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Lacquer is widely used in ancient times. The antiques unearthed from Qin Terra-Cotta Warriors bear traces of lacquer painting massively. The lacquer paintings on the surface of the Qin Terra-Cotta Warriors fully demonstrate the characteristics and development level of lacquer painting at that time. However, the painted films unearthed appear crispy and fragile. In this study, six painted films are chosen from Pit.2 of the Qin Terra-Cotta Warriors and characterized by an ultra-depth-of-field microscope, a metalloscope, a scanning electron microscope, an energy dispersive spectrometer, and infrared spectroscopy. The results show that the painted films are lacquer films on the base layer of Qin terra-cotta warriors. In the wet alkaline environment, a fracture of the polymer chain along polymerization products of urushiol occurs, which produces soluble products containing benzene ring-related molecules, leading to lacquer films’ embrittlement and cracks. Lacquer films have aged.

There is a growing interest in the design and construction of artificial photosythetic materials for solar energy utilization and conversion. Inspired by the structure of thylakoid membrane, we present here a hybrid construct for light-harvesting and oxygen releasing. Our design conjugates chlorophyll to TiO2 in a native-like membrane environment. The natural bilayer structure of lipids is utilized to localize the amphiphilic chlorophyll a and hydrophobic tetrabutyl titanate TBOT in the liposomal membrane during hydration process. The coassembled structure, which mimics the essential organization of the thylakoid membrane, is characterized using a combination of field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometer (EDS), Ramam spectra, pressure (π)-area (Α) isotherms, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) analysis. Our results demonstrate successful insertation of chlorophyll a in the membrane and confirm the in situ formation of TiO2 nanoshell confined at the lipid bilayer/water interface. We further show that the hybrid liposomes exhibit unambiguous photoactivity in visible light-harvesting and oxygen release, likely resulting from a larger specific surface area of the TiO2 shell, an efficient interfacial conjugation of the chlorophyll molecules with the thin TiO2 layer. The density functional theory (DFT) calculations were in accordance with the eletron injection processes.We expect that the present work will open a new insight into interfacial recombination between light-harvesting pigments and their sensitized photocatalysis, and develop a new kind of artificial photosynthetic materials with zero-cost of environmental degradation and high efficiency for the photocatalytic O2 production.

Poly(N-isopropylacrylamide-co-acrylic acid)/copper sulfide (P(NIPAM-co-AA)/CuS) composite microspheres with variable zigzag patterned surfaces have been synthesized by employing an in situ biomimetic mineralization reaction between H2S and Cu2+ immersed in P(NIPAM-co-AA) microspheres for morphology modulation. The morphology and composition of the P(NIPAM-co-AA)/CuS composite microspheres with zigzag patterned surfaces prepared in different conditions were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectrometry (FT-IR). The polymeric microgels swelled by Cu(Ac)2 solution after freeze-drying treatment were of porous structure, indicating that there were polymeric frameworks and rich-water domains in the microgels before the deposition. Furthermore, due to the limited uneven deposition of metal sulfide on the polymeric skeleton of the hydrogel surface, the surface polymeric skeleton will be anisotropically shrunk when the composite microspheres lose water and shrink, thus forming a wrinkle pattern on the surface of the composite microspheres. The factors affecting the deposition amount and distribution of metal sulfide will affect the zigzag patterned morphology. Based on the experimental results, a formation mechanism of the P(NIPAM-co-AA)/CuS composite microspheres with zigzag patterned surface, “the deformed shrinkage of the surface texture”, has been proposed. The formation mechanism of the surface morphology in the composite microspheres is helpful for understanding and controlling the process of mineralization, for preparing materials expected by controlling the experiment conditions, and for expanding the application of the composites.

