Short Separation Time Research Articles

Mechanistic study on the high-selectivity enantioseparation of amino acids using a chiral crown ether-bonded stationary phase and acidic, highly organic mobile phase by liquid chromatography/time-of-flight mass spectrometry

The separation mechanism of amino acid enantiomers using a chiral crown ether-bonded stationary phase, CROWNPAK CR-I(+), and acetonitrile (ACN)-rich mobile phases (MPs) was studied. The retention factors of proteinogenic l-amino acids (except proline) formed U-shaped plots against the ACN content in the MP with a sharp increase at a high ACN content, while d-amino acids showed much smaller increases or monotonous decreases in retention within the same range. The use of an acidic, highly organic MP with trifluoroacetic acid (TFA) provided a high enantioselectivity with a short separation time from the contribution of the increased binding of the ammonium group of the analytes to the crown ether functionality of the stationary phase and electrostatic repulsion counteracting the hydrophilic partition mechanism. Optimizing the sample diluent and MP alleviated the peak distortion caused by a moving water band that accompanied the hydrophilic interaction liquid chromatography-like elution conditions. The liquid chromatography/time-of-flight mass spectrometry method with the optimized MP — ACN/ethanol/water/TFA = 80/15/5/0.5 (v/v/v/v) — enabled the determination of eighteen pairs of proteinogenic amino acid enantiomers within 10 min. The conditions also provided the following advantages: (i) fast and highly reproducible separations under isocratic conditions, (ii) high sensitivity and low backpressure using the MP with a high organic content, and (iii) highly reliable peak identification by combining two columns (CR-I(+) and CR-I(-)), reversing the elution orders of the enantiomers.

Monitoring of adipose tissue metabolism using microdialysis and capillary electrophoresis with contactless conductivity detection

Metabolism of human adipose tissue during acute exercise is monitored by microdialysis. The metabolites are analysed in the microdialysate using capillary electrophoresis (CE) on a short separation path in combination with a contactless conductivity detector (C4D). Four completely new CE/C4D methods were developed for determination of nutrients and metabolites in 10 µL of microdialysate. All methods are characterised by a short separation time and simple sample preparation based primarily on 4-fold dilution of microdialysate. The intra-day repeatability for the migration time varied in the range 0.4 – 0.9% and that for the peak area equalled 0.7 – 2.4%; the inter-day repeatability of the migration time was in the range 1.2 – 2.3% and the range for the peak area was 2.5 – 5.0%; all the values were measured as RSD. The developed determination was employed for sequenced monitoring of the levels of lactate, glycerol and branched chain amino acids in microdialysates taken from the abdominal adipose tissue during acute physical exercise. The stress test lasted 3 h and the metabolites were monitored at 15 min intervals.

A simple gradient equilibrium method for better separation in countercurrent chromatography.

The stationary phase retention is one of the most important parameters in countercurrent chromatography. In this work, a simple gradient equilibrium method was developed to further improve the stationary phase retention based on the optimized condition in the traditional equilibrium model. Meanwhile, this novel gradient equilibrium method was used to separate three flavone model compounds and compared with the conventional isocratic equilibrium method to evaluate the separation efficiency. The results show that better resolution or shorter separation time could be achieved with gradient equilibrium compared to isocratic equilibrium. So this novel equilibrium method has enormous potential for obtaining a better separation or saving the separating time in the preparative separation of target compounds.

Solid-liquid separation: an emerging issue in heavy metal wastewater treatment.

Solid-liquid separation (SLS) plays a dominant role in various chemical industries. Nowadays, low efficiency of SLS also become a significant problem in heavy metal (HM) wastewater treatment, affecting the effluent quality (HM concentration and turbidity) and overall process economy. In this context, we summarize here the occurrence of solids in HM wastewater, as well as typical SLS operations used in HM wastewater treatment, including sedimentation, flotation, and centrifugation. More important, this article reviews the improvement of the SLS operations by some technologies, including coagulation, flocculation, ballasted method, seeding method, granular sludge strategy, and external field enhancement. It is noted that abiological granular sludge strategy and magnetic field enhancement often possess higher SLS efficiency (faster settling velocity or shorter separation time) than other methods. Hence, the two strategies stand out as promising tools for improving SLS in HM wastewater treatment, but further research is required regarding scalability, economy, and reliability.

