Linear Side Research Articles

Benzothiadiazole-based Conjugated Polymers for Organic Solar Cells

Benzothiadiazole (BT) is an electron-deficient unit with fused aromatic core, which can be used to construct conjugated polymers for application in organic solar cells (OSCs). In the past twenty years, huge numbers of conjugated polymers based on BT unit have been developed, focusing on the backbone engineering (such as by using different copolymerized building blocks), side chain engineering (such as by using linear or branch side units), using heteroatoms (such as F, O and S atoms, and CN group), etc. These modifications enable BT-polymers to exhibit distinct absorption spectra (with onset varied from 600 nm to 1000 nm), different frontier energy levels and crystallinities. As a consequence, BT-polymers have gained much attention in recent years, and can be simultaneously used as electron donor and electron acceptor in OSCs, providing the power conversion efficiencies (PCEs) over 18% and 14% in non-fullerene and all-polymer OSCs. In this article, we provide an overview of BT-polymers for OSCs, from donor to acceptor, via selecting some typical BT-polymers in different periods. We hope that the summary in this article can invoke the interest to study the BT-polymers toward high performance OSCs, especially with thick active layers that can be potentially used in large-area devices.

Elucidating the anticancer activities of guanidinium-functionalized amphiphilic random copolymers by varying the structure and composition in the hydrophobic monomer.

Rationale: Use of traditional anticancer chemotherapeutics has been hindered by the multifactorial nature of multi-drug resistance (MDR) development and metastasis. Recently, cationic polycarbonates were reported as novel unconventional anticancer agents that mitigated MDR and inhibited metastasis. The aim of this study is to explore structure-anticancer activity relationship. Specifically, a series of cationic guanidinium-based random copolymers of varying hydrophobicity was synthesized with a narrow polydispersity (Ð = 1.12-1.27) via organocatalytic ring-opening polymerization (OROP) of functional cyclic carbonate monomers, and evaluated for anticancer activity, killing kinetics, degradability and functional mechanism.Methods: Linear, branched and aromatic hydrophobic side chain units, such as ethyl, benzyl, butyl, isobutyl and hexyl moieties were explored as comonomer units for modulating anticancer activity. As hydrophobicity/hydrophilicity balance of the polymers determines their anticancer efficacy, the feed ratio between the two monomers was varied to tune their hydrophobicity.Results: Notably, incorporating the hexyl moiety greatly enhanced anticancer efficiency and killing kinetics on cancer cells. Degradation studies showed that the polymers degraded completely within 4-6 days. Flow cytometry and lactate dehydrogenase (LDH) release analyses demonstrated that anticancer mechanism of the copolymers containing a hydrophobic co-monomer was concentration dependent, apoptosis at IC50, and both apoptosis and necrosis at 2 × IC50. In contrast, the homopolymer without a hydrophobic comonomer killed cancer cells predominantly via apoptotic mechanism.Conclusion: The hydrophobicity of the polymers played an important role in anticancer efficacy, killing kinetics and anticancer mechanism. This study provides valuable insights into designing novel anticancer agents utilizing polymers.

The Restless Hidden Markov Bandit With Linear Rewards and Side Information

In this paper we present a model for the hidden Markovian bandit problem with linear rewards. As opposed to current work on Markovian bandits, we do not assume that the state is known to the decision maker before making the decision. Furthermore, we assume structural side information where the decision maker knows in advance that there are two types of hidden states; one is common to all arms and evolves according to a Markovian distribution, and the other is unique to each arm and is distributed according to an i.i.d. process that is unique to each arm. We present an algorithm and regret analysis to this problem. Surprisingly, we can recover the hidden states and maintain logarithmic regret in the case of a convex polytope action set. Furthermore, we show that the structural side information leads to expected regret that does not depend on the number of extreme points in the action space. Therefore, we obtain practical solutions even in high dimensional problems.

A High Efficiency Linear Power Supply with Pure Sine Wave for High Voltage Test

The input part of the high-voltage test power supply is usually composed of switching devices; however, the pulse-type periodic interference caused by the switching devices makes the monitoring of the test power supply partial discharge more difficult. Therefore, this paper proposes a high-efficiency and distortion-free linear power supply based on piecewise-linearization with all N-type transistor. Under the same DC input, multiple power transistors are connected to different taps of the same transformer. By controlling the period of linear conduction of each power transistor in turn, we ensure that the power transistor works on the linear side (biased towards saturation) to reduce its conduction voltage drop and the output realizes sinusoidal piecewise linearization, so that the converter can greatly improve the system efficiency. After that, from the perspective of the lowest sum of the transistor loss, an optimization method for the design of the multi-winding transformer ratio at each stage is proposed. Finally, a power supply prototype based on four-piece linear converter with an output voltage of 220 V was built. The experimental efficiency reaches 87.03%, and, additionally, if the linear amplification is divided into more sections, the efficiency can be further improved.