Textiles are valuable cultural heritage items that are susceptible to several degradation processes due to their sensitive nature, such as the case of ancient ma colored-paintings. Therefore, it is important to take measures to protect the precious ma artifacts. Generally, ″ma″ includes ramie, hemp, flax, oil flax, kenaf, jute, and so on. In this paper, an examination and analysis of a painted ma textile were the first step in proposing an appropriate conservation treatment. Standard fiber and light microscopy were used to identify the fiber type of the painted ma textile. Moreover, custom-made reinforcement materials and technology were introduced with the principles of compatibility, durability and reversibility. The properties of tensile strength, aging resistance and color alteration of the new material to be added were studied before and after dry heat aging, wet heat aging and UV light aging. After systematic examination and evaluation of the painted ma textile and reinforcement materials, the optimal conservation treatment was established, and exhibition method was established. Our work presents a new method for the conservation of ancient Chinese painted ramie textiles that would promote the protection of these valuable artifacts.

In China, alum-gelatin aqueous solution is historically used to prevent falling off of mineral pigments from paintings and to enhance strength of their paper matrices in the restoration process. However, after a long period of time of preservation, alum-gelatin aqueous solution applied to paintings will hydrolyze and produce free acid, which accelerates aging. To resolve this issue, instead of using alum-gelatin aqueous solution, here we report a new method of using a water-borne fluoropolymer coating to protect paintings. This coating is applied to simulated paintings, and their influences are systematically examined on the antipeeling property of pigment, mechanical properties, thermal stability, chromaticity, surface morphology, and water contact angle. Our results show that the applied coating slightly affects the appearance of the painting without falling off of pigment observed. Moreover, the coating increases the tensile strength and folding endurance of the paper because the polymer fills into the porous structure of paper fibers and covers pigment particles from SEM analysis. The treated painting retains moderate hydrophilicity, which facilitates removal of degradation substances from the paintings by water cleaning and the subsequent mounting procedure. Moreover, this coating is successfully applied to repairing a set of real ancient Chinese paintings of Yuan Dynasty (1271∼1368 A.D.), with practical acceptance. Our work provides a facile yet effective solution to conservation of ancient paintings by applying the modern fluoropolymers.

The white spots known as microbubbles that are formed in cellulose acetate film, significantly affects the texture of the image. However, the formation of microbubbles and their corresponding microstructure are poorly understood. In this paper, cellulose acetate microfilm from the Republic of China (AD 1912–1949) collected in the Second Historical Archives of China was chosen as a prototype to investigate the causes of microbubble disease for the first time. A comparative study was conducted between the film samples with and without microbubbles. Herein, the microstructural analyses including optical and SEM microscopy were conducted. The crystals in the microbubbles proved to be triphenyl phosphate as identified by NMR spectroscopy and SEM–EDX. Comparative properties of the film substrate with and without microbubbles were measured by TG, XRD and FT-IR spectroscopy. The results show that formation of microbubbles was generally accompanied with the vinegar syndrome and was produced between the protective and emulsion layers with the different types of shapes along the closed structure (the diameter of ~ 0.1–2 mm). The formed microbubble was filled with plasticizer. Based on the above-mentioned results, the possible formation process of microbubble was proposed in the present study. The results can provide support for the cause of microbubbles and basis for the conservation of photographic films.

In this work, the self-assembly behavior of cetyltrimethylammonium bromide (CTAB) on the surface of citrate-capped gold nanoparticles (AuNPs) in solution has been studied by UV–vis absorption spectroscopy, fluorescence probe techniques, ζ potentiometric methods, transmission electron microscopy, etc. The UV–vis spectra show that the color with the increase of CTAB for the mixture containing CTAB and a given amount of AuNPs changes from red to blue and then to red. The absolute value of ζ potential corresponding to this color change decreases initially and then increases. Specially, the reversible color change, from red to blue and then to red, could be observed only in the case of a gradual addition of a AuNP solution to a CTAB solution; however, this reversible change is not suitable for the mixture formed in a reverse order of mixing. The results from pyrene used as the fluorescence probe indicate that the features in the fluorescence spectrum (including fluorescence quenching, I1/I3, and the excimer) well correspond to those from the UV–vis spectrum mentioned above. Based on the experimental results, the mechanism of the assembly structure variation of CTAB on the surface of negatively charged AuNPs was proposed. For a given amount of AuNPs, the assembly structure of CTAB on the surface of AuNPs undergoes the transformation from a monolayer to a bilayer with the increase of CTAB. In the case of the concentration of CTAB far beyond its critical micelle concentration (CMC) and the higher ratio of CTAB and AuNPs, there is a possibility of the formation of an extra micellar structure only after the formation of a double-layer structure.

