Gel Permeation Chromatography Traces Research Articles

Characterization of Polyisobutylene Succinic Anhydride (PIBSA) and Its PIBSI Products from the Reaction of PIBSA with Hexamethylene Diamine.

The nature of the end-groups of a PIBSA sample, namely a polyisobutylene (PIB) sample, where each chain is supposedly terminated at one end with a single succinic anhydride group, was characterized through a combination of pyrene excimer fluorescence (PEF), gel permeation chromatography, and simulations. The PIBSA sample was reacted with different molar ratios of hexamethylene diamine to generate PIBSI molecules with succinimide (SI) groups in the corresponding reaction mixtures. The molecular weight distribution (MWD) of the different reaction mixtures was determined by fitting the gel permeation chromatography traces with sums of Gaussians. Comparison of the experimental MWD of the reaction mixtures with those simulated by assuming that the reaction between succinic anhydride and amine occurs through stochastic encounters led to the conclusion that 36 wt% of the PIBSA sample constituted unmaleated PIB chains. Based on this analysis, the PIBSA sample was found to be constituted of 0.50, 0.38, and 0.12 molar fractions of PIB chains that were singly maleated, unmaleated, and doubly maleated, respectively.

A cost‐effective strategy for the synthesis of polystyrene‐polyisobutylene‐polystyrene triblock copolymer (SIBS) based on dicumyl chloride/TiCl4/Ti(OiPr)4 initiating system

AbstractA cost‐effective strategy has been developed for the synthesis of polystyrene‐polyisobutylene‐polystyrene (PS‐PIB‐PS) triblock copolymer (SIBS) with relative narrow molecular weight distribution (MWD) via the addition of Ti(OiPr)4. First, the controlled polymerization of styrene (St) was achieved by using TMPCl/TiCl4/Ti(OiPr)4 initiating system from −80 to −50°C in a cost‐effective solvent mixture n‐Hexane/CH2Cl2 (v/v = 6/4). The –OiPr group was present in the form TiCl3(OiPr) for TiCl4/Ti(OiPr)4 ratio more than 3/1 and moderated the lifetime of the growing PS cation. Subsequently, Ti(OiPr)4 was added to the living charge of PIB initiated by initiator 1,4‐dicumyl chloride (DCC), followed by the addition of styrene monomer. The success of this developed synthesis methodology was confirmed by comparing the findings from GPC (Gel permeation chromatography) traces with and without the addition of Ti(OiPr)4. SIBS with nearly 30% weight content of PS (SIBS30) was successfully obtained with an optimally narrow MWD of 1.49 at −80°C by employing the TiCl4/Ti(OiPr)4 ratio of 6/1. Interestingly, SIBS30 with a very narrow PDI of 1.22 could be successfully synthetized at an elevated temperature of −60°C.

Controllable Polymerization of N -Substituted β-Alanine N -Thiocarboxyanhydrides for Convenient Synthesis of Functional Poly(β-peptoid)s

Controllable Polymerization of <i>N</i> -Substituted β-Alanine <i>N</i> -Thiocarboxyanhydrides for Convenient Synthesis of Functional Poly(β-peptoid)s

In Situ Supramolecular Polymerization via Organometallic-Catalyzed Macromolecular Metamorphosis

In Situ Supramolecular Polymerization via Organometallic-Catalyzed Macromolecular Metamorphosis

Biodegradable PCL-b-PLA Microspheres with Nanopores Prepared via RAFT Polymerization and UV Photodegradation of Poly(Methyl Vinyl Ketone) Blocks.

