Alcohol solvent effect on the self-assembly behaviors of lignin oligomers

The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.

Human islet amyloid polypeptide oligomers stabilized and probed by MAS NMR

The capture and characterization of oligomers are extremely important in the studies of amyloid aggregation of proteins and peptides.Oligomers are critical intermediates that can impact the structures of amyloid fibrils.Moreover,it is widely accepted that oligomers are the most toxic species along the aggregation pathway[1e4].The studies of oligomers are believed to shed light on the molecular mechanism of amyloid fibrillation and probably the medical clues for related diseases.In vitro investigations of amyloid oligomers are challenging due to their transient and polymorphic nature[5].This is particularly evident in the case of human type-2 diabetes-associated islet amyloid polypeptide(hIAPP),which tends to rapidly form polymorphic fibrils within minutes[6].Notably,hIAPP demonstrates a higher propensity for rapid aggregation compared to other amyloid proteins such as a-synuclein[7].

Highly efficient and stable organic solar cells with SnO_(2)electron transport layer enabled by UV-curing acrylate oligomers

The interfaces between the inorganic metal oxide and organic photoactive layer are of outmost importance for efficiency and stability in organic solar cells(OSCs).Tin oxide(SnO_(2))is one of the promising candidates for the electron transport layer(ETL)in high-performance inverted OSCs.When a solution-processed SnO_(2)ETL is employed,however,the presence of interfacial defects and suboptimal interfacial contact can lower the power conversion efficiency(PCE)and operational stability of OSCs.Herein,highly efficient and stable inverted OSCs by modification of the SnO_(2)surface with ultraviolet(UV)-curable acrylate oligomers(SAR and OCS)are demonstrated.The highest PCEs of 16.6%and 17.0%are achieved in PM6:Y6-BO OSCs with the SAR and OCS,respectively,outperforming a device with a bare SnO_(2)ETL(PCE 13.8%).The remarkable enhancement of PCEs is attributed to the optimized interfacial contact,leading to mitigated surface defects.More strikingly,improved light-soaking and thermal stability strongly correlated with the interfacial defects are demonstrated for OSCs based on SnO_(2)/UV cross-linked resins compared to OSCs utilizing bare SnO_(2).We believe that UV cross-linking oligomers will play a key role as interfacial modifiers in the future fabrication of large-area and flexible OSCs with high efficiency and stability.

Cornel iridoid glycoside induces autophagy to protect against tau oligomer neurotoxicity induced by activation of glycogen synthase kinase-3β

Tau oligomers are the etiologic molecules of Alzheimer disease(AD), and correlate strongly with neuronal loss and exhibit neurotoxicity. Recent evidence indicates that small tau oligomers are the most relevant toxic aggregate species. The aim of the present study was to investigate the mechanisms of cornel iridoid glycoside(CIG) on tau oligomers and cognitive functions. We injected wortmannin and GF-109203 X(WM/GFX, 200 μmol·L-1 each) into the lateral ventricles to induce tau oligomer and memory impairment in rats. When oral y administered with CIG at 60 and 120 mg·kg-1 per day for 14 d, CIG decreased the escape latency in Morris water maze test. We also found that CIG restored the expression of presynaptic p-synapsin, synaptophysin, and postsynaptic density-95(PSD-95) decreased by WM/GFX in rat cortex. CIG reduced the accumulation of tau oligomers in the brain of WM/GFX rats and in cells transfected with wild type glycogen synthase kinase-3β(wt GSK-3β). In addition, CIG up-regulated the levels of ATG7, ATG12, Beclin-1, and LC3 II in vivo and in vitro, suggesting the restoration of autophagy function. These results suggest that CIG could ameliorate memory deficits and regulate memory-associated synaptic proteins through the clearance of tau oligomers accumulation. Moreover, CIG clears tau oligomers by restoring autophagy function.

Optical Properties of Oligo（fluorene-vinylene） Functionalized Anthracene Linear Oligomers： Effect of π-extension

The photo-physical properties of oligo（fluorene-vinylene） functionalized anthracene linear oligomers （An-OFVn （n=1-4）） have been systemically investigated through experimental and theoretical methods. The steady-state spectral measurement shows that the increasing of fluorene-vinylene （FV） group could lead to the red shift of absorption spectra and restrain the excimer formation between oligomers. Quantum chemical calculations exhibit that the energy levels of HOMO, LUMO, and the band gap gradually converge to a constant in accompany with the increasing of FV unit. Meanwhile, the electronic cloud which distributes on the branch arms, also gradually enhances and makes the absorption spectral shape of oligomers become similar to that of branch arms step by step. The time-resolved fluorescence tests exhibits that the lifetime of excimer emission would be almost invariable after the number of FV group in oligomer is ≥2. In nonlinear optical test, the two-photon photoluminescence efficiency and two-photon absorption cross-section will both gradually enhance and be close to an extremum after the number of FV unit is equal to 4. These results will provide a guideline for the design of novel photo-electronic materials.

