Effect of Steam Treatment on the Catalytic Performance of ZSM-5 in the Co-conversion of Methanol and n-Hexane to Aromatics

Steam pretreatment is a widely used method for modifying the acidity and structure of zeolites,thereby enhancing their catalytic properties.This study systematically investigated the effects of steam treatment on ZSM-5 zeolites at varying treatment temperatures and durations.The structural evolution of the catalysts was monitored using N2 adsorptiondesorption,X-ray diffraction,inductively coupled plasma optical emission spectroscopy,scanning electron microscopy,NH3 temperature-programmed desorption,in situ pyridine infrared spectroscopy,and thermogravimetric analysis.The characterization results revealed that mesopores were introduced into the ZSM-5 zeolite catalysts through dealumination induced using steam treatment at moderate temperatures(400 and 500℃).Moreover,compared with the parent catalyst,the steam-treated catalysts exhibited a lower amount of acid sites and relative crystallinity,while the n(Si)/n(Al)ratio increased.In the co-conversion of methanol and n-hexane in a fixed bed reactor at 400℃and 0.5 MPa(N2 atmosphere),with a weight hourly space velocity of 1 h−1 and a stoichiometric ratio of 1:1(CH3OH to n-hexane),the steam-treated catalysts displayed a prolonged catalyst lifetime.Particularly,the parent zeolite had a lifetime of 96 h,while the catalyst treated at 500℃for 12 h had a lifetime of up to 240 h.Additionally,the steam-treated catalysts maintained stable n-hexane conversion and improved aromatic selectivity.Notably,these treated catalysts exhibited a lower deactivation rate than the parent catalyst,and would be conducive to industrial scale-up production.

Bimetallic CoNi single atoms supported on three-dimensionally ordered mesoporous chromia:highly active catalysts for n-hexane combustion

Developing the alternative supported noble metal catalysts with low cost,high catalytic efficiency,and good resistance toward carbon dioxide and water vapor is critically demanded for the oxidative removal of volatile organic compounds(VOCs).In this work,we prepared the mesoporous chromia-supported bimetallic Co and Ni single-atom(Co_(1)Ni_(1)/meso-Cr_(2)O_(3))and bimetallic Co and Ni nanoparticle(Co_(NP)Ni_(NP)/mesoCr_(2)O_(3))catalysts adopting the one-pot polyvinyl pyrrolidone(PVP)-and polyvinyl alcohol(PVA)-protecting approaches,respectively.The results indicate that the Co_(1)Ni_(1)/meso-Cr_(2)O_(3)catalyst exhibited the best catalytic activity for n-hexane(C_(6)H_(14))combustion(T_(50%)and T_(90%)were 239 and 263℃ at a space velocity of 40,000 mL g^(-1)h^(-1);apparent activation energy and specific reaction rate at 260℃ were 54.7 kJ mol^(-1)and 4.3×10^(-7)mol g^(-1)_(cat)s^(-1),respectively),which was associated with its higher(Cr^(5+)+Cr^(6+))amount,large n-hexane adsorption capacity,and good lattice oxygen mobility that could enhance the deep oxidation of n-hexane,in which Ni_(1) was beneficial for the enhancements in surface lattice oxygen mobility and low-temperature reducibility,while Co_(1) preferred to generate higher contents of the high-valence states of chromium and surface oxygen species as well as adsorption and activation of n-hexane.n-Hexane combustion takes place via the Mars van Krevelen(MvK)mechanism,and its reaction pathways are as follows:n-hexane→olefins or 3-hexyl hydroperoxide→3-hexanone,2-hexanone or 2,5-dimethyltetrahydrofuran→2-methyloxirane or 2-ethyl-oxetane→acrylic acid→CO_x→CO_(2)and H_(2)O.

