Optimal density-functional theory method for zinc-amino acid complexes determined by analyzing structural and Fourier-transform infrared spectroscopy data.

Metal-amino acid complexes are important compounds for the human body. Their nutritional value and anticancer, antibacterial, and catalytic properties are the focus of several studies. Density functional theory (DFT) can be used to predict their properties by optimizing their structures and performing electron population analyses. However, conventional computational methods cannot adequately determine the parameters of polymeric metal-amino acid complexes. Therefore, intermolecular interactions of polymers must be considered to correctly predict the properties of metal-amino acid and related metal complexes. In this study, different DFT protocols were used to acquire the infrared spectra and determine interatomic distances of two zinc-amino acid complexes, Zn(Gly)2 and Zn(Met)2. The results were compared to spectroscopic and X-ray crystallographic data, revealing that the M06 and M06-L functionals and the 6-311++G(d,p) basis set produced the smallest computational errors. Our results provide a foundation for future theoretical studies on other metal-amino acid and metal-organic complexes.

The Effect of Ni Doping on FeOF Cathode Material for High-Performance Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have emerged as a promising alternative to lithium-ion batteries for large-scale energy storage systems due to the abundance and low price of sodium. Until recently, the low theoretical capacities of intercalation-type cathodes less than 250 mAh g-1 have limited the energy density of SIBs. On the other hand, iron oxyfluoride (FeOF) has a high theoretical capacity of ≈885 mAh g-1 as a conversion-type cathode material for SIBs. However, FeOF suffers from poor cycling stability, rate capability, and low initial Coulombic efficiency caused by its low electrical conductivity and slow ionic diffusion kinetics. To solve these problems, doping aliovalent Ni2+ on FeOF electrodes is attempted to improve the electronic conductivity without using a carbon matrix. The ionic conductivity of FeOF is also enhanced due to the formation of oxygen defects in the FeOF crystal structure. The FeOF-Ni1 electrode shows an excellent cycling performance with a reversible discharge capacity of 450.4 mAh g-1 at 100 mAh g-1 after 100 cycles with a fading rate of 0.20% per cycle. In addition, the FeOF-Ni1//hard carbon full cell exhibited a high energy density of 876.9 Wh kg-1 cathode with a good cycling stability.

Uncovering the centrality of mono-dentate SO32-/SO42- modifiers grafted on a metal vanadate in accelerating wet NOX reduction and poison pyrolysis.

NOX rarely binds with labile oxygens of catalytic solids, whose Lewis acidic (LA) species possess higher binding strengths with NH3 (ENH3) and H2O than Brönsted acidic counterparts (BA--H+; -OH), oftentimes leading to elevate energy barrier (EBARRIER) and weaken H2O tolerance, respectively. These limit NH3-assisted wet NOX reduction via Langmuir-Hinshelwood-type or Eley-Rideal (ER)-type model on LA species, while leaving ER-type analogue on BA--H+ species proper to reduce wet NOX. Given hard-to-regulate strength/amount of -OH species and occasional association between ENH3 and EBARRIER, Ni1V2O6 (Ni1) was rationally chosen as a platform to isolate mono-dentate SO32-/SO42- species for use as BA--H+ bonds via protonation to increase collision frequency (k'APP,0) alongside with disclosure of advantages of SO32-/SO42--functionalized Ni1V2O6 (Ni1-S) over Ni1 in reducing wet NOX. Ni1-S outperformed Ni1 in achieving a larger BA--H+ quantity (k'APP,0↑), increasing H2O tolerance, and elevating oxygen mobility, thus promoting NOX reduction activity/consequences under SO2-excluding gases. V2O5-WO3 composite simulating a commercial catalyst could isolate mono-dentate SO32-/SO42- species and served as a control (V2O5-WO3-S) for comparison. Ni1-S was superior to V2O5-WO3-S in evading ammonium (bi-)sulfate (AS/ABS) poison accumulation and expediting AS/ABS pyrolysis efficiency, thereby improving AS/ABS resistance under SO2-including gases, while enhancing resistance against hydro-thermal aging.