A simple photolysis route was proposed to prepare Amphiphilic Janus Particles (AJP) based on SiO2 microspheres. The surface of SiO2 microspheres were modified by photoactive alkoxysilane, which was synthesized by dealcoholization condensation of 6-nitroveratroyloxycarbonyl and isocyanatopropyl-triethoxysilane. UV irradiation caused eater-breaking allowed for the precise control of hydrophilic modification of the hemispherical exposed particles surfaces. The component and morphology of the obtained particles were characterized by fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy, and the Janus feature was evaluated by scanning electron microscopy, transmission electron microscopy, and dispersity in the oil–water dual-phases. The following results were obtained. The AJP with 450 nm size processes the hydrophilic amino groups on one side and the hydrophobic 6-nitroveratryloxycarbonyl moieties on the other. Additionally, the AJP were located at the phase boundary between water and n-hexane, and the negative charged gold nanoparticles with 25 nm size were adsorbed only onto the side with the positive charged amino groups. The AJP have interfacial adsorption energies that can be as much as three times larger than that of homogeneous particles and thus exhibit excellent surface activities.

Paper acidification causes paper relics to undergo embrittlement and decay, to form dregs, and even to break upon a single touch; therefore, reinforcement and deacidification treatments are essential steps for paper conservation and to retard the deterioration and prolong the life of objects. Polymeric adhesives play an essential role in reinforcement and deacidification treatments, although it is not well studied. In this work, the effect of polymeric adhesives on the conservation process and their protective effects on acidified paper relics were studied. Firstly, three polymeric adhesives, including wheat starch paste, polyvinyl butyral (PVB), and polyvinyl alcohol (PVA), were selected as research objects. Subsequently, their effects on four popular conservation methods were further discussed, including traditional mounting, hot-melt with silk net, alcohol-soluble cotton mesh, and water-soluble cotton mesh. Additionally, as an example, the reversibility and long-term durability of water-soluble adhesive PVA-217 were assessed. Using a computer measured and controlled folding endurance tester, pendulum tensile strength tester, tear tester, burst tester, FT-IR, video optical contact angle tester, and other instruments, the conservation application of water-soluble adhesives in paper relics was evaluated. This study provides a scientific basis and experimental data for the application of polymeric adhesives in the conservation of paper relics.

Curling disease in long historical photos significantly affects the presentation of cultural heritage information. However, people lack attention to the formation process and microstructural changes of photo curling. In this article, a long historical photo (1912–1949 AD) collected by the Second Historical Archives of China was taken as the research object, and the formation process and cause of the curling were further explored. Firstly, Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray energy disperse spectrometer (EDS), and other instruments were used to analyze the material composition of the long historical photo. It was found that the photographic paper was made of gelatin, barium sulfate, and plant fiber layers. Then, the effects of hygrothermal environments on curling and contraction in the gelatin layer and simulated photographic paper were explored. Meanwhile, the formation process and main influence factors of the curling were preliminarily revealed. The morphological analysis by SEM was carried out to identify the inner correlation between the microstructure and curling of photos. Finally, the possible formation cause of photo curling was analyzed. This study provides a scientific basis and experimental data for the preservation and restoration of long historical photos based on gelatin.

