Mixture Of Styrene Research Articles

Modification of Sulfur Cake—Waste from Sulfuric Acid Production

In the production of sulfuric acid, sulfur cake—a waste product of the sulfur purification process—is formed in large quantities, which requires its disposal and use. For its use in composite materials, modification is necessary to convert sulfur into a polymer form. The aim of the study was to develop a method for modifying sulfur cake—a waste product of sulfuric acid production—for its disposal. Available reagents—styrene, glycerol, and oleic acid—were tested as modifiers in the work. The sample compositions consisted of 100% sulfur cake (no. 1) and its mixtures: 97% sulfur cake + 3% styrene (no. 2), 97% sulfur cake + 3% glycerol (no. 3), 97% sulfur cake + 3% oleic acid (no. 4), 95% sulfur cake + 3% styrene, 1% glycerol, and 1% oleic acid (no. 5). Modification of sulfur cake was carried out at a temperature of 140 °C for 30 min. The composition, crystal structure, and thermal properties of the samples of the original and modified sulfur cake were studied using X-ray phase and X-ray structural analyses, IR spectroscopy, differential scanning calorimetry, differential thermal and thermogravimetric analysis. The optimal modifier for sulfur cake was a mixture of styrene, glycerol, and oleic acid, which led to the formation of acetal (polyoxymethylene) and an improvement in the structure due to a decrease in the content of impurities. Modification of sulfur cake with styrene resulted in the appearance of a CAr–S bond band at 571 cm−1, and modification with oleic acid a C–S band in the region of 694 cm−1 in the IR spectra. The results of differential scanning calorimetric analysis showed an increase in the heat of fusion of sulfur by 12.45 J/g in the samples of sulfur cake modified with glycerol and styrene. Modification of sulfur cake with oleic acid and a mixture of reagents resulted in the appearance of a third peak with maxima at 244.2 and 264.0 °C, which demonstrated a significant effect of the indicated additives on the thermal behavior of the sulfur cake. Proposed schemes for modifying sulfur cake with styrene and oleic acid are presented.

Scintillation and structural properties of copolymers and mixtures of styrene, 9-vinylcarbazole and 4-vinylbenzyl chloride based plastic scintillators

The research team has developed new plastic scintillators in the form of microspheres, called PSm, by combining styrene, 9-vinylcarbazole (VK), and 4-vinylbenzyl chloride (VBC). The primary objective of this study was to explore the feasibility of incorporating the fluorescent solute (VK) into the polymer structure to prevent its leaching out when PSm are utilized in liquid flow through detection systems or organic solvents. The secondary aim was to examine the impact of adding the chlorine functional group to the scintillation polymer, with the intention of replacing it with an extractant in the future to create covalently linked PSresins.The findings of the study reveal that the homopolymer of polyvinylcarbazole (PVK) performs poorly while used as a unitary scintillator system for plastic scintillation measurements. However, the incorporation of monomers in the form of copolymers with styrene has a more significant impact on scintillation properties compared to the mixture of homopolymers. In the case of 9-vinylcarbazole (VK), its presence at a weight proportion of 10% leads to an increase in scintillation efficiencies, although it is still inferior to the classical PS. Conversely, the situation is different for 4-vinylbenzyl chloride (VBC), where the chlorine in the copolymer results in higher quenching, and the polymer is also less resistant to organic solvents due to the formation of short polymer chains. For VBC, the mixture of polymers yields better results and enables the production of covalently linked PSresins.

Reactive Polymer Composite Microparticles Based on Glycidyl Methacrylate and Magnetite Nanoparticles

The modified suspension polymerization technique has been used for the preparation of composite microparticles from the mixture of glycidyl methacrylate (GMA), styrene (S), and divinylbenzene (DVB) in the presence of hydrophobized Fe3O4 nanoparticles. The obtained polymer microspheres were characterized using different instrumental and physicochemical techniques, modified with a zero-order PAMAM dendrimer, and impregnated with palladium(II) acetate solutions to immobilize palladium(II) ions. The resulting materials were preliminarily examined as catalysts in the Suzuki reaction between 4-bromotoluene and phenylboronic acid. It was found that the addition of magnetite particles to the composition of monomers provided polymer microparticles with embedded magnetic nanoparticles. The composite microparticles obtained showed a complex, multi-hollow, or raspberry-like morphology. After their modification, they could serve as recyclable catalysts for reactions that include both 4-bromotoluene and several other aryl bromides.

