Cellulose-based yellow-green emitting carbon dots with large Stokes shift as effective "turn off-on" fluorescence platforms for Cr (VI) and AA dual efficacy detection.

BACKGROUND: Hexavalent chromium (Cr (VI)) is highly carcinogenic to humans. Ascorbic acid (AA) deficiency can be hazardous to health. And the dual-effect fluorescence detection of them is an important research topic. Carbon dots (CDs) based on cellulose are excellent candidates for the fluorescence probes due to their low cost and environmental friendliness. But most of them exhibit shortwave emission, small Stokes shift and poor fluorescence performance, all of which limit their use. Therefore, there is an urgent need for cellulose CDs with longer emission wavelengths and larger Stokes shifts in dual-effect fluorescence detection of Cr (VI) and AA. RESULTS: Under optimal conditions (180 °C, 12 h), we prepared cellulose-based nitrogen-doped carbon dots (N-CDs) by a simple one-step hydrothermal process, which display longer emission wavelengths (ex: 370 nm, em: 510 nm), larger Stokes shifts (140 nm) and high fluorescence quantum yield (QY: 19.27 %). The continuous "turn-off" and "turn-off-on" fluorescence detection platforms were constructed based on the internal filtering effect (IFE) between Cr6+ and N-CDs, and Cr6+ reduced to Cr3+ by AA at pH = 6. The platform has been successfully simultaneous detect Cr (VI) and AA with a wide range of 0.01-40 µM and 0.1-100 µM. And the lowest limits of detection (LOD) are 0.0303 µM and 0.072 µM, respectively. In the presence of some other metals, non-metal ions and water-soluble acids in the fruits, this fluorescent platform can demonstrate a high level of interference immunity. SIGNIFICANCE AND NOVELTY: This represents the first yellow-green cellulose-based N-CDs with large Stokes shift for dual-effect detection of Cr (VI) and AA in real water samples and fresh fruits. The fluorescence detection platform has the advantage of low volume detection. Less than 2 mL of sample is required for testing and results are available in <5 min. This method is rare and supply a novel idea for the quantitative monitoring of Cr (VI) and AA.

[Experimental teaching reform of polymer molar mass determination using gel permeation chromatography coupled with light scattering].

Gel permeation chromatography coupled with light scattering (GPC-LS) is among the most common methods for determining the molar masses of polymers. GPC-LS is widely used in polymer science research and has been adopted for many industrial applications owing to its high sensitivity, accuracy, and precision. The determination of polymer molar masses using GPC-LS is an important experimental component of the "Polymer Physics Experiments" course. However, the present GPC-LS experimental teaching content tends to be overly simplistic and lacking in depth. Herein, the original experimental content is expanded and multiple sets of experiments are redesigned: (1) Using commercial polystyrene as an experimental sample, the molar mass, molar mass distribution, radius of gyration, and other molecular structure parameters are determined using GPC-LS; (2) Using two polyacrylonitriles with similar molecular structure parameters, subtle differences in the molar mass distributions of the samples are explored using differential mass distribution curves; (3) By comparing the chromatograms of a series of polyethylene glycols with different molar masses, the effect of molar mass on chromatographic peaks is investigated; and (4) For three different polymers (polyacrylonitrile, poly(methyl methacrylate), and poly(ß-cyclodextrin)), the polymer chain conformations are analyzed using conformation plots (i.e., radius of gyration vs. molar mass). In addition, the experimental teaching method is modified to convert passive learning into active learning, thereby improving the students' self-directed learning ability. This experimental teaching reform will help students obtain a more comprehensive understanding of GPC-LS principles and applications, stimulate their enthusiasm for learning, and improve the teaching quality of the experimental course.

The preparation and dual-mode detection of ascorbic acid based on poly(N-isopropylacrylamide) nanogel with oxidase-like activity.