Due to the favorable retention power and viscosity, the hydrogel that is loaded with an aqueous detergent, represents a promising cleaning tool for removing the foreign matters such as polymer adhesive, starch paste, and animal glue from paper artworks. However, it is still challenging to eliminate other stains, including organic dyes, commercial drinks, foxing, and mildew. Herein, we present an alternative methodology, translucent hydrogel-containing electrolyte-based electrochemical cleaning (EC), which incorporates electrochemical reactions into the hydrogel-based cleaning process using the extremely tough and translucent alginate/polyacrylamide hydrogel as cathode and PbO2 as anode. The proposed approach is generally applicable to eliminate different stains such as organic dyes, commercial drinks, mildew, and foxing from paper under several mA/cm2 and a few minutes in a small controlled area. For the excellent mechanical strength, the hydrogel electrode can be reused for several times without losing its efficiency and easily peeled-off from paper as one body without any gel residues after cleaning. We further demonstrate the effect of EC on the treated paper, including the morphology, degree of polymerization, crystal structure, and mechanical properties. We conclude that the influence of EC on the paper is slight under the mild treatment.

There is a growing interest in the use of hybrid liposomes for various biochemical and biomedical applications. In this study, we report the first preparation and characterization of a class of TiO2-reinforced liposomes by a one-step assembly approach. The amphiphilic natural structure of lipids is exploited to localize a hydrophobic molecule, namely, precursor tetrabutyl titanate (TBOT), in the mid-plane of the liposomal bilayer assemblies in the aqueous phase. In situ TiO2 nanoshell formation is driven by subsequent interfacial hydrolysis of TBOT and the ensuing condensation within the hydrophobic interstices of the lipid bilayer. The core–shell structure, like cell and wall, is demonstrated by means of scanning electron microscopy and transmission electron microscopy images, and the formation of the TiO2 shell is confirmed using energy-dispersive X-ray spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. To study the structural evolution of the hybrid liposomes during titani...

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In view of various explanations regarding the pH response of the nanocomposite of gold nanoparticles (AuNPs) modified with polyacrylic acid (PAA) molecules in reported literature, in this work, AuNPs with a size of 20 nm saturatedly loaded with PAA molecules (AuNPs-PAAs) were used to investigate the following aspects of this issue. We investigated the effects of pH on the stability of AuNPs-PAAs in the presence of salt, CTAB, poly (sodium styrenesulfonate) (PSS), ethanol, and free PAA, respectively. Common techniques were undertaken to evaluate the stability, including UV-Vis spectroscopy, Zeta potential analysis, and TEM. The results show that AuNPs-PAAs could respond to pH variations, having a reversible aggregation-to-disaggregation, accompanying their Zeta potential change. The proposed corresponding mechanism was that this reversible change was attributes to the net charge variation of AuNPs-PAAs induced by a reversible protonation-to-deprotonation of PAA rather than the conformational change. It was found that salt, CTAB, PSS, and free PAA could strengthen the dispersity of AuNPs-PAAs, even though their absolute Zeta potential values were decreased to small values or dropped to nearly zero. This abnormal phenomenon was explained by solvation. It was also found that AuNPs-PAAs have an opposite pH response in aqueous and ethanol solutions, justifying the solvation effect. All these results revealed the conformational stability of PAAs immobilized on AuNPs. The methods and the findings of this investigation give some new insights to understand the pH-response of AuNPs-PAAs composites and the design of AuNPs-PAAs-based functional sensors.

An amendment to this paper has been published and can be accessed via the original article.

There is a growing interest in the design and construction of artificial photosythetic materials for solar energy utilization and conversion. Inspired by the structure of thylakoid membrane, we present here a hybrid construct for light-harvesting and oxygen releasing. Our design conjugates chlorophyll to TiO

