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Single-phase formation of active metal oxides on supports has been vigorously pursued in many catalytic applications to suppress undesired reactions and to determine direct structure-property relationships. However, this is difficult to achieve in nanoscale range because the effect of non-uniform metal-support interfaces becomes dominant in the overall catalyst growth, leading to the nucleation of various metastable oxides. Herein, we develop a supported single-phase corundum-Rh2 O3 (I) nanocatalyst by utilizing controlled interaction between metal oxide and h-BN support. Atomic-resolution electron microscopy and first-principle calculation reveal that single-phase formation occurs via uniform and preferential attachment of Rh2 O3 (I) (110) seed planes on well-defined h-BN surface after decomposition of rhodium precursor. By utilizing the Rh/h-BN catalyst in methane partial oxidation, syngas is successfully produced solely following the direct route with keeping a H2 /CO ratio of 2, which makes it ideal for most downstream chemical processes.

Single-atom catalysts (SACs) have emerged as promising materials in heterogeneous catalysis. Previous studies reported controversial results about the relative level in activity for SACs and nanoparticles (NPs). These works have focused on the effect of metal atom arrangement, without considering the oxidation state of the SACs. Here, we immobilized Pt single atoms on defective ceria and controlled the oxidation state of Pt SACs, from highly oxidized (Pt0 : 16.6 at %) to highly metallic states (Pt0 : 83.8 at %). The Pt SACs with controlled oxidation states were then employed for oxidation of CO, CH4 , or NO, and their activities compared with those of Pt NPs. The highly oxidized Pt SACs presented poorer activities than Pt NPs, whereas metallic Pt SACs showed higher activities. The Pt SAC reduced at 300 °C showed the highest activity for all the oxidations. The Pt SACs with controlled oxidation states revealed a crucial missing link between activity and SACs.

Methane upgrading into more valuable chemicals has received much attention. Herein, we report oxidative methane conversion to ethane using gaseous O2 at low temperatures (

Single-atom catalysts (SACs) have attracted growing attention because they maximize the number of active sites, with unpredictable catalytic activity. Despite numerous studies on SACs, there is little research on the support, which is essential to understanding SAC. Herein, we systematically investigated the influence of the support on the performance of the SAC by comparing with single-atom Pt supported on carbon (Pt SA/C) and Pt nanoparticles supported on WO3-x (Pt NP/WO3-x ). The results revealed that the support effect was maximized for atomically dispersed Pt supported on WO3-x (Pt SA/WO3-x ). The Pt SA/WO3-x exhibited a higher degree of hydrogen spillover from Pt atoms to WO3-x at the interface, compared with Pt NP/WO3-x , which drastically enhanced Pt mass activity for hydrogen evolution (up to 10 times). This strategy provides a new framework for enhancing catalytic activity for HER, by reducing noble metal usage in the field of SACs.

Conversion of carbon dioxide for producing useful chemicals is an attractive method to reduce greenhouse gas emissions and to produce sustainable chemicals. However, the thermodynamic stability of CO₂ necessitates high levels of energy consumption for its conversion to chemicals. Here, we suggest a new catalytic system with an alternative heating system allowing for minimal energy consumption during CO₂ conversion. In this system, electrical energy is transferred as heat energy to the metal supported on carbon catalyst. Fast ramping rates allow for high operating temperatures (Tapp=250 °C) to be reached within 5 minutes, leading to an 80-fold lowering of energy consumption in methane reforming using CO₂ (DRM). In addition, the consumed energy normalized by time during DRM reaction in current-assisted catalysis is 6-fold lower (11.0 kJ·min-1) than conventional heating systems (68.4 kJ·min-1).

