Stable poly (ionic liquids) with unique cross‐linked mesoporous‐macroporous structure as efficient catalyst for alkylation of o‐xylene and styrene

In this work, using divinylbenzene (D), 1‐vinylimidazole (V) and 1‐vinyl‐3‐butylimidazolium bromide ([VBIM][Br]) as monomers, the binary‐monomer poly (ionic liquids) (PILs) and ternary‐monomer PILs were successfully synthesized, via hydrothermal polymerization and anion exchange, sequentially. Compared with each other, the ternary polymeric acidic IL catalyst has a clear spongy porous structure, while having a more stable macroporous structure, a larger specific surface area, more acidic groups and more active sites. Catalytic performance of catalyst was investigated through the alkylation of o‐xylene and styrene. The effect of the amount of IL added and the length of the cation chain on the ternary polymerization of acidic IL was systematically investigated. Under optimal reaction conditions (molar ratio of monomers was D:V:[VBIM][Br] = 2:1:1, the most suitable cation chain length was C₄), the synthesized MPD‐[C₄V]‐[VBIM][SO₃CF₃] has a larger specific surface area (89.47 m²/g), large pore volume (0.29 cm³/g), and abundant mesopores and macropores, which help to improve the contact between the active site and reactants. Moreover, the catalyst could maintain a relatively high conversion of styrene (99.0%), 1,2‐diphenylethane yield (98.7%) and high thermostability under reaction and be easily be divided from the solution, which is critical for heterogeneous solid catalysts.     

Correlating backbone‐to‐backbone distance to ionic conductivity in amorphous polymerized ionic liquids

The morphology and ionic conductivity of poly(1‐n‐alkyl‐3‐vinylimidazolium)‐based homopolymers polymerized from ionic liquids were investigated as a function of the alkyl chain length and counterion type. In general, X‐ray scattering showed three features: (i) backbone‐to‐backbone, (ii) anion‐to‐anion, and (iii) pendant‐to‐pendant characteristic distances. As the alkyl chain length increases, the backbone‐to‐backbone separation increases. As the size of counterion increases, the anion‐to‐anion scattering peak becomes apparent and its correlation length increases. The X‐ray scattering features shift to lower angles as the temperature increases due to thermal expansion. The ionic conductivity results show that the glass transition temperature (T_g) is a dominant, but not exclusive, parameter in determining ion transport. The T_g‐independent ionic conductivity decreases as the backbone‐to‐backbone spacing increases. Further interpretation of the ionic conductivity using the Vogel–Fulcher–Tammann equation enabled the correlation between polymer morphology and ionic conductivity, which highlights the importance of anion hoping between adjacent polymer backbones. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Influence of FeCl3‐modified chloroaluminate ionic liquids on long‐chain alkenes alkylation

The influence of anhydrous ferric chloride on the catalytic properties of chloroaluminate ionic liquids catalyst for Friedel–Crafts alkylation was investigated. The catalysts were characterized by Fourier‐transform infrared (FT‐IR) (acetonitrile molecule as probe), specific gravity, and ²⁷Al NMR. Besides, the effect of the mass ratio of FeCl₃ to AlCl₃, catalysts dosage, toluene/olefin molar ratio, reaction temperature, and reaction time on long‐chain alkenes alkylation were investigated thoroughly. And bromine value and high‐performance liquid chromatography (HPLC) were employed as the evaluation method for alkylation products. It was observed that the addition of anhydrous ferric chloride results in improvement in terms of Lewis acid and its catalytic recyclability. Among these catalysts studied, the catalyst modified with 1.0 wt.% anhydrous FeCl₃ showed the best catalytic performance in terms of yield and stability, which can be attributed to the formation of new stronger acidic ions [Al₂FeCl_l0]^? when the added ferric chloride reacts with acidic ions [Al₂Cl₇]^?.     