Nanozymes have recently become a research hotspot because of the advantages of good stability, excellent catalytic performance and easy storage in comparison to natural enzymes. Nanozymes with oxidase-like activity get special attention because they needn't the participation of hydrogen peroxide. In this paper, poly(N-isopropylacrylamide) nanogel with oxidase-like activity was synthesized for the first time. The catalytic mechanism was explored by EPR and UV spectroscopy after adding specific trapping agents of ROS, and the results showed that PNIPAM NG can catalyze O2 to 1O2. In the presence of PNIPAM NG, o-phenylenediamine (OPD) and ascorbic acid (AA) can be oxidized to 2,3-diaminophenazine (oxOPD) and dehydroascorbic acid (DHA), and DHA can further react with OPD to produce a fluorescence substance. The colorimetric and fluorescence detection platforms for AA were constructed based on the above principles. Both platforms have satisfactory results in real samples. The fluorescence platform has better sensitivity and selectivity than the colorimetric platform.

Water state, thermal transition behavior and structure of hydrated gelatin films.

The state of water, thermal transition behaviors, molecular interactions, crystalline structure, and mechanical performance of hydrated gelatin films were studied by differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), X-ray diffraction, and universal testing instruments. The DSC results showed that with increase of the water content, two types of water, including unfreezable bound water and freezable water, appeared in turn. Below a critical water content of 30%, the glass transition temperature (Tg) of the hydrated gelatin films decreased notably with an increase in water content, which leveled off at water content higher than this threshold. This observation suggests that only the unfreezable water exhibits a plasticizing effect. In addition, the melting temperature (Tm) of hydrated gelatin films decreased continuously with an increase in water content, whereas the melting enthalpy showed a non-monotonic dependence on hydration level. Structural analysis showed that at medium hydration levels up to 13.4% water content, the unfreezable water facilitated the formation of additional triple helices, confirmed by DSC results. Spectral data revealed that the -OH groups of unfreezable water molecules interacted with the -NH groups of the protein via hydrogen bonds. Moreover, the mechanical properties of the hydrated gelatin films were sensitive to their hydration level, and the tensile strength was dominated by the helix content of the protein films. These results show the feasibility of using hydration to regulate the microstructure and properties of biopolymers.

Structure and properties of citric acid cross-linked chitosan/poly(vinyl alcohol) composite films for food packaging applications.

In this study, the composite films of poly(vinyl alcohol) and citric acid cross-linked chitosan were prepared, and the effect of mass ratio on their structure and properties was investigated in detail. Chitosan was cross-linked by citric acid via an amidation reaction at an elevated temperature, which was confirmed by infrared spectra and X-ray photoelectron spectra. Chitosan is miscible with PVA due to the formation of strong hydrogen bonds between them. Among these composite films, 1:1 CS/PVA film showed excellent mechanical properties, good creep resistance, and shape recovery ability, attributing to its high crosslinking degree. In addition, this film possessed hydrophobicity, excellent self-adhesion property, and the lowest WVP, and it was successfully used as a packaging material for cherry. These observations indicate that the cooperative effects of crosslinking and hydrogen bonds control the structure and properties of chitosan/PVA composite film, which is a very potential material for food packaging and preservation.

High capacity and fast removal of Cr(vi) by alkali lignin-based poly(tetraethylene pentamine-pyrogallol) sorbent.

In this work, a novel alkali lignin-based adsorption material, alkali lignin-based poly(tetraethylene pentamine-pyrogallol) (AL-PTAP), was prepared using a Mannich reaction and catechol-amine reaction for removal of Cr(vi). It was characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The effects of tetraethylene pentamine (TEPA) dosage, pyrogallol (PL) dosage, contact time, pH, temperature and other factors on the adsorption behavior of the adsorbent were systematically investigated. These experimental data show that the adsorption behavior conforms to the pseudo-second-order kinetic model and the Langmuir isotherm model. The maximum adsorption capacity is 769.2 mg g-1 at 303 K, which is much higher than that of alkali lignin (AL). AL-PTAP can achieve a removal rate of almost 100% for Cr(vi) solutions with a concentration of less than 90 mg L-1 at 1 min. Furthermore, the toxic Cr(vi) is partly reduced to nontoxic Cr(iii) during the adsorption process. Therefore, AL-PTAP is a fast and efficient alkali lignin-based adsorbent, which is expected to improve the utilization value of alkali lignin in Cr(vi) wastewater treatment.

