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PubMed2000

Fuzzy lattice neurocomputing (FLN) models.

In this work it is shown how fuzzy lattice neurocomputing (FLN) emerges as a connectionist paradigm in the framework of fuzzy lattices (FL-framework) whose advantages include the capacity to deal rigorously with: disparate types of data such as numeric and linguistic data, intervals of values, 'missing' and 'don't care' data. A novel notation for the FL-framework is introduced here in order to simplify mathematical expressions without losing content. Two concrete FLN models are presented, namely 'sigma-FLN' for competitive clustering, and 'FLN with tightest fits (FLNtf)' for supervised clustering. Learning by the sigma-FLN, is rapid as it requires a single pass through the data, whereas learning by the FLNtf, is incremental, data order independent, polynomial theta(n3), and it guarantees maximization of the degree of inclusion of an input in a learned class as explained in the text. Convenient geometric interpretations are provided. The sigma-FLN is presented here as fuzzy-ART's extension in the FL-framework such that sigma-FLN widens fuzzy-ART's domain of application to (mathematical) lattices by augmenting the scope of both of fuzzy-ART's choice (Weber) and match functions, and by enhancing fuzzy-ART's complement coding technique. The FLNtf neural model is applied to four benchmark data sets of various sizes for pattern recognition and rule extraction. The benchmark data sets in question involve jointly numeric and nominal data with 'missing' and/or 'don't care' attribute values, whereas the lattices involved include the unit-hypercube, a probability space, and a Boolean algebra. The potential of the FL-framework in computing is also delineated.

Fuzzy Logic↗
PubMed1998

A fast neural-network algorithm for VLSI cell placement.

Cell placement is an important phase of current VLSI circuit design styles such as standard cell, gate array, and Field Programmable Gate Array (FPGA). Although nondeterministic algorithms such as Simulated Annealing (SA) were successful in solving this problem, they are known to be slow. In this paper, a neural network algorithm is proposed that produces solutions as good as SA in substantially less time. This algorithm is based on Mean Field Annealing (MFA) technique, which was successfully applied to various combinatorial optimization problems. A MFA formulation for the cell placement problem is derived which can easily be applied to all VLSI design styles. To demonstrate that the proposed algorithm is applicable in practice, a detailed formulation for the FPGA design style is derived, and the layouts of several benchmark circuits are generated. The performance of the proposed cell placement algorithm is evaluated in comparison with commercial automated circuit design software Xilinx Automatic Place and Route (APR) which uses SA technique. Performance evaluation is conducted using ACM/SIGDA Design Automation benchmark circuits. Experimental results indicate that the proposed MFA algorithm produces comparable results with APR. However, MFA is almost 20 times faster than APR on the average.

Journal Article↗
PubMed2004

Can randomized trial outcomes for carotid endarterectomy be achieved in community-wide practice?

The benefit of carotid endarterectomy (CEA) is dependent upon achieving procedural outcomes comparable to those observed in randomized trials. We have extensively examined outcomes of the procedure in the community with a complete medical record (hospital chart) review of over 20,000 Medicare patients undergoing CEA in 10 states. In patients with comparable indications, overall risk of stroke or death of 6.9% in our Medicare studies was comparable to the 6.5% combined event rate in the North American Symptomatic Carotid Endarterectomy Trial. In asymptomatic patients, however, the overall Medicare study result of 3.8% was inferior to the benchmark perioperative combined event rate of 1.5% achieved in the Asymptomatic Carotid Atherosclerosis Study. Our data demonstrated that the randomized trial benchmarks could be achieved or even exceeded at a statewide level. Our studies also documented that evidence-based processes that can reduce perioperative stroke and death (eg, perioperative antiplatelet therapy, patching) are underutilized in the community. Overall process and outcomes assessment show considerable room for improvement. All surgeons performing CEA should use a system-based approach to ensure that all evidence-based processes are employed for patients undergoing CEA and should use indication stratification to document their own outcomes for the procedure.