Functional mesoporous poly (ionic liquid) derived from P123: From synthesis to catalysis and alkylation of styrene and o‐xylene

A novel strategy was proposed for the fabrication of high‐performance acidic mesoporous poly ionic liquids catalyst. In this work, mesoporous poly ionic liquids (MPILs) were synthesized with P123 (PEO₂₀PPO₇₀PEO₂₀) served as pore‐forming agent. Then, MPILs were treated with PW^3? anion exchange, thereby fabricating PW/MPIL‐S(x). MPIL and PW/MPIL‐S(x) were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), Thermogravimetric analysis (TA), N₂ adsorption–desorption and Fourier transform infrared (FT‐IR) spectra and X‐ray photoelectron spectroscopy (XPS) spectra. The effect of solvent and concentration of P123 on the morphology and mesoporous structure of MPILs were investigated systematically. And the results show that MPILs were featured with mesoporous channel structure, high surface area (up to 737 m²/g) and large pore volumes (1.16 cm³/g), which benefit heterogeneous phase reaction (such as, alkylation of styrene with o‐xylene). In the alkylation reaction, under optimal reaction conditions, the catalyst PW/MPIL‐THF (4.0 g) shows high conversion of styrene (100%) and PXE yield (96.21%), demonstrating the excellent catalytic activities. Furthermore, PW/MPIL‐S(x) are easy to be separated from the catalytic system by filtration and show no obvious decrease in catalytic activity after 6 cycle runs. The obtained PW/MPIL‐S(x) catalyst exhibit high thermal and mechanical stability as well, indicating extensive application in high temperature acidic catalysis. This work might open up a new method for the synthesizing of porous polymer catalysts in the future.     

离子液体中异丁烷/2-丁烯烷基化反应机理研究

以复合离子液体[Et_3NH]Cl-AlCl_3-CuCl为催化剂,在连续搅拌釜式反应器中进行了异丁烷与2-丁烯烷基化反应;利用氘代异丁烷同位素示踪法研究了催化反应机理。结果表明,在离子液体中异丁烷烷基化的反应诱导期较短;三甲基戊烷产物主要源于异丁烷的自烷基化、丁烷/丁烯的直接烷基化以及C_(12)~+中间体的裂化反应,而大部分二甲基己烷是仲丁基碳正离子与丁烯加成的产物。     

Determination of triazine herbicides in juice samples by microwave‐assisted ionic liquid/ionic liquid dispersive liquid–liquid microextraction coupled with high‐performance liquid chromatography

A novel microextraction method, termed microwave‐assisted ionic liquid/ionic liquid dispersive liquid–liquid microextraction, has been developed for the rapid enrichment and analysis of triazine herbicides in fruit juice samples by high‐performance liquid chromatography. Instead of using hazardous organic solvents, two kinds of ionic liquids, a hydrophobic ionic liquid (1‐hexyl‐3‐methylimidazolium hexafluorophosphate) and a hydrophilic ionic liquid (1‐butyl‐3‐methylimidazolium tetrafluoroborate), were used as the extraction solvent and dispersion agent, respectively, in this method. The extraction procedure was induced by the formation of cloudy solution, which was composed of fine drops of 1‐hexyl‐3‐methylimidazolium hexafluorophosphate dispersed entirely into sample solution with the help of 1‐butyl‐3‐methylimidazolium tetrafluoroborate. In addition, an ion‐pairing agent (NH₄PF₆) was introduced to improve recoveries of the ionic liquid phase. Several experimental parameters that might affect the extraction efficiency were investigated. Under the optimum experimental conditions, the linearity for determining the analytes was in the range of 5.00–250.00 μg/L, with the correlation coefficients of 0.9982–0.9997. The practical application of this effective and green method is demonstrated by the successful analysis of triazine herbicides in four juice samples, with satisfactory recoveries (76.7–105.7%) and relative standard deviations (lower than 6.6%). In general, this method is fast, effective, and robust to determine triazine herbicides in juice samples.     

