesis, the occurrence of various amino acid side chains in the major hydrophobic core of staphylococcal nuclease and 42 homologous proteins was determined. Most such positions in this protein family are usually isoleucine, leucine, or valine. Previously we have constructed and measured the stabilities of 12 single, 44 double, 64 triple, and 32 quadruple mutants, representing all possible permutations of these three side chains at two overlapping sets of four positions in the core of staphylococcal nuclease. The stabilities and interaction energies of those mutants with various combinations of the most common, or consensus, sequence were compared to the stabilities of all other mutants. Mutants which had the consensus side-chain combinations were not necessarily the most stable, but usually were found to have the best interaction energies. In other words, these proteins were far more stable than would be predicted from simply summing the observed energetic effects of the component single mutations, apparently reflecting particularly favorable packing interactions that are possible for the most common side chains. An additional 12 mutants which tested possible alternate explanations of the results were constructed. The stabilities and interaction energies of these mutants also support the conclusion that packing is a crucial determinant guiding the sequence evolution of protein cores.

Amino Acid Sequence↗

PubMed2002

Fecundity and life-history strategies in marine invertebrates.

The reproductive strategies of an organism play a major role in the dynamics of the population and the biogeography and continuity of the species. Numerous processes are involved in reproduction leading to the production of offspring. Although diverse processes are involved in oogenesis (the production of eggs) and spermatogenesis (the production of sperm), the basic patterns of gametogenesis are similar amongst invertebrates, with the proliferation and differentiation of germ cells leading to the final production of mature gametes. The production of gametes, especially eggs, is energetically expensive, and therefore strongly sensitive to selective pressures. An organism can ingest and assimilate a limited amount of energy from the environment. The different ways by which energy is allocated to growth and reproduction in order to maximize fitness forms the basis of the differing life-history strategies that have developed in marine invertebrates. Fecundity is defined as the number of offspring produced by a female in a determined time period. The term fecundity needs to be explicitly defined in each study in order to obtain the maximum information from the data analysed. Because of the variety of egg production patterns found among marine invertebrates, a wide range of methodologies has been developed to quantify fecundity. These include direct egg counts in brooding species, spawning induction in live individuals and histological studies of preserved material. Specific considerations need to be taken into account for colonial organisms, because of their modular organization. The production of eggs requires an optimal allocation of energy into growth and reproduction for the maximization of parental fitness. Fecundity is central in studies of life-history theory and in the development of life-history models because it is directly related to energy allocation and partitioning. There are important relationships and trade-offs between fecundity and other life-history traits, such as egg size, female size and age, age at first reproduction, reproductive effort and residual reproductive value. These trade-offs, together with morpho-functional constraints and genetic variation determine the evolution of life histories through natural selection. Fecundity is a highly plastic character within the limits defined by the bioenergetics and life-history strategy of the organism. Egg production is affected mainly by environmental factors such as food quantity and quality, temperature or presence of toxic elements in the habitat. The differences in fecundity found among closely related species from different biogeographical locations reflect, at least in part, the differing environmental conditions of their habitat.

Adaptation, Physiological↗

PubMed2004

Charge optimization of the interface between protein kinases and their ligands.

Examining the potential for electrostatic complementarity between a ligand and a receptor is a useful technique for rational drug design, and can demonstrate how a system prioritizes interactions when allowed to optimize its charge distribution. In this computational study, we implemented the previously developed, continuum solvent-based charge optimization theory with a simple, quadratic programming algorithm and the UHBD Poisson-Boltzmann solver. This method allows one to compute the best set of point charges for a ligand or ligand region based on the ligand and receptor shape, and the receptor partial charges, by optimizing the binding free energy obtained from a continuum-solvent model. We applied charge optimization to a fragment of the heat-stable protein kinase inhibitor (PKI) of protein kinase A (PKA), to three flavopiridol inhibitors of CDK2, and to cyclin A which interacts with CDK2 to regulate the cell cycle. We found that a combination of global (involving every charge) and local (involving only charges in a local region) optimization can give useful hints for designing better inhibitors. Although some parts of an inhibitor may already contribute significantly to binding, we found that they could still be the most important targets for modifications to obtain stronger binders. In studying the binding of flavopiridol inhibitors to CDK2, comparable binding affinity could be obtained regardless of whether the net charges of the inhibitors were constrained to -2, -1, 0, 1, or 2 during the optimization. This provides flexibility in inhibitor design when a certain net charge of the inhibitor is desired in addition to strong binding affinity. For the study of the PKA-PKI and CDK2-cyclin A interfaces, we identified residues whose charge distributions are already close to optimal and those whose charge distributions could be refined to further improve binding.