Measurement and Correlation of Liquid-liquid Equilibria for 1-Hexene-n-Hexane-3-Methysulfolane

Utilizing solvent extraction to separate alkanes and olefins from catalytic light gasoline is an effective method for maximizing the utility of gasoline fractions.This study presents the determination of liquid-liquid equilibrium data for the ternary system of 1-hexene-n-hexane-3-methylsulfolane at 30℃,40℃,and 50℃under atmospheric pressure.The obtained data facilitated the construction of a ternary phase diagram for the system.The results showed that the extraction selectivity of 1-hexene/n-hexane exceeded 1.5 when using 3-methylsulfolane as the extraction solvent.Furthermore,the thermodynamic consistency of the experimental data was examined using Hand’s equation and the Othmer-Tobias method.The correlation coefficient,R^(2)≥0.9578,indicated the acceptable reliability of the phase equilibrium data.Subsequently,the NRTL(non-random two liquid)model was used to correlate the liquid-liquid phase equilibrium data and derive the binary interaction parameter.Notably,the results demonstrated that the root mean square deviation of the NRTL model correlation values from the experimental values did not exceed 2.5%.

Towards understanding the mechanism of n-hexane tolerance in Synechocystis sp.PCC 6803

Synthetic biology efforts have also led to the development of photosynthetic cyanobacteria as"autotrophic cell factories"for biosynthesis of various biofuels directly from CO_(2).However,the low tolerance to toxicity of biofuels has restricted the economic application of cyanobacterial hosts.In this study,RNAseq transcriptomics was employed to reveal stress responses to exogenous n-hexane in Synechocystis sp.PCC 6803.Functional enrichment analysis of the transcriptomic data showed that signal transduction systems were induced significantly.To further identify regulatory genes related to n-hexane tolerance,a library of transcriptional regulators(TRs)deletion mutants was then screened for their roles in nhexane tolerance.The results showed that a knockout mutant of slr0724 that encodes an Hta R suppressor protein was more tolerant to n-hexane than the wild type,indicating the involvement of slr0724 in nhexane tolerance.This study provides the foundation for better understanding the cellular responses to n-hexane in Synechocystis sp.PCC 6803,which could contribute to the further engineering of nhexane tolerance in cyanobacteria.

Study on the Inhibitory Mechanism of Sophora japonica N-hexane Extract on Microcystis aeruginosa

[Objective] The research aimed to analyze the inhibitory mechanism of Sophora japonica n-hexane extract which significantly inhibited Microcystis aeruginosa in the prior research.[Method] S.japonica n-hexane extract was used to treat M.aeruginosa.By inspecting chlorophyll a content,protein content,cell membrane permeability and superoxide dismutase（SOD） activity,the inhibitory mechanism of S.japonica n-hexane extract on M.aeruginosa was analyzed initially.[Result] S.japonica n-hexane extract destroyed the cell membrane system of M.aeruginosa,and increased the cell membrane permeability.The contents of chlorophyll a and protein respectively declined to 10% and 50% of that in the control group after cultivated for 7 d,which indicated the photosynthetic reaction system of M.aeruginosa was destroyed.In addition,under the effect of S.japonica n-hexane extract,SOD activity of M.aeruginosa increased in the early period and decreased in the latter period.[Conclusion] The possible inhibitory mechanism of S.japonica n-hexane extract on M.aeruginosa was destroying the cell membrane to increase the membrane permeability;destroying the photosynthetic reaction system to decrease the contents of photosynthetic pigment and protein;making SOD activity showing the phased variation.

Effect of secondary pore distribution on adsorption diffusion performance of n-hexane on 5A zeolite pellets

Adsorption rates of n-hexane on the 5A zeolite at 100 to 300 ℃ and 0.01 to 10 kPa are determined by an intelligent gravimetric analyzer （IGA-100）, and the adsorption diffusion performance of n-hexane on 5A zeolite pellets with different secondary pore distributions is analyzed. The results indicate that 5A-1 and 5A-6 zeolites have similar micropore and mesopore size distribution, while the 5A-6 zeolite has a larger secondary pore volume when the pore diameter is between 0.1 and 1 μm and more secondary pores when the pore diameter is less than 0.01 μm. The effective diffusion coefficient of nhexane on the 5A-6 zeolite pellet is 10 ^-6 to 10 4 cm^2/s, about 2 to 5 times higher than that on the 5A-1 zeolite. The effective diffusion coefficient of n-hexane on the 5A-1 zeolite pellet improves from 5 × 10^-7 to 2 × 10 6cm^2/s when the temperature increases from 100 to 300 ~C. However, the effective diffusion coefficient of n-hexane on the 5A-6 zeolite remains almost unchanged at different temperatures. The molecular average free path of n-hexane decreases from 627.15-963.28 to 0.63-0, 96 Ixm with the adsorption pressure increasing from 0.01 to 10 kPa. Such a flee path is close to the secondary pore diameter, resulting in significant Knudsen diffusion in the secondary pores. Thus, the effective diffusion coefficient of n-hexane on the 5A zeolite pellets increases before 1 kPa and decreases after 1 kPa.

