High resolution DLP stereolithography to fabricate biocompatible hydroxyapatite structures that support osteogenesis.

Lithography based additive manufacturing techniques, specifically digital light processing (DLP), are considered innovative manufacturing techniques for orthopaedic implants because of their potential for construction of complex geometries using polymers, metals, and ceramics. Hydroxyapatite (HA) coupons, printed using DLP, were evaluated for biological performance in supporting viability, proliferation, and osteogenic differentiation of the human cell line U2OS and human mesenchymal stem cells (MSCs) up to 35 days in culture to determine feasibility for future use in development of complex scaffold geometries. Contact angle, profilometry, and scanning electron microscopy (SEM) measurements showed the HA coupons to be hydrophilic, porous, and having micro size surface roughness, all within favourable cell culture ranges. The study found no impact of leachable and extractables form the DLP printing process. Cells seeded on coupons exhibited morphologies comparable to conventional tissue culture polystyrene plates. Cell proliferation rates, as determined by direct cell count and the RealTime-GloTM MT Cell Viability Assay, were similar on HA coupons and standard tissue culture polystyrene plates). Osteogenic differentiation of human MSCs on HA coupons was confirmed using alkaline phosphatase, Alizarin Red S and von Kossa staining. The morphology of MSCs cultured in osteogenic medium for 14 to 35 days was similar on HA coupons and tissue culture polystyrene plates, with osteogenic (geometric, cuboidal morphology with dark nodules) and adipogenic (lipid vesicles and deposits) features. We conclude that the DLP process and LithaBone HA400 slurry are biocompatible and are suitable for osteogenic applications. Coupons served as an effective evaluation design in the characterization and visualization of cell responses on DLP printed HA material. Results support the feasibility of future technical development for 3D printing of sophisticated scaffold designs, which can be constructed to meet the mechanical, chemical, and porosity requirements of an artificial bone scaffold.

Evaluation of onion juices quality following heat-treatment and their application as a sugar substitute in Kimchi.

This study was conducted to evaluate the quality of onion juices that had been heat-treated for different times as well as their use as a table sugar substitute in Kimchi. The onions were steamed at 100 ∘C for 30 min and boiled at 90 ∘C for 30, 60, and 120 min. The highest cycloalliin (0.76 mM), free-sugar (sucrose 1.66 g/L, glucose 8.62 g/L, and fructose 7.64 g/L), and malic acid (0.82 g/L) contents were observed in onion boiled at 90 ∘C for 120 min. The possibility of using heat-treated onion juices as an alternative to table sugar in Kimchi was evaluated by comparing the lactic acid bacteria count, pH, acidity, organic acid, and free-sugar in these juices with those in Kimchi prepared using table sugar (control). The total viable bacteria and lactic acid bacteria showed similar growth patterns as in the control. The average pH reduction and increase in titratable acidity (%) in all treated Kimchi samples during fermentation for 4 weeks were 1.18 ± 0.05 and 0.81 ± 0.06, respectively. Kimchi with onion juice heat-treated for 120 min (K120) had the most similar lactic acid and acetic acid contents to that in the control after fermentation for 4 weeks. The highest mannitol level after fermentation for 4 weeks was detected in K120, which showed better sensory qualities compared to the control.

Organic acids as a freshness indicator for tofu (soybean curd).

The aim of this study was to evaluate organic acids as potential indicators of tofu freshness. To achieve this, relationships between organic acids concentrations and the growth of microorganisms in fresh tofu were investigated. The levels of microorganisms (total bacterial count) and organic acids (phytic acid, oxalic acid, citric acid, lactic acid, formic acid and acetic acid) were analyzed in tofu (packed and unpacked) every 3 days during 15 days of storage at different temperatures (4, 10, and 25 °C). Organic acids were analyzed by high performance liquid chromatography and microbial analysis was conducted by plate counting method. The levels of oxalic acid, citric acid and formic acid decreased significantly during the storage period, while the levels of lactic acid and acetic acid increased significantly when stored at 10 °C. The acetic, lactic and formic acids showed significant correlation to the levels of microorganisms in packed tofu, suggesting the use of these organic acids as potential freshness quality indicators of tofu. Current study demonstrated the effective way of predicting freshness of tofu by utilizing organic acid analysis, as opposed to traditional method relying on microbial count.