Though arjunic acid, a triterpene isolated from Terminalia arjuna, was known to have antioxidant, antiinflammatory, and cytotoxic effects, its underlying antitumor mechanism still remains unclear so far. Thus, in the present study, the molecular antitumor mechanism of arjunic acid was examined in A549 and H460 non-small cell lung cancer (NSCLC) cells. Arjunic acid exerted cytotoxicity by 3-[4, 5-dimethylthiazol-2-yl]-2, 5-diphenyl tetrazolium bromide (MTT) assay and significantly increased sub-G1 population in A549 and H460 cells by cell cycle analysis. Consistently, arjunic acid cleaved poly (ADP-ribose) polymerase (PARP), activated Bax, and phosphorylation of c-Jun N-terminal kinases (JNK), and also attenuated the expression of pro-caspase-3 and Bcl-2 in A549 and H460 cells. Furthermore, arjunic acid upregulated the expression of endoplasmic reticulum (ER) stress proteins such as IRE1 α, ATF4, p-eIF2α, and C/EBP homologous protein (CHOP) in A549 and H460 cells. Conversely, CHOP depletion attenuated the increase of sub-G1 population by arjunic acid, and also JNK inhibitor SP600125 blocked the cytotoxicity and upregulation of IRE1 α and CHOP induced by arjunic acid in A549 and H460 cells. Overall, our findings suggest that arjunic acid induces apoptosis in NSCLC cells via JNK mediated ER stress pathway as a potent chemotherapeutic agent for NSCLC.

As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity.

Water, which frequently inhibits organic reactions, improves the hydrodeoxygenation activity of lignin-derived guaiacol on a bifunctional catalyst of Rh/SiO2–Al2O3 in a biphasic mixture of n-decane and water. The unique properties of subcritical water appear to promote hydrodeoxygenation, which improves the production of monooxygenates by removing more oxygen atoms of guaiacol while suppressing the formation of fully deoxygenated hydrocarbons because of the poor solubility of hydrophobic monooxygenates.

This study was designed to investigate the antitumor mechanism of Phytol in hepatocellular carcinomas including Huh7 and HepG2 cells in association with caspase dependent apoptosis and epithelial mesenchymal transition (EMT) signaling. Phytol significantly suppressed the viability of Huh7 and HepG2 cells. Also, Phytol significantly increased the sub G1 population and terminal deoxynucleotidyl transferase deoxyuridine triphosphate nick end labeling (TUNEL) positive cells in a concentration dependent manner in Huh7 and HepG2 cells. Consistently, Phytol cleaved poly (adenosine diphosphate-ribose) polymerase (PARP), activated caspase-9/3, and Bax attenuated the expression of survival genes such as Bcl-2, Mcl-1, and c-Myc in Huh7 and HepG2 cells. Of note, Phytol also suppressed typical morphology change of EMT such as loss of cell adhesion and formation of fibroblast like mesenchymal cells in HepG2 cells. Furthermore, Phytol also reversed the loss of E-cadherin and overexpression of p-smad2/3, alpha-smooth muscle actin, and Snail induced by EMT promoter transforming growth factor beta1 in HepG2 cells. Overall, our findings suggest that Phytol exerts antitumor activity via apoptosis induction through activation of caspas-9/3 and inhibition of EMT in hepatocellular carcinoma cells as a potent anticancer candidate for liver cancer treatment.

Matrix metalloproteinases (MMPs) are matrix-degrading enzymes that play a pivotal role in aggressive behaviours, such as rapid tumour growth, invasion, and metastasis, of several types of solid tumours. In particular, stromal MMP-2 plays important roles in the progression of malignant tumours, but most clinical studies have focused on tumoural MMP-2 and -9 expression, and not stromal MMP-2 expression. One hundred and seventy-seven cases diagnosed as invasive ductal carcinoma of the breast between 2000 and 2005 were included in this study. Expressions of tumoural MMP-2 and -9 and stromal MMP-2 were analysed by immunostaining on a tissue microarray. Subsequently, the associations between those results and various clinicopathological parameters were evaluated. Stromal MMP-2 expression correlated significantly with clinicopathological parameters such as advanced T category, larger tumour size, high histological grade, tumour necrosis, ER- and PR-negative, and HER-2-positive (all p < 0.05). In univariate and multivariate analyses, overall survival was linked with stromal MMP-2 expression as well as dual expression of stromal MMP-2 and tumoural MMP-2 and -9 (all p < 0.05). Stromal MMP-2 expression may play a crucial role in predicting aggressive clinical behaviour in breast cancer patients.