π-CONJUGATED OLIGOMERS IN SUPRAMOLECULAR CRYSTALS AND THEIR OPTOELECTRONIC FUNCTIONS

Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance of these devices relies on the understanding and optimization of several complementary processes. Our goal is to discuss the relationship between the molecular stacking structures and their optoelectronic properties that are of importance in all these areas. The concept of intermolecular interaction should be taken here in the special sense that is inter-dipole coupling. Specifically, we will address the impact of inter-dipole interaction between adjacent molecules in aggregate state on the solid-state emission properties.

A rapid absorbance-based growth assay to screen the toxicity of oligomer Aβ42 and protect against cell death in yeast

Multiple lines of evidence show that soluble oligomer forms of amyloidβprotein(Aβ42)are the most neurotoxic species in the brain and correlates with the degree of neuronal loss and cognitive deficit in Alzheimer’s disease.Although many studies have used mammalian cells to investigate oligomer Aβ42 toxicity,the use of more simple eukaryotic cellular systems offers advantages for large-scale screening studies.We have previously established and validated budding yeast,Saccharomyces cerevisiae to be a simple and a robust model to study the toxicity of Aβ.Using colony counting based methods,oligomeric Aβ42 was shown to induce dose-dependent cell death in yeast.We have adapted this method for high throughput screening by developing an absorbance-based growth assay.We further validated the assay with treatments previously shown to protect oligomer Aβ42 induced cell death in mammalian and yeast cells.This assay offers a platform for studying underlying mechanisms of oligomer Aβ42 induced cell death using gene deletion/overexpression libraries and developing novel agents that alleviate Aβ42 induced cell death.

SYNTHESIS, CHARACTERIZATION AND RING-OPENING POLYMERIZATION OF CYCLIC (ARYLENE PHOSPHONATE) OLIGOMERS

A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yield of cyclic (arylene phosphonate) oligomers is over 85% by using hexadecyltrimethylammoniun bromide as phase transfer catalyst (PTC) at 0 'C . The structures of the cyclic oligomers were confirmed by a combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and IR analysis. These cyclic oligomers undergo facile ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator to give linear polyphosphonate. Free-radical ring-opening polymerization of cyclic(arylene phosphonate) oligomers containing sulfur linkages was also performed in the melt using 2,2'-dithiobis(benzothiazole) (DTB) as the initiator at 270 °C and the resulting polymer had a Mw, of 8 × 103 with a molecular weight distribution of 4. Ring-opening copolymerization of these cyclic oligomers with cyclic carbonate oligomers was also achieved. The average molecular weight of the resulting copolymer is higher than the corresponding homopolymer and the thermal stability of the copolymer is better than the corresponding homopolymer.

SYNTHESIS AND CHARACTERIZATION OF SILAZANE OLIGOMER CONTAINING 1,1,3,3,5,5-HEXAMETHYLCYCLOTRISILAZANE

A new silazane oligomer containing cyclotrisilazane was synthesized by KH-catalyzed dehydro-coupling reactions between diphenylsilane and 1,1,3,3,5,5-hexamethylcyclotrisilazane (D-3(N)).

Synthesis of 1-Octene Oligomer by Rare Earth Coordination Catalyst

The polymerization of 1-octene with Nd(P_(204))_3-AlEt_3 catalyst has been successfully carried out for the first time.Some features of polymerization of 1-octene are described.The 1-octene oligomer prepared has an average molecular weight of about 10~3 with molecular weight distribution of about 2.It has a terminal double bond,which can be transferred into terminal carboxy group by direct oxidation with KMnO_4 in acidic solution, and then can be esterified with polyglycol.

SYNTHESIS AND CHARACTERIZATION OF A NOVEL BLUE LIGHT EMITTING ROD-COIL DIBLOCK OLIGOMER

Four new rod-coil diblock molecules, which had well-defined para-phenylene oligomers (PPP, from biphenyl to quinquephenyl) as rigid segments and poly(ethylene oxide) (PEO, M-w ca. 750) as flexible segments, were synthesized. The chemical structure and the number of repeating unit in PEO coil and PPP rod were characterized by H-1-NMR and MALDI-TOF mass spectrometry. The diblock oligomers showed good solubility in common organic solvents and aggregated in water as characterized by a blue shift in UV-vis absorption spectra, a red shift in emission spectra, quenching of the fluorescence and formation of the microfibrilla and fractal-like structures. The formation of different supramolecular structures meant that this effort might lead to commercial important highly organized functional materials.