Aged↗
PubMed1999

A systematic comparison of protein structure classifications: SCOP, CATH and FSSP.

BACKGROUND: Several methods of structural classification have been developed to introduce some order to the large amount of data present in the Protein Data Bank. Such methods facilitate structural comparisons and provide a greater understanding of structure and function. The most widely used and comprehensive databases are SCOP, CATH and FSSP, which represent three unique methods of classifying protein structures: purely manual, a combination of manual and automated, and purely automated, respectively. In order to develop reliable template libraries and benchmarks for protein-fold recognition, a systematic comparison of these databases has been carried out to determine their overall agreement in classifying protein structures. RESULTS: Approximately two-thirds of the protein chains in each database are common to all three databases. Despite employing different methods, and basing their systems on different rules of protein structure and taxonomy, SCOP, CATH and FSSP agree on the majority of their classifications. Discrepancies and inconsistencies are accounted for by a small number of explanations. Other interesting features have been identified, and various differences between manual and automatic classification methods are presented. CONCLUSIONS: Using these databases requires an understanding of the rules upon which they are based; each method offers certain advantages depending on the biological requirements and knowledge of the user. The degree of discrepancy between the systems also has an impact on reliability of prediction methods that employ these schemes as benchmarks. To generate accurate fold templates for threading, we extract information from a consensus database, encompassing agreements between SCOP, CATH and FSSP.

Databases, Factual↗
PubMed2001

Single centre, single domain validation of the EuroSCORE on a consecutive sample of primary and repeat CABG.

OBJECTIVES: Intra- and interdepartmental benchmarking require scoring systems with excellent performance on several properties: discrimination (resolution), reliability (calibration) and stability over the complete spectrum of peri-procedural risk. This single centre, single domain study validates the European system for cardiac operative risk evaluation (EuroSCORE) on an independent sample of primary and repeat coronary artery bypass grafting (CABG) patients and will evaluate these different properties. METHODS: The study population is a consecutive series of 2051 isolated primary and repeat CABG patients, inclusive of patients in cardiogenic shock or resuscitation, operated on in a single institution from January 1997 to July 2000. The age of the patients was 66+/-9 years, 77% were males and 7% were repeat procedures. The EuroSCORE was 5.0+/-3%, with a range from 0 to 22. The studied event was in-hospital death, defined as mortality during hospital stay, which was unlimited in time and included a stay in a secondary hospital without discharge home. RESULTS: The EuroSCORE predicted 102 deaths versus 81 deaths observed (P=0.14, Fisher exact test). The EuroSCORE described only 20% of the variance of in-hospital mortality. The EuroSCORE created an area under the receiver operating characteristic curve of 0.83+/-0.03. The highest discriminative accuracy was obtained with 8% EuroSCORE risk (only 64% sensitivity and 87% specificity). Further exploration identified an over score in the EuroSCORE range 0-8 (57%, P<0.0001). There was an equal score (-2%, P=1) in the range 9-11, but an under score in the range 12-22 (-133%, P=0.003). CONCLUSIONS: On the condition that these single centre results could be extended to any European cardiac surgery centre, it can be concluded that the overall acceptable performance of the EuroSCORE is the result of an over score in the lower risk and insufficient correction in the higher risk spectrum. The EuroSCORE is probably refined enough for improved informed consent versus aggregated results but should only be used for inter-institutional benchmarking with great caution, preferably below the 12% risk pivot.

Aged↗
PubMed1995

A regional collaborative effort for CQI in cardiovascular disease. Northern New England Cardiovascular Study Group.