Biotransformation of d-Xylose-Rich Rice Husk Hydrolysate by a Rice Paddy Soil Bacterium, Priestia sp. Strain JY310, to Low Molecular Weight Poly(3-hydroxybutyrate).

Poly(3-hydroxybutyrate) (PHB) is a versatile thermoplastic with superior biodegradability and biocompatibility that is intracellularly accumulated by numerous bacterial and archaeal species. Priestia sp. strain JY310 that was able to efficiently biotransform reducing sugars in d-xylose-rich rice husk hydrolysate (reducing sugarRHH) to PHB was isolated from the soil of a rice paddy. Reducing sugarRHH including 12.5% d-glucose, 75.3% d-xylose, and 12.2% d-arabinose was simply prepared using thermochemical hydrolysis of 3% H2SO4-treated rice husk for 15 min at 121 °C. When cultured with 20 g/L reducing sugarRHH under optimized culture conditions in a batch bioreactor, Priestia sp. strain JY310 could produce PHB homopolymer up to 50.4% of cell dry weight (6.2 g/L). The melting temperature, heat of fusion, and thermal decomposition temperature of PHB were determined to be 167.9 °C, 92.1 J/g, and 268.1 °C, respectively. The number average and weight average molecular weights of PHB with a broad polydispersity index value (4.73) were estimated to be approximately 16.2 and 76.8 kg/mol, respectively. The findings of the present study suggest that Priestia sp. strain JY310 can be exploited as a good candidate for the low-cost production of low molecular weight PHB with improved biodegradability and reduced brittleness from inexpensive agricultural waste hydrolysates.

Deciphering Evolution Pathway of Supported NO3 • Enabled via Radical Transfer from •OH to Surface NO3 - Functionality for Oxidative Degradation of Aqueous Contaminants.

NO3 • can compete with omnipotent •OH/SO4 •- in decomposing aqueous pollutants because of its lengthy lifespan and significant tolerance to background scavengers present in H2O matrices, albeit with moderate oxidizing power. The generation of NO3 •, however, is of grand demand due to the need of NO2 •/O3, radioactive element, or NaNO3/HNO3 in the presence of highly energized electron/light. This study has pioneered a singular pathway used to radicalize surface NO3 - functionalities anchored on polymorphic α-/γ-MnO2 surfaces (α-/γ-MnO2-N), in which Lewis acidic Mn2+/3+ and NO3 - served to form •OH via H2O2 dissection and NO3 • via radical transfer from •OH to NO3 - (•OH → NO3 •), respectively. The elementary steps proposed for the •OH → NO3 • route could be energetically favorable and marginal except for two stages such as endothermic •OH desorption and exothermic •OH-mediated NO3 - radicalization, as verified by EPR spectroscopy experiments and DFT calculations. The Lewis acidic strength of the Mn2+/3+ species innate to α-MnO2-N was the smallest among those inherent to α-/ß-/γ-MnO2 and α-/γ-MnO2-N. Hence, α-MnO2-N prompted the rate-determining stage of the •OH → NO3 • route (•OH desorption) in the most efficient manner, as also evidenced by the analysis on the energy barrier required to proceed with the •OH → NO3 • route. Meanwhile, XANES and in situ DRIFT spectroscopy experiments corroborated that α-MnO2-N provided a larger concentration of surface NO3 - species with bi-dentate binding arrays than γ-MnO2-N. Hence, α-MnO2-N could outperform γ-MnO2-N in improving the collision frequency between •OH and NO3 - species and in facilitating the exothermic transition of NO3 - functionalities to surface NO3 • analogues per unit time. These were corroborated by a greater efficiency of α-MnO2-N in decomposing phenol, in addition to scavenging/filtration control runs and DFT calculations. Importantly, supported NO3 • species provided 5-7-fold greater efficiency in degrading textile wastewater than conventional •OH and supported SO4 •- analogues we discovered previously.

Conditioned secretome of adipose-derived stem cells improves dextran sulfate sodium-induced colitis in mice.

