Study on Carbonation of Porcine Blood Hydrogel in the Composite Mortar of Ancient Chinese Architectural Painting.

In the ancient Chinese recipe for composite mortar used in the construction of ground layers for architectural painting, the mixture of porcine blood and lime water is one of the constituent materials. Herein, according to the traditional recipe, the interaction between porcine blood and lime water was systematically and deeply investigated. The experimental investigation demonstrated that porcine blood mixed with lime water at the ratio found in the recipe can form a hydrogel with a hydrophobic surface. During air-drying, the lime water in porcine blood hydrogel can react with CO2 to form calcium carbonate. The crystal morphology of the formed calcium carbonate depends on the surrounding micro-environment of calcium ions in the porcine blood hydrogel. The formed morphology of calcium carbonate includes small calcite crystallites, small graininess calcite crystals with round features, calcite aggregates with layered ladder-like structures, and amorphous calcium carbonate (ACC). Interestingly, the calcium carbonate formed in the inner part of the porcine blood hydrogel exhibits lamellar distribution due to a Liesegang pattern formation. Based on the findings that the porcine blood hydrogel has surface hydrophobicity and brittleness, it can be predicted that in the preparation process of composite mortar for ancient building color painting base course, porcine blood used in the form of a hydrogel is not only easier to be dispersed in hydrophobic tung oil than in liquid porcine blood but also the affinity between porcine blood gel and tung oil is enhanced. As constituent material dispersed in the composite mortar, the layered distribution of calcium carbonate in the porcine blood hydrogel may presumably be beneficial to reduce the internal stress of the composite mortar material.

Rational design of triazine-based conjugated polymers with enhanced charge separation ability for photocatalytic hydrogen evolution.

Triazine-based conjugated polymers (TCPs) are promising organic catalysts for green H2 production, since their photocatalytic performance can be easily regulated via appropriate molecular design. However, apart from weak absorption of visible light, weak charge separation and transport abilities also considerably restrict the photocatalytic performance of TCPs. Herein, we report two novel TCP photocatalysts with donor-acceptor (D-A) and donor-π-acceptor (D-π-A) structures using dibenzo[g,p]chrysene (Dc), thiophene (T), and 2,4,6-triphenyl-1,3,5-triazine (Tz) as the donor, π-spacer, and acceptor, respectively. Compared to Dc-Tz with a D-A structure, Dc-T-Tz exhibits a broader light absorption edge and more efficient charge separation and transmission due to its D-π-A structure and strong dipole effect. These properties enable Dc-T-Tz to display a prominent H2 production rate of 45.13 mmol h-1 g-1 under ultraviolet-visible (UV-Vis) light (λ > 300 nm). Therefore, Dc-T-Tz represents state-of-the-art TCP photocatalysts to date.

An Essential Role of Polymeric Adhesives in the Reinforcement of Acidified Paper Relics.

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.

An Essential Role of Gelatin in the Formation Process of Curling in Long Historical Photos.

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.

Study on the Mechanism of the Reversible Color Change of Polyacrylic Acid Modified Gold Nanoparticles Responding to pH.

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.

Quaternary Alloy Quantum Dots as Fluorescence Probes for Total Acidity Detection of Paper-Based Relics.

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.

Mimicking Thylakoid Membrane with Chlorophyll/TiO2/Lipid Co-Assembly for Light-Harvesting and Oxygen Releasing.

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.

Conformational Stability of Poly (N-Isopropylacrylamide) Anchored on the Surface of Gold Nanoparticles.

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.

Formation mechanism of zigzag patterned P(NIPAM-co-AA)/CuS composite microspheres by in situ biomimetic mineralization for morphology modulation.

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.

Blurring of ancient wall paintings caused by binder decay in the pigment layer.

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).

Study on the Assembly Structure Variation of Cetyltrimethylammonium Bromide on the Surface of Gold Nanoparticles.

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, I 1/I 3, 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.

Facile and Scalable Conservation of Chinese Ancient Paintings Using Water-Borne Fluoropolymer.

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.

Green fluorescent carbon quantum dots functionalized with polyethyleneimine, and their application to aptamer-based determination of thrombin and ATP.

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.

Aggregation of Gold Nanoparticles Caused in Two Different Ways Involved in 4-Mercaptophenylboronic Acidand Hydrogen Peroxide.

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.

One-Step Assembly of TiO2-Liposomes Based on Interfacial Sol-Gel Process within Lipid Bilayer.