BACKGROUND: The Northern New England Cardiovascular Disease Study Group has met at least three times a year since 1987 to improve the care of patients with cardiovascular disease. ADVANTAGES OF GROUP EFFORT: The group's collaborative nature has allowed members to have explicit discussions about medical decision making and practice and to benchmark with one another. By collaborating, members have been able to accumulate a large enough experience to examine the fine structure of adverse events, learn from them, and institute meaningful changes. IMPROVEMENT STRATEGIES: Focusing on coronary artery bypass grafting (CABG) procedures, the group has used three improvement strategies: (1) Outcomes are monitored across institutions. All members receive reports with information on their experience, their organization's experience, and the regional experience. (2) All members received training in quality improvement tools and techniques. (3) Members conduct comparative process analysis and benchmarking efforts to learn best practices for CABG surgery. RESULTS: The average in-hospital mortality associated with CABG surgery in the region has decreased. The group determined that low output failure is the most common cause of post-CABG death across all hospitals, while other causes of death (for example, stroke, bleeding, arrhythmias) have more uneven distributions across hospitals. Individual hospitals have investigated their more unique causes of death; the group as a whole has undertaken a detailed study of more than 400 deaths to determine why patients die of low output failure and what can be done about it. KEYS TO SUCCESS: Factors contributing to the group's success include the fact that a regionally recognized clinician spearheaded the effort, and a physician "carries the banner" at each institution; data, which are kept confidential, are analyzed and returned in a timely fashion so group members can examine their current, not just their past, practice; and there is an organized forum for data discussion.

Coronary Artery Bypass↗
PubMedDate not supplied

Efficiency of new fungal cellulase systems in boosting enzymatic degradation of barley straw lignocellulose.

This study examined the cellulytic effects on steam-pretreated barley straw of cellulose-degrading enzyme systems from the five thermophilic fungi Chaetomium thermophilum, Thielavia terrestris, Thermoascus aurantiacus, Corynascus thermophilus, and Myceliophthora thermophila and from the mesophile Penicillum funiculosum. The catalytic glucose release was compared after treatments with each of the crude enzyme systems when added to a benchmark blend of a commercial cellulase product, Celluclast, derived from Trichoderma reesei and a beta-glucosidase, Novozym 188, from Aspergillus niger. The enzymatic treatments were evaluated in an experimental design template comprising a span of pH (3.5-6.5) and temperature (35-65 degrees C) reaction combinations. The addition to Celluclast + Novozym 188 of low dosages of the crude enzyme systems, corresponding to 10 wt % of the total enzyme protein load, increased the catalytic glucose yields significantly as compared to those obtained with the benchmark Celluclast + Novozyme 188 blend. A comparison of glucose yields obtained on steam-pretreated barley straw and microcrystalline cellulose, Avicel, indicated that the yield improvements were mainly due to the presence of highly active endoglucanase activity/activities in the experimental enzyme preparations. The data demonstrated the feasibility of boosting the widely studied T. reeseicellulase enzyme system with additional enzymatic activity to achieve faster lignocellulose degradation. We conclude that this supplementation strategy appears feasible as a first step in identifying truly promising fungal enzyme sources for fast development of improved, commercially viable, enzyme preparations for lignocellulose degradation.

Ascomycota↗
PubMedDate not supplied

Nonlinear prediction of quantitative structure-activity relationships.

Predicting the log of the partition coefficient P is a long-standing benchmark problem in Quantitative Structure-Activity Relationships (QSAR). In this paper we show that a relatively simple molecular representation (using 14 variables) can be combined with leading edge machine learning algorithms to predict logP on new compounds more accurately than existing benchmark algorithms which use complex molecular representations.

Journal Article↗
PubMedDate not supplied

Improved CoMFA modeling by optimization of settings.