Algorithms↗

PubMed1992

A theoretical study concerning the mode of interaction of the histamine H2-agonist dimaprit.

A theoretical study was performed to elucidate the mode of interaction of the histamine H2-agonist dimaprit with the histamine H2-receptor. For this purpose receptor mapping techniques, including ab initio energy calculations, geometry optimizations and molecular electrostatic potential calculations (MEPs), have been used. The characteristics of dimaprit were compared to those of histamine for which the points of interaction with the H2-receptor are known, as well as its bioactive conformation. In this comparative study two possible models for the interaction of dimaprit with the H2-receptor were considered. In one model the two nitrogen atoms of the isothiourea moiety of dimaprit play an essential role in the recognition of the ligand by the receptor and have the same function as the nitrogen atoms of the imidazole ring of histamine; in the second model this role is fulfilled by a sulphur and a nitrogen atom of the same isothiourea moiety. The comparison to histamine was based on geometrical resemblance as well as on similarity in MEPs. Also the conformational energy of dimaprit in the two interaction models was considered. Results of the investigations reveal that the isothiourea moiety of dimaprit most probably interacts with the histamine H2-receptor through the sulphur and nitrogen atom, the first atom acting as a proton acceptor and the second one as a proton donor. Subsequently, three analogues of dimaprit, namely SK&F 91487, SK&F 91488 and SK&F 92054, were studied. It was possible to explain their pharmacological behavior within the proposed model.(ABSTRACT TRUNCATED AT 250 WORDS)

Computer Simulation↗

PubMed2006

Glucose sensors based on microcapsules containing an orange/red competitive binding resonance energy transfer assay.

Fluorescent sensing systems offer the potential for noninvasive monitoring with implantable devices, but they require carrier technologies that provide suitable immobilization, accessibility, and biocompatibility while maintaining adequate response characteristics. A recent development towards this goal is a highly specific and sensitive competitive binding assay for glucose using apo-glucose oxidase (apo-GOx) as the recognition element and dextran as the competing ligand; this has been demonstrated as a glucose sensor system by encapsulating the competitive binding assay in semipermeable microcapsule carriers. This paper describes the extension of this sensor design to longer wavelengths in an attempt to increase the applicability to in vivo monitoring. The glucose sensitivity of the tetramethylrhodamine isothiocyanate-dextran (TD) and cyanine Cy5-apo-GOx (CAG) complexes showed five to 10 times greater specificity for beta-D-glucose over other sugars. Microcapsules loaded with TD/CAG complexes exhibited a linear, totally reversible response in the range of 0-720 mg/dL, with a sensitivity (percent change in intensity ratio) of 0.06%/(mg/dL). The decrease in sensitivity observed with the use of longer-wavelength dyes is most likely to be compensated with the deeper penetration of light and reduced tissue scattering. These findings imply that the encapsulation of sensing assay elements in microcapsules is a simple and translatable method for the fabrication of stable biosensors, and optimization of resonance energy transfer pairs and assay component preparation will further improve the response to approach clinically relevant performance.

Apoenzymes↗

PubMed2000

Effect of external ultrasound postliposuction: a side-to-side comparison study.

BACKGROUND: External ultrasound (EUS) has been used as a therapeutic modality for more than 30 years by multiple medical specialists, primarily for stimulating the repair of soft tissue injuries and relieving pain. It has also been used to treat postoperative swelling after liposuction. There are no controlled studies documenting the objective and subjective effects of EUS following liposuction. OBJECTIVE: The purpose of this preliminary study was to evaluate the role of EUS in the relief of postoperative symptoms following traditional tumescent liposuction. METHODS: Twenty-five patients underwent tumescent liposuction of the abdomen or hips. Within 2 weeks after the procedure, a double-blind study was initiated in which EUS therapy was applied at therapeutic energies to one-half of the treated area, while the other side was treated with placebo settings. Patients were treated biweekly for a total of six to eight treatments. Both objective and subjective parameters were assessed during the subsequent side-by-side evaluations by the patient and observer. RESULTS: After four treatments, 18 of 25 patients had the same postoperative symptoms on each side. Two had fewer symptoms on the EUS side and five were worse on the EUS side. After completion of all treatments, 17 of 25 again had the same symptoms on the therapeutic and placebo sides. Three had improved symptoms and five were worse on the EUS side. The subjective findings revealed that all patients believed the treatment helped significantly on both the placebo and EUS-treated sides. CONCLUSION: EUS after liposuction of the abdomen at the study parameters provided no objective benefit compared to placebo in postoperative recovery. Patient acceptance and perception of benefit are high. Further studies are needed to determine the optimal timing and energies required for therapeutic value.