Microbubble-Triggered Spontaneous Separation of Transparent Thin Films from Substrates Using Evaporable Core-Shell Nanocapsules.

The spontaneous separation of a polymer thin film from a substrate is an innovative technology that will enable material recycling and reduce manufacturing cost in the film industry, and this can be applied in a wide range of applications, from optical films to wearable devices. Here, we present an unprecedented spontaneous strategy for separating transparent polymer films from substrates on the basis of microbubble generation using nanocapsules containing an evaporable material. The core-shell nanocapsules are prepared from poly(methyl methacrylate)-polyethyleneimine nanoparticles via the encapsulation of methylcyclohexane (MCH). A spherical nanostructure with a vaporizable core is obtained, with the heat-triggered gas release ability leading to the formation of microbubbles. Our separation method applied to transparent polymer films doped with a small amount of the nanocapsules encapsulating evaporable MCH enables spontaneous detachment of thin films from substrates via vacuum-assisted rapid vaporization of MCH over a short separation time, and clear detachment of the film is achieved with no deterioration of the inherent optical transparency and adhesive property compared to a pristine film.

Highly effective hydrogen isotope separation by cryogenic gas chromatography in a new stationary phase material MnCl2@CPL-1@γ-Al2O3

In this work, metal-organic framework compound CPL-1 of a formula {[Cu2(pzdc)2(pyz)]⋅2H2O}n (pzdc = pyrazine-2,3-dicarboxylate, pyz = pyrazine) possessing kinetic quantum sieving effect on H2/D2 separation was selected to prepare two new chromatography stationary phase materials CPL-1@γ-Al2O3 and MnCl2@CPL-1@γ-Al2O3 by loading CPL-1 on γ-Al2O3 particles with size 80–100 mesh through repeating in situ crystallization process, and afterwards by loading MnCl2 on CPL-1@γ-Al2O3 via impregnation approach. The two optimized materials were thoroughly characterized by IR, XRD, SEM, EDS and TG/DTA method. The experimental results showed that, under liquid nitrogen temperature by using just 1-m chromatographic column and cheap He gas as carrier gas, the MnCl2@CPL-1@γ-Al2O3 can solve the problem of long separation time and trailing phenomenon existing in the CPL-1@γ-Al2O3 column, can realize highly effective hydrogen isotope H2/D2 separation with good separation resolution (R = 1.62) and approximate Gauss distribution of chromatographic peak, can be used for both qualitative and quantitative analysis of hydrogen isotope H2/D2 with short separation time of 6.5 min.

Cobalt porphyrin supported on N and P co-doped graphene quantum dots/graphene as an efficient photocatalyst for aerobic oxidation of alcohols under visible-light irradiation

The research and development of the new heterogeneous photocatalysts for selective organic transformations under visible-light irradiation and environmentally friendly conditions is still considered as one of the hot topics in the fine chemical industry. Here, we report the synthesis of cobalt porphyrin-supported nitrogen and phosphorus co-doped graphene quantum dots/graphene (CoPP@N, P: GQD/G) and their impressive performance as efficient, recyclable, and noble metal free heterogeneous photocatalysts in the aerobic oxidation reaction of alcohols under visible-light irradiation. In terms of catalytic activity, these catalysts afford much higher conversion (ca. 92%) and selectivity (ca. 86%) than most reported photocatalysts under the same reaction conditions. This work notes the considerable potential of CoPP@N, P: GQD/G photocatalysts in the aerobic oxidation reaction owning to high activity and selectivity, short reaction time, reusability and easy separation under ambient and green conditions.