The possibility of improving the predictive ability of comparative molecular field analysis (CoMFA) by settings optimization has been evaluated to show that CoMFA predictive ability can be improved. Ten different CoMFA settings are evaluated, producing a total of 6120 models. This method has been applied to nine different data sets, including the widely used benchmark steroid data set, as well as eight other data sets proposed as QSAR benchmarking data sets by Sutherland et al. (J. Med. Chem. 2004, 47, 5541-5554). All data sets have been studied using training and test sets to allow for both internal (q(2)) and external (r(2)(pred)) predictive ability assessment. CoMFA settings optimization was successful in developing models with improved q(2) and r(2)(pred) as compared to default CoMFA modeling. Optimized CoMFA is compared with comparative molecular similarity indices analysis (CoMSIA) and holographic quantitative structure-activity relationship (HQSAR) models and found to consistently produce models with improved or equivalent q(2) and r(2)(pred). The ability of settings optimization to improve model predictive ability has been validated using both internal and external predictions, and the risk of chance correlation has been evaluated using response variable randomization tests.

Journal Article↗
PubMedDate not supplied

Data visualization during the early stages of drug discovery.

Multidimensional compound optimization is a new paradigm in the drug discovery process, yielding efficiencies during early stages and reducing attrition in the later stages of drug development. The success of this strategy relies heavily on understanding this multidimensional data and extracting useful information from it. This paper demonstrates how principled visualization algorithms can be used to understand and explore a large data set created in the early stages of drug discovery. The experiments presented are performed on a real-world data set comprising biological activity data and some whole-molecular physicochemical properties. Data visualization is a popular way of presenting complex data in a simpler form. We have applied powerful principled visualization methods, such as generative topographic mapping (GTM) and hierarchical GTM (HGTM), to help the domain experts (screening scientists, chemists, biologists, etc.) understand and draw meaningful decisions. We also benchmark these principled methods against relatively better known visualization approaches, principal component analysis (PCA), Sammon's mapping, and self-organizing maps (SOMs), to demonstrate their enhanced power to help the user visualize the large multidimensional data sets one has to deal with during the early stages of the drug discovery process. The results reported clearly show that the GTM and HGTM algorithms allow the user to cluster active compounds for different targets and understand them better than the benchmarks. An interactive software tool supporting these visualization algorithms was provided to the domain experts. The tool facilitates the domain experts by exploration of the projection obtained from the visualization algorithms providing facilities such as parallel coordinate plots, magnification factors, directional curvatures, and integration with industry standard software.

Drug Design↗
PubMed2004

Measures of overall persistence and the temporal remote state.

The overall persistence, Pov, has been suggested as an indicator that integrates single media half-lives and phase partitioning. However, the application of this indicator is hindered by the fact that there are different definitions of Pov and that the most common measure of Pov, the residence time at steady state, depends heavily on the release pattern. Here, different measures are compared that can be used to compute Pov from the mass of a chemical in the environment as a function of time in a dynamic multimedia model. These measures include the equivalence width, which corresponds to the residence time at steady state, the mean value of the function of mass vs time ("mean time"), and the clearance time. The temporal remote state is defined as the state of the model system long after the stop of emissions; it is independent of the release pattern of a chemical. The mean time in the temporal remote state reflects the long-term removal rate of a chemical and is used as a persistence benchmark. Correlations of the three measures of Pov to the persistence benchmark are analyzed. The maximum equivalence width, which is obtained with release to one of the media air, water, or soil, is a good approximation of the mean time in the temporal remote state. Because the maximum equivalence width is identical to the maximum residence time at steady state, the mean time in the temporal remote state can be estimated with existing steady-state models.

Environmental Monitoring↗
PubMed2006

Deriving site-specific 2,2-bis(chlorophenyl)-1,1-dichloroethylene quality criteria of water and sediment for protection of common tern populations in Bohai Bay, North China.

