Artificial intelligence-based analysis of the spatial distribution of abnormal computed tomography patterns in SARS-CoV-2 pneumonia: association with disease severity.

BACKGROUND: The substantial heterogeneity of clinical presentations in patients with severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pneumonia still requires robust chest computed tomography analysis to identify high-risk patients. While extension of ground-glass opacity and consolidation from peripheral to central lung fields on chest computed tomography (CT) might be associated with severely ill conditions, quantification of the central-peripheral distribution of ground glass opacity and consolidation in assessments of SARS-CoV-2 pneumonia remains unestablished. This study aimed to examine whether the central-peripheral distributions of ground glass opacity and consolidation were associated with severe outcomes in patients with SARS-CoV-2 pneumonia independent of the whole-lung extents of these abnormal shadows. METHODS: This multicenter retrospective cohort included hospitalized patients with SARS-CoV-2 pneumonia between January 2020 and August 2021. An artificial intelligence-based image analysis technology was used to segment abnormal shadows, including ground glass opacity and consolidation. The area ratio of ground glass opacity and consolidation to the whole lung (GGO%, CON%) and the ratio of ground glass opacity and consolidation areas in the central lungs to those in the peripheral lungs (GGO(C/P)) and (CON(C/P)) were automatically calculated. Severe outcome was defined as in-hospital death or requirement for endotracheal intubation. RESULTS: Of 512 enrolled patients, the severe outcome was observed in 77 patients. GGO% and CON% were higher in patients with severe outcomes than in those without. Multivariable logistic models showed that GGO(C/P), but not CON(C/P), was associated with the severe outcome independent of age, sex, comorbidities, GGO%, and CON%. CONCLUSION: In addition to GGO% and CON% in the whole lung, the higher the ratio of ground glass opacity in the central regions to that in the peripheral regions was, the more severe the outcomes in patients with SARS-CoV-2 pneumonia were. The proposed method might be useful to reproducibly quantify the extension of ground glass opacity from peripheral to central lungs and to estimate prognosis.

Hydroxypyridinate-bridged paddlewheel-type dirhodium complex as a catalyst for photochemical and electrochemical hydrogen evolution.

Electrochemical and photochemical hydrogen (H2) evolution activities of a 6-fluoro-2-hydroxypyridinate (fhp-)-bridged paddlewheel-type dirhodium (Rh2) complex, [Rh2(fhp)4], were investigated through experimental and theoretical approaches. In DMF, the [Rh2(fhp)4] underwent a one-electron reduction (assigned to Rh24+/3+) at -1.31 V vs SCE in the cathodic region. Adding trifluoroacetic acid as a proton source to the electrochemical cell containing [Rh2(fhp)4], the significant catalytic current, i.e., electrochemical H2 evolution, was observed; the turnover frequency and overpotential of electrochemical H2 evolution were 18 244 s-1 and 732 mV, respectively. The reaction mechanism of electrochemical H2 evolution catalyzed by [Rh2(fhp)4] in DMF was examined in detail by theoretically predicting the redox potentials and pKa values of the reaction intermediates using density functional theory calculations. The calculations revealed that (i) the formation of a one-electron reduced species, [Rh2(fhp)4]-, triggered for H2 evolution and (ii) the protonation and reduction processes of [Rh2(fhp)4]- to further reduced hydride intermediates proceeded directly via a concerted proton-electron transfer mechanism. Moreover, [Rh2(fhp)4] was shown to be a highly efficient H2 evolution catalyst (HEC) for photochemical proton reduction reactions when combined with an artificial photosynthetic (AP) system containing [Ir(ppy)2(dtbbpy)]PF6 and triethylamine, which served as a photosensitizer and a sacrificial electron donor, respectively. Under visible light irradiation, the total amount of H2 evolved and its turnover number (per Rh ion) were 1361.0 µmol and 13 610, respectively, which are superior to those of previously reported AP systems with rhodium complexes as HEC.