To verify the temperature sensitive failure of poly (N-isopropylacrylamide) (PNIPAM) anchored on the surface of gold nanoparticles (AuNPs), the UV-Vis spectra with temperature variations of the following aqueous solutions respectively containing AuNPs-PNIPAM, Au-PNIPAM/PNIPAM, PNIPAM, in different media (including salt, ethanol, HCl and cetyltrimethylammoniumbromide (CTAB)), were systematically determined. The results indicated that the UV-Vis spectrum of AuNPs-PNIPAM suspension hardly changed even above the Lower Critical Solution Temperature (LCST) of PNIPAM, but that of Au-PNIPAM/PNIPAM sharply increased only in absorbance intensity. A possible mechanism of the failed temperature sensitivity of PNIPAM anchored on the surface of AuNPs was proposed. Being different from free PNIPAM molecules, a strong interaction exists among PNIPAM molecules anchored on the surface of AuNPs, restraining the change in conformation of PNIPAM. The temperature sensitivity of Au-PNIPAM/PNIPAM originates from the free PNIPAM molecules rather than the anchored PNIPAM one. The changing electrostatic interaction could effectively regulate the aggregation behavior of AuNPs-PNIPAM and enhance its sensitivity to temperature.

In this paper, the effect of binder decay rather than a change in the pigments on the blurring of ancient wall paintings was researched. The simulated wall paintings were prepared by brushing an aqueous solution containing gelatine and ochre grains on the surface of cylindrical compressed soil samples. Then, the dried samples were calcined at 650 °C for 2 h to obtain the simulated wall paintings with the degraded binder gelatine. Next, the calcined samples were brushed with a certain amount of acetone solution containing an ionic liquid ([BMIm]PF6) to obtain the corresponding repaired samples. Based on the results from various characterization methods (UV–vis, FTIR, XRD, XPS, SEM, TG), the following conclusions were drawn. The degradation of the binder caused by calcination increases the surface roughness of the painting layer, resulting in enhanced scattering. In this case, because scattering decrease the light absorption by the pigments, even if unchanged pigment exists in the painting layer, its colour can become blurred. The filling of the ionic liquid into the pores caused by gelatine decay in the painting layer can decrease the scattering, and the blurred colour can be restored to some extent. As typical examples, this principle was successfully applied to restore the blurred colour of an ancient Chinese wall painting (Tang Dynasty) and a pottery (Eastern Han Dynasty).

Microbubble disease observed in cellulose acetate microfilm is accompanied by the production of vinegar syndrome, which affects the image integrity. In the present study, samples of cellulose acetate microfilm with microbubble disease were selected to investigate potential treatment methods. Samples were sourced from the Republic of China (AD 1912-1949) microfilm collections held in the Second Historical Archives of China. A combination of optical microscopy and a stainless-steel needle was used to remove plasticizer exudation within microbubbles. The plasticizer was effectively removed by infiltrating butan-1-ol into the microbubble from a small hole made by the stainless-steel needle. SEM and confocal microscopy were used to study the morphology and roughness of the internal surface of the microbubbles. It was found that the blurry image could be attributed to light scattering from the rough surface. Ethyl cellulose was used to fill the interior of the microbubble to obtain a clearer image. To determine the protective potential of this filling material, the chemical and mechanical properties of coated film after dry heat, hygrothermal and UV accelerated ageing were measured. Based on the above-mentioned results, it is encouraging that a new microrepair method and its corresponding method are offered in film treatment work.

As a kind of textile, hemp artifact is a valuable cultural heritage. Suffering from several degradation factors in the preservation of cultural relics, some ancient hemp colored-paintings have been damaged, further affected their ornamental values. Therefore, it is urged to take the suitable conservation measures to protect the precious hemp artifacts for the historical culture succession. In this paper, an examination and analysis of the hemp colored paintings were the first step to propose an appropriate conservation treatment. Ultra-depth-of-field microscope was used to identify the kinds of fiber, and scanning electron microscope (SEM) was utilized to observe their condition and surface morphology. The element distribution and composition were identified by SEM, energy disperse spectroscopy (EDS) and X-ray fluorescence spectroscopy (XRF). Gas chromatography-mass spectrometer (GC-MS) was applied to identify the kinds of binding media and amino acid composition. Moreover, novel reinforcement materials and technology were proposed with the principle of compatibility and feasibility. The properties of tensile strength, aging resistance and chromatic aberration were tested before and after dry heat aging, wet heat aging and UV light aging. After systematic examination and evaluation of the hemp colored paintings and reinforcement materials, the optimal conservation treatment was finally established, and the Chinese hemp painting as an example has been protected successfully. This paper provides new methods and ideas for the restoration and protection of the linen cultural relics, which would promote the progress of protecting valuable cultural heritages.

