Synthesis and ring-opening metathesis polymerisation of o-alkoxy benzothiadiazole paracyclophane-1,9-dienes.

ortho-Diethylhexyloxyphenylene benzothiadiazole paracyclophane-1,9-diene as a mixture of diastereomers was synthesized by a sequential benzyne-induced Stevens rearrangement, oxidation and pyrolysis of a dithia[3.3]paracyclophane. Reaction of these highly strained cyclophanedienes with the second generation Grubbs catalyst showed that they can be ring opened to alternating cis,trans-phenylenevinylene polymers. In situ NMR experiments showed that one isomer 8a polymerised to 90% conversion, whereas the other 8b gave only 9% conversion due to steric hindrance on both faces of the alkene bridges of this isomer. The resulting polymers can be readily isomerized in dilute solution using visible light to the all-trans isomer and the optical and electrochemical properties of these polymers were examined by theory and experiment.

Malodour classification with low-cost flexible electronics.

Understanding body malodour in a measurable manner is essential for developing personal care products. Body malodour is the result of bodily secretion of a highly complex mixture of volatile organic compounds. Current body malodour measurement methods are manual, time consuming and costly, requiring an expert panel of assessors to assign a malodour score to each human test subject. This article proposes a technology-based solution to automate this task by developing a custom-designed malodour score classification system comprising an electronic nose sensor array, a sensor readout interface and a machine learning hardware fabricated on low-cost flexible substrates. The proposed flexible integrated smart system is to augment the expert panel by acting like a panel assessor but could ultimately replace the panel to reduce the test and measurement costs. We demonstrate that it can classify malodour scores as good as or even better than half of the assessors on the expert panel.

Electrolyte-Gated Organic Field-Effect Transistors for Quantitative Monitoring of the Molecular Dynamics of Crystallization at the Solid-Liquid Interface.

Quantitative measurements of molecular dynamics at the solid-liquid interface are of crucial importance in a wide range of fields, such as heterogeneous catalysis, energy storage, nanofluidics, biosensing, and crystallization. In particular, the molecular dynamics associated with nucleation and crystal growth is very challenging to study because of the poor sensitivity or limited spatial/temporal resolution of the most widely used analytical techniques. We demonstrate that electrolyte-gated organic field-effect transistors (EGOFETs) are able to monitor in real-time the crystallization process in an evaporating droplet. The high sensitivity of these devices at the solid-liquid interface, through the electrical double layer and signal amplification, enables the quantification of changes in solute concentration over time and the transport rate of molecules at the solid-liquid interface during crystallization. Our results show that EGOFETs offer a highly sensitive and powerful, yet simple approach to investigate the molecular dynamics of compounds crystallizing from water.

Modular synthesis of unsymmetrical [1]benzothieno[3,2-b][1]benzothiophene molecular semiconductors for organic transistors.

A modular approach to underexplored, unsymmetrical [1]benzothieno[3,2-b][1]benzothiophene (BTBT) scaffolds delivers a library of BTBT materials from readily available coupling partners by combining a transition-metal free Pummerer CH-CH-type cross-coupling and a Newman-Kwart reaction. This effective approach to unsymmetrical BTBT materials has allowed their properties to be studied. In particular, tuning the functional groups on the BTBT scaffold allows the solid-state assembly and molecular orbital energy levels to be modulated. Investigation of the charge transport properties of BTBT-containing small-molecule:polymer blends revealed the importance of molecular ordering during phase segregation and matching the highest occupied molecular orbital energy level with that of the semiconducting polymer binder, polyindacenodithiophene-benzothiadiazole (PIDTBT). The hole mobilities extracted from transistors fabricated using blends of PIDTBT with phenyl or methoxy functionalized unsymmetrical BTBTs were double those measured for devices fabricated using pristine PIDTBT. This study underscores the value of the synthetic methodology in providing a platform from which to study structure-property relationships in an underrepresented family of unsymmetrical BTBT molecular semiconductors.

Synthesis and Ring-Opening Metathesis Polymerization of o-Dialkoxy Paracyclophanedienes.