A cross-sectional study to assess variability in knee frontal plane movement during single leg squat in patients with anterior cruciate ligament injury.

BACKGROUND: Single leg squat (SLS) tests help predict anterior cruciate ligament injuries. However, the variability in joint movement during this test has not been fully investigated. The aim of this study was to examine the knee frontal plane movement variability during SLS in patients with anterior cruciate ligament (ACL) injury. METHODS: In this cross-sectional study, we enrolled 56 patients with ACL injury (28 males; 28 females) and 46 healthy subjects (23 males; 23 females). All participants underwent SLS tests. All kinematic variables were joint angle of trunk, pelvis and lower limb, center of gravity (COG), center of pressure (COP). These data were obtained at the frontal plane and the coefficient of variation (CV) were calculated. Multiple comparisons were performed between healthy subjects and the injured leg and uninjured leg of patients with ACL injury. The correlation of the CV in knee varus/valgus range of motion (ROM) with the CV in other kinematic variables were investigated in patients with ACL injury. RESULTS: Compared with healthy subjects, patients with ACL injury exhibited significantly larger the CV in knee varus/valgus ROM. A positive correlation was observed between the CV in knee varus/valgus ROM and the CV in pelvic lateral inclination ROM in patients with ACL injury. CONCLUSIONS: Knee frontal plane movement variability during SLS may help evaluate the risk of ACL injury/re-injury. In addition, pelvic lateral inclination variability during SLS may need to be evaluated in conjunction with knee frontal plane movement variability.

Lower limb kinematics of single-leg squat performance in patients with anterior cruciate ligament deficiency.

[Purpose] This study investigated the parameters that characterize the knee, hip, and pelvic kinematics during a single-leg squat in preoperative anterior cruciate ligament rupture injury. [Participants and Methods] Overall, 15 patients with unilateral anterior cruciate ligament deficiency were enrolled in this study. For each single-leg squat, data from two-dimensional video cameras and three-dimensional motion analysis were collected. Measurement indices included the articular angles of the knee, hip, and trunk. The anterior cruciate ligament-injured leg was compared with the uninjured leg. [Results] The maximum knee valgus and flexion angles during a single-leg squat were smaller in the injured leg than in the uninjured leg. During the single-leg squat, the effect of "compensatory mechanisms" appeared as knee valgus and flexion movements. In particular, the knee valgus angle decreased in the anterior cruciate ligament-injured leg compared to that in the uninjured leg. [Conclusion] This phenomenon suggests that it is possible to utilize recurrence prevention training for anterior cruciate ligament injury.

Redox-triggered reversible modulation of intense near-infrared and visible absorption using a paddlewheel-type diruthenium(III) complex.

A new paddlewheel-type diruthenium complex with 2-amino-3-(trifluoromethyl)pyridine (amtfmp) [Ru2(amtfmp)4Cl2] ([1]), which shows intense and characteristic near-infrared (NIR) and visible absorption, has been developed and structurally characterized by single crystal X-ray diffraction (SCXRD) analyses. This complex exhibits reversible and dramatic NIR and visible electrochromic behavior from deep-blue ([1]) to pink ([1]-) due to the ON-OFF switching of its characteristic ligand-to-metal charge transfer (LMCT) and d-d absorption bands in response to an external voltage or chemical reagent such as decamethylcobaltocene (CoCp*2). The one-electron reduced species of [1], i.e., [CoCp*2][1], was successfully isolated and fully characterized via SCXRD, the temperature dependence of the magnetic susceptibility, and mass spectroscopy, proving that this electrochromic behavior occurs without significant structural reorganization of [1].

Joint movement variability during landing in patients with anterior cruciate ligament reconstruction.