Biodegradable triblock copolymers based on poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) were synthesized via ring-opening polymerization of L-lactide followed by reversible addition–fragmentation chain-transfer (RAFT) polymerization of poly(methyl vinyl ketone) (PMVK) as a photodegradable block, and characterized by FT-IR and 1H NMR spectroscopy for structural analyses, and by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) for their thermal properties. Porous, biodegradable PCL-b-PLA microspheres were fabricated via the oil/water (O/W) emulsion evaporation method, followed by photodegradation of PMVK blocks by UV irradiation. The macro-chain transfer agent (CTA) synthesized by reacting a carboxylic-acid-terminated CTA—S-1-dodecyl-S′-(a,a′-dimethyl-a′′-acetic acid)trithiocarbonate (DDMAT)—with a hydroxyl-terminated PCL-b-PLA block copolymer was used to synthesize well-defined triblock copolymers with methyl vinyl ketone via RAFT polymerization with controlled molecular weights and narrow polydispersity. Gel permeation chromatography traces indicated that the molecular weight of the triblock copolymer decreased with UV irradiation time because of the photodegradation of the PMVK blocks. The morphology of the microspheres before and after UV irradiation was investigated using SEM and videos of three-dimensional confocal laser microscopy, showing a change in their surface texture from smooth to rough, with high porosity owing to the photodegradation of the PMVK blocks to become porous templates.

One-Pot Synthesis of Supertough, Sustainable Polyester Thermoplastic Elastomers Using Block-Like, Gradient Copolymer as Soft Midblock

It remains challenging to synthesize supertough thermoplastic elastomers (TPEs) since the stretchability and tensile strength are mutually exclusive. Here, we report a one-pot strategy for the prep...

Iodine‐transfer polymerization and CuAAC “click” chemistry: A versatile approach toward poly(vinylidene fluoride)‐based amphiphilic triblock terpolymers

ABSTRACTThis study presents the synthesis and properties of linear PVDF‐based amphiphilic triblock terpolymers with PS and PEO, [PVDF‐b‐PS‐b‐PEO], by adopting a procedure that involves: (a) iodine‐transfer polymerization (ITP) of VDF with 1‐iodoperfluorohexane (C6F13I) serving as chain‐transfer agent (CTA) to afford C6F13‐PVDF‐I, (b) ITP of styrene with the C6F13‐PVDF‐I macromolecular‐CTA to obtain C6F13‐PVDF‐b‐PS‐I diblock copolymer, (c) end‐group exchange from iodo‐ to azido‐group by nucleophilic substitution reaction with NaN3, and (d) copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) with alkyne‐terminated PEO to achieve C6F13‐PVDF‐b‐PS‐b‐PEO triblock terpolymers. The 1H and 19F NMR spectroscopy confirmed the presence of all blocks, while gel permeation chromatography traces showed the living nature of ITP technique. The self‐assembly of these terpolymers was investigated in films (atomic force microscopy and DSC), as well as in aqueous and organic solvents (DLS). The analysis of crystalline phases based on the FTIR spectroscopy indicated the conversion of PVDF α‐phase into α + β‐phases and β + γ‐phases upon the incorporation of PS and PEO blocks, respectively. The synthesized amphiphilic copolymers were evaluated (fluorescence spectroscopy) as carriers of small hydrophobic molecules in water. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 163–171

Bidirectional metal‐free ROMP from difunctional organic initiators

Bidirectional metal‐free ROMP from difunctional organic initiators

Precise preparation, microstructures, micromechanical behavior and morphology of well-defined PS-b-PS/Bd-b-PS triblock copolymers via RAFT seeded miniemulsion polymerization

Reversible addition-fragmentation transfer (RAFT) miniemulsion polymerization was one of the prominent controlled/“living” radical polymerization (CLRP) techniques with environmental friendly, energy saving and high efficient characteristics. The well-defined Polystyrene-block-Polystyrene/butadiene-block-Polystyrene (PS-b-PS/Bd-b-PS) triblock copolymers with uniform, tapered or gradient and pure polybutadiene compositions distribution in the middle block were precisely controllably prepared via RAFT seeded miniemulsion polymerization, in which number-average molecular weigh (Mn) t was from 60.00 ~ 82.00 kg/mol with narrow distribution and substantially the similar PS volume fraction about 0.64 ~ 0.65 and 0.80. The copolymers microstructures were characterized by gel permeation chromatography (GPC), fourier translation infrared spectroscopy (FT-IR) and hydrogen nuclear magnetic resonance spectroscopy (1H-NMR). The GPC traces indicated that type curves remained nearly symmetrical, unimodal molecular weight distribution in the whole PS-b-PS/Bd-b-PS triblock copolymers preparation. FT-IR and 1H-NMR results showed that microstructures of the copolymers were mainly 1, 4-trans butadiene with about 10% content of 1, 2-units. Microphase morphology, micromechanical behavior and thermal property of the copolymers were identified by transmission electron microscopy (TEM), tensile testing and differential scanning calorimetry (DSC). The fracture mechanisms of thin layer yielding and cavitation deformation were corresponding to the lamellar and cylindrical morphology in micromechanical behaviors, respectively. It was indicated that microphase morphologies, micromechanical properties and thermal properties were identical to their molecular microstructures, composition profiles distribution, toughening mechanisms and microphase separation strength.