Microbubble disease observed in cellulose acetate microfilm was accompanied by the production of vinegar syndrome, which has a negative influence on the integrity of image. In the present study, cellulose acetate microfilm with microbubble disease from the Republic of China (AD 1912-1949) collected in the Second Historical Archives of China was chosen as a prototype to investigate its treatment methods. A combination of optical microscopy and a stainless-steel needle was used to remove plasticizer exudation within microbubbles. The plasticizer was effectively removed by infiltrating butan-1-ol into the microbubble from a small hole made by the stainless-steel needle. The SEM and laser confocal microscopy were used to study the morphology and roughness of the internal surface of microbubble. It was found that the blurry image could be attributed to the light scattering from the rough surface. Based on the advantages of ethyl cellulose in conservation science, the optimal concentration of ethyl cellulose was selected and used to fill the interior of the microbubble to obtain a clearer image. To determine the protective potential of this filling material, the chemical and mechanical properties of coated film after dry heat, hygrothermal and UV accelerated ageing were measured. Based on the above-mentioned results, it is encouraging that a new microrepair method and its corresponding method are offered in film treatment work.

Fading and showing mechanisms of ancient color paintings based on light scattering induced by particles were proposed. To confirm the mechanisms, simulated and application experiments were carried out to restore an ancient blurred color painting. Loading TiO2 particles (500–1000 nm) onto a piece of colored paper could result in blurring of the color of the paper, which is attributed to light scattering caused by air voids between the particles. Filling air voids with ionic liquid (a non-volatile solution with a high refractive index) could highlight the color by reducing scattering. These results were experimentally testified by the combination of a fluorescence probe and multi-angle reflectance spectra, in which scattering decreased the incident optical path in the painting layer while the incident optical path was increased by filling the air voids with ionic liquid. As a practical example, the proposed method was applied to highlight an ancient Chinese painting with blurred color. This investigation is very useful to restore faded color paintings.

An improved apparatus for measuring freezing points has been developed. Compared to the traditional Beckmann freezing point instrument, the improved one overcame prior difficulties with solidification of liquid and made the solid–liquid equilibrium reversible with heat compensation from a heating tube. The reliability and accuracy were carefully examined by determining the freezing point of the solvent and solution, as well as calculating the molar mass of the solute. It was found that the molar mass was in good agreement with the literature data. Thus, this improved device can effectively and successfully be used in undergraduate physical chemistry laboratory courses.

Constructing methods for cleaning stains on paper artworks that meet the requirements of preservation of cultural relics are still challenging. In response to this problem, a novel electrochemical cleaning method and the preparation of corresponding electrodes were proposed. For this purpose, the conductive graphene (rGO)/polyacryamide (PAM)/montmorillonite (MMT) composite hydrogel as cathode and PbO2-based material as anode were prepared and characterized. The electrochemical cleaning efficiencies of real sample and mimicking paper artifacts were evaluated, and the effects of the electrochemical cleaning on paper itself were detected. Based on the above experiments, the following results were obtained. The composite hydrogel with attractive mechanical properties is mainly based on the hydrogen bond interactions between PAM chains and MMT. The results of cleaning efficiency revealed that the black mildew stains together with the yellowish foxing stains were almost completely eliminated within 6 min at 8 mA/cm2, and various stains formed by tideline, foxing, organic dyes and drinks could be thoroughly removed at 4 mA/cm2 within 5 min. In addition, the proposed cleaning method has advantages in local selectivity, easy control of cleaning course, and reusability, which represents a potential utility of this approach.