In this paper we first present a method of deriving site-specific water and sediment quality criteria of chemicals for protecting wildlife populations. The method has two steps: (1) identification of the threshold concentration in specific tissue corresponding to a population benchmark response and (2) extrapolating quality criteria on the basis of the bioaccumulation in tissue from the water or sediment (e.g., the bioaccumulation factor (BAF) and biota/ sediment accumulation factor (BSAF)). The method was applied to derive 2,2-bis(chlorophenyl)-1,1-dichloroethylene (p,p'-DDE) quality criteria of water and sediment of Bohai Bay, China, for common tern populations. The benchmark concentration in eggs of the common tern was determined to be 663 ng/g wet weight from the relationship curve between concentration (biotic burden in eggs) and the intrinsic rate of population increase (r) calculated by an age-structured matrix approach. The p,p'-DDE concentrations (mean 58.79 and ranging from 13.14 to 326.60 ng/g wet weight) measured in common tern eggs (n = 35), collected from the Beidagang wetland on the coast of Bohai Bay in China, and those in surface water or sediment from literature values were combined to estimate the probability distribution of BAF and BSAF using the Monte Carlo method. Finally, the marine water and sediment quality criteria of p,p'-DDE in Bohai Bay were estimated to be 4 ng/L and 1.9 ng/g dry weight, respectively.

Animals↗
PubMed2005

Potentiometric, electronic structural, and ground- and excited-state optical properties of conjugated bis[(porphinato)zinc(II)] compounds featuring proquinoidal spacer units.

We report the synthesis, optical, electrochemical, electronic structural, and transient optical properties of conjugated (porphinato)zinc(II)-spacer-(porphinato)zinc(II) (PZn-Sp-PZn) complexes that possess intervening conjugated Sp structures having varying degrees of proquinoidal character. These supermolecular PZn-Sp-PZn compounds feature Sp moieties {(4,7-diethynylbenzo[c][1,2,5]thiadiazole (E-BTD-E), 6,13-diethynylpentacene (E-PC-E), 4,9-diethynyl-6,7-dimethyl[1,2,5]thiadiazolo[3,4-g]quinoxaline (E-TDQ-E), and 4,8-diethynylbenzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole) (E-BBTD-E)} that regulate frontier orbital energy levels and progressively increase the extent of the quinoidal resonance contribution to the ground and electronically excited states, augmenting the magnitude of electronic communication between terminal (5,-10,20-di(aryl)porphinato)zinc(II) units, relative to that evinced for a bis[(5,5',-10,20-di(aryl)porphinato)zinc(II)]butadiyne benchmark (PZnE-EPZn). Electronic absorption spectra show significant red-shifts of the respective PZn-Sp-PZn x-polarized Q state (S0 --> S1) transition manifold maxima (240-4810 cm(-1)) relative to that observed for PZnE-EPZn. Likewise, the potentiometrically determined PZn-Sp-PZn HOMO-LUMO gaps (E1/2(0/+) - E1/2(-/0)) display correspondingly diminished energy separations that range from 1.88 to 1.11 eV relative to that determined for PZnE-EPZn (2.01 eV). Electronic structure calculations provide insight into the origin of the observed PZn-Sp-PZn electronic and optical properties. Pump-probe transient spectral data for these PZn-Sp-PZn supermolecules demonstrate that the S1 --> S(n) transition manifolds of these species span an unusually broad spectral domain of the NIR. Notably, the absorption maxima of these S1 --> S(n) manifolds can be tuned over a 1000-1600 nm spectral region, giving rise to intense excited-state transitions approximately 4000 cm(-1) lower in energy than that observed for the analogous excited-state absorption maximum of the PZnE-EPZn benchmark; these data highlight the unusually large quinoidal resonance contribution to the low-lying electronically excited singlet states of these PZn-Sp-PZn species. The fact that the length scales of the PZn-Sp-PZn species (approximately 25 angstrom) are small with respect to those of classic conducting polymers, yet possess NIR S1 --> S(n) manifold absorptions lower in energy, underscore the unusual electrooptic properties of these conjugated structures.

Electrochemistry↗
PubMed1994

Evaluation of a vitamin-cloaking strategy for oligopeptide therapeutics: biotinylated HIV-1 protease inhibitors.