A Comparative Study of Electrochemical Capacitance of Graphene Oxide Affected by Oligomers of p-phenylenediamine and Hydrazine Hydrate in Solvothermal Condition

A systematic investigation of the graphene oxide composite reduced by either p-phenylenediamine oligomers or hydrazine hydrate was performed with field emission scanning electron microscopy,high resolution transmission electron microscopy,X-ray diffraction,fourier transform infrared,and X-ray photoelectron spectroscopy analyses.The electrical capacitance of the composite was evaluated by a cyclic voltammetry technique,while the properties of these prototype supercapacitors were measured by a chronopotentiometry technique.It was found that,under the solvothermal condition,the graphene oxide reduced by p-phenylenediamine oligomers was observed to have higher electrical capacitance than that reduced by hydrazine.The improved electrical capacitance can be attributed to that p-phenylenediamine oligomers are the more effective spacers for graphene layers;and they could also provide some pseudo-capacitance to the graphene oxide composite based on their conjugate structure.The results imply that graphene oxide modified by diamine oligomers has a good potential in energy storage devices.

Cyclic Oligomers of Phenolphthalein Polyarylene Ether Sulfone (Ketone): Preparation Through Cyclo-depolymerisation of Corresponding Polymers

Cyclic oligomers of phenolphthalein polyarylene ether sulfone(ketone) were prepared through cyclo-depolymerisation of corresponding polymers using CsF as the catalyst in dipolar aprotic solvent DMAc and DMF, and a family of macrocycles containing from dimer up to at least heptamer were confirmed by GPC, HPLC and MALDI-TOF-MS. The yields of cyclics get as high as 86.3% and 87.9% respectively.

Flavonoid oligomers from Chinese dragon’s blood,the red resins of Dracaena cochinchinensis

A detailed chemical investigation of the red resins from Dracaena cochinchinensis(Chinese dragon’s blood)yielded five new flavonoid oligomers,named cochinchinenins D-H(1-5),together with a known biflavonoid,cinnabarone(6),and a mixture of two known biflavonoids,socotrin-4'-ol(7)and homoisosocotrin-4'-ol(8).Of these new compounds,1-3 were biflavonoids and 4 and 5 were triflavonoids.Their structures were determined on the basis of spectroscopic analysis.The isolated compounds were tested for cytotoxicity(Cdc25),antibacterial(PEPT)and antifungal(YNG)activities.

Blue/red-shift of the p-Phenylene-ethynylene Oligomers Absorption Spectra

The absorption spectra of the p-phenylene-ethynylene（p-PPE） oligomers（up to n = 12） were estimated by DFT and TD-DFT methods. The effective conjugation length（ECL） of the corresponding polymer was obtained by extrapolating the first excitation energies of the oligmers to infinite chain length with an alternative exponential function. The absorption spectral red-shift mainly depends on the ？-conjugation segment of oligomers resulting from the planarization of the backbone. The excitation mechanism of the rotamer has been investigated sufficiently by analyzing the orbital density variation upon the conformational rotations around the cylindrical triple-bonded carbon which is believed to impact significantly on the optical spectrum. The calculated results further indicate that rotation about the cylindrical triple bond interrupts the conjugation of rod-like oligomers to lead an angle-dependence of the corresponding excitation energy. The results are helpful to interpret the conformational-dependent spectroscopic phenomena of p-phenyleneethynylene and derivatives oligomers and polymers observed in ensemble and single molecule spectroscopy.

Structure Analysis for Hydrate Models of Ethyleneimine Oligomer by Quantum Chemical Calculation

Structure analyses for hydrate models of ethyleneimine oligomer (5-mer as model of PEI) were investigated by quantum chemical calculations. Conformation energies and structures optimized for hydrate models of (ttt)5 and (tgt)5 conformers were examined. Hydrate ratio, h [h = H2O/N (mol)], was set from 0.5 to 2. In anhydrates, (tg+t)5 conformer was more stable (?1.8 kcal/m.u.) than (ttt)5. In hydrates, (ttt)5 conformers were more stable (?0.7 - ?4.3) than (tg+t)5. These results corresponded to experimental results that anhydrous linear PEI crystal changes from double helical to single planar chain in hydration process. Structures calculated for (ttt)5 agreed in those observed for hydrates of PEI. In all (tg+t)5 conformers, O???H bonds between waters were found with the decreases of N???H bonds between imino group and water. The O???H bonds in (tg+t)5 conformer resulted in its high chain torsion, and strongly related with instability and structure change (large swelling).