We report a hybrid bioactive system inspired by the biosilicification of diatoms. Monodisperse chloroplast/silica hybrid microspheres with core–shell structure were designed and prepared. Natural fresh chloroplasts, the photosynthetic plant organelle, were surfacely covered with silica shell by mild sol–gel process. The charge of chloroplast surface attracts negatively charged silica particles in the sol generated from subsequent hydrolysis and condensation of the tetraethyl orthosilicate (TEOS), which benefits single-chloroplast encapsulation. SEM images confirm the closed topologies, sizes, and dispersions of hybrid microspheres comparable to those of parent chloroplasts. The elemental analysis using EDX, the particle size distribution analyses using DLS, the thermochemical analyses using TGA measurements and structural characterization using XRD provide evidence for the formation of silica coating. Monitoring declines in the visible light absorption production yields information regarding the declines in the light-harvesting ability of chlorophyll, which confirmed that the silica shell in the present work extends the photochemical vitality of chloroplasts. Results from oxygen production measurements also demonstrate the existence of silica shell confers real protection on the bioactivity of chloroplasts. We envisage that the stand-alone chloroplast encapsulation enables preparation of living-cell-templated microspheres exhibiting capacity for photosynthetic bioreactors, sensors, green coatings, catalysts, more generally opening a window for construction of stable, environment friendly, functional hybrid materials.

Brightly fluorescent carbon quantum dots coated with polyethylenimine (PEI-CDs) were prepared using malic acid and PEI as the precursors. The PEI-CDs have a high quantum yield (41%) and green emission (peaking at 502 nm under 430 nm excitation), both of which are not affected by high ionic strength. The PEI-CDs have a positive charge at physiological pH values and can electrostatically bind aptamers with their negative charge. This is shown for aptamers binding thrombin or ATP. Binding of aptamers results in quenching of fluorescence. If thrombin or ATP are introduced, the respective aptamer will bind them, and the complex is then released from the PEI-CDs. Fluorescence increases in proportion to the analyte concentration. Under optimized conditions, thrombin and ATP can be sensitively and selectively detected by fluorometry with lower detection limits of 1.2 and 13 nM, respectively. The assay was successfully applied to the determination of thrombin and of ATP in spiked serum samples. Graphical abstract Green fluorescent carbon quantum dots were functionalized with polyethyleneimine. They were applied to aptamer-based determination of thrombin and ATP. The PEI-functionalized carbon quantum dots (PEI-CDs) have bright green fluorescence are were synthesized by one-step hydrothermal treatment of malic acid and PEI. Employing the PEI-CDs, a fluorometric aptamer-based assay was developed for the determination of thrombin and ATP.

The difference in gold nanoparticle (AuNPs) aggregation caused by different mixing orders of AuNPs, 4-mercaptophenylboronic acid (4-MPBA), and hydrogen peroxide (H2O2) has been scarcely reported. We have found that the color change of a ((4-MPBA + AuNPs) + H2O2) mixture caused by H2O2 is more sensitive than that of a ((4-MPBA + H2O2) + AuNPs) mixture. For the former mixture, the color changes obviously with H2O2 concentrations in the range of 0~0.025%. However, for the latter mixture, the corresponding H2O2 concentration is in the range of 0~1.93%. The mechanisms on the color change originating from the aggregation of AuNPs occurring in the two mixtures were investigated in detail. For the ((4-MPBA + H2O2) + AuNPs) mixture, free 4-MPBA is oxidized by H2O2 to form bis(4-hydroxyphenyl) disulfide (BHPD) and peroxoboric acid. However, for the ((4-MPBA+AuNPs) + H2O2) mixture, immobilized 4-MPBA is oxidized by H2O2 to form 4-hydroxythiophenol (4-HTP) and boric acid. The decrease in charge on the surface of AuNPs caused by BHPD, which has alarger steric hindrance, is poorer than that caused by -4-HTP, and this is mainly responsible for the difference in the aggregation of AuNPs in the two mixtures. The formation of boric acid and peroxoboric acid in the reaction between 4-MPBA and H2O2 can alter the pH of the medium, and the effect of the pH change on the aggregation of AuNPs should not be ignored. These findings not only offer a new strategy in colorimetric assays to expand the detection range of hydrogen peroxide concentrations but also assist in deepening the understanding of the aggregation of citrate-capped AuNPs involved in 4-MPBA and H2O2, as well as in developing other probes.