Synthesis and Properties of α-1,3-Glucan with Branched and Linear Mixed Ester Side Chains

Two series of α-1,3-glucan with branched and linear mixed ester side chains, namely α-1,3-glucan pivalate hexanoate (α-1,3-glucan-Pi-Hex) and α-1,3-glucan isobutyrate hexanoate (α-1,3-glucan-iBu-He...

Impact of morphology on O2 permeability in silicone hydrogel membranes: new insights into domain percolation from experiments and simulations

The transport of oxygen through silicone-hydrogel (SiHy) materials is of great interest in bio-materials' applications. In this study O2 permeability of hydrogels made from UV-cured polyacrylamide containing different siloxane co-monomers were analyzed through the traditional coulometric flux method, as well as by 1H NMR T1 relaxometry. It was shown by coulometric flux methods that the crosslinked polyacrylamide with short, linear siloxane side chains (polydimethylsiloxane (PDMS)) has higher O2 permeability as well as O2 solubility, as calculated from the composite diffusivity, than that with branched siloxane (tris-(trimethylsiloxysilyl-) (TRIS)). On the other hand, based on direct measurement from NMR T1 analyses, a slightly higher O2 solubility was observed for the samples with branched siloxane as expected from its larger free volume. In order to understand the reason behind this discrepancy, a series of morphological studies using 29Si and 1H NMR T2 relaxometry, as well as small-angle X-ray scattering (SAXS) were undertaken. These results are discussed in the context of molecular dynamic simulations undertaken on the same systems which together strongly suggest that morphology plays a critical role in O2 permeability. It is proposed that samples made from the linear silicone, PDMS, has a more pronounced siloxane phase separation than its bulky counterpart, TRIS. Significantly percolating hydrophobic silicone domains with twice the siloxane content are found for the PDMS sample with reduced tortuosity of the hydrophilic domain's percolating path. The mobility in the linear siloxane was also much higher which can be attributed to the molecular structure and to fewer interfacial and topological constraints arising from the different domain structure. Hence, we propose a framework for O2 permeability in SiHys, emphasizing the importance of percolated hydrophobic domain in designing SiHy with optimized O2 permeability. The study demonstrates that while a simple permeability measurement can be used for materials' comparison, the use of multiple orthogonal techniques is critical for developing a more complete understanding of small molecule transport in heterogeneous materials.

Effect of Molecular Architecture on the Self-Assembly of Bottlebrush Copolymers.

The characteristics of a new architecture of bottlebrush copolymers (BBCPs) self-assembly were studied using self-consistent field theory. In this molecule, a series of AB linear diblock side chains were connected at the diblock junction using a C backbone. The control over the linker length and its chemical nature created an additional constraint on the intrinsic AB diblock microphase separation. Increasing side-chain crowding by increasing the grafting density and total degree of polymerization induced improved phase separation. This was reflected in the overall reduction in the effective interaction parameter between the diblocks as well as the abrupt increase in phase density when crossing the order-disorder transition. Side-chain crowding resulted in an increase in the equilibrium domain spacing compared to a linear diblock. On the other hand, the localization of block C at the AB interface generated a diffuse domain boundary and reduction in side-chain stretching. The unique behavior of BBCPs was observed in 1D confined systems where the molecule showed the natural tendency to orient domains parallel to neutral confinement in contrast to the behavior of confined diblocks. Such behavior largely depended on the degree of incompatibility between the AB blocks and BBCP structure. A ternary phase diagram was constructed for different proportions of each block. Rich morphologies of core-shell domains and tiling patterns were observed including octagonal and pentagonal polygons. The unique architecture of this bottlebrush molecule and its improved nanoscale properties make it an attractive candidate for various applications of nanotechnology.

Proteoglycans as Mediators of Cancer Tissue Mechanics.

