Borylborazines as new precursors for boron nitride fibres

A variety of borylborazine-based polymers were successfully converted into boron nitride fibres via the preceramic polymer route. In this procedure, four monomers were polycondensed into highly tractable polymers which could be easily melt-spun into fine-diameter green fibres. These polymeric filaments were then transformed into boron nitride fibres after a well-defined heat-treatment at 1800 °C in a controlled atmosphere. All the resulting ceramic fibres were mechanically tested. In particular, results showed that the promising mechanical properties for two of the polymer-derived fibres were closely related to the structural units of the corresponding preceramic polymers.     

An overview of boron nitride based polymer nanocomposites

Recently, boron nitride (BN) based materials have received significant attention in both academic and industrial sectors due to its interesting properties like large energy band gap, good resistance to oxidation, excellent thermal conductivity, thermal stability, chemical inertness, significant mechanical property and widespread applications. This review article deals with the preparation and properties of boron nitride and its nanocomposites with various polymers. Diverse polymers have been explored for the preparation of boron nitride filled polymer nanocomposites by adopting different mixing methods. Properties of the resulting polymer nanocomposites mainly depend up on filler size and dispersion, mixing conditions and type of interaction between polymer matrix and the filler. Herein, the structure, preparation and properties of various boron nitride based polymer nanocomposites are reviewed in detail along with a brief overview of different classes of BN nanomaterials.     

Effect of hexafluoropropylene oxide plasma polymer particle coatings on the rheological properties of boron nitride/poly(dimethylsiloxane) composites

This work explores the use of conformal nanoscale plasma coatings on the surface of boron nitride (BN) powders to control the rheological properties of BN/poly(dimethylsiloxane) (PDMS) composites. BN particles are conformally coated with hexafluoropropylene oxide (HFPO) in a tumbling RF-plasma reactor. Following the HFPO plasma treatment, XPS evidence indicates the presence of thin coating on the surface of the particles having a F:C ratio of 1.77. Filled BN/PDMS composites are investigated using oscillatory shear rheometry in the concentration range of 0.09-0.41 vol% (varphi). The addition of the plasma treated BN particles to the PDMS matrix reduces the complex viscosity by 40-60% when compared with equally loaded control samples across a broad concentration range. The frequency dependence of the maximum packing fraction (varphi(m)=0.38-0.42) is also observed for both treated and untreated particles. The maximum packing fraction does not appear to be significantly affected by the conformal plasma polymer treatment. The investigation has shown that the relative dynamic viscosity of the BN/PDMS can be described by the modified Mooney equation.     

An N,N′-diaryl urea based conjugated polymer model system

An N,N′-diphenyl urea was designed as a model system for aggregation phenomenon in poly(phenyleneethynylenes) (PPEs). The unmethylated N,N′-diphenyl urea adopts an open, unfolded conformation in which the two diphenyl acetylene fluorophores are far enough away, mimicking the unaggregated state. Dimethylation forces the aromatic surfaces together into π-π contact, mimicking the aggregated state of PPEs. Analogous to bulk PPEs, this model system shows dramatic differences in quantum yield between the folded and unfolded states, with the unfolded urea having greater than 400-fold higher fluorescence quantum yield than its folded equivalent.     

Effects of boron nitride nanopowder on thermal,chemical and gas barrier properties of starch

Starch/boron nitride （starch/BN） bionanocomposites were prepared with the reinforcement of boron nitride nano powder by solution technique. The dispersion of BN in the starch was achieved by a continuous sonication process. The interaction between starch and boron nitride nanopowder was investigated by Fourier transform infrared （FTIR） spectroscopy. The structural properties of starch/BN bionanocomposites was studied by X-ray diffraction （XRD）. The high resolution transmission electron microscopy （HRTEM） was used for the study of dispersion of boron nitride in starch matrix and diffraction patterns were studied by selected area electron diffraction （SAED）. Thermal stability of the starch was increased with rising concentrations of boron nitride due to incorporation of rigid nano BN with starch matrix. The substantial reduction in oxygen permeability was obtained by increasing the concentration of BN. The biodegradability of synthesized bionanocomposites was measured by using activated sludge water. Further, it was noticed that, starch/BN bionanocomposites are resistant towards inorganic acids and bases. The tensile strength of starch/BN bionanocomposites was increased whereas; the water resistance property of the materials was decreased with increasing BN loading.     