Single-step synthesis of internally functionalizable hyperbranched polyethers

Radical catalyzed thiol-ene reaction has become a useful alternative to the Hüisgen-type azide-yne click reaction as it helps expand the variability in reaction conditions as well as the range of clickable entities. In this study, the direct generation of a hyperbranched polyether (HBPE) having decyl units at the periphery and a pendant allyl group on every repeat unit of the polymer backbone is described; the allyl groups serve as a reactive handle for postpolymerization modifications and permits the generation of a variety of internally functionalized HBPEs. In this design, the AB2 monomer carries two decylbenzyl ether units (B-functionality), an aliphatic OH (A-functionality) and a pendant allyl group within the spacer segment; polymerization of the monomer readily occurs at 150 °C via melt transetherification process by continuous removal of 1-decanol under reduced pressure. The resulting HBPE has a hydrophobic periphery due to the presence of numerous decyl chains, while the allyl groups that remain unaffected during the melt polymerization provides an opportunity to install a variety of functional groups within the interior; thiol-ene click reaction with two different thiols, namely 3-mercaptopropionic acid and mercaptosuccinic acid, generated interesting amphiphilic structures. Preliminary field emission scanning electron microscope (FESEM) and Atomic Force Microscopy (AFM) imaging studies reveal the formation of fairly uniform spherical aggregates in water with sizes ranging from 200 to 400 nm; this suggests that these amphiphilic HBPs is able to reconfigure to generate jellyfish-like conformations that subsequently aggregate in an alkaline medium. The internal allyl functional groups were also used to generate intramolecularly core-crosslinked HBPEs, by the use of dithiol crosslinkers; gel permeation chromatography traces provided clear evidence for reduction in the size after crosslinking. In summary, we have developed a simple route to prepare core-clickable HBPEs and have demonstrated the quantitative reaction of the allyl groups present within the interior of the polymers; such HB polymeric systems that carry numerous functional groups within the core could have interesting applications in analyte sequestration and possibly sensing, especially from organic media. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4125–4135

Well-defined poly(N-isopropylacrylamide) with a bifunctional end-group: synthesis, characterization, and thermoresponsive properties

In this study, well-defined poly(N-isopropylacrylamide) (PNIPAM) with a bisalkyne end-group was synthesized by reversible addition-fragmentation chain transfer polymerization using 2-(2-(ethylthiocarbonothioylthio)-2-methylpropanoyl-oxy)ethyl 3,5-bis(prop-2-ynyloxy) benzoate (EMEB) as the chain transfer agent. The molecular weight and polydispersity index of polymer was determined by gel permeation chromatography (GPC). The linear increase in molecular weight with conversion, unimodal, and almost symmetrical peak in GPC trace together with low polydispersity indicated the controlled polymerization process of NIPAM mediated by EMEB. Subsequently, the Cu(I)-catalyzed [3 + 2] Huisgen cycloaddition between the end-group of polymer and azide derivatives was carried out to produce PNIPAM, in which the bisfunctional end-group was modified with phenyl, octyl, amido, and hydroxyl groups. After completing the click reaction, the structure of the polymer was characterized carefully by Fourier transform infrared spectroscopy (FTIR), 1H NMR, and Matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS), indicating the complete consumption of alkyne end-groups. In addition, almost no change in molecular weight as well as the polydispersity was observed by comparison with the GPC traces of polymers before and after click reaction. The cloud point temperatures (T cps) of the resulting PNIPAM derivatives in aqueous solution were investigated in detail by dynamic light scattering. The results showed that the values of T cp were ranged from 22 to 38 °C, which depended largely on end-groups as well as the polymer molecular weights.