Abdomen↗

PubMed2004

Refinement of NMR structures using implicit solvent and advanced sampling techniques.

NMR biomolecular structure calculations exploit simulated annealing methods for conformational sampling and require a relatively high level of redundancy in the experimental restraints to determine quality three-dimensional structures. Recent advances in generalized Born (GB) implicit solvent models should make it possible to combine information from both experimental measurements and accurate empirical force fields to improve the quality of NMR-derived structures. In this paper, we study the influence of implicit solvent on the refinement of protein NMR structures and identify an optimal protocol of utilizing these improved force fields. To do so, we carry out structure refinement experiments for model proteins with published NMR structures using full NMR restraints and subsets of them. We also investigate the application of advanced sampling techniques to NMR structure refinement. Similar to the observations of Xia et al. (J.Biomol. NMR 2002, 22, 317-331), we find that the impact of implicit solvent is rather small when there is a sufficient number of experimental restraints (such as in the final stage of NMR structure determination), whether implicit solvent is used throughout the calculation or only in the final refinement step. The application of advanced sampling techniques also seems to have minimal impact in this case. However, when the experimental data are limited, we demonstrate that refinement with implicit solvent can substantially improve the quality of the structures. In particular, when combined with an advanced sampling technique, the replica exchange (REX) method, near-native structures can be rapidly moved toward the native basin. The REX method provides both enhanced sampling and automatic selection of the most native-like (lowest energy) structures. An optimal protocol based on our studies first generates an ensemble of initial structures that maximally satisfy the available experimental data with conventional NMR software using a simplified force field and then refines these structures with implicit solvent using the REX method. We systematically examine the reliability and efficacy of this protocol using four proteins of various sizes ranging from the 56-residue B1 domain of Streptococcal protein G to the 370-residue Maltose-binding protein. Significant improvement in the structures was observed in all cases when refinement was based on low-redundancy restraint data. The proposed protocol is anticipated to be particularly useful in early stages of NMR structure determination where a reliable estimate of the native fold from limited data can significantly expedite the overall process. This refinement procedure is also expected to be useful when redundant experimental data are not readily available, such as for large multidomain biomolecules and in solid-state NMR structure determination.

Bacterial Proteins↗

PubMedDate not supplied

Critically attained threshold of cerebral hypoperfusion: the CATCH hypothesis of Alzheimer's pathogenesis.

This review discusses the experimental and clinical data which indicate that chronic cerebral hypoperfusion can affect metabolic, anatomic, and cognitive function adversely. In aged but not young animals, chronic brain hypoperfusion results in regional pre- and post-synaptic changes, protein synthesis abnormalities, energy metabolic dysregulation, reduced glucose utilization, cholinergic receptor loss, and visuo-spatial memory deficits. Additionally, aging animals that are kept for prolonged periods of time after chronic brain hypoperfusion, also develop brain capillary degeneration in CA1 hippocampus and neuronal damage extending from the hippocampal region to the temporo-parietal cortex where neurodegenerative tissue atrophy eventually forms. All these pathologic events occur in rodents in the absence of senile plaques and neurofibrillary tangles. Alzheimer brains reveal similar biochemical and structural changes as those experimentally induced in aging animals. Moreover, regional cerebral hypoperfusion is one of the earlier (if not the earliest) clinical manifestations in both the sporadic and familial forms of Alzheimer's disease. In addition, therapy that improves or increases cerebral perfusion is generally of some benefit to Alzheimer patients. Conversely, a variety of disorders with different etiologies that impair or diminish cerebral perfusion are reported to be risk factors for this dementia. These findings have prompted us to propose the concept that advanced aging in the presence of a vascular risk factor can converge to create a critically attained threshold of cerebral hypoperfusion (CATCH) that triggers regional brain microcirculatory disturbances and impairs optimal delivery of energy substrates needed for normal brain cell function. The outcome of this defect generates a chain of events leading to the progressive evolution of brain metabolic, cognitive and tissue pathology that characterize Alzheimer's disease. The possible role of CATCH in familial and early onset Alzheimer's disease is briefly discussed from a theoretical vantagepoint. The growing and most recent evidence in support of the CATCH concept is the focus of this review.

