The Molecular Theory of Sweet Taste: Revisit, Update, and Beyond.

The molecular origin of the sweet taste is still elusive. Herein, the canonical AH-B-X theory of sweet taste is extended by resurveying various sweeteners, which provides deeper insights into an analogous intramolecular connectivity pattern of both glucophores in sweeteners and their interaction counterparts in sweet taste receptor TAS1R2/TAS1R3: electrostatic complementarity and topochemical compatibility. Furthermore, their complementary interaction is elaborately illustrated, accounting for the common molecular feature of eliciting sweetness. Moreover, it highlights that multiple glucophores in a topological system synergistically mediate the elicitation and performance of sweetness. This perspective presents a meaningful framework for the structure-activity relationship-based molecular design and modification of sweeteners and sheds light on the mechanism of molecular evolution of TAS1R2s/TAS1R3s. The link between palatability of sweeteners and harmony relationships between their structural components via stereochemistry and network has significant implications to illuminate the underlying mechanisms by which nature designs chemical reactions to elicit the most important taste.

Encapsulation of apigenin into ß-cyclodextrin metal-organic frameworks with high embedment efficiency and stability.

In an effort to improve the application performance of apigenin, ß-cyclodextrin metal-organic frameworks (BCDMOFs) known as porous materials were used to encapsulate apigenin via an innovative pH-adjusted method. The embedment efficiency had a significant positive pH dependence, reaching a maximum of 79.2 % ± 1.2 % at pH12. Scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis demonstrated formation of apigenin/BCDMOFs composites, and exposure of BCDMOFs pores facilitated high embedment efficiency. Storage stability experiment and kinetic analysis showed degradation of apigenin/BCDMOFs composites was less than that of apigenin alone. Apigenin stability was increased by approximately 18 % after 7 days. BCDMOFs effectively encapsulated and controlled the release of apigenin, and the composites exhibited improved application performance in vitro.

Gold-copper-doped lanthanide luminescent metal-organic backbone induced self-enhanced molecularly imprinted ECL sensors for ultra-sensitive detection of chlorpyrifos.

Herein, a self-enhanced molecularly imprinted polymer luminescence (MIP-ECL) sensing platform based on gold-copper doped Tb-MOFs (Au@Cu:Tb-MOFs) was constructed for ultra-sensitive detection of chlorpyrifos (CPF). In this work, Au@Cu:Tb-MOFs as co-reaction promoters greatly improve the ECL emission signal, while Au@Cu:Tb-MOFs were used as cathode emitters. And chlorpyrifos and 4,7-bis(thiophene-2-yl)benzo [c][1,2,5] thiadiazole were electropolymerized on electrode surface to form MIP, where this films with thiophene derivatives could greatly improve ECL signal. Notably, the introduction of MIP as recognition elements enabled specific identification of target analytes, in which molecular docking technique validated target analyte and functional monomers are tightly bound through Pi-alkyl interaction. As the concentration of CPF increases, the ECL signal gradually decreases, showing a good linear relationship in the range of 0.1-106 pg/mL with a low detection limit (LOD) of 0.029 pg/mL. Moreover, actual sample testing experiment of this method displayed a special correlation in organophosphorus detection and development potential in actual sample analysis.

Photoelectrochemical sensor for the detection of Escherichia coli O157:H7 based on TPA-NO2 and dual-functional polythiophene films.

The detection of Escherichia coli (E. coli) is of great significance for the environment and human health. Herein, a photoelectrochemical (PEC) detection strategy based on molecularly imprinted polymers (MIPs) was proposed for the sensitive detection of E. coli. 4,4',4″-Trinitrotriphenylamine (TPA-NO2) was prepared using a simple nitration reaction. Subsequently, MIP films were polymerized on the surface of TPA-NO2 using 1,3-dihydrothieno[3,2-d]pyrimidine-2,4-dione as the functional monomer with the dual functions of specific recognition and sensitization. The linear range was 10-108 CFU/mL and the limit of detection was 10 CFU/mL. It showed favorable recoveries in real sample tests of milk, orange juice and tomato. Additionally, the ability of functional monomers to bind excellently with E. coli was verified using molecular docking techniques. This research provided broader possibilities for constructing MIPs-PEC sensors and analyzing the interaction mechanism between E. coli and functional monomers.

Maltogenic amylase: Its structure, molecular modification, and effects on starch and starch-based products.