Proteoglycans are a diverse group of molecules which are characterized by a central protein backbone that is decorated with a variety of linear sulfated glycosaminoglycan side chains. Proteoglycans contribute significantly to the biochemical and mechanical properties of the interstitial extracellular matrix where they modulate cellular behavior by engaging transmembrane receptors. Proteoglycans also comprise a major component of the cellular glycocalyx to influence transmembrane receptor structure/function and mechanosignaling. Through their ability to initiate biochemical and mechanosignaling in cells, proteoglycans elicit profound effects on proliferation, adhesion and migration. Pathologies including cancer and cardiovascular disease are characterized by perturbed expression of proteoglycans where they compromise cell and tissue behavior by stiffening the extracellular matrix and increasing the bulkiness of the glycocalyx. Increasing evidence indicates that a bulky glycocalyx and proteoglycan-enriched extracellular matrix promote malignant transformation, increase cancer aggression and alter anti-tumor therapy response. In this review, we focus on the contribution of proteoglycans to mechanobiology in the context of normal and transformed tissues. We discuss the significance of proteoglycans for therapy response, and the current experimental strategies that target proteoglycans to sensitize cancer cells to treatment.

Synthesis and properties of thermoplastic and dissolvable polysiloxanes containing polyhedral oligomeric silsesquioxane

AbstractThere are many benefits associated with thermoplastic silicones, but very few examples exist: silicone resins or rubbers are normally thermosets. In this article, a facile and efficient approach was reported to prepare thermoplastic silicone by introducing a bulky side siloxane group. Monofunctional polyhedral oligomeric silsesquioxane (POSS), as the bulky siloxane group, was grafted onto the linear polysiloxane backbone via thiol–ene click reaction, endowing the liquid polysiloxane with thermoplastic nature. The POSS‐grafted polysiloxane could be remolded by a hot‐melting or solution casting process. It was worth noting that the novel thermoplastic silicone was composed of both linear siloxane main chains and siloxane side groups, which was distinctly different from previous researches on thermoplastic silicones consisted of siloxane main chains and organic side groups. Thermal analysis, rheological characterization and molecular dynamics simulation results revealed the thermoplastic properties of POSS‐grafted polysiloxane depended on the bulky POSS's hindrance to the movement of the polymer backbone rather than the interaction between the organic side groups.

Synthesis and characterization of stereoregular π-conjugated polyarylenynes, (-Ar-(E)-CH=CHC≡C-)n, decorated with branched bis-alkoxy side chains

Novel poly(p-phenyleneethynylenevinylene)s (PPEV) have been synthesized by step-growth oligomerization of 2,5-diethynyl-1,4-dialkoxybenzene monomers promoted by the ruthenium pre-catalyst [{RuCl(μ-Cl)(η6-p-cymene)}2] in the solvent mixture AcOH/CH2Cl2. The presence of the branched side chains 2-ethylhexyloxy or 3,7-dimethyloctyloxy in the phenylene unit allows for the formation of soluble π-conjugated short polymers, with slightly increased degree of polymerization (Xn = 5 - 10) and red-shifted photophysical properties (λem ≅ 515 nm in CHCl3) with respect to the analogues with linear alkoxy side chains. The aggregation properties of the polymer with 2-ethylhexyloxy groups have been investigated by an osmosis driven procedure, yielding nanospheres of different size depending on the adapted solvent/nonsolvent mixture.

How hydrophobic side chain design affects water cluster connectivity in model polymer electrolyte membranes: Linear versus Y-shaped side chains

Dissipative Particle Dynamics is used to model water clustering in ion exchange membranes. We consider polymers with hydrophobic backbone alternatingly grafted with short hydrophilic ([C]) and hydrophobic linear (A6) or Y-shaped side chains (ie. Ap [As][As]; p(s) = 6(0), 4(1), 2(2), 0(3)). At 16% water volume fraction water cluster connectivity (DMC(W), water diffusivity, and inter water domain distance increase with length p and average number of bonds (<NbondA−C>) separating A and nearest C beads. Exchange of the pendent A and C beads for (A [C]A [A6])10 to form (A [A]A [A5C])10 decreases water cluster connectivity. This is because the lower number of bonds between nearest C beads for (A [C]A [A6])10 forces them to join the same water domain. This cooperative mechanism also explains deviations from the increase of DMC(W) with <NbondA−C> for similar ion exchange capacity (IEC). At high IEC (A [Ax+1C])10 architectures favour good connected pores which is surpassed by the H-phobic side chain (A [C]A [Ax])10 architectures at low IEC.

Azaisoindigo-Based Polymers with a Linear Hybrid Siloxane-Based Side Chain for High-Performance Semiconductors Processable with Nonchlorinated Solvents.

