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.

Bidirectional enhancement of Li2S redox reaction by NiSe2/CoSe2-rGO heterostructured bi-functional catalysts.

The high activity barriers of Li2S nucleation and deposition limit the redox reaction kinetics of lithium polysulfides (LiPSs), meanwhile, the significant shuttle effect of LiPSs hampers the advancement of Li-S batteries (LSBs). In this work, a NiSe2/CoSe2-rGO (NiSe2/CoSe2-G) sulfur host with bifunctional catalytic activity was prepared through a hard template method. Electrochemical experiment results confirm that the combination of NiSe2 and CoSe2 not only facilitates the bidirectional catalytic function during charge and discharge processes, but also increases the active sites toward LiPSs adsorption. Simultaneously, the highly conductive rGO network enhances the electronic conductivity of NiSe2/CoSe2-G/S and provides convenience for loading NiSe2/CoSe2 catalysts. Benefitting from the exceptional catalytic-adsorption capability of NiSe2/CoSe2 and the presence of rGO, the NiSe2/CoSe2-G/S electrode exhibits excellent electrochemical properties. At 1C, it demonstrates a low capacity attenuation of 0.087 % per cycle during 500 cycles. The electrode can maintain a discharge capacity of 927 mAh/g at a sulfur loading of 3.3 mg cm-2. The bidirectional catalytic activity of NiSe2/CoSe2-G offers a prospective approach to expedite the redox reactions of active S, meanwhile, this work also offers an ideal approach for designing efficient S hosts for LSBs.

Synergically regulated silver species and surface oxygen on manganese oxide for promoted activity of formaldehyde oxidation.

Formaldehyde (HCHO) is a common indoor pollutant that is detrimental to human health. Its efficient removal has become an urgent demand to reduce the public health risk. In this work, Ag-MnOx-based catalysts were prepared and activated under different atmosphere (i.e., air, hydrogen (H2) and carbon monoxide (CO)) for efficient oxidation of HCHO. The catalyst activated with CO (Ag/Mn-CO) displayed the highest activity among the tested samples with 90% conversion at 100°C under a gas space velocity of 75,000 mL/(gcat·hr). Complementary characterizations demonstrate that CO reduction treatment resulted in synergically regulated content of surface oxygen on support to adsorb/activate HCHO and size of Ag particle to dissociate oxygen to oxidize the adsorbed HCHO. In contrast, other catalysts lack for either abundant surface oxygen species or metallic silver with the appropriate particle size, so that the integrate activity is limited by one specific reaction step. This study contributes to elucidating the mechanisms regulating the oxidation activity of Ag-based catalysts.

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.

High performance rechargeable aqueous zinc-iodine batteries via a double iodine species fixation strategy with mesoporous carbon and modified separator.

With the increasing requirement for high capacity energy storage systems, a large amount of recent work has focused on the development of zinc-iodine batteries (ZIBs) on account of high energy density, fast redox kinetics, and excellent reversibility. Nevertheless, low electron conductivity, the shuttle effect, and highly soluble iodine species (I2, I-, and I3-) have impeded their widespread application. In this study, metal organic framework-5 (MOF-5)-derived mesoporous carbon (MPC) loaded iodine (MPC/I2) cathode and the single-sided ketjen black modified cotton fiber (KB@CF) separator are designed to solve the problems mentioned above. That is, the double fixation strategy using MPC and KB@CF separators for iodine species suppresses the shuttle effect. Therefore, the ZIBs constructed with the MPC/I2 cathode and the KB@CF separator can exhibit excellent electrochemical performance. At the current density of 0.1 A g-1, a high discharge specific capacity of 137 mAh g-1 is still available after 300 cycles. Meanwhile, it exhibits a low capacity decay rate at long cycling (0.030% per cycle over 2000 cycles).

Polyphosphazene-Functionalized Microspheres as Efficient Catalysts for the Knoevenagel Reaction under Mild Conditions.