GC-MS Analysis of Essential oil and n-Hexane Extract from Moso Bamboo

[Objective] This study aimed to analyze the chemical composition and yield of essential oil and n-hexane extract from moso bamboo to find active compounds with potential value. [Method] Essential oil and n-hexane extract were respectively extracted from moso bamboo of four different ages by using hydrodistillation and ultrasonic-assisted extraction with n-hexane, and analyzed with gas chromatography/mass spectrometry （GC/MS）. [Result] The results show that cedrol （46.39%） is the first principal volatile component in essential oil of the middle stem of 7-year old moso bamboo; dibutyl phthalate （59.46%） is the first principal volatile component in n-hexane extract of the middle stem of 3-year old moso bamboo; yield of n-hexane extract is higher than that of essential oil from moso bamboo. [Conclusion] Cedrol is an active compound with potential value.

The Effect of n-Hexane on the Gonad Toxicity of Female Mice

Objective To investigate the toxic effects of n-hexane on the Ganod of female mice.Methods n-Hexane was administered to four groups of mice by inhalation at doses of 0,3.0,15.1,and 75.8 mL/m3 respectivelyfor five weeks.Each group consisted of 10 mice,of which half were injected in first with 10 IU of pregnant mare serum gonadotrophin（PMSG） on the 33rd days,and then with 10 IU of human chorionic gonadotrophin（HCG） 48 hrs later.After the treatment,mouse sera were sampled and ovulating hormone（LH）,follicle-stimulating hormone（FSH）,estradiol（E2）,and progesterone（P4） levels were measured by electrochemiluminescence immunoassays（ECLIA）.In each group,the right ovaries of the non-super-ovulated mice were stained with hematoxylin and eosin while ovaries on the left side were prepared with the TUNEL method in order to detect apoptotic cells.Results The duration of the diestrus stage decreased significantly（P0.05） in the 75.8 mL/m3 group.All super-ovulated mice in each treatment group produced fewer eggs than those in the control group（P0.05）.The number of follicles in ovaries in the 75.8 mL/m3 group was smaller compared with the control group（P0.05）.The serum P4 levels in each treatment group were lower than those in the control group（F=6.196,P0.01）.The cell apoptotic rate in the 75.8 mL/m3 group was higher（P0.05）.Conclusion n-Hexane may have directly mediated via alterations hormone secretion and promoted granulosal cell apoptotic,which may be one of the important mechanisms for n-hexane induced mouse ovary impairment.

Photolysis of mono- through deca-chlorinated biphenyls by ultraviolet irradiation in n-hexane and quantitative structure-property relationship analysis

The photolysis of 16 polychlorinated biphenyls （PCBs） （including mono- through deca-chlorinated） in n-hexane was investigated under ultraviolet irradiation using a 500-W high-pressure mercury lamp. Photolysis of PCBs follows pseudo-first-order reaction kinetics, with photolysis rate constants ranging between 0.0011 s^-1 for PCB-52 and 0.0574 s^-1 for PCB-118. The degradation rates of PCBs by high-pressure mercury lamp irradiation were remarkably independent with respect to the degree of chlorination. Furthermore, partial least squares （PLS） models were developed to provide insight into which aspect of the molecular structure influenced PCB photolysis rate constants. It was found that the photolysis rates of PCBs increased with an increase in the net charge on the carbon atom （qc）, （ELUMO-EHOMO）^2, and the Y-axis dipole moment （μy） values, or the decrease in the energy of the second highest occupied molecular orbital （EHOMO-1）, energy of the lowest unoccupied molecular orbital （ELUMO）, ELUMO ＋ EHOMO, ELUMO - EHOMO, most positive atomic charge （q^＋）, and the twist angle of the chlorine atom （TA） values.