The highly strained ortho-diethylhexyloxy [2.2]paracyclophane-1,9-diene (M1) can be synthesized by ring contraction of a dithia[3.3]paracyclophane using a benzyne-induced Stevens rearrangement. This paracyclophanediene undergoes ring-opening metathesis polymerization to give well-defined 2,3-dialkoxyphenylenevinylene polymers with an alternating cis/trans alkene stereochemistry and controllable molecular weight. Fully conjugated block copolymers with electron-rich and electron-deficient phenylene vinylene polymer segments can be prepared by sequential monomer additions. These polymers can be readily isomerized to the all-trans stereochemistry polymer. The optical and electrochemical properties of these polymers were investigated by theory and experiment.

Real-time monitoring of crystallization from solution by using an interdigitated array electrode sensor.

Monitoring crystallization events in real-time is challenging but crucial for understanding the molecular dynamics associated with nucleation and crystal growth, some of nature's most ubiquitous phenomena. Recent observations have suggested that the traditional nucleation model, which describes the nucleus having already the final crystal structure, may not be valid. It appears that the molecular assembly can range during nucleation from crystalline to partially ordered to totally amorphous phases, and can change its structure during the crystallization process. Therefore, it is of critical importance to develop methods that are able to provide real-time monitoring of the molecular interactions with high temporal resolution. Here, we demonstrate that a simple and scalable approach based on interdigitated electrode array sensors (IESs) is able to provide insights on the dynamics of the crystallization process with a temporal resolution of 15 ms.

Organic Semiconductors Processed from Synthesis-to-Device in Water.

Organic semiconductors (OSCs) promise to deliver next-generation electronic and energy devices that are flexible, scalable and printable. Unfortunately, realizing this opportunity is hampered by increasing concerns about the use of volatile organic compounds (VOCs), particularly toxic halogenated solvents that are detrimental to the environment and human health. Here, a cradle-to-grave process is reported to achieve high performance p- and n-type OSC devices based on indacenodithiophene and diketopyrrolopyrrole semiconducting polymers that utilizes aqueous-processes, fewer steps, lower reaction temperatures, a significant reduction in VOCs (>99%) and avoids all halogenated solvents. The process involves an aqueous mini-emulsion polymerization that generates a surfactant-stabilized aqueous dispersion of OSC nanoparticles at sufficient concentration to permit direct aqueous processing into thin films for use in organic field-effect transistors. Promisingly, the performance of these devices is comparable to those prepared using conventional synthesis and processing procedures optimized for large amounts of VOCs and halogenated solvents. Ultimately, the holistic approach reported addresses the environmental issues and enables a viable guideline for the delivery of future OSC devices using only aqueous media for synthesis, purification and thin-film processing.

Gas Blow Coating: A Deposition Technique To Control the Crystal Morphology in Thin Films of Organic Semiconductors.

Rapid, large-scale, and low-cost coating methods that enable precise control of the crystal growth of organic semiconductors are essential to deliver high-performance devices that are robust and reproducible. In this work, a novel method is presented based on a gas blow coating technique, enabling the deposition of thin films of organic semiconductors, whose morphology can be optimized by adjusting the deposition parameters. We demonstrate the deposition of aligned single crystals of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) by gas blow coating and their use as active layers in organic field-effect transistor (OFET) devices. The OFETs of TIPS-pentacene and C8-BTBT have charge mobilities of 0.15 and 1.4 cm2 V-1 s-1, respectively, with low threshold voltages and on/off ratios exceeding 105. This coating method can also be extended to polymeric semiconductors: films based on poly(3-hexylthiophene) and poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno[3,2-b]thiophene)] are realized, establishing gas blow coating as a novel and efficient technique for the deposition of thin films of organic semiconductors.

One-Volt, Solution-Processed Organic Transistors with Self-Assembled Monolayer-Ta2O5 Gate Dielectrics.