Effects of the predominant bacteria from meju and doenjang on the production of volatile compounds during soybean fermentation.

We inoculated five starter candidates, Enterococcus faecium, Tetragenococcus halophilus, Bacillus licheniformis, Staphylococcus saprophyticus, and Staphylococcus succinus, into sterilized soybeans to predict their effectiveness for flavor production in fermented soybean foods. All of the starter candidates exhibited sufficient growth and acid production on soybean cultures. Twenty-two volatile compounds, such as acids, alcohols, carbonyls, esters, furans, and pyrazines, were detected from the control and starter candidate-inoculated soybean cultures. Principal component analysis of these volatile compounds concluded that E. faecium and T. halophilus produced a similar profile of volatile compounds to soybeans with no dramatic differences in soybean flavor. B. licheniformis and S. succinus produced the crucial volatile compounds that distinguish the flavor profiles of soybean. During soybean fermentation, phenylmethanol and 2,3,5,6-tetramethylpyrazine were determined as odor notes specific to B. licheniformis and 3-methylbutyl acetate as an odor note specific to S. succinus.

Polycyclic aromatic hydrocarbon levels and risk assessment for food from service facilities in Korea.

In this study, levels of benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene (BaP), dibenzo[a,h]anthracene, benzo[g,h,i]perylene and indeno[1,2,3-c,d]pyrene in 412 food items collected from food service facilities in Korea were analysed. The concentrations of the eight polycyclic aromatic hydrocarbons (PAHs) ranged 0.13-0.48 µg/kg. The concentrations of benzo[a]pyrene in all food samples were <1 µg/kg, which is the lowest maximum limit in foods regulated by European Union legislation. PAH contents were employed to conduct exposure and risk assessment. The chronic daily intake of PAHs from 412 food samples was 5.48 × 10-6-4.70 ×x 10-4 µg-TEQBaP/kg/day with margins of exposure of 1.04 × 109-1.16 × 1011.

Safety and technological characterization of coagulase-negative staphylococci isolates from traditional Korean fermented soybean foods for starter development.

To select starters for the production of meju and doenjang, traditional Korean fermented soybean foods, we assessed the safety and technological properties of their predominant isolates, Staphylococcus saprophyticus, Staphylococcus succinus and Staphylococcus xylosus. Phenotypic antibiotic resistance, hemolysis and biofilm formation were strain-specific. None of the S. succinus isolates exhibited antibiotic resistance or hemolytic activities. Thirty-three selected strains, identified through safety assessments of 81 coagulase-negative staphylococci (CNS) isolates, produced cadaverine, putrescine, and tyramine, but not histamine in the laboratory setting. The production of these three biogenic amines may, however, be insignificant considering the high levels of tyramine produced by the control, Enterococcus faecalis. The 33 CNS strains could grow on tryptic soy agar containing 21% NaCl (w/v), exhibited acid producing activity at 15% NaCl, and expressed strain-specific protease and lipase activities. S. succinus 14BME1, the selected starter candidate, produced significant amounts of benzeneacetic acid, 2,3-butanediol, trimethylpyrazine, and tetramethylpyrazine through soybean fermentation.

Reduction of aflatoxins (B1, B2, G1, and G2) in soybean-based model systems.