Co-exposure of petrochemical workers to noise and mixture of benzene, toluene, ethylbenzene, xylene, and styrene: Impact on mild renal impairment and interaction

Epidemiological evidence concerning effects of simultaneous exposure to noise and benzene, toluene, ethylbenzene, xylene, and styrene (BTEXS) on renal function remains uncertain. In 2020, a cross-sectional study was conducted among 1160 petrochemical workers in southern China to investigate effects of their co-exposure on estimated glomerular filtration rate (eGFR) and mild renal impairment (MRI). Noise levels were assessed using cumulative noise exposure (CNE). Urinary biomarkers for BTEXS were quantified. We found the majority of workers had exposure levels to noise and BTEXS below China's occupational exposure limits. CNE, trans, trans-muconic acid (tt-MA), and the sum of mandelic acid and phenylglyoxylic acid (PGMA) were linearly associated with decreased eGFR and increased MRI risk. We observed U-shaped associations for both N-acetyl-S-phenyl-L-cysteine (SPMA) and o-methylhippuric acid (2-MHA) with MRI. In further assessing the joint effect of BTEXS (β, −0.164 [95% CI, −0.296 to −0.033]) per quartile increase in all BTEXS metabolites on eGFR using quantile g-computation models, we found SPMA, tt-MA, 2-MHA, and PGMA played pivotal roles. Additionally, the risk of MRI associated with tt-MA was more pronounced in workers with lower CNE levels (P = 0.004). Multiplicative interaction analysis revealed antagonisms of CNE and PGMA on MRI risk (P = 0.034). Thus, our findings reveal negative dose-effect associations between noise and BTEXS mixture exposure and renal function in petrochemical workers. With the exception of toluene, benzene, xylene, ethylbenzene, and styrene are all concerning pollutants for renal dysfunction. Effects of benzene, ethylbenzene, and styrene exposure on renal dysfunction were more pronounced in workers with lower CNE.

Carbonyl-amine condensation coupled ozonolysis of dipropylamine and styrene: Decay kinetics, reaction mechanism, secondary organic aerosol formation and cytotoxicity

Oxidation of organic amines (OAs) or aromatic hydrocarbons (AHs) produces carbonyls, which further react with OAs to form carbonyl-amine condensation products, threatening environmental quality and human health. However, there is still a lack of systematic understanding of the carbonyl-amine condensation reaction processes of OAs or between OAs and AHs, and subsequent environmental health impact. This work systematically investigated the carbonyl-amine condensation coupled ozonolysis kinetics, reaction mechanism, secondary organic aerosol (SOA) formation and cytotoxicity from the mixture of dipropylamine (DPA) and styrene (STY) by a combined method of product mass spectrometry identification, particle property analysis and cell exposure evaluation. The results from ozonolysis of DPA and STY mixture revealed that STY inhibited the ozonolysis of DPA to different degrees to accelerate its own decay rate. The barycenter of carbonyl-amine condensation reactions was shifted from inside of DPA to between DPA and STY, which accelerated STY ozonolysis, but slowed down DPA ozonolysis. For the first time, ozonolysis of DPA and STY mixture to complex carbonyl-amine condensation products through the reactions of DPA with its carbonyl products, DPA with STY's carbonyl products and DPA's bond breakage product with STY's carbonyl products was confirmed. These condensation products significantly contributed to the formation and growth of SOA. The SOA containing particulate carbonyl-amine condensation products showed definite cytotoxicity. These findings are helpful to deeply and comprehensively understand the transformation, fate and environmental health effects of mixed organics in atmospheric environment.

Controlling the morphology of polystyrene dumbbell particles

Controlling colloidal particles’ shape is one of the new frontiers in colloidal science. Methods that permit synthesizing polymer particles with a non-spherical shape are increasing and advancing. Of all the non-spherical particles, spheres with protrusions are one of the best investigated, and many recipes have been developed to prepare them. One of the best-developed methods, initially proposed by Park et al. (JACS, 2010), starts with linear polystyrene seed particles, which are swelled and subsequently polymerized with a mixture of styrene and 3-(trimethoxysilyl)propyl methacrylate (MPS). The latter monomer’s hybrid nature creates a hydrophilic and partially crosslinked coating. This prevents the formation of core-shell structure upon further swelling and polymerization with styrene and leads to one or more new lobes. In this work, we investigate many parameters affecting the outcome of this method, including the pH, the duration of the hydrolysis of MPS, its concentration, the presence of crosslinkers in the seed particles, and the use of a different monomer in the last step. The investigation shows the importance of pH control during MPS hydrolysis in the coating step. It also demonstrates that its concentration can effectively be used to control the morphology of the resulting particles, which range from simple one-lobed dumbbells with variable roughness to multilobed particles. Furthermore, a shorter version of the dumbbell synthesis protocol has been obtained.