Strong demand for high-performance energy-storage devices has currently motivated the development of emerging capacitive materials that can resolve their critical challenge (i.e., low energy density) and that are renewable and inexpensive energy-storage materials from both environmental and economic viewpoints. Herein, the pseudocapacitive behavior of lignin nanocrystals confined on reduced graphene oxides (RGOs) used for renewable energy-storage materials is demonstrated. The excellent capacitive characteristics of the renewable hybrid electrodes were achieved by synergizing the fast and reversible redox charge transfer of surface-confined quinone and the interplay with electron-conducting RGOs. Accordingly, pseudocapacitors with remarkable rate and cyclic performances (~96 % retention after 3000 cycles) showed a maximum capacitance of 432 F g(-1), which was close to the theoretical capacitance of 482 F g(-1) and sixfold higher than that of RGO (93 F g(-1)). The chemical strategy delineated herein paves the way to develop advanced renewable electrodes for energy-storage applications and understand the redox chemistry of electroactive biomaterials.

Nickel catalysts are typically used for hydrogen production by reforming reactions. Reforming methane with carbon dioxide, called dry reforming of methane (DRM), is a good way to produce hydrogen or syngas (a mixture of hydrogen and carbon monoxide) from two notable greenhouse gases. However, Ni catalysts used for DRM suffer from severe coke deposition. It has been known that small Ni nanoparticles are advantageous to reduce coke formation, but the high reaction temperature of DRM (800 °C) inevitably induces aggregation of the nanoparticles, leading to severe coke formation and degraded activity. Here, we develop highly coke-resistant Ni catalysts by immobilizing premade Ni nanoparticles of 5.2 nm in size onto functionalized silica supports, and then coating the Ni/SiO2 catalyst with silica overlayers. The silica overlayers enable the transfer of reactants and products while preventing aggregation of the Ni nanoparticles. The silica-coated Ni catalysts operate stably for 170 h without any degradation in activity. No carbon deposition was observed by temperature programmed oxidation (TPO), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy. The Ni catalysts without silica coating show severe sintering after DRM reaction, and the formation of filamentous carbon was observed. The coke-resistant Ni catalyst is potentially useful in various hydrocarbon transformations.

This study examines smartphone adoption behavior among American college students by combining all components of innovation diffusion theory (IDT), the technology acceptance model (TAM), the value-based adoption model (VAM), and the social influence (SI) model. Data indicate that the smartphone adoption rates are beyond the early majority and are now approaching the late majority. The findings of analysis of variance tests revealed that all variables of TAM, VAM, and SI varied across the adopter groups: The current adopter's mean values of the variables were the highest, followed by those of potential and nonadoption groups. Multinomial logistic regression (MLR) analyses revealed that perceived value and affiliation mainly determine the different perceptions of adoption groups. Smartphone adoption, however, was relatively unaffected by perceived ease of use and perceived usefulness. Perceived popularity, perceived price, and ethnicity played a role in distinctive determinants between current adopters and nonadopters. The results imply that adopters perceive smartphones as not only a worthwhile device in which to invest money but also a symbolic device to signal their affiliation and timely technology adoption. Another intriguing finding is the differences of interest in contents between current adopters and nonadopters. Social interactions via social networking services, acquisition for lifestyle, information seeking, and entertainment via gaming were the main applications of interest.

Tetramethylammonium-based molten salts bearing a β-amino acid anion (TMAAs) are synthesized through Michael addition reactions of amines with methyl acrylate followed by hydrolysis and subsequent neutralization by using aqueous tetramethylammonium hydroxide. The CO(2) capture performances of the TMAAs are evaluated and are shown to interact with CO(2) in a 1:1 mode in both water and alcohol. FTIR and (13)C NMR spectroscopic studies on the interactions of TMAAs with CO(2) indicate that the type of CO(2) adduct varies with the solvent used. When water is used as the solvent, a bicarbonate species is produced, whereas hydroxyethylcarbonate and methylcarbonate species are generated in ethylene glycol and methanol, respectively. Computational calculations show that the carboxylate groups of TMAAs contribute towards the formation and stabilization of 1:1 CO(2) adducts through hydrogen bonding interactions with the hydrogen atoms of the amino groups.