Self-Assembly of a Diblock Copolymer with Pendant Disulfide Bonds and Chromophore Groups: A New Platform for Fast Release

An amphiphilic block copolymer comprising poly(ethylene glycol) (PEG) and poly(2-(methacryloyl)oxyethyl-2'-hydroxyethyl disulfide) (PMAOHD) blocks was synthesized by atom transfer radical polymerization (ATRP). Pyrenebutyric acid was conjugated to the block copolymer by esterification, and a block copolymer with pendant disulfide bonds and pyrenyl groups (PEG-b-P(MAOHD-g-Py)) was obtained. (1)H NMR and gel permeation chromatography (GPC) results demonstrated the successful synthesis of the block copolymer. The cleavage of the disulfide bonds and the degrafting of the pyrenyl groups were investigated in THF and a THF/methanol mixture. Fluorescence spectroscopy, GPC, and (1)H NMR results demonstrated fast cleavage of the disulfide bonds by Bu(3)P in THF. Fluorescence results showed the ratio of the intensity of the excimer peak to the monomer peak decreased rapidly within 20 min. GPC traces of the block copolymer moved to a long retention time region after addition of Bu(3)P, indicating the cleavage of the disulfide bonds and the degrafting of the pyrenyl groups. PEG-b-P(MAOHD-g-Py) can self-assemble into micelles with poly(MAOHD-g-Py) cores and PEG coronae in a mixture of methanol and THF (9:1 by volume). The dissociation of the micelles in the presence of Bu(3)P was investigated. After cleavage of the disulfide bonds in the micellar cores, a pyrene-containing small molecular compound and a block copolymer with pendant thiol groups were produced. Transmission electron microscopy (TEM), dynamic light scattering (DLS), and (1)H NMR were employed to track the dissociation of the polymeric micelles. All the techniques demonstrated the dissociation of the micelles and the fast release of pyrenyl groups from the micelles.

Synthesis of A2B2 miktoarm star copolymers from a new heterobifunctional initiator by combination of ROP and ATRP

A new heterobifunctional initiator, 2,3-bis(2-bromo-2-methylpropionyloxy) succinic acid, was synthesized and used in preparation of A2B2 miktoarm star copolymers, (polystyrene)2(poly(e-caprolactone))2, by combination of atom transfer radical polymerization (ATRP) and Controlled ring-opening polymerization (ROP). The structures of products were confirmed by the 1H NMR, 13C NMR, FT–IR, elemental analysis, differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). GPC traces show that the obtained polymers have a relatively narrow molecular weight distribution. The compositions of resulting miktoarm star copolymers were very close to theoretical. A new heterobifunctional initiator was synthesized and successfully used in the preparation of miktoarm star block copolymers via a combination of Controlled ring-opening polymerization and atom transfer radical polymerization, in a sequential process.

Synthesis and characterization of poly(styrene‐co‐butyl acrylate)/clay nanocomposite latexes in miniemulsion by AGET ATRP

AbstractPolymer/clay nanocomposite latexes in the form of positively charged nanoparticles were synthesized by a newly developed initiating system, activators generated by electron transfer (AGET), which has been employed in atom transfer radical polymerization (ATRP). These clay‐dispersed latexes were synthesized using AGET ATRP of styrene and butyl acrylate in a miniemulsion system in which, ascorbic acid as a reducing agent was added drop wise to reduce termination reactions. Particle size and particle size distribution of resulted nanocomposite latexes were characterized by dynamic light scattering (DLS). These latexes were in the range of 138 to 171 nm in size. Gel permeation chromatography (GPC) was used to characterize the molecular weight and molecular weight distribution of the resultant copolymer nanocomposites. GPC traces showed that polymers of narrow molecular weight distribution and low Polydispersity Index (PDI) have been synthesized; this clearly shows ATRP reaction is conducted successfully. By increasing nanoclay content, molecular weight of the nanocomposites decreases. The presence of the nanofiller increases the thermal stability of the nanocomposites as investigated by thermogravimetric Analysis (TGA). Glass transition temperature of nanocomposites increases compared with the neat copolymer which was studied by differential scanning calorimetry (DSC). scanning electron microscope (SEM) showed sphere morphology of polymer particles synthesized by miniemulsion polymerization. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that mixed intercalated and exfoliated morphology is obtained. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers

An Easy and Efficient Route to Macrocyclic Polymers Via Intramolecular Radical−Radical Coupling of Chain Ends

Macrocyclic polystrene (PSt) was produced in high yields by an intramolecular atom transfer radical coupling reaction of the chain ends. The slow addition of the dibrominated polystyrene (BrPStBr) precursors, prepared by atom transfer radical polymerization, into a refluxing tetrahydrofuran solution of copper(I) bromide, tris[2-(dimethylamino)ethyl]amine, and copper (0) activated the alkyl bromides at the PSt chain ends, favoring an intramolecular ring closing reaction with only minor competition from intermolecular coupling. Comparison of the gel permeation chromatography traces of the BrPStBr precursor to the cyclic product showed a shift to lower apparent molecular weight values, consistent with the reduced hydrodynamic radius of the macrocycle. Quantitative activation of the chain ends was confirmed by 1H NMR spectroscopy, with the resonance due to the C(H)Br methine termini on the BrPStBr precursor absent on the NMR spectrum of the cyclic product. The cyclic structure was directly confirmed by matrix-assisted laser desorption ionization−time-of-flight spectrometry.

Time-Dependent Polymerization Kinetic Study and the Properties of Hybrid Polymers with Functional Silsesquioxanes

Methacrylate-functionalized cubic silsesquioxane homopolymers [p(MA-CSSQ)] were synthesized by reversible addition-fragmentation chain transfer (RAFT)-mediated living radical polymerization in the presence of dodecyl(dimethylacetic acid)trithiocarbonate (DDTA) chain transfer agent, and their polymerization kinetics were studied. The DDTA-terminated p(MA-CSSQ) was then employed as a macro-RAFT agent in the polymerization of methylmethacrylate (MMA) for the synthesis of a brushlike p(MA-CSSQ)-b-PMMA block copolymer. The kinetics study of p(MA-CSSQ) showed that the monomer to polymer conversion, evaluated by (1)H NMR, was found to be approximately 80% with the maximum number average molecular weight (M(n)) of 24000 and 32300 Da, for the [MA-CSSQ]/[DDTA] ratios of 100 and 200, respectively, as determined by gel permeation chromatography (GPC). The broadening of molecular weight distributions in p(MA-CSSQ) homopolymer GPC traces was observed, presumably due to the presence of the radical-radical termination products. The resultant homopolymer and block copolymer exhibited excellent thermal stability as evidenced by thermogravimetric and differential scanning calorimetric analyses. The surface properties of p(MA-CSSQ) homopolymer and p(MA-CSSQ)-b-PMMA block copolymer, determined by water contact angle and atomic force microscopy (AFM) measurements, strongly indicated the surface enrichment of the hydrophobic silsesquioxane groups. The AFM images showed the microsized granular domains of p(MA-CSSQ) homopolymer, whereas the islandlike phase-separated domains were observed in p(MA-CSSQ)-b-PMMA block copolymer.

Three‐arm star ring opening metathesis polymers via alkyne‐azide click reaction

AbstractThe click chemistry strategy is successfully applied for the preparation of three‐arm star (A3) ring opening metathesis polymers. A well‐defined monoazide end‐functionalized poly(N‐ethyl oxanorbornene) and a poly(N‐butyl oxanorbornene) obtained via ring opening metathesis polymerization using first generation Grubbs' catalyst are simply clicked with the trisalkyne core affording the synthesis of target star polymers. The obtained star polymers are characterized via nuclear magnetic resonance spectroscopy and gel permeation chromatography (GPC). The deconvolution analyses of GPC traces reveal that the click reaction efficiency for the star formation strongly depends on the chemical nature and the molecular weight of ROM polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2344–2351, 2009

GPC observations of branching effects in anionic polymerization of methyl methacrylate: A preliminary study