BACKGROUND: Inflammatory bowel diseases (IBD) is related to uncontrolled immune response. Currently, there is no successful treatment for significant improvement in IBD. Stem cells display their therapeutic effects through their repopulating capacity or secreting factors. AIM: To investigate the effects of conditioned mouse adipose-derived stem cells (mADSCs) secretome on colitis-induced mice. METHODS: mADSCs were isolated from adipose tissue of C57BL/6 mice. Conditioned mADSCs secrectome was obtained by culturing of mADSCs with lipopolysaccharides (LPS, 1 µg/mL) for 24 h. Acute colitis was induced by 2% dextran sulfate sodium (DSS) drinking water for 7 d and then normal drinking water for 4 d. The mice were treated with normal culture medium (NM group), conditioned mADSCs secretome (CM group) or mADSCs (SC group). The length of colon and histopatholgy of colon tissues were evaluated. The mRNA expression levels of inflammatory cytokines in colon tissue and the serum interleukin (IL)-6 levels were determined. RESULTS: The isolated mADSCs maintained the mADSCs specific gene expression profiles during experiment. The conditioned mADSCs secretome released by the treatment of mADSCs with LPS contained mainly inflammatory chemokines, colony-stimulating factors and inflammatory cytokines. The loss of body weight and reduction in colon length were ameliorated in the CM group. The conditioned mADSCs secretome reduced the histological score in colon tissue. The expression of IL-1b and IL-6 mRNAs in colon tissues significantly inhibited in the CM group compared to SC group and NM group, respectively. The elevation of serum IL-6 levels was also ameliorated in the CM group. These results indicate that the conditioned mADSCs secretome suppressed the synthesis of inflammatory cytokines in damaged colon tissue and the elevation of serum IL-6 concentration in DSS-induced mice. CONCLUSION: Conditioned mADSCs secretome might play regenerative roles by the suppression of IL-6 in serum and tissue during acute colitis, and may be more effective than stem cells themselves in the regeneration of colon tissue.

Comparative study of HSOA-/SOA2- versus H3-BPO4B- functionalities anchored on TiO2-supported antimony oxide-vanadium oxide-cerium oxide composites for low-temperature NOX activation.

TiO2-supported antimony oxide-vanadium oxide-cerium oxide (SVC) imparts Lewis acidic (L)/Brönsted acidic (B) sites, labile (Oα)/mobile oxygens (OM), and oxygen vacancies (OV) for selective catalytic NOX reduction (SCR). However, these species are harmonious occasionally, readily poisoned by H2O/sulfur/phosphorus/carbon, thus limiting SCR performance of SVC. Herein, a synthetic means is reported for immobilizing HSOA-/SOA2- (A= 3-4) or H3-BPO4B- (B= 1-3) on the L sites of SVC to form SVC-S and SVC-P. HSOA-/SOA2-/H3-BPO4B- acted as additional B sites with distinct characteristics, altered the properties of Oα/OM/OV species, thereby affecting the SCR activities and performance of SVC-S and SVC-P. SVC-P activated Langmuir-Hinshelwood-typed SCR better than SVC-S, as demonstrated by a greater Oα-directed pre-factor and smaller binding energy between Oα and NO. Meanwhile, SVC-S provided a larger B-directed pre-factor, thereby outperforming SVC-P in activating Eley-Rideal-typed SCR that dictated the overall SCR activities. Compared with SVC-S, SVC-P contained fewer OV species, yet, had higher OM mobility, thus enhancing the overall redox cycling feature, while providing greater Brönsted acidity. Consequently, the resistance of SVC-P to H2O or soot were greater than or similar to that of SVC-S. Conversely, SVC-S revealed greater tolerance to hydro-thermal aging and SO2 than SVC-P. This study highlights the pros and cons of HSOA-/SOA2-/H3-BPO4B- functionalities in tailoring the properties of metal oxides in use as SCR catalysts.

Effective degradation of sulfur mustard simulant using novel sulfur-doped mesoporous zinc oxide under ambient conditions.