Natural terpene derivatives as new structural task‐specific ionic liquids to enhance the enantiorecognition of acidic enantiomers on teicoplanin‐based stationary phase by high‐performance liquid chromatography

We present the specific cooperative effect of a semisynthetic glycopeptide antibiotic teicoplanin and chiral ionic liquids containing the (1R ,2S ,5R )‐(–)‐menthol moiety on the chiral recognition of enantiomers of mandelic acid, vanilmandelic acid, and phenyllactic acid. Experiments were performed chromatographically on an Astec Chirobiotic T chiral stationary phase applying the mobile phase with the addition of the chiral ionic liquids. The stereoselective binding of enantiomers to teicoplanin in presence of new chiral ionic liquids were evaluated applying thermodynamic measurements and the docking simulations. Both the experimental and theoretical methods revealed that the chiral recognition of enantiomers in the presence of new chiral ionic liquids was enthalpy driven. The changes of the teicoplanin conformation occurring upon binding of the chiral ionic liquids are responsible for the differences in the standard changes in Gibbs energy (ΔG ⁰) values obtained for complexes formed by the R and S enantiomers and teicoplanin. Docking simulations revealed the steric adjustment between the chiral ionic liquids cyclohexane ring (chair conformation) and the β‐d ‐glucosamine ring of teicoplanin and additionally hydrophobic interactions between the decanoic aliphatic chain of teicoplanin and the alkyl group of the tested salts. The obtained terpene derivatives can be considered as “structural task‐specific ionic liquids” responsible for enhancing the chiral resolution in synergistic systems with two chiral selectors.     

Design,synthesis, and self‐assembly manipulating of polymerized ionic liquids contained imidazolium based on “Jacketing” effect

A series of novel polymerized ionic liquids (PILs) contained imidazolium, poly (2,5‐bis{[6‐(1‐butyl‐3′‐imidazolium)hexyl] oxy carbonyl}styrene salts) (denoted as P1? X^?, X^??Br^?, BF₄^?, PF₆^? and TFSI^?) were successfully synthesized via radical polymerization. The chemical structures of the monomers and their corresponding PILs were confirmed by ¹H NMR, ¹³C NMR, and Fourier transform infrared spectroscopy. Thermogravimetric analysis results showed that these PILs had excellent thermal stability. The phase transitions and liquid‐crystalline (LC) behaviors of these polymers were investigated by differential scanning calorimetry, polarized light microscopy (PLM), and wide‐angle X‐ray diffraction. The combined experimental results showed that all the PILs could form hexagonal columnar (?H) LC ordered structures because of the strong interaction between the anions and cations in the side groups except for P1? TFSI^?. The conductivities of monomers and PILs were sketchily investigated, and monomers had higher conductivities than those of conprespoding PILs. For comparison, we have synthesized a polymer without counter‐anion, but similar to the chemical structure of P1? X^?, poly (2, 5‐bis{[6‐(4‐butoxy‐4′‐oxy phenyl) hexyl] oxycarbonyl} styrene) (denoted as P2). In this case, phenyl took place of imidazolium of side chain, and LC ordered structure did not form. The comparison between P1? X^? and P2 suggested that ion played an important role in the constructing of LC ordered structure. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Cu对离子液体异丁烷/丁烯烷基化反应选择性的影响研究

合成并表征了[BMIm]Cl-1.8AlCl3-0.5CuCl、[Et3NH]Cl-1.8AlCl3/CuAlCl4等离子液体,考察了含Cu离子液体等酸性催化剂中的异丁烷/丁烯烷基化反应,研究了Cu对离子液体烷基化选择性的影响。结果表明,Cu的引入对离子液体酸性的影响较小,不是反应选择性提高的主要原因,而烷基化过程中CuAlCl5-/CuAlCl4等配合物的存在,以及它们对2-丁烯的络合吸附是改善离子液体催化选择性的关键因素。相同反应条件下,[Et3NH]Cl-1.8AlCl3/CuAlCl4、[BMIm]Cl-1.8AlCl3/CuAlCl4等催化剂的三甲基戊烷选择性最高可达87.5%(质量分数),产物辛烷值100.5,明显优于硫酸、常规氯铝酸离子液体和复合离子液体等烷基化汽油辛烷值。     

Matrix solid‐phase dispersion coupled with homogeneous ionic liquid microextraction for the determination of sulfonamides in animal tissues using high‐performance liquid chromatography