The outstanding limitations to the oligopeptide as a therapeutic agent are poor oral availability and rapid biliary clearance. To address these concerns a series of eight peptidic HIV-1 protease inhibitors containing the structural segment of the vitamin biotin have been prepared. These have been evaluated with regard to the hypothesis that this vitamin would cloak the peptidic character of these oligopeptides, and thus impart to these inhibitors the potential for absorption and distribution via biotin transporters and receptors. By iterative optimization about a -Cha psi[CH-(OH)CH(OH)]Val- core inhibitory insert, three particularly potent inhibitors (K(i) < or = 10 nM) of the HIV-1 protease were obtained. Although excellent cell culture antiviral activity is observed for other peptidic protease inhibitors of comparable affinity, none in this series exhibited satisfactory antiviral activity. This failure is attributed to the incompatibility of the hydrophilic and hydrogen-bonding biotin segment, with the facile membrane permeability and intracellular access presumably required for antiviral activity. The ability of the biotin to cloak the peptide, and thus render the overall appearance of the conjugate as that of a vitamin, was evaluated. Four of this series were evaluated for recognition by the Caco-2 cell intestinal biotin transporter. None inhibited competitively biotin uptake, indicating a lack of recognition. A vitamin may bind to a specific protein carrier, and thus attain an improved serum profile (by resistance to biliary clearance) and advantageous delivery to cells. Therefore, the serum concentrations of three were evaluated following an iv bolus in a rat model for serum clearance. One of the three protease inhibitors (L-idonamide, 6-cyclohexyl-2,5,6-trideoxy-2-(1-methylethyl)-5-[[3-methyl-1-oxo-2-[[5- (hexahydro-2-oxo-1H-thieno[3,4-d]imidazol-4-yl)-1- oxopentyl]amino]butyl]amino]-N-[2-methyl-1-[[(2- pyridinylmethyl)amino]carbonyl]butyl]-, [3aS-[3a alpha, 4 beta (1R*,2R*,3R*),6 alpha]]-) sustained a more than 5-fold increase in serum concentration at all time points relative to the benchmark structure. The remaining two had serum concentrations at least equal to the benchmark, suggestive of improved resistance to clearance. One (L-idonamide,6-cyclohexyl-2,5,6-trideoxy-5-[[2-[[5-(hexahydro-2-ox o-1H- thieno-[3,4-d]imidazol-4-yl)pentyl]thio]benzoyl]amino]-2-(1- methylethyl)-N-[2-methyl-1-[[(2-pyridinyl- methyl)amino]carbonyl]butyl]-, [3aS-[3a alpha, 4 beta(1R*,2R*),6a alpha]]-) was prepared as a complex with the biotin-binding protein avidin. Avidin may resemble an endogenous serum biotin carrier protein.(ABSTRACT TRUNCATED AT 400 WORDS)

Animals↗
PubMed2005

Test of a chemical timing method for measuring absolute vibrational relaxation rate constants for S1 p-difluorobenzene.

A chemical timing (CT) method for measuring absolute rate constants for collisional vibrational relaxation has been tested for the 5(1) state of S(1) p-difluorobenzene (pDFB) where an alternative method exists to provide benchmark values. The CT method was originally developed to treat vibrational energy transfer (VET) in large molecules excited to high vibrational levels where the intramolecular vibrational redistribution (IVR) resulting from large vibrational state densities completely eliminates vibrational structure in the emission spectrum. Here we apply the same method to a low-lying state (5(1) with epsilon(vib) = 818 cm(-1)) located in the low-density region of the vibrational manifold where IVR plays no role. For high vibrational levels, the chemical timing method involves addition of high O(2) pressures (kTorr) to a low-pressure pDFB sample, introducing vibrational structure in the fluorescence spectrum. Response of this spectrum to vibrational relaxation by Ar is then examined. For levels such as 5(1), the fully structured fluorescence spectrum allows the rate constant for single-collision VET into the surrounding vibrational field to be measured directly without the presence of O(2). The measurements of 5(1) VET have been repeated with various O(2) pressures (kTorr) for comparison with the O(2)-free benchmark. In the presence of O(2), the rate constant for VET by Ar is (4.0 +/- 0.5) x 10(6) Torr(-1) s(-1) and independent of high O(2) pressure variations. The rate constant as found by the standard O(2)-free method is (3.6 +/- 0.4) x 10(6) Torr(-1) s(-1). This comparison suggests that the chemical timing method is capable of providing a reasonably accurate measure of the VET rate constant for high vibrational levels provided that details of the kinetics are known.