Ultrathin Membranes for Separations: A New Era Driven by Advanced Nanotechnology.

Ultrathin membranes are at the forefront of membrane research, offering great opportunities in revolutionizing separations with ultrafast transport. Driven by advanced nanomaterials and manufacturing technology, tremendous progresses are made over the last 15 years in the fabrications and applications of sub-50 nm membranes. Here, an overview of state-of-the-art ultrathin membranes is first introduced, followed by a summary of the fabrication techniques with an emphasis on how to realize such extremely low thickness. Then, different types of ultrathin membranes, categorized based on their structures, that is, network, laminar, or framework structures, are discussed with a focus on the interplays among structure, fabrication methods, and separation performances. Recent research and development trends are highlighted. Meanwhile, the performances and applications of current ultrathin membranes for representative separations (gas separation and liquid separation) are thoroughly analyzed and compared. Last, the challenges in material design, structure construction, and coordination are given, in order to fully realize the potential of ultrathin membranes and facilitate the translation from scientific achievements to industrial productions.

Insight into the synergistic adsorption-reduction character of chromium(VI) onto poly(pyrogallol-tetraethylene pentamine) microsphere in synthetic wastewater.

Facile fabrication of the ultra-high-performance adsorbent can effectively ameliorate the Cr(VI)-pollution elimination in sewage control. Herein, a simple synthesis strategy is proposed to tap a versatile chelating resin poly(pyrogallol-tetraethylene pentamine) (PPTA) with respect to Cr(VI) removal from solution. Multiple changing factors which affect the adsorption behavior of PPTA are explored sequentially, such as initial pH, adsorbate concentration, adsorbent dosage, temperature, foreign ions, etc. The microstructure and functional mechanism of synthetic adsorbent are investigated systematically by means of various characterizations including TEM, EDS, FT-IR, XPS, etc. Consequently, the as-prepared PPTA-3 microsphere by reactant ratio of 1: 1 represents a brilliant synergistic adsorption and reduction result for Cr(VI) by the drastic electrostatic interaction of -NH3+ and -OH2+ groups, including satisfactory removal efficiency which closes to 100 % in low concentration, favorable specificity for the influence from coexistent ions (Mo(VI), Mn(VII), Cl-, Cr(III), etc), and passable recyclability. Following the surpassingly fitting with Langmuir isotherm model, its maximum capacity reaches 714.29 mg g-1 at 30 °C. The removal performance is essentially in agreement with the pseudo-second-order kinetics, simultaneously, suffers the rate-limiting impact depending on intra-particle diffusion process. In brief, this newly developed chelating resin presents an effective means with regard to the Cr(VI)-wastewater treatment or other uses in the future.

Facile Synthesis of Polyethylene Glycol@Tannin-Amine Microsphere towards Cr(VI) Removal.

Herein, a synthetic strategy for a rough microsphere Cr(VI)-adsorbent via the reaction of tannic acid (TA) and 1,6-hexanediamine (HA) and using polyethylene glycol (PEG) as surface modifier was presented. This adsorbent was characterized by a Fourier Transform Infrared spectrometer (FTIR), thermogravimetic analysis (TGA), X-ray photoelectron spectroscopy (XPS), etc. Certain factors, including contact time, PEG@poly(tannin-1,6-hexanediamine) (PEG@PTHA) dosage, initial concentration, and experimental temperature affecting the Cr(VI) adsorption performance of adsorbent were explored. PEG@PTHA can adsorb Cr and the Cr(VI) was reduced up to Cr(III) due to the existence of phenolic hydroxyl groups. Its adsorption capacity can reach up to 300 mg/g within 10 min and approximately 100% removal percentage below the initial concentration of 100 mg/L. Its behavior matched well with the Langmuir isotherm model and pseudo-second-order kinetic model. A PEG@PTHA adsorbent with maximum adsorption capacity (450 mg/g) has great prospects in Cr(VI)-sewage treatment.

Probing mesoporous character, desulfurization capability and kinetic mechanism of synergistic stabilizing sorbent CaxCuyMnzOi/MAS-9 in hot coal gas.