Maltogenic amylase (MAA) (EC3.2.1.133), a member of the glycoside hydrolase family 13 that mainly produces α-maltose, is widely used to extend the shelf life of bread as it softens bread, improves its elasticity, and preserves its flavor without affecting dough processing. Moreover, MAA is used as an improver in flour products. Despite its antiaging properties, the hydrolytic capacity and thermal stability of MAA can't meet the requirements of industrial application. However, genetic engineering techniques used for the molecular modification of MAA can alter its functional properties to meet application-specific requirements. This review briefly introduces the structure and functions of MAA, its application in starch modification, its effects on starch-based products, and its molecular modification to provide better insights for the application of genetically modified MAA in starch modification.

Dual cross-linked starch hydrogel for eugenol encapsulation and the formation of hydrogen bonds on textural hydrogel.

Physical and chemical cross-linked hydrogels combining N, N'-Methylenebisacrylamide (MBA)-grafted starch (MBAS) and sorbitol were successfully prepared and encapsulated with eugenol in this work. The dense porous structure with diameter of 10-15 µm and strong skeleton after restructuring inside the hydrogel was confirmed by SEM. The band shifts between 3258 cm-1 and 3264 cm-1 clarified the presence of a large number of hydrogen bonds in physical and chemical cross-linked hydrogels. The robust structure of the hydrogel was confirmed by mechanical and thermal property measurements. Molecular docking techniques were used to help understand the bridging pattern between three raw materials and to assess the advantageous conformation, which demonstrate sorbitol is beneficial to improve the characteristics of textural hydrogel by the formation of hydrogen bonds, creating a denser network, structural recombination and new intermolecular hydrogen bonds between starch and sorbitol afforded considerably junction zones. Compared to ordinary starch-based hydrogels, eugenol-loaded starch-sorbitol hydrogels (ESSG) exhibited a more attractive internal structure, swelling properties, viscoelasticity. Moreover, the ESSG showed excellent antimicrobial activity for typical undesired microorganisms in foods.

T4PPVB-COP composite-driven innovative electrochemiluminescence aptasensor for ultra-sensitive detection of chlorpyrifos.

Herein, an enhanced electrochemiluminescence (ECL) aptasensor driven by a complex (T4PPVB-COP@CdS QDs) with large specific surface area and high stability was constructed for highly sensitive detection of chlorpyrifos (CPF), using electrostatic interactions and signal amplification techniques. In the presence of CPF, the specific binding between the aptamer and CPF caused partial detachment of the aptamer from the sensor, thus restoring the ECL signal. Notably, gold nanoparticles functionalized with streptavidin (SA) as signal enhancers further amplified the ECL signal in specific interactions with aptamers, thereby improving the sensitivity of the assay. Based on this, the proposed ECL aptasensor demonstrated significant detection performance for CPF with a linear range of 1-107 pg/mL and a LOD of 0.34 pg/mL. Furthermore, the feasibility of the ECL aptasensor was validated by the detection and analysis of CPF in real samples, which also provided a broad reference value for bioanalysis.

Green preparation of 3D micronetwork eugenol-encapsuled porous starch for improving the performance of starch-based antibacterial film.

In order to find a non-enzymatically treated alternative wall material with effective encapsulation properties, and to reduce the use of conventional non-biodegradable plastics, a novel 3D-micronetwork porous starch (3D-MPS) was created via a modified sacrificial template method to encapsulate eugenol (3D-EMPS) and used to incorporate with TiO2-starch film, for significantly improving the performance of starch-based antibacterial film. At the template SiO2 nanoparticles concentration of 0.1 %, the 3D-MPS exhibited anticipated alveolate structure with internal aperture of approximately 10 µm confirmed by SEM. With addition of 3D-EMPS, higher tensile strength (29.70 Mpa) and water barrier property (924 g/cm2·24 h) of the composite film was obtained. Moreover, molecular docking technique was used to model the intermolecular forces, which showed that the major forces maintaining the internal bonding of the composite film were hydrogen bonding and the interaction between eugenol and 3D-MPS skeleton in 3D-EMPS. Meanwhile, the composite film demonstrated the expected eugenol retardation and antimicrobial capacity against S. aureus, E. coli, and B. subtilis. Finally, the composite films were used for evaluating the feasibility in the actual food, which largely extended its shelf life compared to the negative control. This high-performance film revealed their potential for packaging materials application.

Developments in molecular docking technologies for application of polysaccharide-based materials: A review.