Alzheimer Disease↗

PubMed2005

Conformational study of the structure of free 18-crown-6.

A conformational search was performed for 18-crown-6 using the CONLEX method at the MM3 level. To have a more accurate energy order of the predicted conformations, the predicted conformations were geometry optimized at the HF/STO-3G level and the 198 lowest energy conformations, according to the HF/STO-3G energy order, were geometry optimized at the HF/6-31+G level. In addition, the 47 nonredundant lowest energy conformations, according to the MP2/6-31+G energy order at the HF/6-31+G optimized geometry, hereafter the MP2/6-31+G//HF/6-31+G energy order, were geometry optimized at the B3LYP/6-31+G level. According to the MP2/6-31+G//B3LYP/6-31+G energy order, three conformations had energies lower than the experimentally known Ci conformation of 18c6. At the MP2/6-31+G//B3LYP/6-31+G level, the S6 lowest energy conformation is more stable by 1.96 kcal/mol than this Ci conformation. This was confirmed by results at the MP2/6-31+G level with an energy difference of 1.84 kcal/mol. Comparison between the structure of the S6 conformation of 18c6 and the S4 lowest energy conformation of 12-crown-4, as well as other important conformations of both molecules, is made. It is concluded that the correlation energy is necessary to have an accurate energy order of the predicted conformations. A rationalization of the conformational energy order in terms of the hydrogen bonding and conformational dihedral angles is given. It is also suggested that to have a better energy order of the predicted conformations at the MM3 level, better empirical force fields corresponding to the hydrogen bond interactions are needed.

Journal Article↗

PubMed1993

Low-energy endocardial defibrillation using an axillary or a pectoral thoracic electrode location.

BACKGROUND: A significant proportion of patients receiving endocardial defibrillation lead systems must accept either high defibrillation thresholds (DFTs) with lower safety margins or lead implantation by thoracotomy. We examined the feasibility of achieving universal application of endocardial leads and lower defibrillation energy requirements by optimizing the lead system location in conjunction with biphasic shocks. METHODS AND RESULTS: Two defibrillation catheter electrodes were positioned in the right ventricle and superior vena cava. Thoracic patch electrodes were placed at three sites (apical, pectoral, and axillary). Fifteen-joule, 10-J, and 5-J bidirectional simultaneous biphasic shocks were delivered across three different triple electrode configurations (right ventricle, superior vena cava, and patch) after inducing ventricular fibrillation (VF), and DFT was determined. All patients in whom VF was reproducibly inducible (14 patients) could be reproducibly defibrillated at 15 J at one or more patch electrode locations. Fifteen-joule shocks were effective at three thoracic electrode locations in 12 patients and at two electrode locations in 6 patients. The lowest mean single-shock DFT was 8.1 +/- 3.8 J. In 4 patients, ventricular flutter was reproducibly induced and reverted at 15 J in all patients. Mean DFT for the axillary location was 8.3 +/- 3.5 J and was significantly lower than apical (12.8 +/- 5.6 J, P = .008) and pectoral (11.6 +/- 4.1 J, P < .04) patch locations. The probability of success was significantly higher at 10 J with axillary location (78% of patients, P < .03 compared with both other sites) and at 15 J (P < .05 compared with the apical location). Low-energy endocardial defibrillation (< or = 10 J) was feasible in 10 of 14 tested patients at more than 1 thoracic electrode location at 10 J, whereas only 1 of 7 successful patients could be reverted at more than 1 electrode location at 5 J (P < .02). CONCLUSIONS: The use of axillary or pectoral patch lead location can allow endocardial defibrillation with biphasic shocks at energies < or = 15 J in this lead configuration. Virtually universal application of endocardial defibrillation lead systems can be predicted from these data. Reduction in maximum pulse generator output to < or = 25 J using these two thoracic electrode locations with bidirectional shocks can be feasible and maintain an adequate safety margin and permit thoracic pulse generator implantation. Lowering endocardial defibrillation energy < 10 J requires increasing specificity of thoracic electrode location.

Aged↗

PubMed1999

Protein tertiary structure prediction using a branch and bound algorithm.

We report a new method for predicting protein tertiary structure from sequence and secondary structure information. The predictions result from global optimization of a potential energy function, including van der Waals, hydrophobic, and excluded volume terms. The optimization algorithm, which is based on the alphaBB method developed by Floudas and coworkers (Costas and Floudas, J Chem Phys 1994;100:1247-1261), uses a reduced model of the protein and is implemented in both distance and dihedral angle space, enabling a side-by-side comparison of methodologies. For a set of eight small proteins, representing the three basic types--all alpha, all beta, and mixed alpha/beta--the algorithm locates low-energy native-like structures (less than 6A root mean square deviation from the native coordinates) starting from an unfolded state. Serial and parallel implementations of this methodology are discussed.

