48 research outputs found
Simulation and Optimization of Distillation Processes for Separating the Methanol–Chlorobenzene Mixture with Separate Heat-Pump Distillation
The methanol–chlorobenzene
mixture has a larger relative
volatility in the low composition range than in the high composition
range. Based on this characteristic, the mixture can be effectively
separated by separate heat-pump distillation (SHPD) with significant
energy savings. The binary interaction parameters of the UNIQUAC equation
were used to predict the vapor–liquid equilibrium by means
of the binary interaction parameters included in the Aspen Plus database.
To minimize the overall annual operating costs, simulations for SHPD
were carried out using Aspen Plus software, including the RadFrac
and Compr blocks, and the optimal operating conditions, such as the
split-point concentration, were determined. Simulations for conventional
distillation, conventional heat-pump distillation, and multieffect
distillation processes were also carried out for comparison. The simulated
results showed that the SHPD process has obvious advantages over the
other distillation processes in the assessment of energy savings and
overall economic efficiency
Simulation and Optimization of Distillation Processes for Separating a Close-Boiling Mixture of <i>n</i>‑Butanol and Isobutanol
Separation
of close-boiling mixtures by conventional distillation
consumes a large amount of energy because of the very high reflux
ratio required. Mechanical vapor recompression heat pumps (MVRHPs)
can recycle the energy of the vapor and can thus be used in such distillation
processes to save energy. Three different distillation schemes, namely,
conventional distillation, top MVRHP distillation, and bottom-flashing
MVRHP distillation, were simulated for the separation of the close-boiling
mixture of <i>n</i>-butanol and isobutanol using Aspen Plus
to determine the economically best option. The research results indicate
that, compared to conventional distillation, the energy savings for
bottom-flashing MVRHP distillation and top MVRHP distillation can
reach 67.92% and 72.92%, respectively, and the TACs correspondingly
decrease by 71.74% and 75.57%
ICPMS-Based Specific Quantification of Phosphotyrosine: A Gallium-Tagging and Tyrosine-Phosphatase Mediated Strategy
Low-abundance
tyrosine phosphorylation is crucial to not only normal
but also aberrant life processes. We designed and synthesized a photocleavable
magnetic nanoparticle-based gallium tag for tagging and enrichment
as well as UV-release of the phosphate-bearing molecules/ions in cells.
HPLC/<sup>71</sup>Ga species-unspecific isotope dilution (<sup>71</sup>Ga-SUID) ICPMS was subsequently developed for specific and absolute
quantification of phosphotyrosine (<b>pY</b>) under the assistance
of a protein tyrosine phosphatase-1B (PTP-1B). <b>pY</b> quantification
was thus achieved via determination of Ga in the Ga-phosphate complexes
that come exclusively from the Ga-tagged <b>pY</b>. In this
way, the method detection limit of <b>pY</b> reached down to
30 amol with the RSD lower than 5.70% (<i>n</i> = 5 at pmol
level). Feasibility of this proposed method was validated using VNQIGTLSE<b>pY</b>IK, VNQIGTL<b>pS</b>E<b>pY</b>IK,
and extracellular regulated protein kinase 1 peptide (-<b>pT</b>E<b>pY</b>-) standards with the recovery of more than 96% (<i>n</i> = 5). It was applied to the absolute quantification of <b>pY</b> in human breast cancer MCF-7 cells, indicating that <b>pY</b> increased by 1.60 nmol (61.1%) in 3.0 × 10<sup>6</sup> MCF-7 cells after 100 nM insulin stimulation. We believe that, not
limited to <b>pY</b> quantification, this element-tagging and
protease-specific reaction mediated ICPMS methodology will pave a
simple path for ever more applications of ICPMS to the studies of
quantitative protein post-translational modifications (PTMs) when
suitable element-tags are designed and specific proteases are available
toward targeted PTMs
Monitoring the adulteration of milk with melamine: a visualised sensor array approach