Developing nonchlorinated solvent-processed polymeric semiconductors to avoid environmental concerns and health hazards caused by chlorinated solvents is especially urgent. Here, a molecular design strategy, composed of backbone fluorination and side chain optimization, is used for preparing high-solubility and high-performance azaisoindigo-based polymers. The effects of different backbones and side chains on the solubility, film crystallinity, molecular stacking, and charge transport properties are mainly investigated. A long linear hybrid siloxane-based chain (C6-Si7) is chosen to improve the solubility, while the incorporation of fluorine (F) is used to enhance the film crystallinity and charge mobility. By optimizing the backbone and side chain, both solubility and charge mobility of the azaisoindigo-based polymer are significantly improved. As a result, PAIIDBFT-Si films processed with toluene, tetrahydrofuran, ether, and alkanes, achieved charge mobilities of 4.14, 3.78, 2.14, and 2.34 cm2 V-1 s-1, respectively. The current study provides an effective strategy for the design and synthesis of high-performance polymeric semiconductors processed with nonchlorinated solvents.

Development of Tetrazolium Test as Vigor Analysis Method of True Seed of Shallot

Uji tetrazolium (TZ) merupakan salah satu metode untuk mengestimasi viabilitas dan vigor benih. Penelitian ini bertujuan untuk memperbaiki metode analisis vigor pada benih botani bawang merah. Pada penelitian ini digunakan dua varietas benih bawang merah, yaitu Trisula dan Tuk-tuk. Pre-treatment dalam uji tetrazolium benih bawang merah dilakukan dengan perendaman benih dalam air selama 18 jam. Sebelum pewarnaan benih disiapkan dengan menggores sisi lurus secara longitudinal sebagai satu-satunya irisan tipis, dan sisi cembung benih ditusuk dengan scalpel. Benih diwarnai selama 18 jam dalam larutan tetrazolium pada suhu 1% suhu 30 oC dalam kondisi gelap. Pola pewarnaan benih diklasifikasikan dalam empat kategori yaitu empat pola normal kuat sebagai kriteria benih vigor, lima pola normal lemah, tujuh pola abnormal, dan empat pola benih mati. Parameter fisiologis viabilitas dan vigor berkorelasi erat dengan hasil pola vigor/ normal kuat. Pola normal kuat memiliki koefisien korelasi (r) yang tinggi dengan parameter uji fisiologis di laboratorium termasuk indeks vigor (r= 0.882), bobot kering kecambah normal (r= 0.899), dan kecepatan tumbuh (r= 0.875). Hal ini mengindikasikan pola pewarnaan vigor dapat memprediksi vigor benih.

Fluorinated poly(fluorenyl ether)s with linear multi-cationic side chains for vanadium redox flow batteries

The cationic group distribution along the polymeric backbones of anion exchange membranes (AEMs) has significant influence on their microscopic morphology and anion conductivity. To develop high-performance AEMs for vanadium redox flow batteries (VRFBs), a series of poly (fluorenyl ether) samples bearing di- and tri-quaternary ammonium side chains with similar ion exchange capacities (IECs) were synthesized by grafting cationic alkyl chains with tertiary amine-containing poly(fluorenyl ether) precursors. The experimental results indicate that the introduction of the multi-cationic side chains facilitates the formation of micro-phase-separated morphologies and enhances anion conductivity. Moreover, the number of spacer atoms between the quaternary ammonium groups on the side chains affects the water uptake of the membranes, thus complicating the relationship between the density of cationic group distribution and anion conductivity. The poly(fluorenyl ether)s with dicationic side chains and six spacing atoms (DQA-PFE-C6) showed the highest anion conductivity. A VRFB assembled with DQA-PFE-C6 exhibited a maximum power density of 239.80 mW cm−2 at 250 mA cm−2, which is significantly higher than a VRFB assembled with Nafion 212. Therefore, side chain engineering is an effective chemical approach to enhance the properties of AEMs for VRFB applications.

Solubilization and Stabilization of Membrane Proteins by Cycloalkane-Modified Amphiphilic Polymers.

Membrane proteins (MPs) need to be extracted from biological membranes and purified in their native state for most structural and functional in vitro investigations. Amphiphilic copolymers, such as amphipols (APols), have emerged as very useful alternatives to detergents for keeping MPs water-soluble under their native form. However, classical APols, such as poly(acrylic acid) (PAA) derivatives, seldom enable direct MP extraction. Poly(styrene maleic anhydride) copolymers (SMAs), which bear aromatic rings as hydrophobic side groups, have been reported to be more effective extracting agents. In order to test the hypothesis of the role of cyclic hydrophobic moieties in membrane solubilization by copolymers, we have prepared PAA derivatives comprising cyclic rather than linear aliphatic side groups (CyclAPols). As references, APol A8-35, SMAs, and diisobutylene maleic acid (DIBMA) were compared with CyclAPols. Using as models the plasma membrane of Escherichia coli and the extraction-resistant purple membrane from Halobacterium salinarum, we show that CyclAPols combine the extraction efficiency of SMAs with the stabilization afforded to MPs by classical APols such as A8-35.