BACKGROUND: Rapid knee valgus and knee internal rotation motions in the initial phase of landing are the known mechanisms for anterior cruciate ligament injury, and many studies have been investigated on knee joint peak angle during landing. However, the variability in joint movement during landing has not been fully investigated. This study aimed to compare the coefficient of variation of lower extremity range of motion in patients with anterior cruciate ligament reconstruction and healthy subjects during landing. METHODS: In this cross-sectional study, 54 patients with anterior cruciate ligament reconstruction and 44 healthy subjects were enrolled. All participants underwent six trials of single-leg hop landing for maximum safe horizontal distance. The kinematic variables were the coefficient of variation during two discrete (0.05 after initial contact and maximum knee flexion) time points for selected three-dimensional hip and knee joint range of motion. Comparisons were performed between the two groups. RESULTS: Compared with healthy subjects, patients with anterior cruciate ligament reconstruction had greater the coefficient of variation in hip internal/external rotation range of motion (patients with anterior cruciate ligament reconstruction had 41.9%, healthy subjects had 25.5%; P=0.0018; effect size: 0.32) and knee internal/external rotation range of motion (patients with anterior cruciate ligament reconstruction had 68.4%; healthy subjects had 48.1%; P=0.0014; effect size: 0.32) for periods that spanned 0.05 s from the initial contact. CONCLUSIONS: Patients with anterior cruciate ligament reconstruction could be disadvantageous in ability to control and adapt hip and knee joint rotations when controlling landings.

Unique vapochromism of a paddlewheel-type dirhodium complex accompanied by dynamic structural and phase transitions.

The one-dimensional coordination polymer [Rh2(HA)4]n (1G; HA = hexanoate) exhibits a drastic vapochromic color change from green to red upon exposure to pyridine (py) vapor. Heating the red discrete complex [Rh2(HA)4(py)2] (1R) at 338 K affords the purple discrete tetrarhodium complex [Rh2(HA)4(py)]2 (1P), which is an intermediate species in the vapochromic transformation of 1G to 1R. The obtained complexes 1G, 1R, and 1P differ not only in their color in the solid state, but also in their temperature-dependent phase transition properties.

Specific Coordination between Zr-MOF and Phosphate-Terminated DNA Coupled with Strand Displacement for the Construction of Reusable and Ultrasensitive Aptasensor.

Electrochemical aptasensors involved in chemical labeling are often single-use and sensitivity-limited because the probes are commonly single-point labeled and irreversible. In this work, the specific coordination between Zr4+ and phosphate group (-PO43-) was employed to construct a new aptasensor that is highly sensitive and reusable, using Ochratoxin A (OTA) as the test model. The OTA binding aptamer (OBA) was hybridized with the thiolated supporting sequence (TSS) immobilized on the surface of a gold electrode. The UiO-66 with a formula of [Zr6O4(OH)4(BDC)6], one of the class of Zr metal-organic frameworks (MOFs), was then particularly grafted on the terminal of OBA through the specific coordination between Zr4+ and 5'-PO43-, i.e., the Zr-O-P coordination bond. Similarly, as much as the 5'-PO43- and 3'-methylene blue dual-labeled sequences (DLS) were further assembled on UiO-66 due to the large surface area of MOF and rich active sites of Zr4+. Owing to the specific coordination for signal amplification, the developed aptasensor shows greatly enhanced sensitivity. A wide detection range from 0.1 fM to 2.0 µM and an ultralow detection limit of 0.079 fM (S/N = 3) for OTA were obtained. Additionally, the TSS can rehybridize with a new OBA to regenerate the aptasensor but without complicated pretreatments, enabling a aptasensor that is readily reusable for OTA detection. The aptasensor was successfully applied for OTA detection in the red wine samples, demonstrating a promising prospect for food safety monitoring.

Photocatalytic Hydrogen Evolution over Exfoliated Rh-Doped Titanate Nanosheets.