Sulfur doped metal oxides were synthesized using a two-step precipitation method. When reacted against neat 2-CEES (2-chloroethyl-ethyl sulfide, a mustard gas simulant) under ambient conditions, sulfur doped mesoporous zinc oxide (MS-Zn) showed higher catalytic activity than the other metal oxides with 92.7% overall conversion in 24 h for a 2.5 µL neat 2-CEES droplet added on top of 2 × 2 cm large 400 mg catalyst layer. The reaction proceeded mainly by hydrolysis and further solvolysis reaction also occurred depending on the extracting solvents. Cyclic sulfonium ion intermediate reaction was thought to be involved in this reaction, and metal oxide surfaces were thought to facilitate the formation of sulfonium ions from adsorbed 2-CEES. All other by-products were also found to form via sulfonium ions, reconfirming the well-known importance of this intermediate species for the degradation reaction to proceed. The sulfur content for MS-Zn was varied and tested for degradation of neat 2-CEES. This modification showed that there is an optimal amount of sulfur content for the peak catalytic activity of MS-Zn for 2-CEES degradation. Adsorption energy of a 2-CEES molecule was calculated on model sulfur doped and non doped zinc oxide surfaces and the different adsorption energy levels were correlated with the catalytic activity of sulfur doped zinc oxide.

Decomposition of the Simulant 2-Chloroethyl Ethyl Sulfide Blister Agent under Ambient Conditions Using Metal-Organic Frameworks.

Metal organic frameworks (MOFs) have been suggested as promising materials for application in the degradation of chemical warfare agents, with the majority of studies to date focusing on nerve agents. One of the most prominent MOFs used in the detoxification of nerve agents is UiO-66, which is of interest as a future nerve agent decontaminant. However, blister agents, which constitute one of the most toxic and highly reactive categories of chemical agents, are yet to be examined as gas-phase decontamination targets using MOF structures. In this study, a novel type of UiO-66 with a smaller particle size, namely, UiO-66S, was used as a decontaminant for the blister agent simulant, 2-chloroethyl ethyl sulfide (2-CEES). The gas-phase chemical adsorption and decomposition of 2-CEES were demonstrated for the first time, with an estimated t1/2 of 1.34 h. This value is the highest reported value for an MOF in gas-phase reaction conditions. The obtained nontoxic degradation products were identified, and the reaction mechanism was studied using density functional theory calculations. Furthermore, the synthesized UiO-66S catalyst also exhibits superior catalytic ability toward nerve agent simulants (diisopropyl fluorophosphate).The results of the study provide a firm basis for the use of UiO-66S as a future decontaminant for both nerve and blister agents.

Investigating multi-functional traits of metal-substituted vanadate catalysts in expediting NOX reduction and poison degradation at low temperatures.

Catalysts are severely poisoned by ammonium sulfate (AS) and ammonium bisulfate (ABS) during selective catalytic NOX reduction (SCR) at low temperatures. To circumvent this issue, metal-substituted vanadates (MV2O6, M = Mn, Co, Ni, or Cu) supported on TiO2 were synthesized and functionalized with SOY2- to form M1 (S) catalysts (Y = 3 or 4). The Mn1 (S) could balance pre-factor and energy barrier required for the SCR, thereby exhibiting the highest NOX consumption rate (activity) among the M1 (S) catalysts. The Mn1 (S) also had desirable redox property, leading to the best SCR performance maximum-obtainable at low temperatures. Notably, the Mn1 (S) substantially reduced the thermal energy needed to decompose AS/ABS poisons. Such unique feature of the Mn1 (S) was pronounced when the Mn1 (S) was promoted by Sb (Mn1-Sb (S)). The resulting Mn1-Sb (S) showed the best SCR performance among all catalysts tested. The Mn1-Sb (S) could minimize the deposition of AS/ABS on the surface and unprecedentedly recovered its performance after regeneration even in the presence of NOX, NH3, SO2, and H2O at 260-280 °C. The temperatures required for the regeneration of the Mn1-Sb (S) were reduced by 100 °C or more in comparison with those of SCR catalysts reported previously.