The effects of chemical, physical, and cooking treatments on the reduction of aflatoxin B1 (AFB1), B2, G1, and G2 in soybean matrix were investigated. A HPLC-FLD with a Kobra cell system was used for the quantitative analysis of aflatoxins (AFs). To decrease the level of AFs during the soaking process, the contaminated soybeans were submerged in organic acid solutions. The reduction rates of AFB1 in 1.0N citric acid, lactic acid, succinic acid, and tartaric acid for 18h were 94.1%, 92.7%, 62.0%, and 95.1%, respectively. In the case of pH and autoclave treatment, the level of AFB1 was significantly decreased during autoclaving process at pH 7.4, 9.0, and 11.1, compared with the non-autoclaved samples (p<0.05). In the case of physical treatment, the heating process at 100 and 150°C for 90min significantly decreased the level of AFB1 by 41.9% and 81.2%, respectively (p<0.05). The reduction rate of AFB1 after cooking was 97.9% for soybean milk and 33.6% for steamed soybeans.

Formation and reduction of carcinogenic furan in various model systems containing food additives.

The aim of this study was to analyse and reduce furan in various model systems. Furan model systems consisting of monosaccharides (0.5M glucose and ribose), amino acids (0.5M alanine and serine) and/or 1.0M ascorbic acid were heated at 121°C for 25 min. The effects of food additives (each 0.1M) such as metal ions (iron sulphate, magnesium sulphate, zinc sulphate and calcium sulphate), antioxidants (BHT and BHA), and sodium sulphite on the formation of furan were measured. The level of furan formed in the model systems was 6.8-527.3 ng/ml. The level of furan in the model systems of glucose/serine and glucose/alanine increased 7-674% when food additives were added. In contrast, the level of furan decreased by 18-51% in the Maillard reaction model systems that included ribose and alanine/serine with food additives except zinc sulphate.

Formation and reduction of furan in a soy sauce model system.

The formation and reduction of furan using a soy sauce model system were investigated in the present study. The concentration of furan fermented up to 30 days increased by 211% after sterilization compared to without sterilization. Regarding fermentation temperature, furan level after 30 days' fermentation was the highest at 30°C (86.21 ng/mL). The furan levels in the soy sauce fermentation at 20°C and 40°C were reduced by 45% and 88%, respectively compared to 30°C fermentation. Five metal ions (iron sulfate, zinc sulfate, manganese sulfate, magnesium sulfate, and calcium sulfate), sodium sulfite, ascorbic acid, dibutyl hydroxyl toluene (BHT), and butylated hydroxyanisole (BHA) were added in a soy sauce model system. The addition of metal ions such as magnesium sulfate and calcium sulfate reduced the furan concentration significantly by 36-90% and 27-91%, respectively in comparison to furan level in the control sample (p<0.05). Iron sulfate and ascorbic acid increased the furan level at 30 days' fermentation in the soy sauce model system by 278% and 87%, respectively. In the case of the BHT and BHA, furan formation generally was reduced in the soy sauce model system by 84%, 56%, respectively.

Development of Diagnostic Reference Levels Using a Real-Time Radiation Dose Monitoring System at a Cardiovascular Center in Korea.

Digital cardiovascular angiography accounts for a major portion of the radiation dose among the examinations performed at cardiovascular centres. However, dose-related information is neither monitored nor recorded systemically. This report concerns the construction of a radiation dose monitoring system based on digital imaging and communications in medicine (DICOM) data and its use at the cardiovascular centre of the University Hospitals in Korea. The dose information was analysed according to DICOM standards for a series of procedures, and the formulation of diagnostic reference levels (DRLs) at our cardiovascular centre represents the first of its kind in Korea. We determined a dose area product (DAP) DRL for coronary angiography of 75.6 Gy cm(2) and a fluoroscopic time DRL of 318.0 s. The DAP DRL for percutaneous transluminal coronary intervention was 213.3 Gy cm(2), and the DRL for fluoroscopic time was 1207.5 s.

Weak ferromagnetic ordering of the Li(+)[TCNE](•-) (TCNE = tetracyanoethylene) organic magnet with an interpenetrating diamondoid structure.