2,5-Furandicarboxylic acid (FDCA) is a promising biobased alternative material to terephthalic acid. In this study, three types of poly(butylene adipamide) (PA-4,6) containing 10, 20, and 30 mol % of poly(butylene-2,5-furandicarboxylamide) (PA-4,F) were synthesized through consecutive prepolymerization and solid-state polymerization (SSP). The incorporation of a 10 mol % PA-4,F component into PA-4,6 resulted in slight increases in the intrinsic viscosity (IV) and glass-transition temperature (Tg) after 12 h of SSP at 220 °C. When the SSP temperature and reaction time increased, IV increased proportionally. The highest IV value of 0.75 was obtained by 48 h of SSP at 240 °C, whereas increases in the PA-4,F content to 20 and 30 mol % gave rise to decreases in IV, Tg, and melting temperature; this interrupted the increase in SSP temperature. The thermal decomposition temperature of the PA-4,F-incorporated polyamide was lower than that with PA-4,6 because of the lower thermal stability of the FDCA component. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43391.

In this paper, a simple and powerful method of producing nanoparticle-anchored graphene oxide (GO) composites using a 'click' reaction is demonstrated. This method affords a facile means of anchoring of nanoparticles with various shapes and sizes on the GO. CuPt nanorods with controlled size, aspect ratio (from 1 to 11), and uniformity are synthesized. Transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy measurements are made to monitor the formation and characterize the properties of the CuPt nanorod-grafted GO composites. Their catalytic properties in the water phase are investigated using an o-phenylenediamine oxidation reaction. The results of this study clearly demonstrate that nonpolar CuPt nanorods immobilized on GO can function as a catalyst in an aqueous solution and that GO can be used as a catalytic nanorod support.

Ring-opening metathesis polymerization (ROMP) of a polycyclic olefin monomer (tetracyclododecene, TCD) was carried out using various catalyst systems. The catalysts included titanium-based ternary system (titanium tetrachloride, TiCl4/triethylaluminum, Et3Al/triethylamine, Et3N), tungsten-based ternary system (tungsten hexachloride, WCl6/triisobutyl aluminum, (i-Bu)3Al/ethanol), and a ruthenium benzylidene catalyst (Grubbs 1st catalyst). The Grubbs 1st catalyst was most active in ROMP of TCD. The tungsten-based catalyst was found to be more active than the titanium-based catalyst. In contrast to the titanium-based and the Grubbs 1st catalysts, ROMP of TCD with the tungsten-based catalyst was very sensitive to gelation in the course of reaction. The effects of ethanol, WCl6 concentration, TCD/WCl6 ratio, and 1-hexane on the polymerization yield and the polymer gel formation were investigated in detail, and optimized ROMP conditions were determined. Chemical structure of synthesized polymer was characterized using one- and two-dimensional 150 MHz 13C and 600 MHz 1H nuclear magnetic resonance spectroscopy, molecular weights were measured using gel-permeation chromatography, and thermal properties were characterized using differential scanning calorimetry. Number-average molecular weights (Mn) of the polymer were in the range of 1.5–4.7 × 104 g/mol, and glass transition temperatures were in the range of 185–220°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

New composite polymer gels were obtained from cellulose triacetate (CTA), N-methyl-N′-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr1,3TFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Analysis by differential scanning calorimeter and scanning electron microscope showed that the ionic gel consisting of CTA, Pyr1,3TFSI, and LiTFSI formed a completely homogeneous phase at the molar ratio of CTA/Pyr1,3TFSI/LiTFSI = 1/3/1.5. The ionic conductivity of the polymer gel was significantly enhanced by the presence of LiTFSI. FTIR study strongly implies that the interaction of lithium ion with the carbonyl group of CTA could be responsible for the increase in conductivity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