Developing structurally stable sorbents for high-temperature H2S direct removal is recognized as a valuable energy-saving strategy for efficient utilization of hot coal gas (HCG), which depends upon their mesoporous features and desulfurization capabilities. Herein, tailored hierarchical CaxCuyMnzOi/MAS-9 sorbents were fabricated via a facile sol-gel method using high-activity phase CaxCuyMnzOi anchored onto versatile mesoporous MAS-9. After O/S-exchange procedure, noteworthy straight channels of MAS-9 (SBET = 808 m2 g-1) provided enough available spaces for the storage of generative large MeSy nanoparticles, which was better than other conventional zeolites. The probing of variables (i.e. support type, active ingredient, loadings, and sulfidation temperature) on H2S removal revealed that 50%Ca3Cu10Mn87Oi/MAS-9 shared an excellent breakthrough sulfur capacity (171.57 mg g-1) at 800 °C, even it experienced six reusable cycles, due to synergistic stabilizing effect of Ca-Cu-Mn and high-temperature tolerance of SiOAl framework of MAS-9. Especially, CaO dopant endowed the sorbent with superficial alkalinity and high-temperature resistance. The brilliant desulfurization behavior was also described by the fast H2S diffusion or component deactivation vs. duration time on stream according to the followed kinetic investigation. Thus, the refined Ca3Cu10Mn87Oi/MAS-9 possesses the expected representative desulfurization nature and great potentiality for raw HCG in practical applications.

Lattice substitution and desulfurization kinetic analysis of Zn-based spinel sorbents loading onto porous silicoaluminophosphate zeolites.

Green Zn-based spinel sorbents for hot coal gas desulfurization have been developed with the assistance of optimization procedures. The pilot study highlights an outstanding ordered mesoporous support (SBET = 323 m2 g-1, Da = 4.3 nm) of SAPO-34@as-prepared SBA-15 (SS) for loading active metal oxides. ZnCo2O4 spinel loaded onto SS (ZnCo2/SS) exhibits a prominent desulfurization performance compared to other sorbents whose partial Co is substituted by Mn or Fe in spinel B-site, owing to the slight effect of PO43- in SS. After systematic evaluation on role of sulfidation condition, 50 wt% ZnCo2/SS sorbent possesses the sulfur storage capacity of 138.08  mg g-1at550 °C and little loss of active species in 5 desulfurization-regeneration cycles. Results of high resolution transmission electron microscopy (HRTEM), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS) etc. demonstrate that 70.42% of initial sulfur capacity of ZnCo2/SS presented in the 2nd utilization is associated with zinc evaporation, existence of high stable sulfides and partial sintering. The improved deactivation kinetic model suitably describes that the H2S concentration distribution relates with the spatial position of fixed-bed reactor and desulfurization time.

Toxic Cr removal from aqueous media using catechol-amine copolymer coating onto as-prepared cellulose.

Green composite adsorbent with low cost and high efficiency towards toxic Cr(VI) removal from the polluted water has a broad application prospect. In this work, a mussel-inspired Cr-adsorbent namely poly(catechol tetraethylenepentamine-p-phenylenediamine)@as-prepared cellulose (PAC@AC) is successful fabricated via catechol-amine copolymer adhering onto as-prepared cellulose (AC). The detailed characterizations of product are run with SEM, FT-IR, TGA, XRD, EDS and XPS analysis. Many factors are investigated to affect the adsorption of Cr(VI) by PCA@AC, including ratio of AC to PCA, adsorbent dosage, contact time, initial Cr(VI) concentration, pH, temperature and exterior ions. The maximum adsorption capacity of PCA@AC for Cr (VI) is obtained by 507.61 mg/g at 30°C using Langmuir model, which is very higher than the pure AC. The removal ability of PCA@AC is ascribed to the electrostatic interaction and reduction reaction of Cr(VI) to Cr(III) during the adsorption process. In addition, the adsorption process is spontaneous and endothermic, not require any external energy. The composite adsorbent (PCA@AC) has great potential for Cr(VI)-wastewater purification with an excellent chelating ability.

Green synthesis of tannin-hexamethylendiamine based adsorbents for efficient removal of Cr(VI).