Algorithms↗

PubMed1997

Low-energy endocardial defibrillation using dual, triple, and quadruple electrode systems.

The feasibility of achieving both universal application of nonthoracotomy leads and low (< or = 15 J) defibrillation energy requirements by optimizing lead system configuration for use with low-output (<30 J) biphasic shock pulse generators was examined. Sixteen patients (mean age 62 +/- 8 years and mean left ventricular ejection fraction of 38 +/- 15%) were included in the study. All patients had either experienced syncope with induced ventricular tachycardia (n = 4) or had documented sustained ventricular tachycardia (n = 7) or ventricular fibrillation (n = 5). Defibrillation threshold testing was performed in 2 stages on different days in these patients. In the first stage, 2 defibrillation catheter electrodes were positioned in the right ventricle and superior vena cava with an axillary cutaneous patch. Fifteen-joule, 10- and 5-J biphasic shocks were delivered across 3 different electrode configurations-right ventricle to superior vena cava, right ventricle to axillary patch, right ventricle to a combination of superior vena cava and axillary patch. In the second stage, an 80-ml can electrode was added subcutaneously in a pectoral location to the previous leads. Configurations compared were the right ventricle to pectoral can, and right ventricle to an "array"-combining superior vena cava, can, and axillary patch leads. The defibrillation threshold was determined using a step-down method. In stage 1, mean defibrillation threshold for the right ventricle to axillary patch (12.7 +/- 5.9 J) and right ventricle to superior vena cava plus axillary patch (9.8 +/- 5.2 J) configurations was lower than the right ventricle to superior vena cava configuration (14.2 +/- 6.4 J, p <0.05). In stage 2, the defibrillation was higher for the right ventricle to pectoral can (9.2 +/- 5.1 J) configuration compared with the right ventricle to the array (5.6 +/- 3.6 J, p < or =0.05). The right ventricle to array had the lowest defibrillation threshold, whereas the right ventricle to pectoral can was the best dual electrode system. Low-energy endocardial defibrillation (< or =10 J) was feasible in 72% of tested patients with > 1 electrode configuration at 10 J, whereas only 53% of successful patients could be reverted at >1 electrode configuration at 5 J (p <0.05). Reduction in maximum pulse generator output to < or =25 J using these electrode configurations with bidirectional shocks is feasible and maintains an adequate safety margin.

Aged↗

PubMed1994

Digestible lysine requirement of gilts with high genetic potential for lean gain, in relation to the level of energy intake.

One hundred gilts were used to determine the optimal ratio between ileal digestible lysine and digestible energy in the diet, and the effect of energy intake level on this optimal ratio for gilts with high genetic potential for lean gain, between 20 and 45 kg BW. In a 2 x 15 factorial arrangement the pigs were fed either 2.5 or 3.0 times the energy requirements for maintenance. Average daily lysine intake in the treatment period ranged from 6.4 to 18.2 g/d in 15 graduated steps. The first 12 increments were .74 g/d, and the last two increments were 1.48 g/d. Average daily gain (ADG), gain/feed, and protein deposition increased curvilinearly (P < .01) with increasing lysine intake. The ADG was maximized at 606 and 768 g/d, gain/feed was maximized at .564 and .604 kg/kg, and protein deposition was maximized at 108 and 128 g/d at the low- and high-energy levels, respectively. The ratio between lipid and protein deposition decreased curvilinearly with increasing lysine intake (P < .01) and reached a minimum of .53 and .75 at the low- and high-energy levels, respectively. The lysine requirements (ileal digestible lysine/DE, grams/megaJoule), determined with a linear-plateau model, were .57 for ADG and gain/feed, and .62 for protein deposition. These estimated requirements were similar for the two energy levels. Consequently, approximately .60 g of ileal digestible lysine/MJ of DE was required to optimize performance in gilts with high genetic potential for lean gain, irrespective of the feed intake level. In addition, a factorial model to estimate the lysine/energy requirements is proposed.

Animal Feed↗

PubMed1984

Experimental iridotomy with the Q-switched neodymium-YAG laser.