This study assessed the knowledge and perception of human biological materials (HBM) and biorepositories among three study groups in South Korea. The relationship between the knowledge and the perception among different groups was also examined by using factor and regression analyses. In a self-reporting survey of 440 respondents, the expert group was found more likely to be knowledgeable and positively perceived than the others. Four factors emerged: Sale and Consent, Flexible Use, Self-Confidence, and Korean Bioethics and Biosafety Action restriction perception. The results indicate that those who are well aware of the existence of biobanks were more positively inclined to receive the Sale and Consent perception. As a result of the need for high quality HBMs and the use of appropriate sampling procedures for every aspect of the collection and use process, the biorepository community should pay attention to ethical, legal, and policy issues.

Pre-treatment of porcine pulmonary xenograft with desmopressin: a novel strategy to attenuate platelet activation and systemic intravascular coagulation in an ex-vivo model of swine-to-human pulmonary xenotransplantation. Xenotransplantation 2008; 15: 27-35. � 2008 Blackwell Munksgaard Abstract: Background: Von Willebrand factor (vWF) has been proposed as a major contributor to the development of coagulopathy in pulmo- nary xenotransplantation. Pretreatment of donor swine with 1-deamino- 8-d-arginine vasopressin (DDAVP), an analog of vasopressin, can reduce the content of vWF in pulmonary xenografts. Here, we investi- gate the effects of DDAVP pre-treatment in an ex-vivo perfusion model of pulmonary xenotransplantation. Methods: We set up and performed the ex-vivo perfusion using porcine pulmonary accessory lobes and fresh human whole blood (n = 12). Half of the donor swine were given 3 lg/kg DDAVP intravenously for 3 days before ex-vivo perfusion (DDAVP group) and half of them were left untreated (control group). The porcine lung was perfused with fresh blood for 1 h and changes in the following parameters were monitored: pulmonary arterial pressure, pulmonary vascular resistance, blood cell counts, fibrinogen, antithrombin, platelet factor 4, D-dimer, C3a, C4d, and xenoreactive IgM. The release of Gala1-3Gal xenoantigen (aGal) from porcine lung which had been perfused and retained for 30 min with human blood was assessed by enzyme-linked immunosorbent assay using aGal-binding lectin. Results: Both DDAVP and control groups showed typical findings of immediate pulmonary dysfunction: an increase of pulmonary vascular resistance and sequestration of leukocytes and platelets after ex-vivo perfusion. However, in the DDAVP group, the increase of platelet factor 4, C3a, and C4d after perfusion was attenuated compared to that in the control group. The release of aGal after blood retention was significantly lower in the DDAVP group than that of the control group. Conclusion: Pre-infusion of DDAVP to the donor swine was beneficial in attenuating platelet activation as well as complement/coagulation activation. These effects of DDAVP are likely to relate to the reduction of porcine vWF content in the xenograft. Therefore, the modulation of vWF secretion in donor lungs could be an additional therapeutic way to reduce systemic coagulopathy in pulmonary xeno- transplantation.

Zwitterionic silver nitrate salts of 1-(1-methyl-3-imidazolio)propane-3-sulfonate, 1-(1-methyl-1-pyrrolidinio)propane-3-sulfonate, and 1-(4-methyl-4-morpholio)propane-3-sulfonate have been prepared and tested as carriers for facilitated olefin transport membranes in the separation of ethylene/ethane, propylene/propane, and C4 mixtures. The interactions of olefins with silver ions bound to sulfonate groups were investigated by FTIR spectroscopy as well as the correlation between the binding affinity of olefins and facilitated transport.

Single atomic Pt catalyst can offer efficient utilization of the expensive platinum and provide unique selectivity because it lacks ensemble sites. However, designing such a catalyst with high Pt loading and good durability is very challenging. Here, single atomic Pt catalyst supported on antimony-doped tin oxide (Pt1/ATO) is synthesized by conventional incipient wetness impregnation, with up to 8 wt% Pt. The single atomic Pt structure is confirmed by high-angle annular dark field scanning tunneling electron microscopy images and extended X-ray absorption fine structure analysis results. Density functional theory calculations show that replacing Sb sites with Pt atoms in the bulk phase or at the surface of SbSn or ATO is energetically favorable. The Pt1/ATO shows superior activity and durability for formic acid oxidation reaction, compared to a commercial Pt/C catalyst. The single atomic Pt structure is retained even after a harsh durability test, which is performed by repeating cyclic voltammetry in the range of 0.05–1.4 V for 1800 cycles. A full cell is fabricated for direct formic acid fuel cell using the Pt1/ATO as an anode catalyst, and an order of magnitude higher cell power is obtained compared to the Pt/C.