Effects of coexposure to noise and mixture of toluene, ethylbenzene, xylene, and styrene (TEXS) on hearing loss in petrochemical workers of southern China.

Many harmful factors existing simultaneously with noise are reported to induce hearing impairment, such as organic solvents. However, the existing hearing safety limits and current risk assessment for hearing loss rely on single noise exposure. It is urgent to clarify the combined effect of noise and other harmful factors on hearing loss. Petrochemical workers are always exposed to noise and organic solvents, mainly benzene, toluene, ethylbenzene, xylene, and styrene (BTEXS), while the combined effect of their coexposure on hearing remains unclear. Herein we conducted a cross-sectional survey, measuring pure-tone audiometry of 1496 petrochemical workers in southern China. Participants exposed to BTEXS were 569, 524, 156, 452, and 177 respectively. Individual cumulative noise exposure (CNE) levels and BTEXS exposure were assessed. The average CNE was 93.27 ± 4.92dB(A)·years, and the concentrations of BTEXS were far below the occupational exposure limits of China. Logistic regression analyses showed that CNE was consistently positively associated with hearing loss (HL) and high-frequency hearing loss (HFHL) but not related to speech-frequency hearing loss (SFHL). Compared with participants in the lowest quartile of CNE, those in the highest quartile showed an OR of 5.229 (95% CI: 3.179, 8.598) for HFHL. Two-pollutant model analysis indicated that TEXS exposure was positively associated with HL (OR 1.679, 95%CI 1.086, 2.597), SFHL (OR 2.440, 95%CI 1.255, 4.744), and HFHL (OR 1.475, 95%CI 1.077, 2.020). However, no interactions were observed between CNE and TEXS coexposure on hearing loss. In our study, covariates including smoking and drinking status, body mass index (BMI), ear protection and personal protective equipment, and use of earphone/headphone were adjusted. In conclusion, coexposure to noise and low-level TEXS could induce more severe damage on hearing function than exposure to each alone, especially SFHL. Therefore, petrochemical workers simultaneously exposed to noise and TEXS, even at low-level, should be included in hearing protection programs.

Simultaneous acidic air biofiltration of toluene and styrene mixture in the presence of rhamnolipids: Performance evaluation and neural model analysis

Biotrickling filters (BTFs) supplied with di-rhamnolipids have been proven to improve biodegradability and bioavailability of singly fed hydrophobic volatile organic compounds (VOCs). However, BTFs performance could be significantly impacted for multi-component mixtures. Herein, the performance of lab-scale fungal-BTF was evaluated for the co-treatment of toluene-styrene gas-phase mixture and compared to previous single runs of both VOCs. For equal ratios of the VOCs, the total removal efficiencies (REtotal) ranged from 89.1% to 74% by varying the total inlet loading rates (LRtotal) from 199.1 to 295.2 g m−3 h−1 at empty bed residence times (EBRT) of 90 and 60 s. Both VOCs were efficiently removed (up to RE 90%) at 199.1 g m−3 h−1 inlet LRtotal and 90 s EBRT. Shortening EBRT to 60 s revealed that styrene degradation was kinetic-limited, whereas toluene was less impacted, indicating styrene inhibition and preferential toluene utilization. Increasing toluene:styrene ratio to 2:1 (v./v.) improved styrene biodegradation and mineralization. Neural network model was developed for the binary mixture which highlighted the interaction effects between input and output variables. The model provided high predictive accuracy (R2-0.993) and revealed significant information towards improving future BTFs design.

High-Luminescence Electrospun Polymeric Microfibers In Situ Embedded with CdSe Quantum Dots with Excellent Environmental Stability for Heat and Humidity Wearable Sensors.