Low-voltage, solution-processed organic thin-film transistors (OTFTs) have tremendous potential to be key components in low-cost, flexible and large-area electronics. However, for these devices to operate at low voltage, robust and high capacitance gate dielectrics are urgently needed. Herein, the fabrication of OTFTs that operate at 1 V is reported. These devices comprise a solution-processed, self-assembled monolayer (SAM) modified tantalum pentoxide (Ta2O5) as the gate dielectric. The morphology and dielectric properties of the anodized Ta2O5 films with and without n-octadecyltrichlorosilane (OTS) SAM treatment have been studied. The thickness of the Ta2O5 film was optimized by varying the anodization voltage. The results show that organic TFTs gated with OTS-modified tantalum pentoxide anodized at 3 V (d ~7 nm) exhibit the best performance. The devices operate at 1 V with a saturation field-effect mobility larger than 0.2 cm2 V-1 s-1, threshold voltage -0.55 V, subthreshold swing 120 mV/dec, and current on/off ratio in excess of 5 × 103. As a result, the demonstrated OTFTs display a promising performance for applications in low-voltage, portable electronics.

Macrocyclic poly(p-phenylenevinylene)s by ring expansion metathesis polymerisation and their characterisation by single-molecule spectroscopy.

Ring expansion metathesis polymerisation (REMP) has proven to be a viable approach to prepare high purity cyclic polymers. Macrocyclic polymers with a fully conjugated defect free backbone are of particular interest as these polymers have no end groups that can act as charge traps. In this work soluble macrocyclic poly(p-phenylenevinylene)s ( cPPVs) have been prepared directly via the REMP of substituted paracyclophanedienes. Single-molecule spectroscopy of the two topological forms of PPV i.e., linear ( lPPV) and cyclic ( cPPV) revealed that lPPV exists in an extended conformation whereas the cPPV adopts a restricted ring-like conformation. Despite such large differences in the chain conformation, the spectral properties of the two compounds are unexpectedly very similar, and are dominated by torsional deformations in relatively short conjugated segments.

C-H Borylation/Cross-Coupling Forms Twisted Donor-Acceptor Compounds Exhibiting Donor-Dependent Delayed Emission.

Benzothiadiazole (BT) directed C-H borylation using BCl3 , followed by B-Cl hydrolysis and Suzuki-Miyaura cross-coupling enables facile access to twisted donor-acceptor compounds. A subsequent second C-H borylation step provides, on arylation of boron, access to borylated highly twisted D-A compounds with a reduced bandgap, or on B-Cl hydrolysis/cross-coupling to twisted D-A-D compounds. Photophysical studies revealed that in this series there is long lifetime emission only when the donor is triphenylamine. Computational studies indicated that the key factor in observing the donor dependent long lifetime emission is the energy gap between the S1 /T2 excited states, which are predominantly intramolecular charge-transfer states, and the T1 excited state, which is predominantly a local excited state on the BT acceptor moiety.

Use of N-methyliminodiacetic acid boronate esters in suzuki-miyaura cross-coupling polymerizations of triarylamine and fluorene monomers.

Polytriarylamine copolymers can be prepared by Suzuki-Miyaura cross-coupling reactions of bis N-methyliminodiacetic acid (MIDA) boronate ester substituted arylamines with dibromo arenes. The roles of solvent composition, temperature, reaction time, and co-monomer structure were examined and (co)polymers prepared containing 9, 9-dioctylfluorene (F8), 4-sec-butyl or 4-octylphenyl diphenyl amine (TFB), and N, N'-bis(4-octylphenyl)-N, N'-diphenyl phenylenediamine (PTB) units, using a Pd(OAc)2/2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos) catalyst system. The performance of a di-functionalized MIDA boronate ester monomer was compared with that of an equivalent pinacol boronate ester. Higher molar mass polymers were produced from reactions starting with a difunctionalized pinacol boronate ester monomer than the equivalent difunctionalized MIDA boronate ester monomer in biphase solvent mixtures (toluene/dioxane/water). Matrix-assisted laser desorption/ionization mass spectroscopic analysis revealed that polymeric structures rich in residues associated with the starting MIDA monomer were present, suggesting that homo-coupling of the boronate ester must be occurring to the detriment of cross-coupling in the step-growth polymerization. However, when comparable reactions of the two boronate monomers with a dibromo fluorene monomer were completed in a single phase solvent mixture (dioxane + water), high molar mass polymers with relatively narrow distribution ranges were obtained after only 4 h of reaction. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2798-2806.

Post-polymerization C-H Borylation of Donor-Acceptor Materials Gives Highly Efficient Solid State Near-Infrared Emitters for Near-IR-OLEDs and Effective Biological Imaging.