Li[TCNE] (TCNE = tetracyanoethylene) magnetically orders as a weak ferromagnet (canted antiferromagnet) below 21.0 ± 0.1 K, as observed from the bifurcation of the field-cooled and zero-field-cooled magnetizations, as well as remnant magnetization. The structure, determined ab initio from synchrotron X-ray powder diffraction data, consists of a planar µ4-[TCNE](•-) bound to four tetrahedral Li(+) ions. The structure consists of two interpenetrating diamondoid sublattices, with closest interlattice distances of 3.43 and 3.48 Å. At 5 K this magnetic state is characterized by a coercivity of ~30 Oe, a remnant magnetization of 10 emu·Oe/mol, and a canting angle of 0.5°.

Structure and magnetic ordering of the anomalous layered (2D) ferrimagnet [NEt4]2Mn(II)3(CN)8 and 3D bridged-layered antiferromagnet [NEt4]Mn(II)3(CN)7 Prussian blue analogues.

The reaction of Mn(II) and [NEt(4)]CN leads to the isolation of solvated [NEt(4)]Mn(3)(CN)(7) (1) and [NEt(4)](2) Mn(3)(CN)(8) (2), which have hexagonal unit cells [1: R3m, a = 8.0738(1), c = 29.086(1) Å; 2: P3m1, a = 7.9992(3), c = 14.014(1) Å] rather than the face centered cubic lattice that is typical of Prussian blue structured materials. The formula units of both 1 and 2 are composed of one low- and two high-spin Mn(II) ions. Each low-spin, octahedral [Mn(II)(CN)(6)](4-) bonds to six high-spin tetrahedral Mn(II) ions through the N atoms, and each of the tetrahedral Mn(II) ions are bound to three low-spin octahedral [Mn(II)(CN)(6)](4-) moieties. For 2, the fourth cyanide on the tetrahedral Mn(II) site is C bound and is terminal. In contrast, it is orientationally disordered and bridges two tetrahedral Mn(II) centers for 1 forming an extended 3D network structure. The layers of octahedra are separated by 14.01 Š(c axis) for 2, and 9.70 Š(c/3) for 1. The [NEt(4)](+) cations and solvent are disordered and reside between the layers. Both 1 and 2 possess antiferromagnetic superexchange coupling between each low-spin (S = 1/2) octahedral Mn(II) site and two high-spin (S = 5/2) tetrahedral Mn(II) sites within a layer. Analogue 2 orders as a ferrimagnet at 27(±1) K with a coercive field and remanent magnetization of 1140 Oe and 22,800 emuOe mol(-1), respectively, and the magnetization approaches saturation of 49,800 emuOe mol(-1) at 90,000 Oe. In contrast, the bonding via bridging cyanides between the ferrimagnetic layers leads to antiferromagnetic coupling, and 3D structured 1 has a different magnetic behavior to 2. Thus, 1 is a Prussian blue analogue with an antiferromagnetic ground state [T(c) = 27 K from d(χT)/dT].

Non-Prussian blue structures and magnetic ordering of Na2Mn(II)[Mn(II)(CN)6] and Na2Mn(II)[Mn(II)(CN)6]·2H2O.

The aqueous reaction of Mn(II) and NaCN leads to the isolation of the 3-D Prussian blue analogue (PBA) Na(2)Mn[Mn(CN)(6)]·2H(2)O (1·H(2)O), which under careful dehydration forms 1. 1·H(2)O is monoclinic [P2(1)/n, a = 10.66744(32) Å, b = 7.60223(23) Å, c = 7.40713(22) Å, ß = 92.4379(28)°], while 1 is rhombohedral [R ̅3, a = 6.6166(2) Å, c = 19.2585(6) Å], and both structures are atypical for PBAs, which are typically face centered cubic. Most notably, the average ∠Mn-N-C angles are 165.3(3)° and 142.4(4)° for 1·H(2)O and 1, respectively, which are significantly reduced from linearity. This is attributed to the ionic nature of high-spin Mn(II) accommodating a reduced ∠Mn-N-C to minimize void space. Both 1 and 1·H(2)O magnetically order as ferrimagnets below their ordering temperature, T(c), of 58 and 30 K, respectively, as determined from the average of several independent methods. 1 and 1·H(2)O are hard magnets with 5 K coercive fields of 15,300 and 850 Oe, and remnant magnetizations of 9075 and 102 emu·Oe/mol, respectively. These data along with previous T(c)'s reported for related materials reveal that T(c) increases as the ∠Mn-N-C deviates further from linearity. Hence, the bent cyanide bridges play a crucial role in the superexchange mechanism by increasing the coupling via shorter Mn(II)···Mn(II) separations, and perhaps an enhanced overlap.