Inspired by the formation of microspheres by hexachlorocyclotriphosphazene and 4, 4'-sulfonyldiphenol, polyphosphazene-functionalized microspheres were developed. Benefits from the supported supper basic phosphazene, the yield exceeded 99 % at room temperature in the manner of second-order reaction kinetics toward Knoevenagel reaction and was still maintained at 99 % after 16 runs. In the experimental temperature from 0 °C to 90 °C, the yield increased from 92 % to 99 %, reflecting that the catalyst had strong applicability under mild conditions. This behavior was conducive to energy conservation. Meanwhile, simple separation and recovery further enhanced this advantage. In addition, the catalyst was also found to be insensitive to aqueous solution or organic solvents such as toluene, THF, EtOH and CH3 CN. This property gave the Knoevenagel reaction a vast choice. All these features exhibit that this novel catalyst is an attractive and applicable alternative in organic synthesis.

A novel fluorescent probe of alkyne compounds for putrescine detection based on click reaction.

Putrescine is a toxic biogenic amine produced in the process of food spoilage, and a high concentration of biogenic amines in foods will cause health problems such as abnormal blood pressure, headaches and tachycardia asthma/worsening asthma. The detection of putrescine is necessary. However, traditional putrescine detection requires specialized instruments and complex operations. To detect putrescine quickly, sensitively and accurately, we designed and successfully prepared a fluorescent probe (DPY) with active alkynyl groups. DPY takes p-dimethoxybenzene as the raw material, adding a highly active alkyne group. It is stable in experimental pH (∼7) because the UV-vis absorption and fluorescence emission spectra in pH = 3-12 have little change. The fluorescence intensity of DPY decreased only about 1% under the irradiation of 420 nm within 2 h, showing its better photostability. DPY has a high selectivity to putrescine because of the amino-alkyne click reaction without any catalyst in presence of different biogenic amines. The obvious response to putrescine was found in 30 seconds at room temperature. The mechanism between DPY and putrescine was investigated before and after adding putrescine by 1H NMR spectra and the Job plot. The results indicated a typical 1 : 1 stoichiometry between the DPY and DAB. Furthermore, the higher sensitivity of DPY to putrescine was obtained with the detection of limit (LOD) of 3.19 × 10-7 mol L-1, which was better than that of the national standard (2.27 × 10-5 mol L-1). The novel fluorescent probe was successfully applied to beer samples to detect putrescine. The proposed strategy is expected to provide some guidance for the development of some new ways to detect food security.

Design of co-continuous structure of cellulose/PAA-based alkaline solid polyelectrolyte for flexible zinc-air battery.

In order to prepare high ionic conductivity and robust mechanical properties of alkaline solid polyelectrolyte (ASPE) for applications in flexible wearable devices, a co-continuous structure membrane was designed using in-situ polymerization to introduce cross-linked polyacrylic acid (N-PAA) into the cellulose network constructed by regenerated degreasing cotton (RDC). The resultant ASPE membrane showed high ionic conductivity (430 mS·cm-1 at 25 °C), strong mechanical properties, and excellent alkaline stabilities, proving the viability of cellulose for use in energy storage systems. Surprisingly, the sandwich-shaped zinc-air battery assembled using RDC/N-PAA/KOH membranes as electrolytes exhibits superior values of cycling stability, discharge time, specific capacity (731.5 mAh·g-1), peak power density (40.25 mW·cm-2), and mechanical flexibility. Even under bending conditions, the zinc-air batteries still possess stable energy supply performance, suggesting this novel solid polyelectrolyte has promising application for wearable technology.

Hofmeister effect in gelatin-based hydrogels with shape memory properties.

The soaking strategy with the Hofmeister effect has been proposed to fabricate gelatin- based hydrogels with excellent properties. However, the modulation mechanism of hydrogels lacks in-depth study. In this work, we studied in detail the effects of Hofmeister ions on the structural, thermal, viscoelastic and mechanical properties of gelatin hydrogels. The results showed that kosmotropic anions (Cit3-, SO42-, H2PO4- and S2O32-) enhanced hydrogen bonds and hydrophobic interactions between gelatin molecules, resulting in increases in the length and content of triple helices and thus improving the properties of gelatin hydrogels. In contrast, chaotropic anions (I- and SCN-) weakened the interactions between gelatin molecules, and thus attenuated the properties. Based on the Hofmeister effect, we successfully fabricated gelatin poly N-methylolacrylamide (PNMA) double network hydrogels with shape memory properties. The Hofmeister effect provides an excellent route for the rational design and fabrication of functional gelatin-based hydrogels.