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 titania formation, fluorescence probe technique and surface pressure versus molecular area (π- A) isotherms are designed. The results demonstrate that the incorporation of TBOT into the mid-membrane of the lipid and titania in the core of the membrane strengthened the assembly of the lipid bilayer. We further demonstrate that titania shell improved the stability and release property of liposomes. We expect that the reported new TiO2-coated liposomes by co-assembly will be valuable in designing hybrid liposomes, exhibiting integrative capacity for drug encapsulation, compartment reaction, and photocatalysis.

Effect of TC(002) on the Output Current of a ZnO Thin-Film Nanogenerator and a New Piezoelectricity Mechanism at the Atomic Level.

Understanding the piezoelectricity mechanism is crucial for developing new materials for better performance. Here, we developed a nanogenerator based on the ZnO thin films having various TC(002) values. The output current well correlated to the magnitude of (002) texture coefficient (TC(002)). Additionally, the TC(002)-dependent photovoltaic and rectification properties are observed. When the film is subjected to persistent compression, the photovoltaic, rectification, and piezoelectric properties fade away. Based on our observation that the ZnO polar structure always shows a spontaneous electron field (SEF), we thus propose a new piezoelectricity mechanism. The [001]-orientated ZnO thin film with the SEF is equivalent to a capacitor, the compression functions as a discharging process, and the removal of the external stress serves as a charging process. The physical mechanism provides an insight into various energy conversion processes that will inspire advanced designs of high-performance nanogenerators, solar cells, and other optoelectronic devices.

Efficient removal of Cr(VI) from water by quaternized chitin/branched polyethylenimine biosorbent with hierarchical pore structure.

A novel chitin-based biosorbent (QCP) was synthesized by cross-linking quaternized chitin and branched polyethylenimine with the aid of epichlorohydrin for efficient removal of Cr(VI) from water. Because it possessed both quaternary ammonium groups and amino groups as well as the hierarchical pore structure, QCP presented a maximum adsorption capacity of 387.7 mg/g according to the Langmuir isotherm at 25 °C. The biosorption of QCP achieved the equilibrium within 40 min and followed the pseudo-second-order kinetic model. QCP worked well even in the solution with high pH and high content of competing anions and, it exhibited an excellent reusability. The main Cr(VI) uptake mechanism was confirmed to be electrostatic attractions between Cr(VI) anions and quaternary ammonium groups as well as the protonated amino groups, and followed by partial reduction of Cr(VI) to Cr(III) by amines and hydroxyls. This work may provide a potential for Cr(VI) removal by chitin-based biosorbents.

Electrochemical removal of stains from paper cultural relics based on the electrode system of conductive composite hydrogel and PbO2.

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.

A New Route to Liposil Formation by an Interfacial Sol-Gel Process Confined by Lipid Bilayer.

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.

Is the contribution of cis and trans protonated 5-methylcytosine-SO3(-) isomers equal in the conversion to thymine-SO3(-) under bisulfite conditions? A theoretical perspective.

Cytosine (Cyt) can be converted to 5-methylcytosine (5-MeCyt) in CpG sequences of DNA. Conventional bisulfite sequencing can discriminate Cyt from 5-MeCyt, however inappropriate conversion of 5-MeCyt to thymine and a failure to convert Cyt to uracil always occur when Cyt and 5-MeCyt are treated with bisulfite, which would lead to erroneous estimates of DNA methylation densities. Here, the direct hydrolytic deamination of cis (paths A-C) and trans (paths A'-C') 5-MeCytN3(+)-SO3(-) isomers with bisulfite have been explored at the MP2/6-311++G(3df,3pd)//B3LYP/6-311++G(d,p) level. The activation free energies (ΔG(s-a≠)) of the cis and trans 5-MeCytN3(+)-SO3(-) isomers' paths exhibit no obvious differences, implying both isomers may make an equal contribution to the hydrolytic deamination of 5-MeCyt under bisulfite conditions. It is greatly expected that these results could aid experimental scientists to explore new methods to avoid the formation of the deaminated reactants (5-MeCytN3(+)-SO3(-)). Meanwhile, the HSO3(-)-induced direct hydrolytic deamination of cis and trans 5-MeCytN3(+)-SO3(-) isomers is represented by paths A and A', respectively, and has been further explored in the presence of two water molecules. It was found that the contribution of two water molecules renders the HSO3(-)-induced direct hydrolytic deamination of cis and trans 5-MeCytN3(+)-SO3(-) isomers by paths A and A' favourable. In addition, the ΔG(s-a≠) values (85.74-85.34 kJ mol(-1)) of the rate-limiting steps of the two water-mediated paths A and A' are very close to that of the theoretical value for CytN3(+)-SO3(-) (88.18 kJ mol(-1)), implying that the free barrier gap between Cyt and 5-MeCyt is very small under bisulfite conditions. This further suggests that bisulfite sequencing technology may be easily influenced by the external environment.