Optical sensors based on hybrid DNA/conjugated polymer complexes

Single-stranded DNA (ss-DNA) can specifically bind to various targets, including a complementary ss-DNA, ions, proteins, drugs, and so forth. When binding takes place, the oligonucleotide probe often undergoes a conformational transition. This conformational change of the negatively charged ss-DNA can be detected by using a water-soluble, cationic polythiophene derivative, which transduces the complex formation into an optical (colorimetric or fluorometric) signal without any labeling of the probe or the target. This simple and rapid methodology has enabled the specific and sensitive detection of nucleic acids and human thrombin. This new biophotonic tool can easily be applied to the detection of various other biomolecules and is also useful in the high-throughput screening of new drugs.     

High performance pliable supercapacitor fabricated using activated carbon nanospheres intercalated into boron nitride nanoplates by pulsed laser ablation technique

Pliable supercapacitor, yielding specific capacitance (C_s) and energy density as high as 348 F g⁻¹ and 48.3 Wh Kg⁻¹ respectively was fabricated using modified activated carbon electrodes. The nanospheres of activated carbon (AC) were anchored on the nanoplates of boron nitride (BN) by employing the facile technique of pulsed laser ablation in liquid (PLAL) using 532 nm focused laser beam. Four different variants of electrode materials were synthesized by varying the weight percentage (1%, 3%, 5% and 10%) of BN in AC in the PLAL precursor solution. The morphological characteristics, the elemental composition and the structural analysis of the synthesized electrode materials were studied respectively by FESEM, XPS and XRD. The morphological studies indicated that the PLAL synthesis of the electrode materials resulted in proper intercalation of carbon nanospheres into BN nanoplates, which resulted in the observed enhanced performance of the fabricated supercapacitor. Four supercapacitors in this work were fabricated using the four variants of synthesized electrode materials in conjunction with gel polymer electrolyte (GPE). GPE are well known for their non-corrosive nature and best sealing ability to avoid any leakage that results in increasing the cycle life of the device. The performance of the fabricated supercapacitors was evaluated using cyclic voltammetry (CV), galvanostatic charge discharge (GCD) measurement and electrochemical impedance spectroscopy (EIS). The results indicate that the supercapacitor fabricated using 3% BN in AC as electrode material manifested the best specific capacitance and energy density. Also it was found that the supercapacitor maintained 85% of its initial capacitance even after 5000 charge/discharge cycles.     

Enrichment and desalting of tryptic protein digests and the protein depletion using boron nitride

Sample preparation still remains a great challenge in modern bioanalysis and the interest in new efficient solid phase extraction (SPE) materials still remains high. In this work, hexagonal boron nitride (h-BN) is introduced as a new SPE material for the isolation and enrichment of peptides. The h-BN is isoelectronic and structurally similar to graphite. It has remarkable properties including good thermal conductivity, excellent thermal and chemical stability and a better oxidation resistance than graphite. BN attracts increasing interest because of its wide range of applicability. In the present work, the great potential of h-BN, as a new SPE-material, on the enrichment, preconcentration and desalting of tryptic digest of model proteins is demonstrated. A special attention was dedicated to the efficient enrichment of hydrophilic phosphopeptides. Two elution protocols were developed for the enrichment of peptides compatible for subsequent MALDI-MS and ESI-MS analysis. In addition, the recoveries of 5 peptides and 3 phosphopeptides with wide range of pI values utilizing h-BN materials with different surface areas were investigated. 84–106% recovery rate could be achieved using h-BN materials. The results were compared with those obtained using graphite and silica C18 under the same elution conditions, and lower recoveries were obtained. In addition, h-BN was found to have a capability of protein depletion, which is requisite for the peptide profiling.     