AbstractThe anionic polymerization of methyl methacrylate was performed in tetrahydrofuran (THF) at −78°C, using sec‐butyllithium/1,1‐diphenylethylene (DPE) as the initiation system. The effects of polymerization time and initiator concentration on the branching reaction were studied. High vacuum was used to prevent contamination during the polymerization. Gel permeation chromatography (GPC) was used to characterize the branching effect qualitatively. Experimental results indicated that the monomer conversion reached more than 98% in a polymerization time of 10 min. The branching reaction occurred after high monomer conversion, resulting in a tail of high molecular weight in the GPC trace. This branching effect, observed by GPC, increased with polymerization time. Rapid termination was thus probably required immediately after all of the monomer was consumed in the preparation of a well‐defined PMMA without a high‐molecular‐weight tail in this diphenylbutylllithium/THF/−78°C system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Studies on the development of branching in ATRP of styrene and acrylonitrile in the presence of divinylbenzene

Branching atom transfer radical polymerization (ATRP) of styrene and acrylonitrile was attempted in the presence of divinylbenzene targeting toward soluble branched copolymer. The kinetics and the development of branching with monomer conversion were studied in detail. Gas chromatography (GC), gel permeation chromatography (GPC) coupled with multi-angle laser light scattering (MALLS), proton nuclear magnetic resonance (1H NMR) spectroscopy and intrinsic viscosity determination were used to monitor the polymerization process and characterize the obtained copolymer. Analysis of conversion of reactants, the growth manner of molecular weight with monomer conversion and GPC traces proved that the primary chains with low polydispersity formed mainly at the early stage and then were linked in a statistical manner to start the branching at the middle or late stage. The more the branching agent was used, the earlier the branching occurred, and too much higher level of branching agent resulted in gelation. For the selected ratio of [t-BBiB]/[DVB]/[St]/[AN]=1/0.9/15/15, with monomer conversion less than 40%, primary chains with low polydispersity formed from the polymerization of St, AN and DVB, and only a part of the primary chains contained pendent vinyl group. When monomer conversion was up to 40%, the pendent vinyl groups participated in polymerization, resulting in the linking of the primary chains statistically to start the branching. The branching became significant at monomer conversion up to 50%, giving rise to a steep increase in molecular weight and width in molecular weight distribution. As the polymerization proceeded, the polymer composition gradually approached the feed composition, identifying the obtained branched copolymer provided some gradients are in its primary chains. Finally, branched copolymer bearing about six primary chains was prepared at monomer conversion near to 80%, its absolute weight average molecular weight was about 8.87×104.

Controlled radical polymerization of N‐vinylcaprolactam mediated by xanthate or dithiocarbamate

AbstractControlled radical polymerization of N‐vinylcaprolactam (NVCL) via reversible addition‐fragmentation chain transfer (RAFT) polymerization or macromolecular design via the interchange of xanthate (MADIX) was described, employing 2‐diphenylthiocarbamoylsulfanyl‐2‐methyl‐propionic acid (CTA1), ((O‐ethylxanthyl)methyl)benzene (CTA2) and (1‐(O‐ethylxanthyl)ethyl)benzene (CTA3) as chain transfer agents (CTA). It was found that all the CTAs led to controlled radical polymerization of NVCL, with the molecular weight increased along with the conversion of monomer and a relatively narrow molecular weight distribution could be obtained, as determined with matrix‐assisted laser desorption and ionization time‐of‐flight (MALDI‐TOF) and gel permeation chromatography (GPC), the polydispersity indices, as determined by MALDI‐TOF, were typically on the order of 1.24, but the polymerization did not proceed in a strictly living manner. The chain transfer ability of these CTAs was in the following order: CTA1 ≈ CTA2 &lt; CTA3. MALTI‐TOF measurement showed that the major population of polymer retained the chain‐end functional group, but minor population deactivated by radical coupling. In preparation of the block copolymer of NVCL and vinyl acetate (VAc) by sequential polymerization, the sequence of monomer addition was important. Using VAc as the first monomer could lead to a block copolymer presenting a unimodal GPC trace and a narrow PDI index, and if NVCL was used as the first monomer, the polymerization was less well controlled. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3756–3765, 2008