Multiple Solutions for a Kirchhoff-Type Equation

In this paper, we study a class of Kirchhoff-type equation with asymptotically linear right-hand side and compute the critical groups at a point of mountain pass type under suitable Hilbert space. The existence results of three nontrivial solutions under the resonance and non-resonance conditions are established by using the minimax method and Morse theory.

Pronounced Dependence of All-Polymer Solar Cells Photovoltaic Performance on the Alkyl Substituent Patterns in Large Bandgap Polymer Donors.

For all-polymer solar cells which are composed of polymer donors and polymer acceptors, the effect of alkyl side chains on photovoltaic performance is a matter of some debate, and this effect remains difficult to forecast. In this concise contribution, we demonstrate that three alkyls namely branched alkyl 2-butyloctyl (2BO), long linear alkyl n-dodecyl (C12), and double-short linear alkyl n-hexyls (DC6) incorporated into the side chains of large bandgap polymer donor PBDT-TTz can induce considerable, of significance, and different electronic, optical, and morphological parameters. Systematic studies shed light on the critical role of the double-short linear alkyl n-hexyls (DC6) in (i) producing large ionization potential value, (ii) increasing propensity of the polymer to order along the π-stacking direction, (iii) generating polymer crystallites with more preferential "face-on" orientation, consequently, (iv) improvement of carriers transportation, (v) suppression of charge recombination, (vi) reduction of energy loss in all-polymer devices. In parallel, we unearth that the PBDT-TTz with double-short linear alkyl n-hexyls (DC6) represents the highest efficiency of 8.3 %, whereas, the other two PBDT-TTz analogues (2BO, C12) yield efficiencies of less than 3 % in optimized all-polymer solar cells. Though branched or long linear alkyl side chains (2BO, C12) have been applied to provide the solution processability of conjugated polymers, motifs bearing multiple short linear alkyl substituents (DC6) are proved critical to the development of high performing polymers.

Numerical analysis of triangular labyrinth side weir in triangular channel

ABSTRACT Labyrinth side weir is a type of lateral weirs which used for diversion of flow and head regulator in the sewage system, irrigation and drainage engineering. Discharge coefficient of labyrinth side weir is more than linear side weirs. An investigation has been carried out by many researchers on labyrinth side weirs with rectangular parent channel. In this study, computational Fluid Dynamics (CFD) volume of fluid method was used to investigate the coefficient of discharge of triangular labyrinth side weirs in the triangular straight main channel. Dimensionless parameters like dimensionless nape height h/p, Froude number, the Apex angle of triangular labyrinth side weir, dimensionless weir width and included angle of triangular parent channel affecting on the coefficient of discharge of triangular labyrinth side weirs obtained from CFD simulations are used for an empirical equation. The surface profile also studied for triangular labyrinth side weirs. Comparison of simulation results and experimental results have a good agreement. According to the results, coefficient of discharge of 45° labyrinth side weir is higher than 60° and 90° labyrinth side weirs.

Linear hybrid siloxane-based side chains for highly soluble isoindigo-based conjugated polymers.

Three isoindigo-based conjugated polymers modified with linear hybrid siloxane-based side chains were synthesized (PIID-Cm-Si7, m = 5-7). All polymers showed good solubilities in halogenated hydrocarbons, aromatic hydrocarbons, ethers, alkanes, and esters. The polymer films of PIID-C5-Si7, PIID-C6-Si7, and PIID-C7-Si7 achieved mobilities of 0.32, 0.82, and 1.58 cm2 V-1 s-1, respectively.

A General Perceptual Infrared and Visible Image Fusion Framework Based on Linear Filter and Side Window Filtering Technology

Recently, edge-preserving filters have achieved great success in infrared (IR) and visible (VI) image fusion field. However, most edge-preserving filters are complex. In this paper, with the side window filtering technology by which most filters can improve their edge-preserving capabilities, we propose a general perceptual IR and VI image fusion framework with simple linear filter. Firstly, the source images are decomposed into edge feature components, hybrid components and base components by using linear filter and its side window version. Then, these components are combined by max-absolute fusion rule and improved max-absolute fusion rule. Finally, the fused image is reconstructed by adding all the fused components. In our experiments, two popular linear filters, i.e., box filter and Gaussian filter, are used to verify the effectiveness of the proposed framework. Experimental results show that the proposed fusion framework can obtain better perceptual fusion results than compared methods.