In this paper, hydrophobic luminescent CdSe quantum dots are successfully dispersed in a mixture of styrene and methyl methacrylate through the oleic to methacrylic acid ligand exchange. Further in situ solution polymerization of the quantum dots in a mixture of styrene and methyl methacrylate followed by electrospinning allowed us to prepare luminescence hybrid styrene-co-methyl methacrylate fibers embedded with quantum dots. CdSe@P(S+MMA) hybrid fibers with 27% quantum yield showed excellent moisture, heat and salt resistance with a photoluminescence output below 120 °C. When dry heated, the hybrid fibers of the fluorescence signals decreased with temperature to 79%, 40%, 28%, 20% and 13% at 120 °C, 140 °C, 160 °C, 180 °C and 200 °C, respectively, due the to the chemical degradation of CdSe QDs. Such hybrid fibers show the potential to manufacture wearable moisture- and heat-sensing protective clothing in a 120–200 °C range due to the thermal-induced quenching of quantum dot photoluminescence.

The Process of Natural and Styrene–Butadiene Rubbers Biodegradation by Lactobacillus plantarum

The ability of Lactobacillus plantarum to degrade different mixtures of styrene–butadiene and natural rubbers was investigated. In experiments, 12 various compositions of rubber waste mixtures were investigated. Lactobacillus plantarum cultivation was carried out in a medium with the addition of individual mixtures at the temperature of 30 °C for 14 days. The presence of cellulose on the surface of bioreactors indicated the activity of bacteria. After cultivation, the rubber mixtures were tested again. Analyses of the elemental composition and mass balance of waste were carried out. The experiments showed that the culture media supplemented by various natural rubber mixtures allowed bacteria to produce bacterial cellulose. The mean thickness of bacterial cellulose was 3–6 mm after 14 days of culturing. In samples where the cellulose appeared, about 4% average mass loss was observed. The average carbon content in the rubber material used as the carbon source for bacteria, before the culture process, was about 89.07–95.40%. After 14 days of culturing, the carbon content was reduced from 31.15% to 56.45–65.7%.

Association between exposure to a mixture of benzene, toluene, ethylbenzene, xylene, and styrene (BTEXS) and small airways function: A cross-sectional study

BackgroundLung is one of the primary target organs of benzene, toluene, ethylbenzene, xylene, and styrene (BTEXS). Small airways dysfunction (SAD) might be a sensitive indicator of early chronic respiratory disease. Here, we explored the relationships between exposure to BTEXS and small airways function, and identified the priority control pollutants in BTEXS mixtures. Methods635 petrochemical workers were recruited. Standard spirometry testing was conducted by physicians. The cumulative exposure dose (CED) of BTEXS for each worker was estimated. The peak expiratory flow (PEF), forced expiratory flow between 25 and 75% of forced vital capacity (FEF25∼75%), and the expiratory flow rate found at 25%, 50%, and 75% of the remaining exhaled vital capacity (MEF25%, MEF50%, and MEF75%) were measured. SAD was also evaluated based on measured parameters. The associations between exposure to BTEXS individuals or mixtures and small airways function were evaluated using generalized linear regression models (GLMs) and quantile g-computation models (qgcomp). Meanwhile, the weights of each homolog in the association were estimated. ResultsThe median CED of BTEXS are 9.624, 19.306, 24.479, 28.210, and 46.781 mg/m3·years, respectively. A unit increase in ln-transformed styrene CED was associated with a decrease in FEF25∼75% and MEF50% based on GLMs. One quartile increased in BTEXS mixtures (ln-transformed) was significantly associated with a 0.325-standard deviation (SD) [95% confidence interval (CI): −0.464, −0.185] decline in FEF25∼75%, a 0.529-SD (95%CI: −0.691, −0.366) decline in MEF25%, a 0.176-SD (95%CI: −0.335, −0.017) decline in MEF75%, and increase in the risk of abnormal of SAD [risk ratios (95%CI): 1.520 (95%CI: 1.143, 2.020)]. Benzene and styrene were the major chemicals in BTEXS for predicting the overall risk of SAD. ConclusionOur novel findings demonstrate the significant association between exposure to BTEXS mixture and small airways function decline and the potential roles of key homologs (benzene and styrene) in SAD.