Matrix solid‐phase dispersion coupled with homogeneous ionic liquid microextraction was developed and applied to the extraction of some sulfonamides, including sulfamerazine, sulfamethazine, sulfathiazole, sulfachloropyridazine, sulfadoxine, sulfisoxazole, and sulfaphenazole, in animal tissues. High‐performance liquid chromatography was applied to the separation and determination of the target analytes. The solid sample was directly treated by matrix solid‐phase dispersion and the eluate obtained was treated by homogeneous ionic liquid microextraction. The ionic liquid was used as the extraction solvent in this method, which may result in the improvement of the recoveries of the target analytes. To avoid using organic solvent and reduce environmental pollution, water was used as the elution solvent of matrix solid‐phase dispersion. The effects of the experimental parameters on recoveries, including the type and volume of ionic liquid, type of dispersant, ratio of sample to dispersant, pH value of elution solvent, volume of elution solvent, amount of salt in eluate, amount of ion‐pairing agent (NH₄PF₆), and centrifuging time, were evaluated. When the present method was applied to the analysis of animal tissues, the recoveries of the analytes ranged from 85.4 to 118.0%, and the relative standard deviations were lower than 9.30%. The detection limits for the analytes were 4.3–13.4 μg/kg.     

Use of ionic liquid for the enzyme‐catalyzed polymerization of phenols

Ionic liquid and buffer mixture media are first reported in the peroxidase‐catalyzed polymerization of phenol. Yield of 100% with molecular weights of 7000 KDa, as assessed by size‐exclusion chromatography (SEC), were attained using 1‐butyl‐3‐methylimidazolium tetrafluoroborate–buffer mixtures with added hydrogen peroxide. The simplicity of the process and the low vapor pressure of the solvent media allow an eco‐friendly alternative to the general synthesis of polyphenolic‐type biopolymers. Evidence for the consequent polyphenol (PPO) was obtained from solid‐state ¹³C cross‐polarization magic angle spinning (CP‐MAS) NMR spectroscopy and FT‐IR. Copyright © 2009 John Wiley & Sons, Ltd.     

Dicationic imidazolium ionic liquid modified silica as a novel reversed‐phase/anion‐exchange mixed‐mode stationary phase for high‐performance liquid chromatography

A dicationic imidazolium ionic liquid modified silica stationary phase was prepared and evaluated by reversed‐phase/anion‐exchange mixed‐mode chromatography. Model compounds (polycyclic aromatic hydrocarbons and anilines) were separated well on the column by reversed‐phase chromatography; inorganic anions (bromate, bromide, nitrate, iodide, and thiocyanate), and organic anions (p‐aminobenzoic acid, p‐anilinesulfonic acid, sodium benzoate, pathalic acid, and salicylic acid) were also separated individually by anion‐exchange chromatography. Based on the multiple sites of the stationary phase, the column could separate 14 solutes containing the above series of analytes in one run. The dicationic imidazolium ionic liquid modified silica can interact with hydrophobic analytes by the hydrophobic C₆ chain; it can enhance selectivity to aromatic compounds by imidazolium groups; and it also provided anion‐exchange and electrostatic interactions with ionic solutes. Compared with a monocationic ionic liquid functionalized stationary phase, the new stationary phase represented enhanced selectivity owing to more interaction sites.     

Preparation of a solution‐processable,nanostructured ionic polyacetylene

Polymerization of a self‐assembled 1‐dodecyl‐3‐propargylimidazolium bromide ionic liquid (IL) yields a nanostructured ionic polyacetylene. A 1:1 aqueous mixture of the amphiphilic IL produces an ordered lyotropic mesophase that adopts a hexagonal perforated lamellar structure. Rh (I)‐mediated polymerization of the assembled mixture yields a hexagonal modulated lamellar structured polymer. FTIR spectroscopy reveals that the polymer was self n‐doped. The polymer was fractioned into three components with the majority product, possessing an intermediate molecular weight that is soluble in polar organic solvents. In methanol, the optical band gap of the main fraction was determined to be 2.38 eV and was nonemissive. The solution‐processable polymer was airbrush sprayed onto glass substrates to give a liquid‐crystalline, lamellar structured semiconductive film (7.02 × 10^?5 S cm^?1). The polymer resisted oxidation (degradation) upon storage in air as monitored by vibrational spectroscopy. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1215–1227     

碱处理对β分子筛催化苯与苯甲醇液相傅-克烷基化反应性能的影响

采用Na OH水溶液对β分子筛进行碱处理,利用XRD、N_2-Physisorption、XRF、NH_3-TPD及SEM等表征手段,使用苯与苯甲醇为反应物进行傅-克烷基化反应,对碱处理前后β分子筛的物性和反应性能进行了研究.实验结果表明:随着碱处理程度的加深,β分子筛的孔径增大,催化剂外比表面积显著增加,β分子筛的弱酸强度和弱酸总量有所下降,由此带来的反应结果是苯甲醇的转化率显著提高.对于孔径最大的催化剂,在常压下80℃时进行反应,当反应时间为140 min时,苯甲醇的转化率已达到100%,选择性有所提高.     