Pt supported on Zn modified silicalite-1 zeolite as a catalyst for n-hexane aromatization

Platinum(Pt)supported on Zinc(Zn)modified silicalite-1(S-1)zeolite(denoted as Pt-Zn/S-1)was prepared by using a wetness-impregnation method and applied in the n-hexane aromatization reaction for the first time.Both Lewis and Bronsted acid sites were detected in Pt-Zn/S-1 catalyst by means of FT-IR adsorption of NH3 experiment,which were identified as mostly weak and medium ones.Besides,Pt and Zn species showed strong interaction,as revealed by the TPR(Temperature-programmed reduction)and XPS(X-ray photoelectron spectroscopy)experiments.Pt-Zn/S-1 catalyst exhibited excellent aromatization function rather than isomerization and cracking side reactions in the conversion of n-hexane.Pulse experimental study showed that 75.6%of n-hexane conversion and 76.8%of benzene selectivity were obtained over Pt0.1-Zn60/S-l catalyst at 550℃ and under atmospheric pressure.By spectroscopy tests and pulse experimental results,it was concluded that the n-hexane aromatization over Pt-Zn/S-1 catalyst follows a metal-acid bifunctional mechanism.Furthermore,with the assistance of Zn,the electron-deficient Pt species in Pt-Zn/S-1 showed good sulfur tolerance performance.

The impact of n-hexane on the secretion of mouse estrogen and progesterone

Aim: To study the toxic effect of n-hexane on sex hormone levels, including its effect on ovarian sex hormone secretion levels and the underlying mechanism. 1) In vivo experiment: The mice were exposed to n- hexane by static inhalation of doses of 0, 3.0, 15.1 or 75.8 ml/m3 once a day (4 hours), 7 days a week, for 5 consecutive weeks. After exposure, mouse sera were sampled to measure estradiol (E2) and progesterone (P4) levels by electrochemiluminescence immunoassays (ECLIA). 2) In vitro experiment: mice at different stages of the estrous cycle were sacrificed and their minced tissue pieces were incubated in medium containing hexane-2,5-dione (2,5-HD). Then, the E2 and P4 levels in the media were measured by ECLIA. In vivo assays, the serum P4 levels in each group were lower than the control group, which was statistically significant (F = 6.196, P 2 level of 75.8 mL/m3 dosage group was decreased (96.9522 ± 7.8652)) compared to the control group (119.1600 ± 25.6420), with statistical significance (P 4 levels of 15.1 mL/m3 and 75.8 mL/m3 dosage groups were also decreased (18.5938 ± 12.485pmol/L, 13.5550 ± 5.7789 pmol/L) and were statistically significantly (F = 6.196, P In vitro, the E2 levels at various stages of the estrous cycle were significantly different from the control groups (P In vitro, different concentrations of 2, 5-HD significantly inhibited the P4 level (P 4 levels at various stages of the estrous cycle were also significantly different from controls (P 0.05). The results indicate that n-hexane may inhibit release of ovarian E2 and P4, which may be the main reason for the interference of the reproductive endocrine system by n-hexane.

N-hexane Alters the Maturation of Oocytes and Induces Apoptosis in Mice

Objective This study was aimed to determine the effects of n-hexane on the maturation of mouse oocytes. Methods Cell culture was used to observe the maturation of mouse oocytes and CLSM was employed to determine their apoptosis. Results Germinal vesicle breakdown （GVBD） and extrusion of the first polar body in mouse oocytes were significantly inhibited by n-hexane. After fertilization, the number of eggs in the mouse was significantly reduced by n-hexane. Mitochondrial membrane potentials （A^Um） were altered in mouse oocytes that were leading to apoptosis of the oocytes. Conclusion N-hexane might have affected the maturation of oocytes, causing alteration of ~qJm and leading to apoptosis which maybe one of the most imn（~rt^nt rnpch^ni^nn~

Influence of Wind Deviation Angle on n-Hexane Evaporation Loss of Internal Floating-Roof Tanks

With the increasing attention to environmental protection,it is still necessary to strictly control the oil evaporation loss from the IFRT(internal floating-roof tank)to the atmosphere.Upon using n-hexane as a representative of light oil,the effects of the WDAs(wind deviation angles)on airflow distribution,the wind speed,the n-hexane vapor concentration,and the evaporation loss rate in the IFRT were investigated,and the mass transfer of the vapor-air was analyzed.The results are shown as follows:when the WDA is 0°,the vapor concentration in the gas space above the floating deck is the lowest;when the WDA is 22.5°,the oil evaporation loss rate is the largest;when the WDA is 45°,the vapor concentration is the highest,but the evaporation loss rate is the smallest.It is recommended to arrange the vent to the wind direction with an angle of 45°to reduce the evaporation loss and protect the atmospheric environment.