<div><p>Melamine, a toxic triazine, is illegally used as an additive in milk to apparently increase the amount of protein, causing acute renal failure in thousands of Chinese infants. In this study, a rapid, simple, sensitive and selective colourimetric sensor array is reported as a potential screening tool for monitoring the adulteration of raw milk with melamine. Using chemically responsive dyes (mainly porphyrins and pH indicators) as the recognition elements, determination of melamine at different concentrations (0.1, 0.5, 1.0, 1.5 and 2.0 mg kg<sup>−1</sup>) and a detection limit of 0.1 mg kg<sup>−1</sup> were achieved because of diverse and strong molecular interactions. Furthermore, the colourimetric sensor array was successfully able to discriminate between melamine and its analogues. The unique “fingerprint” of melamine was obtained with a novel signal processing method named “two-step subtraction”, which made it possible for the detection results to be easily observed with the naked eye even without any statistical analysis. In addition, the process including sample pre-treatment and detection process took only 12 min at room temperature. The merits (such as simplicity, rapidity, low cost, visual colourimetry, sensitivity and selectivity) make the proposed method especially useful for on-site screening of melamine levels in milk.</p></div
Evaluation of BDE-47 Hydroxylation Metabolic Pathways Based on a Strong Electron-Withdrawing Pentafluorobenzoyl Derivatization Gas Chromatography/Electron Capture Negative Ionization Quadrupole Mass Spectrometry
Understanding
the metabolic pathways of polybrominated diphenyl
ethers (PBDEs) is a key issue in the evaluation of their cytotoxicity
after they enter the biota. In order to obtain more information concerning
the metabolic pathways of PBDEs, we developed a strong electron-withdrawing
pentafluorobenzoyl (PFBoyl) derivatization capillary gas chromatography/electron
capture negative ionization quadrupole mass spectrometry (GC/ECNI-<i>q</i>MS). PFBoyl esterification greatly improves separation
of the metabolites of PBDEs such as hydroxylated PBDEs (OH-PBDEs)
and bromophenols (BPs) metabolites in rat liver microsomes (RLMs).
On the other hand, the strong electron-withdrawing property of PFBoyl
derivatized on OH-PBDEs and/or BPs makes cleavage of the ester bond
on ECNI easier resulting in higher abundance of the structure-informative
characteristic fragment ions at a high <i>m</i>/<i>z</i> region, which facilitate the identification of OH-PBDEs
metabolites. Subsequent quantification can be performed by monitoring
not only <sup>79</sup>Br<sup>–</sup> (or <sup>81</sup>Br<sup>–</sup>) but also their characteristic fragment ions, achieving
more accurate isotope dilution quantification using GC/ECNI-<i>q</i>MS. These merits allow us to identify totally 12 metabolites
of BDE-47, a typical example of PBDEs, in the RLMs <i>in vitro</i> incubation systems. In addition to the already known metabolites
of BDE-47, one dihydroxylated 3,6-di-OH-BDE-47 and one dihydroxylated
3,5-di-OH-tetrabrominated dioxin were found. Moreover, the second
hydroxylation took place on the same bromophenyl ring, where the first
hydroxyl group was located, and was further confirmed via the identification
of the dihydroxylated 2′,6′-di-OH-BDE-28 of an asymmetric
2′-OH-BDE-28. This methodological development and its subsequent
findings of the
metabolic pathways of BDE-47 provided experimental evidence for understanding
its dioxin-like behavior and endocrine disrupting risk
Real-Time Imaging of Mitochondrial Hydrogen Peroxide and pH Fluctuations in Living Cells Using a Fluorescent Nanosensor
Mitochondrial reactive oxygen species
(ROS) and pH fluctuations
are closely correlated with mitochondrial dysfunctions, which are
implicated in various human diseases including neurodegenerative disorders
and cancers. Simultaneously monitoring the changes of ROS and pH of
mitochondria remains a major challenge in the mitochondrial biology.