Dual-Active Au@PNIPAm Nanozymes for Glucose Detection and Intracellular H2O2 Modulation.

As a nanozyme, gold nanoparticles have some advantages compared with natural enzymes, such as stable structure, adjustable catalytic activity, multifunctionality, and recyclability. Due to their special dimension, they are easy to aggregate rapidly and lose their catalytic performance when exposed to normal saline or special pH environment. To avoid such a situation, Au@PNIPAm nanozymes with core-shell structure are constructed and their mimic peroxidase and glucose oxidase enzymatic activities are investigated. Kinetic examinations manifest that Au@PNIPAm nanozymes exhibited a high affinity for 3,3,5,5-tetramethylbenzidine (TMB), hydrogen peroxide (H2O2), and glucose. These predominant peroxidase-like and glucose-like oxidase Au@PNIPAm catalytic activities are successfully used in the detection of H2O2 or glucose (LOD is 2.43 mM or 5.07 mM). Otherwise, the potential Au@PNIPAm nanozymes are provided with a clear ability for decomposing the intracellular H2O2 in living cells. And it could protect cells from oxidative stress damage with inducing by H2O2. Therefore, it is easy to consider that Au@PNIPAm nanozymes show a certain possibility to retard cell senescence and increase the production of the hydroxyl radical which could prevent carcinogenesis of the cell.

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.

ZIF-8 derived porous carbon to mitigate shuttle effect for high performance aqueous zinc-iodine batteries.

Rechargeable aqueous zinc-iodine batteries (ZIBs) with low environmental impacts and abundant natural reserves have emerged as promising electrochemical energy storage devices. However, the shuttle effect and low conductivity of the iodine species cause poor electrochemical performance and hinder their practical application. Herein, we propose a ZIF-8 derived porous carbon (ZPC) for iodine species immobilization in ZIBs. The rich porous structure and highly conductive framework of ZPC provide efficient iodine loading and allow the fast transmission of electrons. In addition, the presence of N, Zn and ZnO in the carbon framework can build chemical anchoring with the iodine species to mitigate the shuttle effect. Thus, the ZPC/I2 cathode exhibits a reversible capacity of 156 mAh g-1 after 100 cycles at 100 mA g-1 and a long-term stability of 1000 cycles at a high rate. This study will open a new paradigm for devolving highly reversible ZIBs.

Hofmeister effect on the viscosity properties of gelatin in dilute solutions.

The effect of various Hofmeister anions on the molecular conformation of gelatin in dilute solutions was investigated by viscosity, optical rotation and dynamic light scattering (DLS). The results showed that the intrinsic viscosity of gelatin decreased in the presence of the kosmotropic anions such as Citrate3-, SO42-, H2PO4- and MeCOO-, whereas it was increased with the addition of chaotropes such as Cl- and KSCN-. Furthermore, the intrinsic viscosity of gelatin was directly correlated to the hydration entropy of kosmotropic anions, suggesting that the decrease of the intrinsic viscosity was attributed to the strong hydration effect of kosmotropes. The strong dehydration of gelatin facilitated the folding of the polymer chains into helix bundles, validated by the results of optical rotation. On the contrary, the chaotropic anions could interact directly with polypeptide backbones, and the intrachain hydrogen bonds were destroyed. As a result, the polymer chains expanded, which was confirmed by DLS data, and the intrinsic viscosity was increased. These observations indicate that the molecular conformation of gelatin can be modulated by Hofmeister anions.

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.

Study on the synthesis and thermal stability of silicone resins reinforced by Si-O-Ph cross-linking.