Ion-pairing reversed-phase chromatography coupled to inductively coupled plasma mass spectrometry as a tool to determine mercurial species in freshwater fish

Most of analytical community is focused on reversed phase high performance liquid chromatography (RP-HPLC) for mercury speciation by employing mobile phases comprising of high salts and moderate amounts of organic solvents. This study aims at rapid mercury speciation analysis by ion-pairing RP-HPLC with inductively coupled plasma mass spectrometry (ICP-MS) detection only using low salts for the sake of green analytical chemistry. Two ion-pairing HPLC methods were developed on individual usage of positively and negatively charged ion-pairing reagents (tetrabutylammonium hydroxide –TBAH and sodium dodecylbenzene sulfonate –SDBS), where sodium 3-mercapto-1-propysulfonate (MPS) and l-cysteine (Cys) were individually added in mobile phases to transform mercury species into negative and positive Hg-complexes for good resolution. Addition of phenylalanine was also utilized for rapid baseline separation in combination of short C18 guard columns. Optimum mobile phases of 2.0mM SDBS+2.0mM Cys+1.0mM Phe (pH 3.0) and 4.0mM TBAH+2.0mM MPS+2.0mM Phe (pH 6.0) both achieved baseline separation of inorganic mercury (Hg2+), methylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg) on two consecutive 12.5-mm C18 columns. The former mobile phase was selected for mercury speciation in freshwater fish because of short separation time (3.0min). Detection limits of 0.015 for Hg2+, 0.014 for MeHg, 0.028 for EtHg and 0.042μgL−1 for PhHg were obtained along with satisfactory precisions of peak height and area (1.0-2.8% for 5.0μgL−1 Hg-mixture standard). Good accordance of determined values of MeHg and total mercury in certified reference materials of fish tissue (GBW 10029) and tuna fish (BCR-463) with certified values as well as good recoveries (91–106%) proved good accuracy of the proposed method. An example application to freshwater fish indicated its potential in routine analysis, where MeHg was presented at 3.7–20.3μgkg−1 as the dominate species.

Preparation and evaluation of diblock copolymer-grafted silica by sequential surface initiated-atom transfer radical polymerization for reverse-phase/ion-exchange mixed-mode chromatography.

A novel approach that involved the grafting of diblock copolymer with two types of monomer onto substrate by sequential surface initiated-atom transfer radical polymerization was proposed to prepare a mixed-mode chromatographic stationary phase. The distinguishing feature of this method is that it can be applied in the preparation of various mixed-mode stationary phases. In this study, a new reverse-phase/ion-exchange stationary phase was prepared by grafting hydrophobic styrene and cationic sodium 4-styrenesulfonate by the proposed approach onto silica surface. The chromatographic properties of the prepared stationary phase were evaluated by the separation of benzene derivatives, anilines, and β-agonists, and by the effect of pH values and acetonitrile content on the retention. Compared with typical RP columns, the prepared stationary phase achieved the better resolution and higher selectivity at a shorter separation time and lower organic content. Moreover, the application of the prepared column was proved by separating widely distributed polar and charged compounds simultaneously.

Enhanced treatment of dispersed dye-production wastewater by self-assembled organobentonite in a one-step process with poly-aluminium chloride

Organobentonite has been successfully applied in industrial wastewater treatment. However, the solid-liquid separation in wastewater treatment still needs improvement. This study presents an enhanced approach with high removal efficiency and short separation time for dispersed dye-production wastewater using self-assembled organobentonite in a one-step process with poly-aluminium chloride (PAC). The enhanced effects of PAC on wastewater treatment by organobentonite were comprehensively evaluated. Following the primary decontamination by the self-assembled organobentonite, the removal efficiency for dispersed dye-production wastewater was strengthened with PAC coagulation. The removal rates of TOC and organic pollutants were 55.0% and 63.5%, respectively, with the PAC-enhanced approach and were 1.3- and 1.6-fold higher, respectively, than those with the self-assembled organobentonite approach. The combination of PAC with self-assembled organobentonite was able to break the stability of the organobentonite suspension and enlarge the floc size, and thus reduce the solid-liquid separation time from 30 min to 10 min. Additionally, this enhanced approach could improve the biodegradability of wastewater with the BOD5/CODCr ratio increasing from 0.22 to 0.39, which was 4.1-fold higher than that of only organobentonite in a one-step process. Therefore, the PAC-enhanced approach could be a promising technology for wastewater pretreatment in practical industrial applications.