Journal Article↗
PubMed2006

Cluster model for the ionic product of water: accuracy and limitations of common density functional methods.

In the present study, the performance of six popular density functionals (B3LYP, PBE0, BLYP, BP86, PBE, and SVWN) for the description of the autoionization process in the water octamer was studied. As a benchmark, MP2 energies with complete basis sets limit extrapolation and CCSD(T) correction were used. At this level, the autoionized structure lies 28.5 kcal.mol(-1) above the neutral water octamer. Accounting for zero-point energy lowers this value by 3.0 kcal.mol(-1). The transition state of the proton transfer reaction, lying only 0.7 kcal.mol(-1) above the energy of the ionized system, was identified at the MP2/aug-cc-pVDZ level of theory. Different density functionals describe the reactant and product with varying accuracy, while they all fail to characterize the transition state. We find improved results with hybrid functionals compared to the gradient-corrected ones. In particular, B3LYP describes the reaction energetics within 2.5 kcal.mol(-1) of the benchmark value. Therefore, this functional is suggested to be preferably used both for Carr-Parinello molecular dynamics and for quantum mechanics/molecular mechanics (QM/MM) simulations of autoionization of water.

Journal Article↗
PubMed2006

PdnCO (n = 1,2): accurate Ab initio bond energies, geometries, and dipole moments and the applicability of density functional theory for fuel cell modeling.

Electrode poisoning by CO is a major concern in fuel cells. As interest in applying computational methods to electrochemistry is increasing, it is important to understand the levels of theory required for reliable treatments of metal-CO interactions. In this paper we justify the use of relativistic effective core potentials for the treatment of PdCO and hence, by inference, for metal-CO interactions where the predominant bonding mechanism is charge transfer. We also sort out key issues involving basis sets and we recommend that bond energies of 17.2, 43.3, and 69.4 kcal/mol be used as the benchmark bond energy for dissociation of Pd2 into Pd atoms, PdCO into Pd and CO, and Pd2CO into Pd2 and CO, respectively. We calculated the dipole moments of PdCO and Pd2CO, and we recommend benchmark values of 2.49 and 2.81 D, respectively. Furthermore, we tested 27 density functionals for this system and found that only hybrid density functionals can qualitatively and quantitatively predict the nature of the sigma-donation/pi-back-donation mechanism that is associated with the Pd-CO and Pd2-CO bonds. The most accurate density functionals for the systems tested in this paper are O3LYP, OLYP, PW6B95, and PBEh.

Journal Article↗
PubMed2006

Lattice Boltzmann simulations of droplet formation in a T-shaped microchannel.

We investigated the formation of a droplet from a single pore in a glass chip, which is a model system for droplet formation in membrane emulsification. Droplet formation was simulated with the lattice Boltzmann method, a method suitable for modeling on the mesoscale. We validated the lattice Boltzmann code with several benchmarks such as the flow profile in a rectangular channel, droplet deformation between two shearing plates, and a sessile drop on a plate with different wetting conditions. In all cases, the modeling results were in good agreement with the benchmark. A comparison of experimental droplet formation in a microchannel glass chip showed good quantitative agreement with the modeling results. With this code, droplet formation simulations with various interfacial tensions and various flow rates were performed. All resulting droplet sizes could be correlated quantitatively with the capillary number and the fluxes in the system.

Journal Article↗

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