There is a growing interest in the use of hybrid liposomes for various biochemical and biomedical applications. In this study, we report the first preparation and characterization of a class of TiO

Traditionally, the acidity of paper-based relics was determined by an extraction method and using a pH meter. This method could not obtain the total acidity of the paper-based relics because it only detected the concentration of free protons in the aqueous soaking solution. To overcome this defect, a new method for determining the total acidity of paper-based relics has been established by using quaternary alloy quantum dots. The quantum dots, CdZnSeS, modified by p-Aminothiophenol (pATP) were prepared, and their composition and structure were characterized. The fluorescence behavior of prepared quantum dots with acidity was investigated. The following results were obtained. The fluorescence of CdZnSeS-pATP quantum dots could decrease with increases in acidity because pATP dissociated from the surfaces of the quantum dots due to protons or undissociated weak acids. Based on this feature, a method for determining the acidity of paper-based relics was constructed, and this method was used to evaluate the acidity of actual paper-based relics. Obviously, for a given paper sample, since both free protons and bound protons can be determined by this method, the acidity measured by this method is more reasonable than that by pH meter.

Recent years have witnessed significant progress in bio-based epoxy thermosets. A variety of epoxy thermosets have been synthesized from various bioresources. In particular, epoxy thermosets derived from bio-based monomeric phenols, either naturally occurring or biotransformed, such as cardanol, eugenol, vanillin, tannin acid, gallic acid, and so forth. This review summarizes the research regarding this theme and highlights the molecular transformations and ultimate properties of the resultant epoxy thermosets and materials. The relevant epoxy monomers, prepolymers, curing agents, additives, cured thermosets, functional materials and biocomposites are discussed based on their molecular structures and properties of crosslinked networks. Finally, the challenges and opportunities in developing sustainable epoxy thermosets and materials from bio-based monomeric phenols are presented.

We report a new method to prepare bimodally porous, macroporous–mesoporous silica materials utilizing TEOS co-constructed template with colloidal liquid aphrons (CLAs). The macroporous and mesoporous texture of obtained silica is characterized using a combination of fluorescence microscopy, SEM, TEM, and nitrogen volumetric adsorption analysis. The appearance of macropores is attributed to the interfacial confined hydrolysis–condensation of silica source where as the mespore formation is consistent with the pores resulting from the compact packing of nanometer silica particles under weak base-catalysed reaction condition. This bimodally porous silica materials can be prepared either as monoliths or ascisolated spherical particles by adjusting the TEOS concentration in the oil phase.

We report a new and simple approach to prepare a class of silica-reinforced liposomes with hybrid core-shell nanostructures. The amphiphilic natural structure of lipids was exploited to sequester hydrophobic molecules, namely precursor TEOS and pyrene, in the hydrophobic midplane of liposomal bilayer assemblies in the aqueous phase. Subsequent interfacial hydrolysis of TEOS at the bilayer/water interface and ensuing condensation within the hydrophobic interstices of the lipid bilayer drives silica formation in situ, producing a novel class of silica-lipid hybrid liposils. Structural characterization by scanning- and transmission electron microscopy confirm that the liposils so generated preserve closed topologies and size-monodipersity of the parent lecithin liposomes, and DSC-TGA and XRD measurements provide evidence for the silica coating. Monitoring fluorescence measurements using embedded pyrene yield detailed information on microenvironment changes, which occur during sol-gel process and shed light on the structural evolution during silica formation. We envisage that liposils formed by this simple, new approach, exploiting the hydrophobic core of the lipid bilayer to spatially localize silica-forming precursors enables preparation of stable liposils exhibiting capacity for cargo encapsulation, bicompatibility, and fluorescence monitoring, more generally opening a window for construction of stable, functional hybrid materials.