Iridotomies were performed on pigmented rabbits with a Q-switched ophthalmic neodymium-YAG (Nd-YAG) laser and an argon laser. Because short-pulsed Nd-YAG lasers are effective in performing capsulotomies of the crystalline lens, injury to the underlying lens was evaluated by slit-lamp biomicroscopy at various intervals following the iridotomy, and then lenses were examined in vitro with the use of procion yellow, an extracellular dye. Patent iridotomies were produced with one to two pulse applications of the Nd-YAG laser. Focal areas of pigment deposition on the lens capsule and focal lens capsule opacities underlying the iridotomy site were observed, but no inadvertent capsulotomies occurred. Lens injury could be minimized through optimal focusing and energy selection. Minimal hemorrhage occurred with Nd-YAG laser iridotomy; prior treatment with the argon laser was not necessary to achieve hemostasis.

Animals↗

PubMed2002

The nature of the indenyl effect.

The eta(5)-to-eta(3) coordination shift of cyclopentadienyl (Cp=C(5)H(5)(-)) and indenyl (Ind=C(9)H(7)(-)) ligands in molybdenocene complexes, [(eta(5)-Cp')(eta(5)-Cp)Mo(CO)(2)](2+) (Cp'=Cp or Ind), driven by a two-electron reduction of those species, was studied and compared by means of molecular orbital calculations (B3LYP HF/DFT hybrid functional, DZP basis sets). The results obtained, in terms of optimized geometries, relative energies, and bond analysis parameters, compare well with the experimental data, and verify the well-known indenyl effect, that is, a significantly more facile eta(5)-to-eta(3) rearrangement for the indenyl ligand when compared to cyclopentadienyl. However, the study of the folding of free Cp and Ind, combined with the (eta(5/3)-Cp')-M bond analysis, shows that the observed difference is not the result of an intrinsic characteristic of the indenyl ligand, such as the traditionally accepted aromaticity gain in the benzene ring formed in eta(3)-Ind complexes. Instead, it is directly related to the Cp'-M bond strength. While the difference in the energy required to fold the two free ligands is negligible (< or =1 kcal mol(-1) for folding angles up to 20 degrees), the (eta(5)-Cp)-M bond is stronger than that of (eta(5)-Ind)-M; however, the opposite situation is found for the eta(3) coordination mode. The net result, for Cp'=Ind, is a destabilization of the eta(5) complexes and a stabilization of the eta(3) intermediates or transition states yielding smaller activation energies and faster reaction rates for processes in which that is the rate-determining step.

Journal Article↗

PubMed2002

On the intermediates in chiral bis(oxazoline)copper(II)-catalyzed enantioselective reactions--experimental and theoretical investigations.

The intermediates in the chiral bis(oxazoline)copper(II)-catalyzed reactions have been investigated by means of experimental and theoretical investigations. It is shown that the absolute configuration of the hetero-Diels-Alder adduct obtained from the reaction of ethyl glyoxylate with 1,3-cyclohexadiene in the presence of the chiral bis(phenyloxazoline)copper(II) is dependent on the solvent. In this case, a linear relationship between the enantiomeric excess (ee) and the dielectric constant of the solvent was observed. However, the enantiomeric excess for the adduct obtained with the chiral bis(tert-butyloxazoline)copper(II) complex is independent of the solvent. The addition of different coordinating solvents to the chiral catalysts was investigated and no effect on the enantioselectivity of the reaction was observed. A series of chiral bis(tert-butyloxazoline)-, bis(phenyloxazoline)-, and bis(indaneoxazoline)copper(II) complexes has been prepared and characterized by X-ray analysis, and the similarity between the structures is discussed. For comparison, two related chiral bis(tert-butyloxazoline)- and bis(phenyloxazoline)zinc(II) complexes were also prepared and characterized. A series of chiral bis(oxazoline)copper(II)-substrate (the substrate being glyoxal or methyl glyoxylate) complexes was investigated by means of ab initio calculations. Calculation of the total energy of the optimized structure of 17-, 19-, and 21-electron bis(oxazoline)copper(II)-substrate complexes give the 17-electron complex as the most stable and the most reactive complex, while the 21-electron complex is less stable and also much less reactive. The optimized structures of both the 17-electron bis(tert-butyloxazoline)- and bis(phenyloxazoline)copper(II)-substrate complexes show that the plane of the substrate molecule is twisted by approximately 40-45 degrees out of the bis(oxazoline)copper(II) plane, in agreement with the X-ray structures. On the basis of the experimental results, X-ray structures, and ab initio calculations, the structure of the intermediate(s) and reactivity of the chiral bis(oxazoline)copper(II)-substrate complexes are discussed.

Journal Article↗