In this study, we develop a novel mitochondria-targeted fluorescent
nanosensor for real-time imaging of the fluctuations of hydrogen peroxide
(H<sub>2</sub>O<sub>2</sub>) and pH in living cells. The fluorescence
probes for detecting pH and H<sub>2</sub>O<sub>2</sub> were loaded
in the small-sized mesoporous silica nanoparticles (MSN). Then the
polyethylenimine was attached to cap the pores of MSN, the triphenylphosphonium
was further modified to target mitochondria in living cells. Confocal
fluorescence imaging indicated that the nanosensor could effectively
target mitochondria and successfully achieved real-time imaging of
mitochondrial H<sub>2</sub>O<sub>2</sub> and pH fluctuations in living
cells. Notably, this is a single nanosensing system that is capable
of visualizing multiple subcellular analytes at the same time and
position by multicolor fluorescence imaging. The current approach
can provide a promising tool to investigate the interplaying roles
of various subcellular analytes in living cells
Nanosemiconductor-Based Photocatalytic Vapor Generation Systems for Subsequent Selenium Determination and Speciation with Atomic Fluorescence Spectrometry and Inductively Coupled Plasma Mass Spectrometry
We reported novel Ag–TiO<sub>2</sub>- and ZrO<sub>2</sub>-based photocatalytic vapor generation (PCVG) systems as effective
sample introduction techniques for further improving the sensitivity
of the atomic spectrometric determination of selenium for the first
time, in which the conduction band electron served as a “reductant”
to reduce selenium species including Se<sup>VI</sup> and convert them
directly into volatile H<sub>2</sub>Se, which was easily separated
from the sample matrix and underwent more effectively subsequent atomization
and/or ionization. These two PCVG systems helped us to overcome the
problem encountered in the most conventional KBH<sub>4</sub>/OH<sup>–</sup>–H<sup>+</sup> system, in that Se<sup>VI</sup> was hardly converted into volatile selenium species without the
aid of prereduction procedures. The limits of detection (LODs) (3σ)
of the four most typical Se<sup>IV</sup>, Se<sup>VI</sup>, selenocystine
((SeCys)<sub>2</sub>), and selenomethionine (SeMet) species were,
respectively, down to 1.2, 1.8, 7.4, and 0.9 ng mL<sup>–1</sup> in UV/Ag–TiO<sub>2</sub>–HCOOH, and 0.7, 1.0, 4.2,
and 0.5 ng mL<sup>–1</sup> in UV/ZrO<sub>2</sub>–HCOOH
with the relative standard deviations (RSDs) lower than 5.1% (<i>n</i> = 9 at 1 μg mL<sup>–1</sup>) when using atomic
fluorescence spectrometry (AFS) under flow injection mode. They reached
10, 14, 18, and 8 pg mL<sup>–1</sup> in UV/Ag–TiO<sub>2</sub>–HCOOH, and 6, 7, 10, and 5 pg mL<sup>–1</sup> in UV/ZrO<sub>2</sub>–HCOOH with the RSDs lower than 4.4%
(<i>n</i> = 9 at 10 ng mL<sup>–1</sup>) when using
inductively coupled plasma mass spectrometry (ICPMS). After the two
PCVG systems were validated using certified reference materials GBW(E)080395
and SELM-1, they were applied to determine the total Se in the selenium-enriched
yeast sample and used as interfaces between high-performance liquid
chromatography (HPLC) and AFS or ICPMS for selenium speciation in
the water- and/or enzyme-extractable fractions of the selenium-enriched
yeast
Zero-Interfacing μHPLC to ICPMS
The chromatography–mass spectrometry hyphenated
technique
is the most widely adopted tool for quantifying trace analytes in
a complex biosample. One issue we frequently encountered, however,
is that the separated analyte-containing chromatographic peaks broaden
and even remix prior to mass spectrometric quantification due to the
inevitable molecular diffusion within the dead-volume introduced by
hyphenation. We developed a zero-interfacing approach for coupling
microbore (μ) HPLC with inductively coupled plasma mass spectrometry
(ICPMS). Zero-interfacing μHPLC to ICPMS has been achieved by
a column-nebulizer assembly (COL-NEB) of a self-designed glass framework
with a tapered nozzle, in which a capillary chromatographic column
can be harbored while an Ar gas flow is blown through the nozzle mouth.