H3PW12O40/mpg‐C3N4 as an efficient and reusable catalyst in the alkylation of o‐xylene and styrene

A heterogeneous catalyst (HPW/mpg‐C₃N₄) for the alkylation of o‐xylene and styrene reaction was acquired by the immobilization of phosphotungstic acid (HPW) on mesoporous graphitic carbon nitride (mpg‐C₃N₄) through electrostatic interaction. The results of Fourier transform infrared spectroscopy (FT‐IR), X‐ray powder diffraction (XRD), X‐ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) proved that HPW was successfully immobilized on the protonated mpg‐C₃N₄ by electrostatic interaction. The textural properties and morphology of HPW/mpg‐C₃N₄ were characterized by N₂ adsorption–desorption, scanning electron microscopy (SEM). Among them, 40% HPW/mpg‐C₃N₄ displays the best catalytic performance in the alkylation reaction with 91.8% yield and 96.5% selectivity to 1, 2‐diphenylethylane. Moreover, protonated mpg‐C₃N₄ not only displays as a support to facilitate great dispersion of HPW but also promotes the alkylation product diffusion effectively. Besides, the HPW/mpg‐C₃N₄ catalyst could be recycled easily without significant loss of catalytic activity, which is demonstrate by the recyclability of HPW/mpg‐C₃N₄ catalyst test.     

Micro/macrotribological properties of several nano‐scale ionic liquid films on modified silicon wafers

Three kinds of alkylimidazolium base room temperature ionic liquids (RTILs) were synthesized and their nano‐scale lubricant films were prepared on modified silicon wafers by dip‐coating method. The thicknesses of these films were measured and their relationship between thickness and solution concentration was obtained. Their surface morphologies were observed and contact angles of water on these films were determined. The adhesions and friction coefficients of these films were detected by contact mode AFM. As comparison, their macrotribological properties were evaluated on a UMT‐2MT tribo‐tester. It was found that, in microscale, 1‐hexyl‐3‐methyl‐imidazolium hexafluorophosphate performed the best tribological properties, while in macroscale, its tribological properties were similar with that of 1‐hexyl‐3‐methyl‐imidazolium tetrafluoroborate and better than that of 1‐hexyl‐3‐methyl‐imidazolium adipate. Copyright © 2009 John Wiley & Sons, Ltd.     

Multiple monolithic fiber solid‐phase microextraction based on a polymeric ionic liquid with high‐performance liquid chromatography for the determination of steroid sex hormones in water and urine

The development of a simple and sensitive analytical approach that combines multiple monolithic fiber solid‐phase microextraction with liquid desorption followed by high‐performance liquid chromatography with diode array detection is proposed for the determination of trace levels of seven steroid sex hormones (estriol, 17β‐estradiol, testosterone, ethinylestradiol, estrone, progesterone and mestranol) in water and urine matrices. To extract the target analytes effectively, multiple monolithic fiber solid‐phase microextraction based on a polymeric ionic liquid was used to concentrate hormones. Several key extraction parameters including desorption solvent, extraction and desorption time, pH value and ionic strength in sample matrix were investigated in detail. Under the optimal experimental conditions, the limits of detection were found to be in the range of 0.027–0.12 μg/L. The linear range was 0.10–200 μg/L for 17β‐estradiol, 0.25–200 μg/L estriol, ethinylestradiol and estrone, and 0.50–200 μg/L for the other hormones. Satisfactory linearities were achieved for analytes with the correlation coefficients above 0.99. Acceptable method reproducibility was achieved by evaluating the repeatability and intermediate precision with relative standard deviations of both less than 8%. The enrichment factors ranged from 54‐ to 74‐fold. Finally, the proposed method was successfully applied to the analysis of steroid sex hormones in environmental water samples and human urines with spiking recoveries ranged from 75.6 to 116%.     