A novel silicone resin (SR-OH) containing phenolic hydroxyl (Ph-OH) groups was designed and synthesized via co-hydrolysis/condensation and catalytic hydrogenation. During the curing process, the cross-linking degree of the resin was further increased by the Si-O-Ph bonds formed by the reaction of the Ph-OH and terminal Si-OH groups. Thermogravimetric analysis (TGA) showed that the cured resin product exhibited excellent thermal and thermo-oxidative stability, which was much higher than that of a typical methyl phenyl silicone resin (SR-Ph). The temperature at which 5% weight loss occurs (T d5) was up to 606 °C (nitrogen) and 542 °C (air), and its char yield at 800 °C was 91.1% and 85.3% in nitrogen and air, respectively. The significant improvement in thermal stability was mainly attributed to the formation of Si-O-Ph bonds which not only increases the cross-linking degree of the resin but also significantly prevents degradation by the 'back-biting' and oxidative cleavage.

Strengthening gelatin hydrogels using the Hofmeister effect.

A simple yet effective soaking treatment has been proposed to fabricate hydrogels with desirable mechanical properties, but the strengthening mechanism of hydrogels lacks an in-depth study. Here, we investigated the influence of kosmotropic citrate anion on the structure and properties of immersed gelatin hydrogels. The obtained hydrogels possessed the properties of high strength, modulus and toughness simultaneously. The dehydration of hydrogels facilitated the interactions among gelatin molecules, resulting in the formation of helix structures. Both the content and length of the triple helices increase with an increase in citrate concentration, which in turn contributes to the strengthening of hydrogels. The excellent mechanical performances of these hydrogels may open up new applications for protein materials.

Study on the Synthesis and Thermal Stability of Silicone Resin Containing Trifluorovinyl Ether Groups.

Silicone resin is a high-temperature resistant material with excellent performance. The improvement of its thermal stability has always been the pursuit of researchers. In this paper, a sequence of silicone resins containing trifluorovinyl ether groups were prepared by the co-hydrolysis-polycondensation of methyl alkoxysilane monomers and {4-[trifluorovinyl(oxygen)]phenyl}methyldiethoxysilane. The structures of the silicone resins were characterized by FT-IR and 1H NMR. The curing process of them was studied by DSC and FT-IR spectra, and results showed that the curing of the resins included the condensation of the Si-OH groups and the [2 + 2] cyclodimerization reaction of the TFVE groups, which converted to perfluorocyclobutane structure after curing. The thermal stability and thermal degradation behavior of them was studied by TGA and FT-IR spectra. Compared with the pure methyl silicone resin, silicone resins containing TFVE groups showed better thermal stability under both N2 and air atmosphere. Their hydrophobic properties were characterized by contact angle test. Results showed that PFCB structure also improved the hydrophobicity of the silicone resin.

Effect of Homochirality of Dipeptide to Polymers' Degradation.

As natural polymer materials, proteins are readily biodegradable, interestingly, the synthetic polyamides (PAs) that are based on the same amide bonds (also called peptide bonds in proteins) are barely degradable. Whether did the chirality and configuration of the amino acids play an important role. By using different configuration of amino acids, 4 types of polyamide-imides (PAIs) containing dipeptides of LL, DL, LD, and DD configurations, respectively, were synthesized. It was found that the PAIs based on natural LL configuration of dipeptide structure are much more readily biodegradable than those based on non-natural LD, DL, and DD configuration of dipeptides. It was confirmed that the natural L-configuration of amino acids play a critical role in degradability of proteins. And it also suggested that different type and amount of peptide fragments can be introduced in polymer to create series of polymer materials that can be biodegraded at controllable speed.

The Thermal Properties and Degradability of Chiral Polyester-Imides Based on Several l/d-Amino Acids.

Eight kinds of chiral diacid monomers were prepared with amino acids with different side groups or configurations. Polyester-imides (PEIs) were synthesized from these diacid monomers and diphenol monomers through polycondensation reaction, and the performances and properties were compared with the chiral polyamide-imides (PAIs) previously synthesized by our work group. Their thermal properties were analyzed by thermo gravimetric analysis (TGA) and dynamic thermomechanical analysis (DMA), and it was found that the glass transition temperature (Tg) of PEI was mainly affected by the volume of side groups. Their degradability was studied through buffer degradation experiments, and the changes in their water contact angle, molecular weight, structure and appearance during the degradation process were characterized by contact angle tester, gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). With degradation, the hydrophilicity of PEI was improved, and when amino acids with larger side groups or D configuration were introduced into the backbone of PEI, the degradability decreased.