Various amounts of Rh-doped titanate nanosheets (Ti3NS:Rh(x), where x is doped amount) were prepared to develop a new nanostructured photocatalyst based on metal oxide compounds that can split water to produce H2 under sunlight. Ti3NS:Rh(x) was obtained by acid exchange, intercalation, and exfoliation of Rh-doped layered sodium titanate compound (Na2Ti3-x Rh x O7). A new energy gap was found in the diffuse reflection spectrum of the Ti3NS:Rh(x) colloidal suspension solution; this new energy gap corresponds to electrons in the 4d level of Rh3+ or Rh4+, which are doped in the Ti4+ site. A photocatalyst activity of Ti3NS:Rh(x) for H2 evolution in water with triethylamine (TEA) as an electron donor was investigated. The appropriate amount of Rh doping can improve the photocatalytic activity of Ti3NS for H2 evolution from water using triethylamine (TEA) as a sacrifice agent. The reason was related to the rich state of Rh3+ or Rh4+ doped in the Ti4+ site of Ti3NS. Doping Rh 1 mol % of Ti, Ti3NS:Rh(0.03) shows the H2 evolution rates up to 1040 nmol/h, which is about 25 times larger than that of nondoped Ti3NS under UV irradiation (>220 nm) and 302 nmol/h under near-UV irradiation (>340 nm). These results show that the development of new nanostructured photocatalyst based on Rh-doped titanate compounds that can produce H2 under near-UV irradiation present in sunlight was a success.

Photocatalytic and electrocatalytic hydrogen production using nickel complexes supported by hemilabile and non-innocent ligands.

Nickel complexes with non-innocent ligands generated by one-electron reduction of octahedral Schiff base nickel(ii) complexes with hemilabile ligands exhibited excellent catalytic activities of over 5000 TONs through a metal-ligand cooperation mechanism for hydrogen evolution from water under visible light irradiation.

Photooxidation Reactions of Cyclometalated Palladium(II) and Platinum(II) Complexes.

New C,N,S-cyclometalated palladium(II) and platinum(II) complexes have been synthesized and their structural, electrochemical, and photochemical properties examined. The blue color of these complexes in solution changed to yellow under visible-light irradiation. By measurement of the absorption spectra for quantifying changes in color, isosbestic points for each complex clearly indicated the presence of only two species responsible for the change of color. X-ray analysis revealed that the visible-light-induced yellow species were S-oxygenated sulfinato complexes. Photosensitized generation of singlet oxygen (1O2) was confirmed by the direct detection of singlet oxygen luminescence at 1275 nm. The present cyclometalated palladium(II) and platinum(II) complexes are efficient photosensitizers of singlet oxygen, which rapidly reacts with coordinating sulfur atoms.

Paddlewheel-type diruthenium(iii,iii) tetrakis(2-aminopyridinate) complexes with NIR absorption features: combined experimental and theoretical study.

The reactions of [Ru2(O2CCH3)4Cl] with 2-aminopyridine (Hamp) and 2-amino-4-methylpyridine (Hammp) afforded two novel Ru2 complexes, [Ru2(amp)4Cl2] (1) and [Ru2(ammp)4Cl2] (2), respectively. Single crystal X-ray diffraction analyses revealed that 1 and 2 adopted typical paddlewheel-type structures, where the Ru2 units are coordinated with four aminopyridinate ligands with a cis-2:2 arrangement at the equatorial positions and two chloride ligands at the axial positions. The stabilities of 1 and 2 were supported by unrestricted density functional theory (uDFT) calculations. The zero-point energies of the three structural isomers (trans-2:2, 3:1, and 4:0 arrangements) of 1 and 2 were less stable than those of the respective cis-2:2 arrangements. Temperature-dependences of the magnetic susceptibility measurements and uDFT calculations showed that the oxidation and spin states of the Ru2 units in 1 and 2 were commonly Ru26+ and triplet states, respectively. Cyclic voltammetry showed that 1 and 2 underwent one-electron reduction processes, i.e., 1/1- and 2/2-, at redox potentials (E1/2) of -0.08 and -0.18 V vs. SCE, respectively. These results agreed well with the DFT-calculated E1/2 values of 1 (-0.08 V vs. SCE) and 2 (-0.18 V vs. SCE) and were theoretically attributed to Ru2-centred (δ*(Ru2)) redoxes. Moreover, 1 and 2 showed unique near-infrared absorption bands at approximately 1200-1500 nm, which were theoretically attributed to the ligand-to-metal charge transfer (LMCT) with π(amp or ammp) →δ*(Ru2) transition characteristics.