Unravelling lewis acidic and reductive characters of normal and inverse nickel-cobalt thiospinels in directing catalytic H2O2 cleavage.

(Inverse) spinel-typed bimetallic sulfides are fascinating H2O2 scissors because of the inclusion of S2-, which can regenerate metals (Mδ+, δ ≤ 2) used to produce •OH via H2O2 dissection. These sulfides, however, were under-explored regarding compositional, structural, and electronic tunabilities based on the proper selection of metal constituents. Motivated by S-modified Niδ+/Coδ+ promising to H2O2 cleavage, Ni2CoS4, NiCo2S4, NiS/CoS were synthesized and contrasted with regards to their catalytic traits. Ni2CoS4 provided the greatest activity in dissecting H2O2 among the catalysts. Nonetheless, Ni2CoS4 catalyzed H2O2 scission primarily via homogeneous catalysis mediated by leached Niδ+/Coδ+. Conversely, NiCo2S4, NiS, and CoS catalyzed H2O2 cleavage mainly via unleached Niδ+/Coδ+-enabled heterogeneous catalysis. Of significance, NiCo2S4 provided Lewis acidic strength favorable to adsorb H2O2 and desorb •OH compared to NiS and CoS, respectively. Of additional significance, NiCo2S4 provided S2- with lesser energy required to reduce M(δ+1)+ via e- transfer than NiS/CoS. Hence, NiCo2S4 prompted H2O2 scission cycle per unit time better than NiS/CoS, as evidenced by kinetic assessments. NiCo2S4 was also superior to Ni2CoS4 because of the elongated lifespan anticipated as •OH producer, resulting from heterogeneous catalysis with moderate Niδ+/Coδ+ leaching. Furthermore, NiCo2S4 revealed the greatest recyclability and mineralization efficiency in decomposing recalcitrants via •OH-mediated oxidation.

Adsorptive treatment via simultaneous removal of copper, lead and zinc from soil washing wastewater using spent coffee grounds.

In the present work, the performance of spent coffee grounds (SCG) as an adsorbent in the treatment of real soil washing wastewater (SWW) was evaluated. Scanning electron microscopy, Fourier transform infrared spectroscopy, zeta potential measurement and Brunauer-Emmett-Teller analysis were utilized to determine the physicochemical characteristics of SCG. Maximum removal efficiency of 68.73% for Cu(II), 57.23% for Pb(II) and 84.55% for Zn(II) was attained at 2.5 g SCG, 300 min and 328 K. Error analysis was performed using root mean square error (RMSE) and sum of square error (SSE). Equilibrium data correlated well with the Langmuir isotherm for Pb(II) adsorption and Freundlich model for the removal of Cu(II) and Zn(II). The kinetic study shows that adsorption of the heavy metals using SCG can be satisfactorily described using the pseudo-second order equation (R2 ≥ 0.9901; RMSE ≤ 15.0539; SSE ≤ 145.1461). Activation parameters including activation energy, change in free energy of activation, activation entropy change (ΔS*) and activation enthalpy change (ΔH*) were determined using Arrhenius and Eyring equations. Thermodynamic studies show that adsorption of the heavy metals using SCG is spontaneous, endothermic (ΔH° ≥ 9.80 kJ/mol·K) and results in increased randomness at the solid/solution interface (ΔS° ≥ 2.28 J/mol).

Treatment of soil washing wastewater via adsorption of lead and zinc using graphene oxide.