With the increasing pollution of the planet, the search for natural multifunctional alternatives to petroleum-based plastics has assumed to be a great important proposition. Polysaccharides, an inexhaustible natural resource with good biocompatibility as well as mechanical properties, are considered as an ideal alternative to petroleum-based materials. However, blind experimentation and development will inevitably lead to waste of raw materials and contamination of reagents. Therefore, researchers desire a technology which can assist in predicting and screening experimental materials at the higher level. Molecular docking simulations, an emerging computer technology that can effectively predict the structure of interactions between molecules and analyze the optimal conformation, are a common aid for materials and drug design. In this review, we describe the origins and development of molecular docking techniques, mainly performed an overview of various molecular docking software on their applications in the field of different polysaccharide materials.

Self-healing properties of retrograded starch films with enzyme-treated waxy maize starch as healing agent.

Waxy maize starch (WMS) was modified using sequential α-amylase and transglucosidase to create enzyme-treated waxy maize starch (EWMS) with higher branching degree and lower viscosity as an ideal healing agent. Self-healing properties of retrograded starch films with microcapsules containing WMS (WMC) and EWMS (EWMC) were investigated. The results indicated that EWMS-16 had the maximum branching degree of 21.88 % after transglucosidase treatment time of 16 h, and A chain of 12.89 %, B1 chain of 60.76 %, B2 chain of 18.82 % and B3 chain of 7.52 %. The particle sizes of EWMC ranged from 2.754 to 5.754 µm. The embedding rate of EWMC was 50.08 %. Compared to retrograded starch films with WMC, water vapor transmission coefficients of retrograded starch films with EWMC were lower, while tensile strength and elongation at break values of retrograded starch films were almost similar. Retrograded starch films with EWMC had higher healing efficiency of 58.33 % as compared to that Retrograded starch films retrograded starch films with WMC was 44.65 %.

Effects of primary, secondary and tertiary structures on functional properties of thermoplastic starch biopolymer blend films.

To better understand the correlation between structure and properties in thermoplastic starch biopolymer blend films, the effects of amylose content, chain length distribution of amylopectin and molecular orientation of thermoplastic sweet potato starch (TSPS) and thermoplastic pea starch (TPES) on microstructure and functional properties of thermoplastic starch biopolymer blend films were studied. After thermoplastic extrusion, the amylose contents of TSPS and TPES decreased by 16.10 % and 13.13 %, respectively. The proportion of the chains with the degree of polymerization between 9 and 24 of amylopectin in TSPS and TPES increased from 67.61 % to 69.50 %, and from 69.51 % to 71.06 %, respectively. As a result, the degree of crystallinity and molecular orientation of TSPS and TPES films increased as compared to sweet potato starch and pea starch films. The thermoplastic starch biopolymer blend films possessed a more homogeneous and compacter network. The tensile strength and water resistance of thermoplastic starch biopolymer blend films increased significantly, whereas thickness and elongation at break of thermoplastic starch biopolymer blend films decreased significantly.

Highly selective adsorption of Hg (II) from aqueous solution by three-dimensional porous N-doped starch-based carbon.

For the first time, N-doped carbon materials with 3D porous-layered skeleton structure was synthesized through a one-step co-pyrolysis method, which was fabricated by co-pyrolysis of natural corn starch and melamine using metal catalysts (Ni (II) and Mn (II)). The 3D-NC possessed a heterogeneously meso-macroporous surface with a hierarchically connected sheet structure inside. Batch adsorption experiments suggested that highly selective adsorption of Hg (II) by the 3D-NC could be completed within 90 min and had maximum adsorption capacities as high as 403.24 mg/g at 293 K, pH = 5. The adsorption mechanism for Hg (II) was carefully evaluated and followed the physical adsorption, electrostatic attraction, chelation, and ion exchange. Besides, thermodynamic study demonstrated that the Hg (II) adsorption procedure was spontaneous, endothermic, and randomness. More importantly, the 3D-NC could be regenerated and recovered well after adsorption-desorption cycles, showing a promising prospect in the remediation of Hg (II)-contaminated wastewater.

The relationship between molecular structure and film-forming properties of thermoplastic starches from different botanical sources.

To illustrate the correlations between molecular structures and the film-forming properties of thermoplastic starch from various botanical sources, starches from cereal, tuber and legume were modified by thermoplastic extrusion and the corresponding thermoplastic starch films were prepared including thermoplastic corn starch (TCS), thermoplastic rice starch (TRS), thermoplastic sweet potato starch (TSPS), thermoplastic cassava starch (TCAS) and thermoplastic pea starch (TPES) films. TPES film displayed a higher tensile strength (6.28 MPa) and stronger water resistance, such as lower water solubility (15.70 %), water absorption (42.35 %), and water vapor permeability (0.285 g·mm·h-1·m-2·kPa-1) due to higher contents of amylose and B1 chains. TCAS showed a smoother and more amorphous film due to higher amylopectin content, resulting higher elongation at break and larger opacity. TCS film was the most transparent due to a compacter network and more ordered crystallinity structure, which was suit for the packaging of fresh vegetables and aquatic products, whereas TCAS film was the opaquest, which protected package foods from light such as meat products, etc. The outcome would provide an innovative theory to regulate accurately the functional properties of thermoplastic starch films for different food needs.