Newly developed adsorbents, poly(tannin-hexamethylendiamine) (PTHA), were fabricated by varying the mole ratio of tannin (TA) and hexamethylendiamine (HA) under one-pot reaction. The specific forming process of the adsorbent which had undergone the transition from hydrogen bonds to covalent bonds was subsequently explored. Based on the efficiency of Cr(VI) removal from aqueous solution over all prepared adsorbents, the PTHA-4 (mole ratio of TA/HA = 1:12.5) exhibited an excellent adsorption behavior. Adsorption experiments affected by contact time and ionic strength have been conducted successively by PTHA-4, and the equilibrium was reached at 24 h. The kinetic data revealed that the adsorption was good agreement with pseudo-second order model and needed to undergo the rate-controlling step. The maximum adsorption capacity was 283.29 mg/g at 30 °C, relying on the isothermal curve suitably described by Langmuir model. Furthermore, toxic Cr(VI) had been reduced to the low toxic Cr(III) during adsorption process. The structures and adsorption performance of adsorbent were confirmed by means of SEM, FT-IR, XPS etc. Thus, the cheap-sustainable adsorbents have a superior feature for Cr(VI)-wastewater purification in future.

A novel label-free photoelectrochemical sensor based on N,S-GQDs and CdS co-sensitized hierarchical Zn2SnO4 cube for detection of cardiac troponin I.

A novel label-free photoelectrochemical (PEC) sensor based on graphene quantum dots doped with nitrogen and sulfur (N,S-GQDs) and CdS co-sensitized hierarchical Zn2SnO4 cube was fabricated to detect cardiac troponin I (cTnI). The unique hierarchical Zn2SnO4 cube was synthesized successfully by the solvothermal method, which has a large specific surface to load functional materials. N,S-GQDs nanoparticles were assembled to the surface of cubic Zn2SnO4 coated ITO electrode, which efficiently accelerated the electronic transition and improved photo-to-current conversion efficiency. Then, CdS nanoparticles further were modified by in-situ growth method to form Zn2SnO4/N,S-GQDs/CdS composite with prominent photocurrent, which was 30 times that of the Zn2SnO4 cube alone. In this work, the specific immune recognition between cTnI antigens and cTnI antibodies (anti-cTnI) reduced the intensity of the photoelectric signal. And the intensity decreased linearly with the logarithm of cTnI concentration range from 0.001 ng/mL to 50 ng/mL with a detection limit of 0.3 pg/mL. With high sensitivity, excellent selectivity, good stability and reproducibility, the fabricated PEC sensor showed promising applications in the sensor, clinical diagnosis of myocardial infarction and PEC analysis.

Highly Sensitive Detection of Melamine Based on the Fluorescence Resonance Energy Transfer between Conjugated Polymer Nanoparticles and Gold Nanoparticles.

Adding melamine as additives in food products will lead to many diseases and even death. However, the present techniques of melamine detection require time-consuming steps, complicated procedures and expensive analytical apparatus. The fluorescent assay method was facile and highly sensitive. In this work, a fluorescence resonance energy transfer (FRET) system for melamine detection was constructed based on conjugated polymer nanoparticles (CPNs) and gold nanoparticles (AuNPs). The energy transfer efficiency is up to 82.1%, and the system is highly selective and sensitive to melamine detection with a lower detection limit of 1.7 nmol/L. Moreover, the interaction mechanism was explored. The results showed that the fluorescence of CPNs were firstly quenched by AuNPs, and then restored after adding melamine because of reducing FRET between CPNs and AuNPs. Lastly, the proposed method was carried out for melamine detection in powdered infant formula with satisfactory results.

Effect of salt on the coil-helix transition of gelatin at early stages: Optical rotation, rheology and DSC studies.

The influence of the concentration and type of salt on the physical gelation of gelatin at early stages was explored by polarimeter, rheometer and differential scanning calorimetry (DSC). With the increase of salt concentration, both the triple helix content and the storage modulus of gelatin increased slightly and then decreased in CaCl2 solutions, whereas they decreased monotonically in NaCl and CrCl3 solutions. The addition of CaCl2 at low concentrations facilitated the coil-helix transition of gelatin, which could be significantly inhibited by high salt concentrations. The melting temperature of gels was nearly unchanged with varying salt concentration, but the melting enthalpy decreased monotonically with salt addition. This result indicates that salt additions mainly affect the nucleation of triple helices, but had minor effect on its growth. In addition, the coil-helix transition of gelatin in salt solutions at early stages could be treated successfully by an equation of first order kinetics.

