Capturing the spin state diversity of iron(III)-aryl porphyrins: OLYP is better than TPSSh

Conradie, Marrigje M.; Conradie, Jeanet; Ghosh, Abhik

doi:10.1016/j.jinorgbio.2010.09.010

Cited by 43 publications

(34 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A combined experimental and theoretical endeavor (e.g., CECAM workshop) is needed to bring forward such a database of complicated systems. A number of systems are already known such as, for example, the spin states of Fe II -porphyrin with an axial histidine (or models for it); [3] the structurally similar monopyridylmethylamine Fe II (amp) 2 Cl 2 and dipyridylmethylamine Fe II (dpa) 2 2þ complexes with opposite spin groundstates; [32] Fe III -aryl porphyrins with different halide substitutions and different spin states; [37] Mn-oxo corrole and corrolazine. [8] However, until these are combined into a general database of complicated spin-state systems, the field does not advance and it will be difficult to value and validate new computational methods such as Deeth's LFMM method or new density functionals, let alone to give a rigorous estimate of the viability/validity of results obtained for a particular system.…”

Section: Discussionmentioning

confidence: 99%

Spin states of (bio)inorganic systems: Successes and pitfalls

Swart

2012

Int J of Quantum Chemistry

112

127

View full text Add to dashboard Cite

The calculation of spin-state splittings of transition-metal complexes is known to be very sensitive to the level of theory and the quality of the basis set. The performance of density functionals is in general understood, with older pure functionals overstabilizing low spin states, and Hartree-Fock and hybrid functionals doing the same for the high spin states. More recent functionals (OLYP/OPBE, TPSSh, SSB-D, M06-L) seem to improve on these, but there are still some systems that prove difficult. This Perspective describes some of the recent successes and pitfalls in the description of spin states and treats both methodology and applications such as metal-oxo complexes, exchange-enhanced reactivity, spin-state catalysis, and spin-crossover compounds.

show abstract

Section: Discussionmentioning

confidence: 99%

Spin states of (bio)inorganic systems: Successes and pitfalls

Swart

2012

Int J of Quantum Chemistry

112

127

View full text Add to dashboard Cite

show abstract

“…A combined experimental and theoretical endeavor (e.g., CECAM workshop) is needed to bring forward such a database of complicated systems. A number of systems are already known such as, for example, the spin states of Fe II –porphyrin with an axial histidine (or models for it);3 the structurally similar monopyridylmethylamine Fe II (amp) 2 Cl 2 and dipyridylmethylamine Fe II (dpa) 2 2+ complexes with opposite spin ground‐states;32 Fe III –aryl porphyrins with different halide substitutions and different spin states;37 Mn‐oxo corrole and corrolazine 8. However, until these are combined into a general database of complicated spin‐state systems, the field does not advance and it will be difficult to value and validate new computational methods such as Deeth's LFMM method or new density functionals, let alone to give a rigorous estimate of the viability/validity of results obtained for a particular system.…”

Section: Discussionmentioning

confidence: 99%

Long‐term effects of chondroitins 4 and 6 sulfate on knee osteoarthritis: The study on osteoarthritis progression prevention, a two‐year, randomized, double‐blind, placebo‐controlled trial

Kahan

Uebelhart

Vathaire

et al. 2009

Arthritis & Rheumatism

242

151

View full text Add to dashboard Cite

Objective. To assess the long-term effects of chondroitins 4 and 6 sulfate (CS) on the radiographic progression of, and symptom changes associated with, knee osteoarthritis (OA).Methods. We performed an international, randomized, double-blind, placebo-controlled trial in which 622 patients with knee OA were randomly assigned to receive either 800 mg CS (n ‫؍‬ 309 patients) or placebo (n ‫؍‬ 313 patients) once daily for 2 years. Radiographs of the target knee, using the Lyon schuss view, were obtained at the time of enrollment and at 12, 18, and 24 months. The minimum joint space width (JSW) of the medial compartment of the tibiofemoral joint was assessed by digital image analysis. The primary outcome was the loss in minimum JSW over 2 years.Results. The intent-to-treat analysis demonstrated a significant reduction (P < 0.0001) in minimum JSW loss in the CS group (mean ؎ SEM ؊0.07 ؎ 0.03 mm) as compared with the placebo group (؊0.31 ؎ 0.04 mm). The percentage of patients with radiographic progression >0.25 mm was significantly reduced in the CS group compared with the placebo group (28% versus 41% [P < 0.0005]; relative risk reduction 33% [95% confidence interval 16-46%]). The number of patients needed to treat was 8 (95% confidence interval 5-17). Pain improved significantly faster in the CS group than in the placebo group (P < 0.01). There were no differences in safety between groups.Conclusion. The long-term combined structuremodifying and symptom-modifying effects of CS suggest that it could be a disease-modifying agent in patients with knee OA.

show abstract

“…[22] A second study by the latter authors added to these three systems CASPT2 results for the [Fe II (N H S 4 )L] series, [23] which indicated that OLYP performed better than PBE0 (25 % HF exchange), B3LYP, and B3LYP*, although all four DFT methods give identical trends (vide infra). Ghosh and coworker also favour OLYP, albeit they tested it on somewhat different systems including Fe III porphyrins, [24,25] as do Tewary et al [26] for the interesting case of computing magnetic exchange interactions and their possible effects on SCO, which involves "non-innocent" oxazolidine N-oxide iron nitroxide complexes.…”

Section: Introductionmentioning

confidence: 99%

Spin‐State Energetics of Fe^II Complexes – The Continuing Voyage Through the Density Functional Minefield

Houghton

Deeth

2014

Eur J Inorg Chem

View full text Add to dashboard Cite

Novel nanostructured sulfur (S)–carbide derived carbon (CDC) composites with ordered mesopores and high S content are successfully prepared for lithium sulfur batteries. The tunable pore‐size distribution and high pore volume of CDC allow for an excellent electrochemical performance of the composites at high current densities. A higher electrolyte molarity is found to enhance the capacity utilization dramatically and reduce S dissolution in S‐CDC composite cathodes during cycling.

show abstract

Capturing the spin state diversity of iron(III)-aryl porphyrins: OLYP is better than TPSSh

Cited by 43 publications

References 55 publications

Spin states of (bio)inorganic systems: Successes and pitfalls

Spin states of (bio)inorganic systems: Successes and pitfalls

Long‐term effects of chondroitins 4 and 6 sulfate on knee osteoarthritis: The study on osteoarthritis progression prevention, a two‐year, randomized, double‐blind, placebo‐controlled trial

Spin‐State Energetics of Fe^II Complexes – The Continuing Voyage Through the Density Functional Minefield

Contact Info

Product

Resources

About

Capturing the spin state diversity of iron(III)-aryl porphyrins: OLYP is better than TPSSh

Cited by 43 publications

References 55 publications

Spin states of (bio)inorganic systems: Successes and pitfalls

Spin states of (bio)inorganic systems: Successes and pitfalls

Long‐term effects of chondroitins 4 and 6 sulfate on knee osteoarthritis: The study on osteoarthritis progression prevention, a two‐year, randomized, double‐blind, placebo‐controlled trial

Spin‐State Energetics of FeII Complexes – The Continuing Voyage Through the Density Functional Minefield

Contact Info

Product

Resources

About

Spin‐State Energetics of Fe^II Complexes – The Continuing Voyage Through the Density Functional Minefield