In situ generated PtNPs to enhance electrochemiluminescence of multifunctional nanoreactor COP T4VTP6 for AFB1 detection.

Herein, a competitive quenching electrochemiluminescence immunosensor towards aflatoxin B1 (AFB1) detection was constructed by in-situ forming platinum nanoparticles (PtNPs) on ECL emitter COP T4VTP6 and effective ECL signal quencher Fc-CHO/Phe. In this system, cationic covalent organic polymer COP T4VTP6 emitted stronger cathode ECL signal at 765 nm, it acted as an interesting nanoreactor to immobilize PtCl62- through electrostatic adsorption, and directly in situ catalyzed the redox reaction to produce PtNPs without adding any external reducing agent, where PtNPs not only served as the substrate for antibody immobilization, but also played the role of coreaction accelerator to catalyze the production of SO4-, significantly improving more stable ECL signal. Moreover, the Fc-CHO/Phe labeled BSA-AFB1 was used for competitive reaction. Based on the efficient sensing strategy, ECL signal increased accordingly and exhibited linear signal responses with increasing AFB1, which realized a detection limit of 4.56 fg/mL, providing a promising potential on food analysis.

Construction of reversible enol-to-keto-to-enol tautomerization covalent organic polymer for sensitive, selective and multi-channel detection of iron (III).

As an important element in organism, the lack and excess of ferric ions (Fe3+) may lead to an extensive range of diseases presenting with distinct clinical manifestations. In our design, a multi-channel probe with reversible enol-to-keto-to-enol tautomerization for the specific recognition and high sensitivity detection of Fe3+ was prepared. This paper reported a novel Cop-NC probe, Tris (4-formylphenyl) amine bearing 1,4-cyclohexanedione groups, which provides binding site for Fe3+ and also contributes both fluorescent and electrochemical signals. The as-synthesized Cop-NC exhibit intense fluorescence under an excitation wavelength at 378 nm with a quantum yield of 26%. Results of spectroscopic measurement show that Fe3+ can significantly cause a "Switch-off" fluorescence intensity effect. Simultaneously, the addition of Fe3+ can cause a "Switch-on" effect in electrochemical channel. It has realized the detection of Fe3+ with concentration as low as 0.4 µM and 1.0 nM in the fluorescence channel and redox channel, respectively. The development of the joint probe with multi-channel signals provides a more convenient and rapid detection method for food, medical treatment, environmental monitoring and other fields.

Determination of nitrite in food based on its sensitizing effect on cathodic electrochemiluminescence of conductive PTH-DPP films.

Herein, a novel strategy for electrochemiluminescence (ECL) detection of nitrite based on its sensitization effect on cathode ECL emission of 3,6-di(2-thienyl)-2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione (TH-DPP) polymeric films (PTH-DPP) was formulated, by means of a one-step electropolymerization of TH-DPP with a short time on the glassy carbon electrode (GCE). It was shown that the PTH-DPP film-modified GCE exhibited a strong ECL response when S2O82- was used as a co-reactant. The ECL emission could be greatly enhanced by PTH-DPP with nitrite in a K2S2O8/PBS solution system and occurred at a relatively lower potential in comparison with traditional cathode ECL emitter, leading to high sensitivity and good selectivity. The ECL sensor exhibits excellent linear relationship in the ranges of 0.3 to 100 µM and 100 to 1000 µM for nitrite detection, with an outstanding detection limit of 0.08 µM (S/N = 3). The ECL sensor provides an impressive outcome for the detection of practical samples.

Electrochemiluminescent sensor based on an aggregation-induced emission probe for bioanalytical detection.

In recent years, with the rapid development of electrochemiluminescence (ECL) sensors, more luminophores have been designed to achieve high-throughput and reliable analysis. Impressively, after the proposed fantastic concept of "aggregation-induced electrochemiluminescence (AIECL)" by Cola, the application of AIECL emitters provides more abundant choices for the further improvement of ECL sensors. In this review, we briefly report the phenomenon, principle and representative applications of aggregation-induced emission (AIE) and AIECL emitters. Moreover, it is noteworthy that the cases of AIECL sensors for bioanalytical detection are summarized in detail, from 2017 to now. Finally, inspired by the applications of AIECL emitters, relevant prospects and challenges for AIECL sensors are proposed, which is of great significance for exploring more advanced bioanalytical detection technology.