Post-polymerization modification of the donor-acceptor polymer, poly(9,9-dioctylfluorene-alt-benzothiadiazole), PF8-BT, by electrophilic C-H borylation is a simple method to introduce controllable quantities of near-infrared (near-IR) emitting chromophore units into the backbone of a conjugated polymer. The highly stable borylated unit possesses a significantly lower LUMO energy than the pristine polymer resulting in a reduction in the band gap of the polymer by up to 0.63 eV and a red shift in emission of more than 150 nm. Extensively borylated polymers absorb strongly in the deep red/near-IR and are highly emissive in the near-IR region of the spectrum in solution and solid state. Photoluminescence quantum yield (PLQY) values are extremely high in the solid state for materials with emission maxima ≥ 700 nm with PLQY values of 44% at 700 nm and 11% at 757 nm for PF8-BT with different borylation levels. This high brightness enables efficient solution processed near-IR emitting OLEDs to be fabricated and highly emissive borylated polymer loaded conjugated polymer nanoparticles (CPNPs) to be prepared. The latter are bright, photostable, low toxicity bioimaging agents that in phantom mouse studies show higher signal to background ratios for emission at 820 nm than the ubiquitous near-IR emissive bioimaging agent indocyanine green. This methodology represents a general approach for the post-polymerization functionalization of donor-acceptor polymers to reduce the band gap as confirmed by the C-H borylation of poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2c,2cc-diyl) (PF8TBT) resulting in a red shift in emission of >150 nm, thereby shifting the emission maximum to 810 nm.

A General Protocol for the Polycondensation of Thienyl N-Methyliminodiacetic Acid Boronate Esters To Form High Molecular Weight Copolymers.

Thienyl di-N-methyliminodiacetic acid (MIDA) boronate esters are readily synthesized by electrophilic C-H borylation producing bench stable crystalline solids in good yield and excellent purity. Optimal conditions for the slow release of the boronic acid using KOH as the base in biphasic THF/water mixtures enables the thienyl MIDA boronate esters to be extremely effective homo-bifunctionalized (AA-type) monomers in Suzuki-Miyaura copolymerizations with dibromo-heteroarenes (BB-type monomers). A single polymerization protocol is applicable for the formation of five alternating thienyl copolymers that are (or are close analogues of) state of the art materials used in organic electronics. The five polymers were produced in excellent yields and with high molecular weights comparable to those produced using Stille copolymerization protocols. Therefore, thienyl di-MIDA boronate esters represent bench stable and low toxicity alternatives to highly toxic di-trimethylstannyl AA-type monomers that are currently ubiquitous in the synthesis of these important alternating copolymers.

Highly Emissive Far Red/Near-IR Fluorophores Based on Borylated Fluorene-Benzothiadiazole Donor-Acceptor Materials.

Stille, Suzuki-Miyaura and Negishi cross-coupling reactions of bromine-functionalised borylated precursors enable the facile, high yielding, synthesis of borylated donor-acceptor materials that contain electron-rich aromatic units and/or extended effective conjugation lengths. These materials have large Stokes shifts, low LUMO energies, small band-gaps and significant fluorescence emission >700 nm in solution and when dispersed in a host polymer.

Alkyl substituted [2.2]paracyclophane-1,9-dienes.

[2.2]Paracyclophane-1,9-dienes substituted with n-octyl chains have been synthesised from the corresponding dithia[3.3]paracyclophanes using a benzyne induced Stevens rearrangement. The use of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and tetra-n-butylammonium fluoride as the in situ benzyne source gave significantly improved yields over traditional sources of benzyne and enabled the preparation of n-octyl substituted [2.2]paracyclophane-1,9-dienes on a multi-gram scale.

Sulfoxide-directed metal-free cross-couplings in the expedient synthesis of benzothiophene-based components of materials.

A metal-free approach combining sulfoxide-directed metal-free C-H cross-couplings with tuneable electrophile-mediated heterocyclizations and carbocyclative dimerizations, allows expedient access to benzothiophene-based systems that are components of important materials or are proven organic materials in their own right. As benzothiophene-based materials are typically prepared using Pd-catalyzed cross-coupling processes, our approach allows potential issues of metal cost and supply, and metal-contamination of products, to be avoided.