Optimization of ultra-performance liquid chromatography (UPLC) with fluorescence detector (FLD) method for the quantitative determination of selected neurotransmitters in rat brain.

Glutamate (Glu) and γ-aminobutyric acid (GABA) are the main neurotransmitters in the central nervous system for excitatory and inhibitory processes, respectively. Monitoring these neurotransmitters is an essential tool in establishing pathological functions, among others in terms of occupational exposure to toxic substances. We present modification of the HPLC (high-performance liquid chromatography) to the UPLC (ultra-performance liquid chromatography) method for the simultaneous determination of glutamate and γ-aminobutyric acid in a single injection. The isocratic separation of these neurotransmitter derivatives was performed on Waters Acquity BEH (ethylene bridged hybrid) C18 column with particle size of 1.7 μm at 35°C using a mobile phase consisting of 0.1 M acetate buffer (pH 6.0) and methanol (60:40, v/v) at a flow rate of 0.3 ml/min. The analytes were detected with the fluorescence detector (FLD) using derivatization with o-phthaldialdehyde (OPA), resulting in excitation at 340 nm and emission at 455 nm. Several validation parameters including linearity (0.999), accuracy (101.1%), intra-day precision (1.52-1.84%), inter-day precision (2.47-3.12%), limit of detection (5-30 ng/ml) and quantification (100 ng/ml) were examined. The developed method was also used for the determination of these neurotransmitters in homogenates of selected rat brain structures. The presented UPLC-FLD is characterized by shorter separation time (3.5 min), which is an adaptation of the similar HPLC methods and is an alternative for more expensive references techniques such as liquid chromatography coupled with tandem mass-spectrometry (LC-MS/MS) methods. Med Pr 2017;68(5):583-591.

Development of a New Method Based on Chiral Ligand-Exchange Chromatography for the Enantioseparation of Propranolol.

A new chromatographic procedure was proposed for the separation of propranolol (PRN) enantiomers based upon enantioselective chiral ligand-exchange chromatography. The separation was carried out on a short C8 column leading to considerably short separation time. L-alanine and Cu2+ were applied as chiral selector and central bivalent complexing ion, respectively. It was found that the kind of copper salt could influence the enantioseparation efficiency. The separation on the C8 stationary phase was more efficient than that on the C18 column. It was shown that the pH of mobile phase, organic modifier content of mobile phase, mole ratio of chiral ligand to bivalent ion and Cu (L-alanine) 2 concentration in the mobile phase were important in enantioseparation efficiency. Water/methanol (70:30) mixture containing L-alanine-Cu2+ (7:1) was found to be the best mobile phase condition for PRN enantioseparation. All effective parameters were optimized in order to improve the separation efficiency. The optimized HPLC method was utilized for analysis of propranolol enantiomers in spiked human blood plasma samples.

THE TWINS' SITUATION IMPACT ON THE PERSONALITY DEVELOPMENT

Since the moment of their birth between the twins develop a relationship that differs from the brother and sister relationships. Two children of the same age, growing under the same conditions, promote and develop their personalities. The twins' connections are so close that at a short time separation from each other, the twins suffer the same as been separated from their mother. The aim of the research: to research the twins' situation impact on the child's personality development. The research involves the analysis of the scientific pedagogical and psychological literature, structured interviews are used in the empirical research. The obtained data from the parents interviews of 37 twins' pairs have been analyzed. Results: the role distribution, the twins bilateral/reciprocal competitiveness, speech-therapist's necessity, self-contentedness inside the pair, communication with other children, amount of vocabulary at an early age are clarified in the twins pair, presence of cryptophasia, emphasizing of similarity, difference, difficulty to formulate thoughts and emotions by words. Conclusions: twins' situations impact essentially differs, depending on the type of twins: MZ, DZ or different gender. Their bilateral/reciprocal interrelation indexes are different: the role distribution in the pair, desire to competitiveness, be closely self-contained inside their pair and disallow to let others into their dyad or to be open to communication with other people.