In the present work, graphene oxide (GO) was synthesized via the modified Hummers method and utilized in treating real soil washing wastewater via adsorptive removal of lead (Pb) and zinc (Zn). Characterization analysis of GO was performed using X-ray diffraction, Brunauer-Emmett-Teller method, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and zeta potential analysis. The Van't Hoff, Eyring, and Arrhenius equations were applied to determine the activation and thermodynamic parameters namely activation energy (Ea), standard Gibbs energy change (ΔG°), standard enthalpy change (ΔH°), standard entropy change (ΔS°), change in activation Gibbs energy (ΔG#), change in activation enthalpy (ΔH#), and change in activation entropy (ΔS#). Based on the high coefficient of determination values (0.8882 ≥ R2 ≥ 0.9094) and low values of SSE (0.0292 ≤ SSE ≤ 0.0511) and ARE (0.8014 ≤ ARE ≤ 0.8822), equilibrium data agreed well with the Freundlich isotherm. The maximum adsorption capacity for Pb(II) and Zn(II) was determined to be 11.57 and 4.65 mg/g, respectively. Kinetic studies revealed that pseudo-second-order equation fitted well with the experimental data, which indicates that chemisorption is the rate-determining step of the adsorption system. Results have shown the possibility of GO as a potential adsorbent material in the treatment of soil washing wastewater.

Hierarchically Structured Core-Shell Design of a Lithium Transition-Metal Oxide Cathode Material for Excellent Electrochemical Performance.

Tuning geometrical parameters of lithium-mixed transition-metal oxide (LiTM) cathode materials is a promising strategy for resource-efficient design of high-performance Li-ion batteries. In this paper, we demonstrate that simple and facile geometrical tailoring of the secondary microstructure of LiTM cathode materials without complex chemical modification or heterostructure engineering can significantly improve overall electrochemical performance of the active cathode materials. An optimized LiTM with a bimodal size distribution of primary particles inside the secondary particles exhibits a 53.8% increase in capacity at a high discharge rate (10 C) compared to a commercially available reference and comparable rate capability after 100 charge/discharge cycles. The key concept of this approach is to maximize the beneficial effects arising from the controlled sizes of primary particles. Multimodal/multiscale microscopic characterizations based on electron tomography and scanning transmission electron microscopy, combined with electron energy-loss spectroscopy and energy-dispersive X-ray spectroscopy from the atomic level to the microscale level, were employed to elucidate structural origins of enhanced battery performance. This study paves the way for the resource-efficient microstructure design of LiTM cathode materials to maximize capacity and stability via simple adjustment of processing conditions, which is advantageous for mass-production applications.

Preparation and In Vitro Release Studies of Ibuprofen Loaded Nanoparticles Made from PHO and PEGMA-g-PHO.

Monoacrylate-poly(ethylene glycol) grafted poly(3-hydroxyoctanoate) (PEGMA-g-PHO) copolymer was obtained by UV irradiation and ibuprofen (IBU) loaded nanoparticles with PHO or PEGMA-g-PHO polymers were successfully prepared by a single emulsion process. Size of IBU-loaded nanoparticles was about 300 nm based on particle size measurement. Their shapes were spherical. To study drug release properties, IBU release from nanoparticles were performed with FBS buffer. Higher burst release of IBU was observed with the highest graft density of PEGMA groups and 100% drug release was found in 3, 6, and 12 days for PHO, PEGMA-g-PHO0.05, and PEGMA-g-PHO0.15, respectively. Our results suggest that hydrophobic PHO and more hydrophilic PEGMA-g-PHO could be regarded as good candidates of drug release carriers.

Identification of five novel genetic loci related to facial morphology by genome-wide association studies.