Single-Crystalline Covalent Organic Frameworks as High-Performance Liquid Chromatographic Stationary Phases for Positional Isomer Separation

Vigorously developing new stationary phases to meet the requirements for the separation of positional isomers that have similar physicochemical properties is still an urgent topic in separation science. Herein, a single-crystalline covalent organic framework (COF-300) packed column for the separation of positional isomers in high-performance liquid chromatography (HPLC) was reported for the first time. Benefitting from its regular shape, excellent chemical and thermal stability, microporous feature, and strong hydrophobicity of single-crystalline COF-300, the single-crystalline COF-300-packed column showed excellent resolution for the separation of positional isomers, including nitroaniline, dichlorobenzene, dibromobenzene, diiodobenzene, diethylbenzene, chloronitrobenzene, bromonitrobenzene, and iodonitrobenzene isomers, which cannot be all separated on commercial columns and a polycrystalline COF-300-packed column. Especially, the resolution values for m-/p-diiodobenzene and o-/m-diiodobenzene were 4.45 and 2.53. Moreover, the alkylbenzene, monosubstituted aromatics, polycyclic aromatic hydrocarbons, and the mixture of ethylbenzene and styrene were also baseline separated on the single-crystalline COF-300-packed column. This successful application not only confirmed the great potential of single-crystalline COFs in HPLC separation of positional isomers but also pioneered the utilization of single-crystalline COFs in separation science.

Optimizing Host–Guest Selectivity for Ethylbenzene Capture Toward Superior Styrene Purification

The separation of ethylbenzene (EB) and styrene (ST) mixtures to obtain pure ST has been an enduring challenge for the petrochemical industry. So far, adsorptive separation using porous materials has mainly focused on capturing ST rather than EB, where high temperatures are needed to reactivate the sieving materials and collect the product. Here, we tuned the host–guest interactions in thienothiophene-based trianglimine (ThT-TI) macrocycles to selectively adsorb the unreacted EB over ST, after a dehydrogenation reaction, to readily provide pure ST without the need for further thermal treatments. This is the first report on the selective adsorptive separation of EB over ST using macrocycles as molecular hosts. Both crystalline and amorphous ThT-TI can be used to separate EB with 96% uptake capacity. Single-crystal and powder X-ray diffraction patterns suggest that this selective adsorption arises from a guest-induced structural reordering and involvement of the sulfur atoms in host/guest C–H···π interactions. We believe that this work paves the way for a new generation of molecular sieves that are designed to afford high-purity products by in situ capturing of the unreacted starting materials.

Reactive diluent strategy for general benzoxazine to achieve high performance thermoset via a combination of styrene and glycidyl methacrylate

AbstractMost of polybenzoxazines suffer from intrinsic processability problems, while application of the conceptual strategy of reactive diluent remains challenge in benzoxazine field. Here, we reported a new methodology employing a mixture of styrene (St) and glycidyl methacrylate (GMA) as a reactive diluent to dissolve benzoxazine. A commercially available benzoxazine, bis(4‐(3,4‐dihydro‐2H‐1,3‐benzoxazine‐3‐yl))phenylmethane (PH‐ddm), was used as a model benzoxazine monomer for a variety of evaluation tests. GMA and St are capable of passing a robust radical polymerization to form linear copolymers, while offer epoxy groups to crosslink the PH‐ddm polymer resulting from the ring opening polymerization. Moreover, the benzoxazine mixture solutions show advantages in preparing composites with glass fibers. By comparing to bulk benzoxazine, the mixture solutions allow significant improvement in terms of tensile strength and elongation of the composites. The main contributor for the enhanced properties is their low‐viscosity nature and the capability to increase crosslinking density of the cured resin. The methodology presented here shows great potential for improving processability of benzoxazines, particularly in large‐scale manufacturing of composite.

Detection of binary and ternary mixtures of volatile organic compounds using quartz tuning fork based sensor array

Polymer modified Quartz tuning fork based sensors are a versatile replacement for the conventional sensors available in the market for the development of sensor array for electronic nose applications. However, there is not enough work towards detection of mixture of analytes using these sensors. In this work, a sensor array is developed to detect mixture of styrene, propylbenzene and acetone. Based on the working principle of the sensor, parameters like recovery time, response time, and frequency shift, among others, are utilized for data classification of the sensor response. The data collected from the sensor is used to classify the several groups using ensemble classifier, where, support vector machines, k-nearest neighbour and artificial neural network participated as the voting algorithms. Initially, the classifier was able to make prediction with approximately 93% accuracy. After modification in the prediction process where classifier was trained in a progressive manner, in which it predicted only if the data point belonged to mixture or not and subsequently, if it belonged to binary or ternary mixture. This improved the overall accuracy to 98%. The work demonstrate that the combination of QTF sensor array and a suitable classifier can be used to detect binary and ternary mixtures and therefore, can be used for several applications of electronic nose.