The COL-NEB can be positioned just before the base of the Ar-ICP serving
as the central sampling channel of a conventional Ar-ICP torch for
online nebulization and transportation of the analytes separated on
μHPLC into ICPMS, maintaining the molecular resolution obtained
on μHPLC and the limit of detection (LOD) of ICPMS. For example,
the full width at half-maximum of a SLUGT peptide chromatographic
peak was reduced to 1.71 ± 0.07 s (n = 5) with
a 0.72 fg LOD (3σ) of 80Se. Moreover, at least 32
Se-containing peptides were determined in the trypsin lysate of the
water-soluble fraction (≥3000 MW) from Se-enriched yeast CRM
SELM-1 within a 10 min run, the highest record to date. We believe
such an approach paves the way to determining accurate information
on a heteroatom and its binding biomolecules that play key roles during
life processes
Conversion of Inhibition Biosensing to Substrate-Like Biosensing for Quinalphos Selective Detection
Since all of the organophosphorus
pesticides (OPP) inhibit the
cholinesterases with a common mechanism, it is still challenging to
detect OPP selectively with inhibition-based biosensors. This study
focuses on the conversion of a typical inhibition biosensing to a
selective substrate-like biosensing. The interaction of quinalphos
with plant-esterase involves not only a decrease in enzyme activity
but also a heterolytic bond cleavage of quinalphos. The leaving group
eliminated from quinalphos is an ideal biomarker due to its specificity
in most OPP. Thus, using 2-hydroxyquinoxaline (HQO), the leaving group
of quinalphos, as the biomarker and <i>meso</i>-tetra (4-sulfonatophenyl)
porphine (TPPS<sub>4</sub>) as an optical probe, quinalphos can be
selectively detected. The molecular recognition between TPPS<sub>4</sub> and HQO leads to a considerable sensitivity of the detection. The
spectral responses of TPPS<sub>4</sub> show a linear dependence on
quinalphos concentration in the presence of plant-esterase within
the 0.01–1 mg kg<sup>–1</sup> range. The detection limit
is 0.01 mg kg<sup>–1</sup>, well below the maximum residue
limits (MRLs) defined by European Union (0.05 mg kg<sup>–1</sup>) and China (0.2 mg kg<sup>–1</sup>)
Single-Probe-Based Colorimetric and Photothermal Dual-Mode Identification of Multiple Bacteria
Effective
identification of multiple pathogenic bacteria in unknown
samples is important for disease prevention and control but remains
a challenge yet. A single-mode array-based sensing approach is simple
and sensitive, but it usually relies on the use of multiple cross-reactive
receptors to construct sensor arrays, which is cumbersome and insufficiently
accurate. Here, we developed a sensor array with colorimetric and
photothermal dual mode of differentiating multiple pathogenic bacteria.
The sensor array was based on boronic acid-functionalized Au–Fe3O4 nanoparticles (BA–GMNPs), which not only
possess localized surface plasmon resonance properties, showing a
burgundy color similar to that of AuNPs, but also exhibit mild superparamagnetism,
allowing for the differentiation of bacteria before and after binding
to the nanoparticles. Immobilization of BA–GMNPs on the bacterial
cell surface by covalent bonding would diminish NaCl-induced assembly
of BA–GMNPs. Different BA–GMNPs@bacterial complexes
differed in their ability to resist assembly and produced different
colorimetric and photothermal response signals. A unique molecular
fingerprint of each bacterium was obtained by linear discriminant
analysis of the response patterns, demonstrating an effective differentiation
among the six species studied. Compared with single-mode sensing arrays
based on multiple receptors, this method only requires the preparation
of a single nanomaterial, which produces two signal outputs for the
identification of multiple bacteria with better differentiation. It
can distinguish not only multiple pathogenic bacteria but also Gram-negative
and Gram-positive bacteria, and, more importantly, it can perform
preliminary discrimination of unknown samples