BACKGROUND: Face morphology is strongly determined by genetic factors. However, only a small number of genes related to face morphology have been identified to date. Here, we performed a two-stage genome-wide association study (GWAS) of 85 face morphological traits in 7569 Koreans (5643 in the discovery set and 1926 in the replication set). RESULTS: In this study, we analyzed 85 facial traits, including facial angles. After discovery GWAS, 128 single nucleotide polymorphisms (SNPs) showing an association of P < 5 × 10- 6 were selected to determine the replication of the associations, and meta-analysis of discovery GWAS and the replication analysis resulted in five genome-wide significant loci. The OSR1-WDR35 [rs7567283, G allele, beta (se) = -0.536 (0.096), P = 2.75 × 10- 8] locus was associated with the facial frontal contour; the HOXD1-MTX2 [rs970797, A allele, beta (se) = 0.015 (0.003), P = 3.97 × 10- 9] and WDR27 [rs3736712, C allele, beta (se) = 0.293 (0.048), P = 8.44 × 10- 10] loci were associated with eye shape; and the SOX9 [rs2193054, C allele, beta (se) (ln-transformed) = -0.007 (0.001), P = 6.17 × 10- 17] and DHX35 [rs2206437, A allele, beta (se) = -0.283 (0.047), P = 1.61 × 10- 9] loci were associated with nose shape. WDR35 and SOX9 were related to known craniofacial malformations, i.e., cranioectodermal dysplasia 2 and campomelic dysplasia, respectively. In addition, we found three independent association signals in the SOX9 locus, and six known loci for nose size and shape were replicated in this study population. Interestingly, four SNPs within these five face morphology-related loci showed discrepancies in allele frequencies among ethnic groups. CONCLUSIONS: We identified five novel face morphology loci that were associated with facial frontal contour, nose shape, and eye shape. Our findings provide useful genetic information for the determination of face morphology.

Cis-trimethoxy resveratrol induces intrinsic apoptosis via prometaphase arrest and prolonged CDK1 activation pathway in human Jurkat T cells.

Cis-trimethoxy resveratrol (cis-3M-RES) induced dose-dependent cytotoxicity and apoptotic DNA fragmentation in Jurkat T cell clones (JT/Neo); however, it induced only cytostasis in BCL-2-overexpressing cells (JT/BCL-2). Treatment with 0.25 µM cis-3M-RES induced G2/M arrest, BAK activation, Δψm loss, caspase-9 and caspase-3 activation, and poly (ADP-ribose) polymerase (PARP) cleavage in JT/Neo cells time-dependently but did not induce these events, except G2/M arrest, in JT/BCL-2 cells. Moreover, cis-3M-RES induced CDK1 activation, BCL-2 phosphorylation at Ser-70, MCL-1 phosphorylation at Ser-159/Thr-163, and BIM (BIMEL and BIML) phosphorylation irrespective of BCL-2 overexpression. Enforced G1/S arrest by using a G1/S blocker aphidicolin completely inhibited cis-3M-RES-induced apoptotic events. Cis-3M-RES-induced phosphorylation of BCL-2 family proteins and mitochondrial apoptotic events were suppressed by a validated CDK1 inhibitor RO3306. Immunofluorescence microscopy showed that cis-3M-RES induced mitotic spindle defects and prometaphase arrest. The rate of intracellular polymeric tubulin to monomeric tubulin decreased markedly by cis-3M-RES (0.1-1.0 µM). Wild-type Jurkat clone A3, FADD-deficient Jurkat clone I2.1, and caspase-8-deficient Jurkat clone I9.2 exhibited similar susceptibilities to the cytotoxicity of cis-3M-RES, excluding contribution of the extrinsic death receptor-dependent pathway to the apoptosis. IC50 values of cis-3M-RES against Jurkat E6.1, U937, HL-60, and HeLa cells were 0.07-0.17 µM, whereas those against unstimulated human peripheral T cells and phytohaemagglutinin A-stimulated peripheral T cells were >10.0 and 0.23 µM, respectively. These results indicate that the antitumor activity of cis-3M-RES is mediated by microtubule damage, and subsequent prometaphase arrest and prolonged CDK1 activation that cause BAK-mediated mitochondrial apoptosis, and suggest that cis-3M-RES is a promising agent to treat leukemia.

Active contour configuration model for estimating the posterior ablative margin in image fusion of real-time ultrasound and 3D ultrasound or magnetic resonance images for radiofrequency ablation: an experimental study.