A tutorial review: Metabolomics and partial least squares-discriminant analysis--a marriage of convenience or a shotgun wedding.

The predominance of partial least squares-discriminant analysis (PLS-DA) used to analyze metabolomics datasets (indeed, it is the most well-known tool to perform classification and regression in metabolomics), can be said to have led to the point that not all researchers are fully aware of alternative multivariate classification algorithms. This may in part be due to the widespread availability of PLS-DA in most of the well-known statistical software packages, where its implementation is very easy if the default settings are used. In addition, one of the perceived advantages of PLS-DA is that it has the ability to analyze highly collinear and noisy data. Furthermore, the calibration model is known to provide a variety of useful statistics, such as prediction accuracy as well as scores and loadings plots. However, this method may provide misleading results, largely due to a lack of suitable statistical validation, when used by non-experts who are not aware of its potential limitations when used in conjunction with metabolomics. This tutorial review aims to provide an introductory overview to several straightforward statistical methods such as principal component-discriminant function analysis (PC-DFA), support vector machines (SVM) and random forests (RF), which could very easily be used either to augment PLS or as alternative supervised learning methods to PLS-DA. These methods can be said to be particularly appropriate for the analysis of large, highly-complex data sets which are common output(s) in metabolomics studies where the numbers of variables often far exceed the number of samples. In addition, these alternative techniques may be useful tools for generating parsimonious models through feature selection and data reduction, as well as providing more propitious results. We sincerely hope that the general reader is left with little doubt that there are several promising and readily available alternatives to PLS-DA, to analyze large and highly complex data sets.

Facile Arylation of Four-Coordinate Boron Halides by Borenium Cation Mediated Boro-desilylation and -destannylation.

The addition of AlCl3 to four-coordinate boranes of the general formula (C-N-chelate)BCl2 results in halide abstraction and formation of three-coordinate borenium cations of the general formula [(C-N-chelate)BCl]+. The latter react with both arylstannanes and arylsilanes by boro-destannylation and -desilylation, respectively, to form arylated boranes. Catalytic quantities of AlCl3 were sufficient to effect high-yielding arylation of (C-N-chelate)BCl2. Boro-destannylation is more rapid than boro-desilylation and leads to double arylation at the boron center, whereas in reactions with arylsilanes either single or double arylation occurs dependent on the nucleophilicity of the arylsilane and on the electrophilicity of the borenium cation. The electrophilicity of the borenium cation derived from 2-phenylpyridine was greater than that of the benzothiadiazole analogues, enabling the boro-desilyation of less nucleophilic silanes and the direct electrophilic borylation of 2-methylthiophene.

A comparison of different chemometrics approaches for the robust classification of electronic nose data.

Accurate detection of certain chemical vapours is important, as these may be diagnostic for the presence of weapons, drugs of misuse or disease. In order to achieve this, chemical sensors could be deployed remotely. However, the readout from such sensors is a multivariate pattern, and this needs to be interpreted robustly using powerful supervised learning methods. Therefore, in this study, we compared the classification accuracy of four pattern recognition algorithms which include linear discriminant analysis (LDA), partial least squares-discriminant analysis (PLS-DA), random forests (RF) and support vector machines (SVM) which employed four different kernels. For this purpose, we have used electronic nose (e-nose) sensor data (Wedge et al., Sensors Actuators B Chem 143:365-372, 2009). In order to allow direct comparison between our four different algorithms, we employed two model validation procedures based on either 10-fold cross-validation or bootstrapping. The results show that LDA (91.56% accuracy) and SVM with a polynomial kernel (91.66% accuracy) were very effective at analysing these e-nose data. These two models gave superior prediction accuracy, sensitivity and specificity in comparison to the other techniques employed. With respect to the e-nose sensor data studied here, our findings recommend that SVM with a polynomial kernel should be favoured as a classification method over the other statistical models that we assessed. SVM with non-linear kernels have the advantage that they can be used for classifying non-linear as well as linear mapping from analytical data space to multi-group classifications and would thus be a suitable algorithm for the analysis of most e-nose sensor data.