A new ionic liquid surface‐imprinted polymer for selective solid‐phase‐extraction and determination of sulfonamides in environmental samples

Toward improving the selective adsorption performance of molecularly imprinted polymers in strong polar solvents, in this work, a new ionic liquid functional monomer, 1‐butyl‐3‐vinylimidazolium bromide, was used to synthesize sulfamethoxazole imprinted polymer in methanol. The resulting molecularly imprinted polymer was characterized by Fourier transform infrared spectra and scanning electron microscopy, and the rebinding mechanism of the molecularly imprinted polymer for sulfonamides was studied. A static equilibrium experiment revealed that the as‐obtained molecularly imprinted polymer had higher molecular recognition for sulfonamides (e.g., sulfamethoxazole, sulfamonomethoxine, and sulfadiazine) in methanol; however, its adsorption of interferent (e.g., diphenylamine, metronidazole, 2,4‐dichlorophenol, and m‐dihydroxybenzene) was quite low. ¹H NMR spectroscopy indicated that the excellent recognition performance of the imprinted polymer was based primarily on hydrogen bond, electrostatic and π‐π interactions. Furthermore, the molecularly imprinted polymer can be employed as a solid phase extraction sorbent to effectively extract sulfamethoxazole from a mixed solution. Combined with high‐performance liquid chromatography analysis, a valid molecularly imprinted polymer‐solid phase extraction protocol was established for extraction and detection of trace sulfamethoxazole in spiked soil and sediment samples, and with a recovery that ranged from 93–107%, and a relative standard deviation of lower than 9.7%.     

Formation and tribological properties of two‐component ultrathin ionic liquid films on Si

Several single‐component and two‐component imidazolium ionic liquids (ILs) ultrathin films were formed on Si substrates by a dip‐coating and heat treatment process. The formation and surface properties of the films were analyzed by means of ellipsometric thickness measurement, X‐ray photoelectron spectra and atomic force microscope. The adhesive and nanotribological behaviors of the films were evaluated by a homemade colloidal probe. A ball‐on‐plate tribometer was used to test the microtribological performances of these films. As a result, the two‐component ILs ultrathin film containing 80% solid‐like ILs phase shows more homogenous surface morphologies and optimal micro/nano‐tribological properties as compared to single‐component ILs films, which is ascribed to a synergic effect between the steady solid‐like ILs phase as the backbone and the proper amount of flowable liquid‐like ILs phase. By studying the influence of various solid/liquid ILs ratios on tribological properties of the two‐component ILs films, we might find the way to design ILs films with excellent comprehensive tribological properties. Copyright © 2010 John Wiley & Sons, Ltd.     

Interactions of ionic liquids with polysaccharides. VI. Pure cellulose nanoparticles from trimethylsilyl cellulose synthesized in ionic liquids

Trimethylsilyl cellulose (TMSC) can be efficiently synthesized with 1,1,1,3,3,3‐hexamethyldisilazane (HMDS) by applying the ionic liquids (ILs) 1‐ethyl‐3‐methylimidazolium acetate, 1‐ethyl‐3‐methylimidazolium chloride, and 1‐butyl‐3‐methylimidazolium chloride as reaction medium, yielding pure biopolymer derivatives with degrees of substitution (DS) up to 2.89. Cosolvents, for example, chloroform, could be used to adjust the viscosity of the system and to achieve the miscibility of the components. During the synthesis of highly functionalized derivatives precipitation of the TMSC occurred, which simplifies the recycling of the IL. The high tendency of TMSC toward the formation of supermolecular structures was exploited for the formation of nanoparticles studying a simple dialysis process. Amazingly, pure cellulose nanoparticles can be obtained by dissolving TMSC in tetrahydrofurane or N,N‐dimethyl acetamide and dialysis against water. FTIR spectroscopy confirmed the complete removal of the TMS functions during this process. Scanning electron microscopy, dynamic light scattering, atomic force microscopy, and particle size distribution analysis showed that cellulose particles down to a size of 170 nm are accessible in this simple manner. The nanoparticle suspensions exhibit viscosities in the range of water. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4070–4080, 2008