PURPOSE: The purpose of this study was to evaluate the accuracy of an active contour model for estimating the posterior ablative margin in images obtained by the fusion of real-time ultrasonography (US) and 3-dimensional (3D) US or magnetic resonance (MR) images of an experimental tumor model for radiofrequency ablation. METHODS: Chickpeas (n=12) and bovine rump meat (n=12) were used as an experimental tumor model. Grayscale 3D US and T1-weighted MR images were pre-acquired for use as reference datasets. US and MR/3D US fusion was performed for one group (n=4), and US and 3D US fusion only (n=8) was performed for the other group. Half of the models in each group were completely ablated, while the other half were incompletely ablated. Hyperechoic ablation areas were extracted using an active contour model from real-time US images, and the posterior margin of the ablation zone was estimated from the anterior margin. After the experiments, the ablated pieces of bovine rump meat were cut along the electrode path and the cut planes were photographed. The US images with the estimated posterior margin were compared with the photographs and post-ablation MR images. The extracted contours of the ablation zones from 12 US fusion videos and post-ablation MR images were also matched. RESULTS: In the four models fused under real-time US with MR/3D US, compression from the transducer and the insertion of an electrode resulted in misregistration between the real-time US and MR images, making the estimation of the ablation zones less accurate than was achieved through fusion between real-time US and 3D US. Eight of the 12 post-ablation 3D US images were graded as good when compared with the sectioned specimens, and 10 of the 12 were graded as good in a comparison with nicotinamide adenine dinucleotide staining and histopathologic results. CONCLUSION: Estimating the posterior ablative margin using an active contour model is a feasible way of predicting the ablation area, and US/3D US fusion was more accurate than US/MR fusion.

Preparation and biocompatibility of crosslinked poly(3-hydroxyundecenoate).

A sticky polymer, poly(3-hydroxyundecenoate) (PHU), was produced by Pseudomonas oleovorans when nonanoate and undecenoate were used as carbon sources. Crosslinked PHU (CL-PHU) was prepared by heating using benzoyl peroxide as a crosslinker. According to the degree of crosslinking in the polymer, three types of CL-PHU were prepared: CL-PHU50, CL-PHU60 and CL-PHU70. Fourier transform-infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry results suggested that crosslinking of PHU was successfully achieved by heat, which increased the crosslinking density and decreased stiffness and flexibility of the polymer. Water contact angle measurements revealed no differences of hydrophilicity as the crosslinking density. Slight morphological changes of CL-PHU film surfaces were observed by atomic force microscopy. Chinese hamster ovary cells were used to investigate the biocompatibility of CL-PHU films using poly(l-lactide) surfaces as control. Surface properties of the film, such as roughness and adhesive force, enhanced the adhesion and proliferation of cells on the films. CL-PHU might be useful for cell compatible biomedical applications.

Mori Folium water extract alleviates articular cartilage damages and inflammatory responses in monosodium iodoacetate­induced osteoarthritis rats.

Mori folium, the leaf of Morus alba L. (Moraceae), has been widely used in traditional medicine for the treatment of various diseases. It has been recently reported that Mori folium possesses potential chondroprotective effects in interleukin (IL)­1ß­stimulated human chondrocytes; however, its protective and therapeutic potential against osteoarthritis (OA) in an animal model remains unclear. In this study, as part of an ongoing screening program to evaluate the anti­osteoarthritic potential of Mori folium, the protective effects of a water extract of Mori folium (MF) on cartilage degradation and inflammatory responses in a monosodium iodoacetate (MIA)­induced OA rat model were evaluated. The results demonstrated that administration of MF had a tendency to attenuate the damage to articular cartilage induced by MIA, as determined by knee joint swelling and the histological grade of OA. The elevated levels of matrix metalloproteinases­13 and two bio­markers for the diagnosis and progression of OA, such as the cartilage oligomeric matrix protein and C­telopeptide of type II collagen, were markedly ameliorated by MF administration in MIA­induced OA rats. In addition, MF significantly suppressed the production of pro­inflammatory cytokines, including IL­1ß, IL­6 and tumor necrosis factor­α. MF also effectively inhibited the expression of inducible nitric oxide (NO) synthase and cyclooxygenase­2, thus inhibiting the release of NO and prostaglandin E2. Although further work is required to fully understand the critical role and clinical usefulness, these findings indicate that MF may be a potential therapeutic option for the treatment of OA.