OPTICAL VARIABILITY OF AGNs IN THE PTF/iPTF SURVEY

ABSTRACT We characterize the optical variability of quasars in the Palomar Transient Factory and intermediate Palomar Transient Factory (PTF/iPTF) surveys. We re-calibrate the r-band light curves for ∼28,000 luminous, broad-line active galactic nuclei from the SDSS, producing a total of ∼2.4 million photometric data points. We utilize both the structure function (SF) and power spectrum density (PSD) formalisms to search for links between the optical variability and the physical parameters of the accreting supermassive black holes that power the quasars. The excess variance (SF2) of the quasar sample tends to zero at very short time separations, validating our re-calibration of the time-series data. We find that the the amplitude of variability at a given time-interval, or equivalently the timescale of variability to reach a certain amplitude, is most strongly correlated with luminosity with weak or no dependence on black hole mass and redshift. For a variability level of SF(τ) = 0.07 mag, the timescale has a dependency of . This is broadly consistent with the expectation from a simple Keplerian accretion disk model, which provides . The PSD analysis also reveals that many quasar light curves are steeper than a damped random walk. We find a correlation between the steepness of the PSD slopes, specifically the fraction of slopes steeper than 2.5, and black hole mass, although we cannot exclude the possibility that luminosity or Eddington ratio are the drivers of this effect. This effect is also seen in the SF analysis of the (i)PTF data, and in a PSD analysis of quasars in the SDSS Stripe 82.

Improved Separations of Proteins and Sugar Derivatives Using the Small-Scale Cross-Axis Coil Planet Centrifuge with Locular Multilayer Coiled Columns.

Countercurrent chromatography (CCC) is liquid-liquid partition chromatography without using a solid support matrix. This technique requires further improvement of partition efficiency and shortening theseparation time. The locular multilayer coils modified with and without mixer glass beads were developed for the separation of proteins and 4-methylumbelliferyl (MU) sugar derivatives using the small-scale cross-axis coil planet centrifuge. Proteins were well separated from each other and the separation was improved at a low flow rate of the mobile phase. On the other hand, 4-MU sugar derivatives were sufficiently resolved with short separation time at a highflow rate of the mobile phase under satisfactory stationary phase retention. Effective separations were achieved using the locular multilayer coil for proteins with aqueous-aqueous polymer phase systems and for 4-MU sugar derivatives with organic-aqueous two-phase solvent systems by inserting a glass bead into each locule.

Cationic Ionic Liquids Organic Ligands Based Metal-Organic Frameworks for Fabrication of Core-Shell Microspheres for Hydrophilic Interaction Liquid Chromatography.

In this study, new metal-organic frameworks (MOFs) nanocrystals modified SiO2 core-shell microspheres were designed with cationic ionic liquids (ILs) 1,3-bis(4-carboxybutyl)imidazolium bromide (ILI) as organic ligands. By further adjustment the growth cycles, the new ILI-01@SiO2 core-shell stationary phase was facilely fabricated. The developed stationary phase was respectively characterized via element analysis, thermogravimetric analysis, scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectrometry. Because the introduction of cationic imidazolium-based ILs ILI for fabrication of the MOFs nanocrystals shell, the new stationary phase exhibits the retention mechanism of hydrophilic interaction liquid chromatography (HILIC). Many polar samples, such as amides, vitamins, nucleic acid bases, and nucleosides, were utilized to investigate the performance of the prepared ILI-01@SiO2 column. Compared to the conventional aminosilica column, the new ILI-01@SiO2 column displays high separation selectivity in a shorter separation time. Furthermore, the new ILI-01@SiO2 column was also used for detection of illegal melamine addition in the baby formula. All the above results demonstrate the new ILI-01@SiO2 core-shell stationary phase is of good potentials for high-selectivity separation the polar samples.