Heterogeneity of Adsorption Sites and Adsorption Kinetics of n-Hexane on Metal–Organic Framework MIL-101(Cr)

The heterogeneity of adsorption sites and adsorption kinetics of n-hexane on a chromium terephthalate-based metal-organic framework MIL-10^1 （Cr） were studied by gravimetric method and temperature-programmed desorption （TPD） experiments. The MIL-101 crystals were synthesized by microwave irradiation method. The ad- sorption isotherms and kinetic curves of n-hexane on the MIL-101 were measured. Desorption activation energies of n-hexane from the MIL-10^1 were estimated by TPD experiments. The resulthowed that equilibrium amount ofn-hexane adsorbed on the MIL-10^1 was up to 5.62 mmol.g- 1 at 298 K and 1.6 x10^4 Pa, much higher than that of some activated carbons, zeolltes and so on. The isotherms of n-hexane on the MIL-101 could be well fitted with Langmuir-Freundlich model. TPD spectra exhibit two types of adsorption sites on the MIL-101 with desorption activation energies of 39.41 and 86.69 kJ. mol-1. It reflects the surface energy heterogeneity on the MIL-10I frameworks for n-hexane adsorption. The diffusion coefficients of n-hexane are in the range of （1.35- 2.35 ） x 10 - 1 o cm2. s - 1 with ad sorotion activation enerv of 16.33 kl. mol - 1.

N-Hexane Isomerization on Ni-Pt/Catalysts Supported on Mordenite

The aim of this work was to evaluate the catalytic properties for n-hexane isomerization of bifunctional monometallic (Ni or Pt) and bimetallic catalysts (Pt-Ni), using HMOR zeolite as support. The method used for metal dispersion in the zeolite was competitive ion exchange using ammine complexes [Ni(NH3)6]Cl2 and [Pt(NH3)4]Cl2 as precursors. The catalysts were characterized by X-Ray diffraction, X-Ray energy dispersion spectroscopy, temperature-programmed reduction and transmission electron microscopy. The n-hexane isomerization reaction using the catalysts was carried out to evaluate the catalyst activity. The reaction was carried out in a fixed bed reactor operating at 250?C, 1 atm, H2/C6 = 9 molar ratio. The profiles obtained from TPR suggest that, for bimetallic catalysts, the presence of platinum facilitates the reduction of Ni2+ cations. The bimetallic catalysts presented a higher activity in the isomerization of n-hexane when compared to the monometallic ones, as well better stability as the Pt content in the solid increases.

Antipyretic and anticonvulsant activity of n-hexane fraction of viola betonicifolia

Objective:To investigate the antipyretic and anticonvulsant activities of n-hexane fraction of Viola betonicifolia(V.betonicifolia).Methods:The antipyretic effect was scrutinized using brewer's yeast induced pyrexia and anticonvlsion effect was tested using pentylenetetrazol and strychnine induced convulsion in mice.Results:N-hexane fraction of V.betonicifolia demonstrated highly significant antipyretic activity during various assessment times(1-5 h)when challenged in yeast induced pyrexia test.The effect was in a dose dependent manner with maximum attenuation(82.50%)observed at 300 mg/kg i.p.When tested in pentylenetetrazol induced convulsion test,the 1st stage(Ear and facial twitching)and 2nd stage(Convulsive wave through the body)was 100%protected during 24 h at all the test doses(300,400 and 500 mg/kg i.p.),while the latency time of remaining stages was significantly increased.The maximum effect was observed by n-hexane fraction of V.betonicifolia at 400 and 500 mg/kg i.p.,as the latency time for generalized clonic-tonic seizure(5th stage)was increased up to 25.34 min.However,n-hexane fraction of V.betonicifolia had no protection in strychnine induced convulsion test.Conclusions:In conclusion,phytopharmacological studies provide scientific foundation to the folk uses of the plant in the treatment of pyrexia and neurological disorders.