Facile Preparation of Tannic Acid-Poly(vinyl alcohol)/Sodium Alginate Hydrogel Beads for Methylene Blue Removal from Simulated Solution.

A novel hydrogel bead [tannic acid (TA)-poly(vinyl alcohol) (PVA)/sodium alginate (SA)] with high strength prepared by biocompatible PVA, TA, and biocompatible SA via an instantaneous gelation method was applied to remove methylene blue (MB) from aqueous solution. The obtained TA-PVA/SA hydrogel beads were fully characterized by thermogravimetric analysis, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and so on. The adsorption performances of TA-PVA/SA hydrogel beads for MB were investigated by changing the factors of TA content, initial concentration, pH, adsorbent dosage, contact time, and temperature systematically. The maximum capacity of TA-PVA/SA hydrogel beads for MB removal was obtained to be 147.06 mg/g at 30 °C, whose capability was better than that without TA. After fitting the adsorbed data, it was basically consistent with the Langmuir isotherm and pseudo-second-order kinetic model. Thermodynamic studies indicated that MB removal was spontaneous and exothermic in nature. It is concluded that the low-cost TA-PVA/SA hydrogel beads as an easily recoverable adsorbent have a great potential on the removal of hazardous dyes from wastewater.

Removal of Cu(II) from aqueous solution using synthetic poly(catechol-diethylenetriamine-p-phenylenediamine) particles.

A novel poly(catechol-diethylenetriamine-pphenylenediamine)(PCEA) adsorbent was synthesized in methanol, with chelating groups supplied by catechol and diethylenetriamine, which showed a strong removal performance and efficient adsorption toward Cu(II) ions in aqueous solution. The adsorbent was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Besides, factors such as adsorbent dosage, pH, initial ionic and metal concentrations, contact time, and temperature on the adsorption of Cu(II) were studied. The data revealed that the adsorption followed a pseudo-second order kinetic model and the adsorption rate was influenced by the intra-particle diffusion. Furthermore, the adsorption process followed the Langmuir isotherm model, and the maximum adsorption capacity (Qm) was 44.2mg/g at 298K in simulated wastewater. The value of ΔG (kJ/mol) and ΔH (kJ/mol) also demonstrated that the adsorption process was spontaneous and endothermic. Studies revealed that PCEA particles were powerful and stable for the removal of Cu(II) in water, and it could be directly applied to the Cu(II)-contaminated water.

Self-healing surface hydrophobicity by consecutive release of hydrophobic molecules from mesoporous silica.

The paper reports a novel approach to achieve self-healing surface hydrophobicity. Mesoporous silica is used as the reservoir for hydrophobic molecules, i.e., octadecylamine (ODA), that can release and refresh the surface hydrophobicity consecutively. A polymdopamine layer is used to further encapsulate silica-ODA, providing a reactive layer, governing release of the underlying ODA, and improving the dispersivity of silica nanoparticles in bulk resin. The approach arrives at self-healing (super)hydrophobicity without using any fluoro-containing compounds.

Highly selective uptake and release of charged molecules by pH-responsive polydopamine microcapsules.

A systematic study of the permeation of small molecules through Pdop microcapsules is reported. The zwitterionic Pdop microcapsules are prepared by oxidative polymerization of dopamine on polystyrene microspheres followed by core removal with THF. Rhodamine 6G, methyl orange and alizarin red are chosen as differently charged probing dyes. The loading amount is affected by pH and dye concentration. Highly selective and unidirectional uptake and release of charged molecules through Pdop microcapsules can be achieved by controlling pH value: at low pH, the Pdop particles incorporate cationic dye (rhodamine 6G); at high pH, they incorporate anionic dyes (methyl orange and alizarin red). In each case, the uptake is highly selective.