Synthesis of ultraviolet luminescent turbostratic boron nitride powders via a novel low-temperature, low-cost, and high-yield chemical route

A novel chemical route has been established for the synthesis of ultraviolet luminescent turbostratic boron nitride (t-BN) powders, by the reaction of NH₄BF₄ with NaNH₂ at 320 °C for 10 h, and the yield is as high as 90%. The synthesized brown-yellow samples were characterized by XRD, XPS, FT-IR, SAED, and HRTEM, which matched with t-BN. The electronic and optical properties of the product were investigated by PL and UV absorption. UV spectra revealed that the product has two obvious band gaps (∼5.8 and 4.6 eV) and PL spectra showed that it has an ultraviolet emission at 337 nm (). SEM image indicated that the particle size of the synthesized t-BN is mainly in the range of 1-10 μm. The renascent BF₃ and Na₃N intermediates are believed to be responsible for the growth of t-BN under mild conditions.     

氮化硼催化低碳烷烃氧化脱氢的活性起源探讨（英文）

页岩气的急速开采推动了以天然气替代石油的资源革命.除主组分甲烷外,天然气、页岩气中还包含大量乙烷、丙烷等低碳烷烃资源,将这些储量丰富的碳资源直接转化为烯烃等基础化学品有望革新以原油为基础的化学工业.现有烷烃催化脱氢制烯烃工艺中,直接脱氢过程吸热、热力学受限,且存在催化剂迅速失活的难题;而氧化脱氢是放热过程、无平衡限制,也无积碳等引发催化剂失活的问题,有利于提高反应效率、降低能耗,代表了更为高效和经济的新路线.但作为一个热力学爬坡过程,目前金属氧化物催化剂上烯烃产物很容易深度氧化到CO_2,选择性仍有待提高.非金属氮化硼能够有效活化低碳烷烃中的C-H键,促进烷烃氧化脱氢,并能够有效抑制深度氧化产物的生成,解决低碳烷烃临氧脱氢过程中产物易深度氧化的固有难题.本文综述了近期氮化硼在乙烷、丙烷、丁烷等低碳烷烃氧化脱氢制烯烃反应中的研究进展.以丙烷氧化脱氢为例,通过比较文献报道的几种氮化硼材料的氧化脱氢性能,发现羟基化氮化硼显示了最高的烯烃选择性和时空收率,以20.6%的丙烷转化率为基准,烯烃选择性超过90%,而时空收率可达6.8 golefin gcat~(-1) h~(-1).在此基础上,本文重点讨论了对于氮化硼材料催化活性起源的认识.主要实验事实和结论包括:氮化硼自身几乎没有氧化脱氢活性,而在烷烃氧化脱氢反应条件下存在活性诱导期;活性诱导期伴随着氮化硼边沿氧官能团化过程;氮化硼边沿B-O官能团没有脱氢活性,而B-OH官能团参与了氧化脱氢过程,辅助分子氧引发低碳烷烃脱氢反应;分子氧在羟基氮化硼边沿解离活化,反应过程中与边沿结构氧存在动态交换;氮化硼边沿羟基化定向合成过程可显著增强氧化脱氢反应活性.氮化硼作为一类新型烷烃氧化脱氢催化剂,目前正处于研究的初始阶段.因此,本文最后总结了一些关于氮化硼烷烃脱氢催化体系仍需深入研究的科学问题.     

Through-space conjugated polymers based on cyclophanes

Conjugated polymers display unique electronic and optical properties, which favor their use in applications as optoelectronic materials and molecular devices. Despite the recent remarkable progress in the chemistry of conjugated polymers, the synthesis of conjugated polymers containing cyclophane units in the main chain is limited to only a few examples. This Minireview presents recent developments in the synthesis, properties, and applications of through-space conjugated polymers based on cyclophanes.     