Preparation of magnetic Levextrel resin for cadmium(II) removal

In the present paper, the authors investigated the adsorption of cadmium on magnetic Levextrel resin containing about 352 mg g−1 Cyanex 272 (C272) as adsorbent. Magnetic Levextrel resin (mPst-DVB-C272) was synthesized through adding Cyanex 272 and oleic acid-coated magnetite nanoparticles directly to the mixture of styrene (st) and divinylbenzene (DVB) monomers during the bead polymerization. It is a new method for preparing magnetic Levextrel resins with less organic solvents and less steps MPst-DVB-C272 was characterized with scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravity (TG) and differential thermal gravity (DTG), and vibrating sample magnetometry (VSM). Then mPst-DVB-C272 was applied to remove cadmium. The effects of pH, initial Cd(II) concentration, and contact time on Cd(II) removal were investigated in batch experiments. The optimized pH value for the Cd(II) adsorption was 6.5. The maximum adsorption capacity was 18.77 mg g−1 for mPst-DVB-C272. The adsorption reached equilibrium within 90 min and the experimental data fit the pseudo-second-order model.

Surface Molecular Imprinting with Bacteria: Visualizing Re-Binding and Selectivity

Introduction Surface molecular imprinting [1,2] is one of the preferred techniques when it comes to generating biomimetic recognition for sensing bioanalytes. Limiting oneself to the surface of the respective molecularly imprinted polymer (MIP) usually is no problem, because biospecies are usually large enough that few binding events lead to measurable sensor responses, e.g. for mass-sensitive bacteria detection [3]. However, the detection limits of quartz crystal microbalances (QCM) do usually not meet the needs for detecting contamination of real-life samples when it comes to pathogen detection. The (geometrical) limitation of surface MIP in that regard makes it necessary to think about suitable systems for pre-concentration prior to the sensor measurement. Herein, we report Raman Microscopy studies on bacteria surface MIP aiming at visualizing different areas of the polymer and distinguishing between different species bound to the surface. Furthermore, we assess the binding properties of MIP resulting from Pickering emulsion polymerization [4] as a possible approach to selectively pre-concentrate bacteria. Experimental For molecular imprinting, we chose a non-pathogenic strain of Escherichia coli (E. coli) as a model species. We prepared surface MIP of two different morphologies based on polystyrenes cross-linked with divinyl benzene utilizing azo-bisisobutyronitrile (AIBN) as a radical initiator. For MIP thin films, we prepared respective mixtures of monomer and crosslinker, pre-polymerized at 70°C, and then spin-coated onto the respective devices. In parallel, we prepared stamps comprising E. coli on their surfaces. Then, we pressed the stamp into the oligomer thin films on the respective surface and cured the system at 80°C over night. We took all spectra on a confocal Raman Microscopy system (WiTec alpha300RAS) at an excitation wavelength of l=532nm. Chemometric data evaluation relied on the software package Solo&Mia by Eigenvector. For Pickering emulsion, we prepared mixtures of styrene and divinylbenzene and used bacteria to emulsify them in either distilled water, or a suitable buffer system (e.g. 10mM PBS) and polymerized the bacteria stabilized droplets at 37°C. Then, we removed E. coli cells from the polymer surface via solvent extractions in acetic acid + SDS, water and methanol. Results and Discussion In a first step it was essential to clarify if one can use the Raman spectra of different bacteria species and polymer, to differentiate between those, respectively. Polymer and bacteria spectra obviously differ from each other enough to distinguish them by the naked eye. However, this is not the case for the Raman emission spectra of different bacteria species, because they all contain nucleic acids, proteins, and lipids. Therefore it is necessary to rely on chemometric strategies – modified partial least squares discriminant analysis (PLS-DA) in the concrete case – to achieve such goal. This is indeed possible: Fig. 1A shows the outcome for four different bacteria species, namely Escherichia coli, Lactococcus lactis, Bacillus cereus and Staphylococcus epidermidis that clearly demonstrates separation of the species according to their spectral properties. Knowing the specific spectral ranges also allows for generating false-color images showing which areas of a bacteria MIP surfaces reveal pure polymer and which parts contain bacteria of different species. It is even possible to go one step further: Comparing AFM and false color so-called RamanTV images (see Fig. 1B) for an example of the latter) demonstrates that the Raman microscope is even useful for distinguishing polymer surface and imprinted cavities. For such micrometer-sized analytes, the combination of Raman microscopy and AFM hence allows for generating maps showing all possible types of surfaces, i.e. polymer matrix as well as both unoccupied cavities and different bacteria species present at the polymer surface. This opens the perspective of directly visualizing occupancy and selectivity of the respective MIP.AFM turned out useful to visualize such imprints not only on flat surfaces, but also on curved ones: Figure 1C) and 1D) reveal an imprinted site on the surface of a miroparticle resulting from emulsion polymerization, Fig. 1E) an SEM image showing occupied and empty cavities. One can generate such cavities in different polymer matrices, for instance when replacing divinyl benzene as a cross-linker by trimethyolylpropane trimethacrylate (TRIM), or ethylene glycol dimethacrylate (EGDMA). In both cases, the respective imprinted surface reveal cavities that fit the size and shape of the template bacteria. Scanning electron microscopy also revealed that bacteria re-occupy those cavities if one exposes the particles to to bacteria suspensions. This leads to two conclusions: first, one can tune polymer properties without destroying the emulsion structure necessary for Pickering emulsion. This is of interest for bringing the artificial system closer to physiological conditions. Second, those particles are inherently suitable for selectively pre-concentrating those species from larger samples. Figure 1