Shape-controlled nanoparticles with well-defined facets can be used as heterogeneous catalysts with enhanced activity and selectivity. The surface crystalline structure has a significant effect on the surface reaction, and shape control can be a way to obtain a desirable surface structure to improve the catalytic properties of nanoparticles. The shape of the nanoparticle can be formed by controlling the nucleation and overgrowth steps. Surface-capping agents are typically used to prevent aggregation of the nanoparticles during the overgrowth, but the subsequent treatment for their removal should be performed carefully. The extent of surface cleanness and the type of organic remnant can yield different catalytic properties. The surface agents, however, can also contribute to modulating the electronic structure or oxidation state of the surface, inducing improved catalytic activity and durability. Examples showing enhancements in the activity and selectivity of shape-controlled nanoparticles with well-defined facets are presented in this review, including electrocatalytic reactions, coupling reactions of organic compounds, water-gas shift reactions, CO oxidation, reforming reactions, and photocatalytic reactions. The well-defined facets control the adsorption of reactants to the surface, bond cleavage at the surface, desorption of products from the surface, and degree of surface-poisoning, resulting in enhanced activity and selectivity. However, the issues of shape preservation and mass production should be addressed further to apply the shaped nanoparticles in practical applications.

The highly selective dry complex membrane AgBF4-cellulose acetate (CA) was prepared and tested for the separation of ethylene/ethane and propylene/propane mixtures. The maximum selectivity for olefin over paraffin was found to be 280 for the ethylene/ethane mixture and 200 for the propylene/propane mixture. Solid-state interactions of AgBF4 with cellulose acetate (CA) and/or olefins have been investigated by using FT-IR, UV, and X-ray photoelectron spectroscopy (XPS). FT-IR and XPS studies clearly show that the silver ions are coordinated by carbonyl oxygen atoms among three different types of oxygen atoms present in CA-two in the acetate group and one in the ether linkage. Upon incorporation of AgBF4 into CA, the carbonyl stretching frequency of the free cellulose acetate at 1750 cm(-1) shifts to a lower frequency by about 41 cm(-1). The binding energy corresponding to a carbonyl oxygen atom in the O 1s XPS spectrum shifts to a more positive binding energy by the incorporation of AgBF4. Reversible olefin coordination to silver ions has been observed by FT-IR and UV studies. Treatment of the AgBF4-CA membrane placed in a gas cell with propylene produces a propylene-coordinated membrane in which coordinated propylene is easily replaced by other olefins such as 1,3-butadiene.

Platinum nano-dendrites of various sizes were applied as cathode catalysts in a proton exchange membrane fuel cell (PEMFC). The membrane electrode assembly (MEA) fabricated with Pt nano-dendrites showed very high ORR activity at high potential ranges due to lower activation overpotential. But it showed the cell performance only comparable to commercial Pt/C due to Ohmic and mass transfer resistance at high current density ranges. These results demonstrate that both high intrinsic activity of the catalysts and the formation of three-phase interface with efficient proton, electron, and mass transfer should be considered together when shape-controlled metal nanoparticles are used as cathode catalysts in a PEMFC.

p-Hydroxybenzylation of arenes can be performed efficiently using a Mannich base and (MeO)2SO2 at reflux in the presence of ZnCl2.

Primary and secondary hydroxybenzyl alcohols react with LiAlH 4 in chlorobenzene to give the corresponding alkylphenols. The reaction proceeds through the formation of benzoquinone methide as an intermediate. An example of [4+2] cycloaddition of benzoquinone methide is also reported.