Synthesis and characterization of novel conjugated polymers based on 3-cyclobutene-l,2-dione moiety

Three novel conjugated polymers bearing 3,4-bis(4-hexylthiophen-2-yl)-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.Their molecular structures have been confirmed by FT-IR,~1H NMR and ~(13)C NMR.All these copolymers exhibit broad and strong absorption bands in UV-vis region,and their optical band gaps are calculated to be 1.6-2.0 eV.suggesting that they have good coverage with the solar spectrum.These polymers...     

Design of thermal hybrid composites based on liquid crystal polymer and hexagonal boron nitride fiber network in polylactide matrix

Development of high thermally conductive and electrically insulative composites is of interest for electronic packaging industry. Advancements in smaller and more compact electronic devices required improvements in packing materials, including their weight, thermal conductivity, and electrical resistivity. In addition, with the increasing environmental awareness, the usage of green (bio‐based) alternatives was equally important. In the present study a hybrid based on fibers of highly concentrated hexagonal boron nitride (hBN) in liquid crystal polymer (LCP) matrix were fabricated. These hybrids were formed by arranging hBN platelets into LCP fiber form to reach high filler concentration and then randomly mix it in polylactide (PLA) matrix. With appropriate filler interaction within the hybrid, thermal conductivity similar to that of pure fiber could be achieved. Filler interaction may be tailored by optimizing the fibers aspect ratio. This study demonstrated the effect of random fillers in fibers shape in increasing the overall thermal conductivity of PLA polymeric hybrid using hBN and LCP fibers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 457–464     

A facile synthesis of 2,4,6-trichloroborazine from boron trichloride-dimethylsulfide complex and ammonium chloride

<正>2,4,6-Trichloroborazine has been recognized as a desirable monomer for the preparation of high-performance boron nitride fibers through polymer derived ceramics route.So a high yield and facile synthesis of 2,4,6-trichloroborazine is essential in practice. Using boron trichloride-dimethylsulfide complex((CH_3)_2S·BCl_3) and ammonium chloride(NH_4Cl) as starting materials and toluene(C_6H_5CH_3) as solvent,the synthesis of 2,4,6-trichloroborazine to give high yield is reported.     

Electrostatic Assembly of Dendrimer Electrolytes: Negatively and Positively Charged Dendrimer Porphyrins

Carboxylate and ammonium functionalities—32 of each— facilitate electrostatic interaction between oppositely charged dendrimer electrolytes and porphyrin cores, which leads in protic media to a supramolecular, fluorescence-active aggregate of two chromophores that communicate and have a predictable topology (see drawing on the right; A=acceptor, D=donor). In contrast to the complexation of linear polyelectrolytes, the contact area for the two dendrimer molecules is very limited, just as one would expect for an assembly of spherical molecules.     

Synthesis and characterization of novel conjugated polymers based on 3-cyclobutene-1,2-dione moiety

Three novel conjugated polymers bearing 3,4-bis（4-hexylthiophen-2-yl）-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.Their molecular structures have been confirmed by FT-IR,¹H NMR and ¹³C NMR.All these copolymers exhibit broad and strong absorption bands in UV-vis region,and their optical band gaps are calculated to be 1.6-2.0 eV.suggesting that they have good coverage with the solar spectrum.These polymers have good thermostability and solubility in common organic solvents.Moreover,all these objective macromolecules possess high electron affinity of～3.8 eV determined from cyclic voltammetry measurement,implying that they are potential n-type polymeric photovoltaic materials.     

Morphology controllable conjugated network polymers based on AIE-active building block for TNP detection

Luminescent conjugated network polymer is one of the most promising chemo-sensors owing to their good chemical/optical stability and multiple functionalization.Herein,three conjugated network polymers were prepared by using aggregation-induced emission active 1,1,2,2-tetrakis(4-formyl-(1,1'-biphenyl))-ethane(TFBE) unit as monomer and hydrazine as linker.Through regulating the synthetical condition,the polyme ric network can form either unifo rm two-dimensional azine-linked nanosheets(ANS),conjugated microporous polymers(A-CMP) or covalent organic frameworks(A-COF).All of these polymers exhibited good stability and high fluorescence quantum efficiency with the quantum yield of6.31% for A-NS,5.26% for A-CMP,and 5.80% for A-COF,as well as fast and selective fluorescence quenching response to 2,4,6-trinitrophenol(TNP).And the best TNP sensing performance with the Stern-Volmer constants(K_(sv)) values up to 8 × 10~5 L/mol and a detection limit of 0.09 μmol/L was obtained for A-NS.The study explores various strategies to construct conjugated polymers with different nanoarchitectures based on the same building block for sensitive detection of explosives.     