STRUCTURAL STUDIES ON THE OLIGOMERS FROM THE POLYSACCHARIDE OF GRACILARIA TEXTORII (RHODOPHYTA) USING β-AGARASE AND 13C-NMR SPECTROSCOPY

The 60% ethanolic extract from Gracilaria textorii (Rhbdophyta) was degraded with B- agarase, and certain charged (sulfated) and neutral oligosaccharides were separated by using DEAE Sephadex A 25 and Bio- gel P6 , P2 chromatographic techniques . Some of the charged oligomers were verified to be neoagarotetraose - 63- sulfate ( DP2 ). neoagarohexaose- 63 】 65 - disulfate ( DP3 ) and neoagarooctaose- 63, 65, 67-trisulfate (DP4) by using 13C-and ’H-NMR spectroscopy . One neutral oligomer was assumed to be a mixture of methylated neoagarotetraoses (DP2 ) by 1H-NMR spectroscopy .These oligomers assigned by their chemical shifts may be used as the model compounds for the structural investigation of the agar- type sulfated polysaccharides using the B- agarase degradation method .

Can we switch production of toxic Aβ oligomers to neuroprotective Aβ monomers to allow synapse regeneration?

Alzheimer＇s disease （AD） is a complex neurological disor- der characterized by a progressive dementia. The amyloid hypothesis states that pathogenesis is driven by the accumu- lation of amyloid β（Aβ） peptides within the brain （Hardy and Higgins, 1992）, which have multiple effects including activation of glial cells and synapse degeneration. For many years therapeutic strategies were based upon the discovery of compounds that reduced the production of Aβ in vitro and in vivo. However, the amyloid hypothesis is not universally accepted; critics pointed out poor correlations between con- centrations of Aβ in the brain and clinical disease and that, although numerous compounds reduced the production of Aβ in animal models, few had any clinical benefit in AD pa- tients. The failure of Aβ-1owering therapies in translational research has resulted in important modifications of the amy- loid hypothesis.

DIMENSIONS OF ATACTIC POLY(α-METHYLSTYRENE)CHAINS WITH SIDE GROUPS

An improved configurational-confomational statistical method is developed and the mean-square radius of gyration for atactic poly（α-methylstyrene）（PαMS） chains is studied, in which the effect of large side groups is considered. The deduced formulas, based on the rotational isomer state theory, are used to investigate the configuration-dependent properties of the atactic polymer chain, and the statistical correlation of the unperturbed polymer chain dimension and structure parameters are calculated. For the fraction of meso dyads Wm= 0.4, the dependence of the radius of gyration Rg and the intrinsic viscosity [η] on the molecule mass M are Rg = 2.63×10^-2 M^0.50 nm and [η] = 7.36 × 10^-2 M^0.497, respectively, which are in agreement with the previous experimental data for the PαMS samples. A small hump is detected in the curve of the characteristic ratio of the unperturbed mean-square radius of gyration versus the chain length for short PαMS chains. The Rg increases linearly with the temperature T, and the effects of the chain length and the tacticity on the temperature coefficient are remarkable. These are quite different from the results for PαMS chains not considering side groups or for the monosubstituted polystyrene chain.

DNA vaccines targeting amyloid-βoligomer ameliorate cognitive deficits of aged APP/PS1/tau triple-transgenic mouse models of Alzheimer’s disease

The amyloid-β(Aβ)oligomer,rather than the Aβmonomer,is considered to be the primary initiator of Alzheimer’s disease.It was hypothesized that p(Aβ3-10)10-MT,the recombinant Aβ3-10 gene vaccine of the Aβoligomer has the potential to treat Alzheimer’s disease.In this study,we intramuscularly injected the p(Aβ3-10)10-MT vaccine into the left hindlimb of APP/PS1/tau triple-transgenic mice,which are a model for Alzheimer’s disease.Our results showed that the p(Aβ3-10)10-MT vaccine effectively reduced Aβoligomer levels and plaque deposition in the cerebral cortex and hippocampus,decreased the levels tau protein variants,reduced synaptic loss,protected synaptic function,reduced neuron loss,and ameliorated memory impairment without causing any cerebral hemorrhaging.Therefore,this novel DNA vaccine,which is safe and highly effective in mouse models of Alzheimer’s disease,holds a lot of promise for the treatment of Alzheimer’s disease in humans.