Synthesis of julolidines via one‐pot cascade three component Povarov reaction in the presence of silica sulfuric acid

AbstractIn this report, synthesis of julolidines via one‐pot cascade reaction of aniline derivatives with a mixture of styrene and formaldehyde in the presence of silica sulfuric acid as an efficient catalyst has been studied under aerobic condition. By presented method, various julolidines are obtained under mild and transition metal‐free conditions. The reaction is proceeded with imine formation and followed by an Aza‐Diels‐Alder cycloaddition with styrene gave julolidine derivatives. The catalyst can be recycled and reused multiple times to catalyze the reaction.

Temperature Variation Enables the Design of Biobased Block Copolymers via One-Step Anionic Copolymerization.

A one-pot approach for the preparation of diblock copolymers consisting of polystyrene and polymyrcene blocks is described via a temperature-induced block copolymer (BCP) formation strategy. A monomer mixture of styrene and myrcene is employed. The unreactive nature of myrcene in a polar solvent (tetrahydrofuran) at -78°C enables the sole formation of active polystyrene macroinitiators, while an increase of the temperature (-38°C to room temperature) leads to poly(styrene-block-myrcene) formation due to polymerization of myrcene. Well-defined BCPs featuring molar masses in the range of 44-117.2kgmol-1 with dispersities, Ð, of 1.09-1.21, and polymyrcene volume fractions of 30-64% are accessible. Matrix assisted laser desorption ionization-time of flight mass spectrometry measurements reveal the temperature-controlled polymyrcene block formation, while both transmission electron microscopy and small-angle X-ray scattering measurements prove the presence of clearly microphase-separated, long range-ordered domains in the block copolymers. The temperature-controlled one-pot anionic block copolymerization approach may be general for other terpene-diene monomers.

Concentration Fluctuations and Nanosegregation in a Simplified Industrial Blend with Large Dynamic Asymmetry

Applying small-angle neutron scattering (SANS) on isotopically labeled samples, we have characterized the thermally driven concentration fluctuations (TCFs), one of the main factors in the phenomenology of blend dynamics, in mixtures of styrene–butadiene rubber (SBR) and oligomers of polystyrene (PS) with different compositions. This system displays a large dynamic asymmetry and is thus a good model to explore the tunability of properties of interest in the rubber industry. The SANS experiments, complemented with neutron diffraction with polarization analysis, have allowed one to determine the UCST behavior of the blend and establish its phase diagram. We find a close vicinity of the spinodal and vitrification lines for intermediate concentrations and samples rich in PS. This induces the freezing of the correlation length for TCF when decreasing the temperature and also has an impact on the reported dielectric response of these mixtures. Furthermore, we have deduced the relevant length scale for segmental relaxation from the comparison of SANS and dielectric results. The values found (≈1.5–2 nm) are close to the Kuhn lengths of the components. The relevance of nanometric length scales in this system could also be tentatively attributed to an underlying nanodomain structure associated with the segregation of phenyl rings and main chains, supported by complementary X-ray diffraction experiments.