Intrinsic hydrogen evolution capability and a theoretically supported reaction mechanism of a paddlewheel-type dirhodium complex.

The intrinsic capability of the paddlewheel-type dirhodium tetraacetate complex, [Rh2(O2CCH3)4(H2O)2] ([1(H2O)2]), as a hydrogen evolution catalyst (HEC) for photochemical hydrogen evolution from aqueous solution was illustrated. This was achieved by using an optimized artificial photosynthesis (AP) system with a cyclometalated iridium complex [Ir(ppy)2(bpy)](PF6) ([Ir-PS-1]) and triethylamine (TEA) serving as a photosensitizer (PS) and a sacrificial donor, respectively. The total amount of hydrogen evolution and the turnover number (TON) of catalysis using this AP system were 385.7 µmol and 3857 (per Rh ion), respectively; these values are higher than those of [Rh(dtBubpy)3](PF6)3, which is the most efficient HEC among the mononuclear rhodium complexes, and RhCl3. Moreover, the catalytic performance of [1(H2O)2] was further accelerated by using [Ir(ppy)2(dtBubpy)](PF6) [Ir-PS-3] as a PS; 9886 TON (H2 per Rh ion) was verified after 12 h of irradiation. In addition, the detailed mechanism of hydrogen evolution catalyzed by [1(H2O)2] was clarified by combining electro- and photochemical analyses and DFT calculations. The optimized geometries of [1(H2O)2], [1], hydride intermediates [H-Rh2(O2CCH3)4] ([H-1]), and their reduced species were theoretically verified by DFT calculations. Moreover, their redox potentials were theoretically estimated and compared with the observed potentials. Their combination analyses indicated that (i) the formation of [1], which has an open-metal site for hydrogen evolution and can be reduced by the one-electron reduced species of [Ir-PS-1], is a trigger for hydrogen evolution; (ii) [H-1] and its reduced species, which are verified by CV analyses, are key intermediate species in this reaction; and (iii) photochemical hydrogen evolution catalyzed by [1(H2O)2] occurred by two-electron reduction processes.

Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II) Tetra-µ-(n-naphthoate) Complexes: An Experimental and Theoretical Study.

The reactions of [Rh2(O2CCH3)4(OH2)2] with n-naphthalenecarboxylic acids (n = 1: 1-HNC, n = 2: 2-HNC) afford the dirhodium tetra-µ-(n-naphthoate) complexes [Rh2(1-NC)4] (1) and [Rh2(2-NC)4] (2), respectively. Single crystal X-ray diffraction analyses of [1(OCMe2)2] and [2(OCMe2)2], which were obtained by recrystallization from acetone (OCMe2) solutions of 1 and 2, reveal that the dirhodium cores are coordinated by four equatorially bridging naphthoate ligands and two axial OCMe2 ligands. Density functional theory (DFT) calculation confirmed that (i) the single Rh⁻Rh bond is formed between the two Rh ions and (ii) the electronic structures between two Rh ions in [1(OCMe2)2] and [2(OCMe2)2] are best described as π4δ²σ²Î´*²π*4 and δ²π4σ²Î´*²π*4, respectively. Time-dependent DFT (TDDFT) calculations clarify the absorption band characters of [1(OCMe2)2] and [2(OCMe2)2]; the former shows the bands due to d⁻d and metal⁻to⁻metal-ligand charge transfer (MMLCT) excitations in the visible light region, whereas the latter shows the bands due to only d⁻d excitations in the same region. The electrochemical properties and thermal stabilities of [1(OCMe2)2] and [2(OCMe2)2] were also investigated in this study.