An efficient aggregation-induced electrochemiluminescent immunosensor by using TiO2 nanoparticles as coreaction accelerator and energy donor for aflatoxin B1 detection.

Herein, we fabricated a label-free ECL immunosensor for aflatoxin B1 (AFB1) detection. In this system, a small organic aggregation-induced electrochemiluminescence luminophore, 2,5-di-tetraphenylethylene-ylthiazolo [5,4-d] thiazole, was designed, named TPETTZ. Polyaniline-wrapped TiO2 nanoparticles (PANI/TiO2 NPs) complex was synthesized through one-step in situ oxidation polymerization of aniline, and performed excellent electrical conductivity and abundant amino groups. As an ECL accelerator, TiO2 nanoparticles (TiO2 NPs) promoted the oxidation of tri-n-propylamine (TPA) to generate more TPA•; in addition, it also acted as a donor to improve the ECL intensity of TPETTZ (acceptor) through electrochemiluminescence resonance energy transfer (ECL-RET). Encouraged by the above, under the existence of TPA, TPETTZ displayed a strong and continuously stable ECLanode signal due to the introduction of PANI/TiO2 NPs. Therefore, the immunosensor was constructed for AFB1 detection based on the quenching effect of target on the ECL signal, and a linearly decreasing ECL signal was obtained as the increasement of AFB1 in the range of 75 fg/mL to 100 ng/mL, with a lower detection limit of 27.5 fg/mL. Moreover, the as-prepared sensing platform performed a satisfactory anti-interference, stability, and reproducibility, and appeared a good accuracy in walnut sample analysis, presenting a promising application in the future.

Comparison of structural and functional properties of maize starch produced with commercial or endogenous enzymes.

To explore an effective and economic method to prepare higher contents of resistant starch (RS), different enzyme treatments including single pullulanase (PUL), commercial α-amylase (AA) or/and ß-amylase (BA) with PUL, and malt endogenous amylase (MA) with PUL were used and the structural, physicochemical properties and digestibility of all modified starches (MS) were compared. All the enzyme-treated starches displayed a mixture of B and V-type diffraction patterns. The MA/PUL-MS showed higher V-type diffraction peak intensity as compared to other modified starches. Compared to the combination of commercial enzyme treatment, the combination of malt enzyme treatment led to higher apparent amylose contents (45.56%), RS content (53.93%) and thermal stability (302 °C), whereas it possessed lower solubility indices and predicted glycaemic index. The apparent viscosity and shear resistance of MA/PUL-MS were lower than that of AA/PUL-MS, whereas that of MA/PUL-MS was higher than that of BA/PUL-MS and BA/AA/PUL-MS. These findings would provide a theoretical and applicative basis to produce foods with lower GI in industrial production.

An ultrasensitive ratiometric immunosensor based on the ratios of conjugated distyrylbenzene derivative nanosheets with AIECL properties and electrochemical signal for CYFRA21-1 detection.

Aggregation-induced electrochemiluminescence reagent, a distyrylbenzene derivative with donor-acceptor conjugated nanosheet structure, namely TPAPCN, was used as a trace label and modified on the electrode through the formation of classical sandwich complex of antibody-antigen-antibody in this work. In aggregate state, TPAPCN with twisted structure was limited in nanometer space through intermolecular π - π stacking interactions, which not only restricts the intramolecular motions but also combines a large number of singlet excitons to greatly trigger electrochemiluminescence (ECL). The ECL signal of this system enhanced with more captured cytokeratin 19 fragment 21-1 (CYFRA21-1) on the modified electrode. Three-dimensional graphene/platinum nanoparticles with large specific surface, and excellent electroconductivity and biocompatibility were prepared and acted as excellent carriers for thionine handling (3D-GN/PtNPs/Th), which was employed for improving the loading of antibodies and generating internal electrochemical signal. Consequently, a novel ratiometric sandwich immunosensor for CYFRA21-1 detection was fabricated based on TPAPCN and 3D-GN/PtNPs/Th, that is, a rapid and reliable detection was achieved through the ratio between ECL and electrochemical signals. The prepared sensor performed good linearity in the range of 50 fg/mL to 1 ng/mL with a detection limit as low as 16 fg/mL. Moreover, the detection results revealed well in the analysis of human serum samples, demonstrating a significant application for clinical monitoring and biomolecules detection.