Separation of argon from environmental samples for Ar-37 and Ar-39 analyses

High purity argon is required for ultra-low background measurements of 37Ar and 39Ar. Both short separation times and high argon recovery are required. Here we report the development of an argon separation line from gas samples of 10–120 l volume by a chromatographic desorption from Li-LSX at −120 °C. Gases desorb in the order Ar < O2 < Kr < CH4 ≈ N2 < CO2, in agreement with published heats of adsorption. The optimum temperature of −120 °C for Ar separation from atmospheric air is achieved by a combination of cryogenic cooling with liquid nitrogen and counter-heating. So far, ∼16,500 l of sample gas have been processed on the separation line. The final purity of the argon is >99.99% with a recovery of >94%. The separation process for 80 l atmospheric air requires 3–4.5 h, which allows the purification of 2 samples per working day.

A robust multistage mesoflow reactor for liquid–liquid extraction for the separation of Co/Ni with cyanex 272

Solvent extraction is a key principle for separations of components often requiring relatively large separation times due to large droplet size distributions. A continuous mesoflow reactor setup was evaluated for solvent extraction and phase separation in terms of efficiency of Co/Ni separation with cyanex 272 as extractant in a kerosene mixture. Several mixer types have been evaluated for the solvent extraction capability combined with a thin film coalescer/separator, expediting separation times, resulting in a settling volume that was only 1–2 times the volume of the mixer effectively reducing total residence time compared to classic mixer-settlers, where the ratio is 4–8 times higher. This was mainly attributed to the droplet homogeneity generated in the mixer, resulting is a short separation time. The thin film coalescer partitions in the settler expedited the phase separation further reducing the required settler volume. This paper shows that continuous mesoflow reactor setups can be utilized for small-scale liquid extractions with narrowly defined droplet sizes, enhancing the phase separation time, making it a viable screening utility. It also shows that the useful volume is much higher than those for conventional mixer-settler with a phase-separation-volume-to-equilibrium-volume ratio of 1–2 compared to 4–8 for the conventional mixer-settler expediting parameter screening.

Temporal correlations in neuronal avalanche occurrence

Ongoing cortical activity consists of sequences of synchronized bursts, named neuronal avalanches, whose size and duration are power law distributed. These features have been observed in a variety of systems and conditions, at all spatial scales, supporting scale invariance, universality and therefore criticality. However, the mechanisms leading to burst triggering, as well as the relationship between bursts and quiescence, are still unclear. The analysis of temporal correlations constitutes a major step towards a deeper understanding of burst dynamics. Here, we investigate the relation between avalanche sizes and quiet times, as well as between sizes of consecutive avalanches recorded in cortex slice cultures. We show that quiet times depend on the size of preceding avalanches and, at the same time, influence the size of the following one. Moreover we evidence that sizes of consecutive avalanches are correlated. In particular, we show that an avalanche tends to be larger or smaller than the following one for short or long time separation, respectively. Our analysis represents the first attempt to provide a quantitative estimate of correlations between activity and quiescence in the framework of neuronal avalanches and will help to enlighten the mechanisms underlying spontaneous activity.

ChemInform Abstract: A Facile and Green Approach for the Synthesis of Spiro[naphthalene‐2,5′‐pyrimidine]‐4‐carbonitrile via a One‐Pot Three‐Component Condensation Reaction Using DBU as a Catalyst.

A series of functionalized spiro[naphthalene-2,5′-pyrimidine]-4-carbonitrile derivatives were synthesized using 1,3-dimethylbarbituric acid, aldehydes and cyclohexylidene malononitrile in the presence of DBU. The structures were confirmed by spectral data. X-Ray crystallographic studies of one of the compounds confirmed the structure. The crystal packing shows eight molecules in a single unit cell. The crystal structure also revealed intermolecular and intramolecular hydrogen bonding. Mild reaction conditions, high yields, short reaction time and easy separation are some of the salient features of the present protocol.