Orientational ordering, tilting and lone-pair activity in the perovskite methylammonium tin bromide, CH3NH3SnBr3.

Synchrotron powder diffraction data from methylammonium tin bromide, CH(3)NH(3)SnBr(3), taken as a function of temperature, reveal the existence of a phase between 230 and 188 K crystallizing in Pmc2(1), a = 5.8941 (2), b = 8.3862 (2), c = 8.2406 (2) A. Strong ferroelectric distortions of the octahedra, associated with stereochemical activity of the Sn 5s(2) lone pair, are evident. A group analysis and decomposition of the distortion modes of the inorganic framework with respect to the cubic parent is given. The primary order parameters driving this upper transition appear to be an in-phase tilt (rotation) of the octahedra coupled to a ferroelectric mode. The precise nature of the lower-temperature phase remains uncertain, although it appears likely to be triclinic. Density-functional theory calculations on such a triclinic cell suggest that directional bonding of the amine group to the halide cage is coupled to the stereochemical activity of the Sn lone pair via the Br atoms, i.e. that the bonding from the organic component may have a strong effect on the inorganic sublattice (principally via switching the direction of the lone pair with little to no energy cost).

Anomalous non-Prussian blue structures and magnetic ordering of K(2)Mn(II)[Mn(II)(CN)(6)] and Rb(2)Mn(II)[Mn(II)(CN)(6)].

The reaction of Mn(II) and KCN in aqueous and non-aqueous media leads to the isolation of three-dimensional (3-D) Prussian blue analogues, K(2)Mn[Mn(CN)(6)] (1a-d, 1e, respectively). Use of RbCN forms Rb(2)Mn[Mn(CN)(6)] (2). 1 and 2 are isomorphic {monoclinic, P2(1)/n: 1 [a = 10.1786(1) A, b = 7.4124(1) A, c = 6.9758(1) A, beta = 90.206(1)(o)]; 2 [a = 10.4101(1) A, b = 7.4492(1) A, c = 7.2132(1) A, beta = 90.072(1)(o)]}, with a small monoclinic distortion from the face centered cubic (fcc) structure that is typical of Prussian blue structured materials that was previously reported for K(2)Mn[Mn(CN)(6)]. Most notably the average Mn-N-C angles are 148.8 degrees and 153.3 degrees for 1 and 2, respectively, which are significantly reduced from linearity. This is attributed to the ionic nature of high spin Mn(II) accommodating a reduced M-CN-M' angle and minimizing void space. Compounds 1a,b have a sharp, strong nu(OH) band at 3628 cm(-1), while 1e lacks a nu(OH) absorption. The nu(OH) absorption in 1a,b is attributed to surface water, as use of D(2)O shifts the nu(OH) absorption to 2677 cm(-1), and that 1a-e are isostructural. Also, fcc Prussian blue-structured Cs(2)Mn[Mn(CN)(6)] (3) has been structurally [Fm3m: a = 10.6061(1) A] and magnetically characterized. The magnetic ordering temperature, T(c), increases as K(+) (41 K) > Rb(+) (34.6 K) > Cs(+) (21 K) for A(2)Mn[Mn(CN)(6)] in accord with the increasing deviation for linearity of the Mn-N-C linkages [148.8 (K(+)) > 153.3 (Rb(+)) > 180 degrees (Cs(+))], decreasing Mn(II)...Mn(II) separations [5.09 (K(+)) < 5.19 (Rb(+)) < 5.30 A (Cs(+))], and decreasing size of the cation (increasing electrostatic interactions). Hence, the bent cyanide bridges play a crucial role in the superexchange mechanism by increasing the coupling via shorter Mn(II)...Mn(II) separations, and perhaps enhanced overlap. In addition, the temperature dependent magnetic behavior of K(4)[Mn(II)(CN)(6)].3H(2)O is reported.