Experimental and theoretical study of dimer-of-dimers-type tetrarhodium(ii) complexes bridged by 1,4-benzenedicarboxylate linkers.

Two dimer-of-dimers-type tetrarhodium complexes, [Rh4(piv)6(BDC)] ([1]; piv = pivalate) and [Rh4(piv)6(F4BDC)] ([2]), in which two paddlewheel-type dirhodium units are linked by 1,4-benzenedicarboxylate (BDC) and 1,4-tetrafluorobenzenedicarboxylate (F4BDC), respectively, have been synthesized and characterized via single-crystal X-ray diffraction analyses, ESI-MS, 1H NMR, infrared spectroscopy, Raman spectroscopy, and elemental analyses. Crystal structure analyses of [1(THF)4] and [2(THF)4], which are crystallized from THF solutions of [1] and [2], respectively, revealed that dihedral angles (φ) between two -CO2 units and phenyl rings of the BDC linker in [1(THF)4] are almost co-planar (φ = 2.8°), whereas those of the F4BDC linker in [2(THF)4] are largely inclined (φ = 78.3°). Density functional theory calculations clarified that (i) their dihedral angles of optimized geometries of [1(THF)4] and [2(THF)4] are almost the same as their experimental geometries, and (ii) the rotation energy barriers of phenyl moieties in [1(THF)4] and [2(THF)4] estimated by potential energy surface analyses are 12.0 and 8.4 kcal mol-1, respectively, indicating that hydrogen bondings are formed between two -CO2 units and four hydrogen atoms of phenyl rings of the BDC linker in [1(THF)4], whereas two -CO2 units and four fluorine groups on the phenyl ring of the F4BDC linker in [2(THF)4] are electrostatically and sterically repulsed. Electrochemical properties and electronic structures of [1(THF)4] and [2(THF)4] are strongly influenced by the electronic states of dicarboxylate linkers, whereas absorption spectra are strongly influenced by the dihedral angles between two -CO2 units and phenyl rings of dicarboxylate linkers.

Photo- and Electrocatalytic Hydrogen Production Using Valence Isomers of N2S2-Type Nickel Complexes.

Three Schiff-base-type nickel(II) complexes (1a-3a) and the corresponding noninnocent-type complexes (1b-3b) were synthesized, and the equilibria between these valence isomers were observed in tetrahydrofuran (THF) at room temperature. The electronic state of the noninnocent-type nickel complex was also confirmed by isolation of the one-electron-reduced species. The catalytic ability for the photogeneration of hydrogen from water was examined about 1a-3a and 1b-3b in the presence of a photosensitizer and a sacrificial electron donor. Then, a Schiff-base-type complex with chlorine atoms (2a) and a noninnocent-type complex with methyl groups (3b) on the pendant phenyl rings being present as the minor species in THF exhibited high activity of over 400 turnover numbers. The dynamic light scattering and transmission electron microscopy measurements suggested the formation of NiSx-like aggregate species under photocatalytic conditions. The electrocatalytic activities of the nickel complexes for hydrogen production were also investigated, and a plausible reaction mechanism was proposed on the basis of a combined electrochemical and density functional theory study.

An unprecedented up-field shift in the 13C NMR spectrum of the carboxyl carbons of the lantern-type dinuclear complex TBA[Ru2(O2CCH3)4Cl2] (TBA+ = tetra(n-butyl)ammonium cation).

A large up-field shift (-763 ppm) has been observed for the carboxyl carbons of the dichlorido complex TBA[Ru(2)(O(2)CCH(3))(4)Cl(2)] (TBA(+) = tetra(n-butyl)ammonium cation) in the (13)C NMR spectrum (CD(2)Cl(2) at 25 °C). The DFT calculations showed spin delocalization from the paramagnetic Ru(2)(5+) core to the ligands, in agreement with the large up-field shift.