Study on Pt/KL Zeolite Catalyst for n-Hexane Aromatization Modified by Lanthanum

Xe-129-NMR and TEM were used to study the location and dispersion of Pt particles in KL zeolite with lanthanum incorporation. Owing to the interaction between Pt and La, more Pt particles accompanying La3+ were located in the inner channels of KL zeolite, rather than agglomerated in the external surface. The dispersion of Pt particles was therefore improved. Pt/KL zeolite modified by La showed a little lower reactivity for aromatization of n-hexane, but much higher resistance to sulfur-poisoning because of the existence of new acidic sites.

Immunomodulation and Nigerian mistletoe immunomodulatory activities of n-hexane and methanol extracts of Loranthus micranthus Linn,parasitic on Parkia biglobosa.

Loranthus micranthus is the species of mistletoe peculiar to the eastern province of Nigeria.It has been shown to possess anti-diabetic,anumotility,antimicrobial and antihypertensive activities which are host-tree dependent. The antimicrobial activity was found to vary with the season during which the plant was harvested.We are of the opinion that this species should possess immunomodulating potentials as have been reported for the European species,Viscum album.In our efforts to establish the bio-activities and active principles in our local mistletoe, the immunomodulatory activity of n-hexane and methanol extracts from Loranthus micranthus parasitic on Persea americana was assessed at three dose levels ranging from 100 to 400 mg/kg body weight using delayed type hypersensitivity reaction(DTHR) and cyclophosphamide-induced myelosuppression models in mice.This was compared with responses from a standard immunostimulatory drug,levamisole.Preliminary phytochemical analysis of the plant showed the presence of tannins,flavonoids,alkaloids,terpenoids,carbohydrates and saponins.Regression analysis indicated a dose-dependent response relationship in the parameters measured with over 170%increase for both extracts at the highest dose level.The one way ANOVA test showed significant variation in the parameters between the controls and the different dose levels.However,at 95%confidence level,(P【0.05),there was no statistically significant difference between the two extracts, an indication that the active immunomodulant(s) could be both in the polar and non-polar crude extract.In conclusion,the present results have established some immune stimulating actions of the Eastern Nigeria mistletoe, Loranthus micranthus thus indicating that this variant of the semi parasitic plant holds a strong promise as an immunostimulatory candidate.There is therefore,a basis for further detailed investigation on the fractions and specific constituents.Thus,these extracts from Loranthus micranthus possess pronounced immune stimulating action comparable to Levamisole in mouse-based models.

High Pressure Vapor-Liquid Equilibrium of Supercritical Carbon Dioxide+n-Hexane System

Vapor-liquid equilibrium data of supercritical carbon dioxide ＋ n-hexane system were measured at 31.3.15 K, 333.15 K, 353.15 K, and 373. 15 K and their molar volumes and densities were measured both in the subcrJtical and supercritical regions ranging from 2. 15 to 12.63 MPa using a variable-volume autoclave. The thermodynamic properties including mole fractions, densities, and molar volumes of the system were calculated with an equation of state by Heilig and Franck, in which a repulsion term and a square-well potential attraction term for intermolecular interaction was used. The pairwise combination rule was used to calculate the square-well molecular interaction potential and three adjustable parameters （ω, kω, kσ ） were obtained. The Heilig-Franck equation of state is found to have good correlation with binary vapor-liquid equilibrium data of the carbon dioxide ＋ n-hexane system.

Preparation of hybridizing zeolitic imidazolate frameworks with carboxymethylcellulose for adsorption separation of n-hexane/3-methylpentane

A novel ZIF-8-CMC hybrid material was fabricated from the hybridization of ZIF-8 and carboxymethylcellulose(CMC) by impregnation method for n-hexane/3-methylpentane separation.The surface properties of ZIF-8 were tailored by introducing CMC into ZIF-8 nanoparticles.In this work,adsorption separation of n-hexane(nHEX) and 3-methylpentane(3 MP) on ZIF-8-CMC were investigated by batch vapor-phase adsorption and liquid-phase breakthrough adsorption.The adsorption selectivity of nHEX/3 MP reversed from preferable adsorption of nHEX to preferable adsorption of 3 MP upon the increasing of CMC containing in the hybrid materials.As the temperature increases,the adsorption amounts of nHEX and 3 MP decrease.With the increasing of CMC contents,the nHEX uptake decreased,the uptake capacity of 3 MP increased gradually.For liquid-phase breakthrough adsorption,the dynamic adsorption capacity of nHEX also decreased with the increasing of temperature.