Synthesis and investigation of photovoltaic properties for polymer semiconductors based on porphyrin compounds as light-harvesting units

We reported on two polymer semiconducting copolymers based on porphyrin compounds, poly[9,9-dioctylfluorene-co-5,15-bis(hexoxybenzyl)-10,20-bis(benzo-4-yl)porphyrin] (PFPor) and poly[9-(heptadecan-9-yl)carbazole-co-5,15-bis(hexoxybenzyl)-10,20-bis(benzo-4-yl)porphyrin] (PCPor), for use as organic photovoltaic materials. The thermal, optical, electrochemical, and photovoltaic properties of the two polymers were investigated. In addition, PC₆₁BM and PC₇₁BM were introduced as acceptor materials to confirm the acceptor effect in bulk heterojunction photovoltaic devices. Moreover, in order to establish acceptor effects, morphologies of polymer/PCBM blend films were analyzed through atomic force microscopy (AFM). PFPor and PCPor exhibited the best device performance with power conversion efficiencies (PCE) of 0.62% and 0.76%, respectively, upon the introduction of PC₇₁BM as the acceptor in the device where 86 wt.% of the PC₇₁BM was contained in the active layer (pol:PC₇₁BM = 1:6, w/w).     

Evolution of structural features and mechanical properties during the conversion of poly[(methylamino)borazine] fibers into boron nitride fibers

Poly[(methylamino)borazine] (PolyMAB) green fibers of a mean diameter of 15 μm have been pyrolyzed under ammonia up to 1000°C and heat treated under nitrogen up to 2000°C to prepare boron nitride (BN) fibers. During the polymer-to-ceramic conversion, the mechanical properties of the green fibers increase within the 25-400°C temperature range owing to the formation of a preceramic material and remain almost constant up to 1000°C. Both the crystallinity and the mechanical properties slightly increase within the 1000-1400°C range, in association with the consolidation of the fused-B₃N₃ basal planes. A rapid increase in tensile strength (σ^R) and elastic modulus (Young's modulus E) is observed in relation with crystallization of the BN phase for fibers treated between 1400°C and 1800°C. At 2000°C, “meso-hexagonal” BN fibers of 7.5 μm in diameter are finally obtained, displaying values of σ^R=1.480 GPa and E=365 GPa. The obtention of both high mechanical properties and fine diameter for the as-prepared BN fibers is a consequence of the stretching of the green fibers on a spool which is used during their conversion into ceramic.     

Noncovalent functionalization and solubilization of carbon nanotubes by using a conjugated Zn-porphyrin polymer

A highly soluble, conjugated Zn-porphyrin polymer was synthesized and found to strongly interact with the surface of single-walled carbon nanotubes, producing a soluble polymer-nanotube complex. Successful complexation required the addition of trifluoroacetic acid to the solvent (THF). It was found that the complex remained soluble after excess free polymer was removed from solution, and could be centrifuged at high speed with no observable sedimentation. Furthermore, the polymer-nanotube assembly resulted in enhanced planarization and conjugation within the porphyrin polymer, which was manifested in a 127 nm bathochromic shift of the Q-band absorption. Control experiments with the Zn-porphyrin monomer indicated that homogeneous solutions could be prepared by means of sonication, but the monomer-nanotube interactions were significantly weaker, leading to nanotube precipitation within minutes. Atomic force microscopy (AFM) studies indicated that the polymer enables exfoliation of nanotube bundles and is able to "stitch" multiple nanotubes together into a series of long, interconnected strands.