Effects of transient forebrain ischemia on the hippocampus of the Mongolian gerbil (Meriones unguiculatus): an immunohistochemical study.

In the Mongolian gerbil, bilateral common carotid artery occlusion (BCCAO) for several minutes induces ischemia and delayed neuronal cell death in the CA1 region of the hippocampus due to their incomplete Circle of Willis. In the present study, the expression of fibroblast growth factor 2 (FGF2), its receptors (FGFR1 and FGFR2), glial fibrillary acidic protein (GFAP), and isolectin B4 (ISLB4) was investigated by immunohistochemical and lectin-binding methods after BCCAO was performed for 5 min in gerbils. One day after BCCAO, the pyramidal cells of the CA1 region of the hippocampus showed degenerative changes and lowered expression of FGF2, FGFR1, and FGFR2. Three days after BCCAO, there was an increase in GFAP-positive astrocytes and ISLB4-positive microglial cells. From five to 10 days after BCCAO, intense neuronal cell death in the stria pyramidale of the hippocampal CA1 region was observed, as well as an increase in GFAP-positive astrocytes and decrease in ISLB4-positive microglial cells. These results indicate that transient forebrain ischemia induces neuronal cell death with lowered expression of FGF2 and its receptors, and that the activation of glial cells may not directly lead to neuronal cell death.

Photochemical hydrogen production from water using three-dimensional Zn-Pd metal-organic frameworks.

A Zn-Pd heterometallic metal-organic framework (MOF) based on 3,5-pyridine-dicarboxylic acid (H2-pydc), namely [Zn2(H2O)3{PdCl2(pydc)2}]n (Zn-Pd-2) was successfully synthesized by a slow diffusion method and characterized by single-crystal X-ray diffraction, CHN elemental analysis, FT-IR spectroscopy, thermogravimetric (TG) analysis and N2 gas adsorption measurement. The single-crystal X-ray analysis revealed that the framework morphology of Zn-Pd-2 is as same as that of [Zn2(DMF)3{PtCl2(pydc)2}]n. The Zn-Pd-2 was found to be an effective catalytic performance for the photochemical reduction of water in a well-known photo-system made up of [Ru(bpy)3Cl2] (bpy = 2,2'-bipyridine), MV(2+) (methyl-viologen) and Na2 EDTA (Disodium ethylenediaminetetraacetate); 20.2 turnover based on Zn-Pd-2 was achieved at 4 h irradiation.

Photochemical production of hydrogen from water using microporous porphyrin coordination lattices.

In this study, we investigated the photochemical production of hydrogen from water using bio-inspired heterogeneous microporous porphyrin coordination lattices (PCLs), [Ru2(MTCPP)BF4] (M = H2 (PCL-1), Zn (PCL-2); TCPP = Tetrakis(4-carboxyphenyl)porphyrin), under visible (380 nm <) and UV (320 nm <) light irradiations. In the presence of Na2EDTA (as a sacrificial donor) and MV2+ (methyl-vilologen; as a electron relay), PCLs exhibits photocatalytic activity for hydrogen evolution; the maximum amounts of turnover numbers (TONs) of PCL-1 and PCL-2 at 24 h irradiation were 20.8 and 29.9, respectively. In the catalytic reactions, the relation between PCLs and MV2+ was similar to the relation between a [cytochrome c3 hydrogenase] pair and lysine residues in enzymatic reactions. By using the hydrogen production rate and the MV+ (methyl-vilologen radical-cation) concentration, kinetic parameters such as affinities between MV+ and PCLs, maximum reaction rate, and total efficiency of the reaction are introduced using the Michaelis-Menten equation. These parameters indicated that PCLs are good artificial enzyme model catalysts. The stability of the PCLs after the catalytic reactions was confirmed by X-ray photoelectron spectroscopy and Fourier transform-infrared spectra. These results indicated that the frameworks of PCLs are stable for this catalytic reaction.