Diruthenium tetracarbonate trianion, [Ru(II/III)(2)(O(2)CO)(4)](3-), based molecule-based magnets: three-dimensional network structure and two-dimensional magnetic ordering.

H(x)K(1-x)M(II)[Ru(2)(CO(3))(4)](H(2)O)(y)(MeOH)(z) (M = Mn, Fe, Co, Ni, Mg) were synthesized from the reaction of M(II) and K(3)[Ru(2)(CO(3))(4)] in water and are isomorphous with an orthorhombic three-dimensional network structures based on mu(3)-CO(3)(2-) linkages to Ru(2) moieties forming layers and also to trans-M(II)(OH(2))(4) sites forming linked chains that connect the layers. They, as well as non-isomorphous M = Cu, magnetically order as canted ferrimagnets with T(c) = 4.4 +/- 1.0 K. The presence of S = 0 M(II) = Mg(II) has essentially no effect on T(c) suggesting that the main magnetic pathway does not occur the through M(II)-based chains, but only via Ru(2)...Ru(2) linkages that reside in layers. This is a rare example of a magnet based upon a second row transition metal.

Structure and magnetic interactions in the organic-based ferromagnet decamethylferrocenium tetracyanoethenide, [FeCp*2]*+ [TCNE]*-.

The structures of three temperature-dependent polymorphs of solvent-free decamethylferrocenium tetracyanoethenide, [FeCp*(2)][TCNE], are determined from high-resolution synchrotron powder diffraction data. [FeCp*(2)][TCNE] is the first organic-based ferromagnetic material to be synthesized and is known to have two structural phase transitions at 249 and 282 K. The low-temperature phase, which exhibits spontaneous ferromagnetic order below 4.8 K, was determined at 12 K. At that temperature, it has monoclinic space group P2(1)/c [a = 9.6637(4) A, b = 14.1217(5) A, c = 18.6256(7) A, beta = 113.231(2) degrees, Z = 4] and consists of parallel chains of alternating [Fe(C(5)Me(5))(2)](*+) and [TCNE](*-) ions, with an intrachain Fe...Fe distance of 10.45 A. Structures of the intermediate and ambient temperature phases, also studied here, are characterized by increasing disorder. At 250 K, the unit cell space group is P2(1)/m [a = 9.7100(3) A, b = 14.4926(4) A, c = 9.4997(3) A, beta = 113.153(1) degrees, Z = 2]. At ambient temperature, the lattice, albeit quite disordered, belongs to the orthorhombic space group Cmcm [a = 10.629(1) A, b = 16.128(1) A, c = 14.593(1) A, Z = 4]. Nearest-neighbor magnetic interactions were evaluated for the 12 K structure by CASSCF and CASSCF/MCQDPT calculations (a methodology similar to the CASPT2 method). Similar trends are observed in computations with and without inclusion of spin-orbit coupling. The strongest are two intrachain [FeCp*(2)](*-)...[TCNE](*-) interactions (ferromagnetic with values of approximately 45 and approximately 29 cm(-1)), although weaker, nonnegligible, ferro- or antiferromagnetic interchain interactions of less than +/-0.2 cm(-1) are also present. Magnetic interactions that lead to ordering are therefore three-dimensional, despite the vastly different intra- and interchain coupling strengths.

Crystal structure of Li2B12H12: a possible intermediate species in the decomposition of LiBH4.

The crystal structure of solvent-free Li2B12H12 has been determined by powder X-ray diffraction and confirmed by a combination of neutron vibrational spectroscopy and first-principles calculations. This compound is a possible intermediate in the dehydrogenation of LiBH4, and its structural characterization is crucial for understanding the decomposition and regeneration of LiBH4. Our results reveal that the structure of Li2B12H12 differs from other known alkali-metal (K, Rb, and Cs) derivatives.