DNA as a template for synthesis of fluorescent gold nanoclusters

Water-soluble blue-emitting gold nanoclusters have been synthesized using dsDNA as a template without any additional reducing agent. The features of the formed nanoclusters have been revealed by fluorescence and electronic absorption spectroscopy as well as transmission electron microscopy. The prepared gold nanoclusters have been highly stable at physiological pH without any further modification.     

Facile preparation of water-soluble fluorescent silver nanoclusters using a polyelectrolyte template

We report a new approach for the synthesis of fluorescent and water-soluble Ag nanoclusters, using the common polyelectrolyte poly(methacrylic acid) as the template.     

Two-component hydrogels comprising fatty acids and amines: structure, properties, and application as a template for the synthesis of metal nanoparticles

Stearic acid or eicosanoic acid mixed with di- or oligomeric amines in specific molar ratios form stable gels in water. The formation of such hydrogels depends on the hydrophobicity of the fatty acid, and also on the type of amine used. The gelation properties of these two-component systems were investigated using electron microscopy, FTIR spectroscopy, 1H NMR spectroscopy, differential scanning calorimetry (DSC), and both single-crystal and cast-film X-ray diffraction. Results of FTIR spectral analysis suggest salt formation during gelation. 1H NMR analysis of the gels indicates that the fatty acid chains are immobilized in the gel state and when the gel melts, these chains regain their mobility. Analysis of DSC data indicates that increase in the spacer length in the di-/oligomeric amine lowers the gel-melting temperature. Two of these gelator salts developed into crystals and structural details of such systems could be secured by single-crystal X-ray diffraction analysis. The structural information of the salts thus obtained was compared with the XRD data of the self-supporting films of those gels. Such analyses provided pertinent structural insight into the supramolecular interactions that prevail within these gelator assemblies. Analysis of the crystal structure confirmed that multilayered lamellar aggregates exist in the gel and it also showed that the three-dimensional ordering observed in the crystalline phase is retained in only one direction in the gel state. Finally, the hydrogel was used as a medium for the synthesis of silver nanoparticles. The nanoparticles were found to position themselves on the fibers and produced a long, ordered assembly of gel-nanoparticle composite.     

Pyrene-containing peptide-based fluorescent organogels: inclusion of graphene into the organogel

The N-terminally pyrene-conjugated oligopeptide, Py-Phe-Phe-Ala-OMe, (Py=pyrene 1-butyryl acyl) forms transparent, stable, supramolecular fluorescent organogels in various organic solvents. One of these organogels was thoroughly studied using various techniques including transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), Fourier-transform infrared (FTIR) spectroscopy, photoluminescence (PL) spectroscopy, and rheology. Unfunctionalized and non-oxidized graphene was successfully incorporated into this fluorescent organogel in o-dichlorobenzene (ODCB) to form a stable hybrid organogel. Graphene is well dispersed into the gel medium by using non-covalent π-π stacking interactions with the pyrene-conjugated gelator peptide. In the presence of graphene, the minimum gelation concentration (mgc) of the hybrid organogel was lowered significantly. This suggests that there is a favorable interaction between the graphene and the gelator peptide within the hybrid organogel system. This hybrid organogel was characterized using TEM, AFM, FTIR, PL, and rheological studies. The TEM study of graphene-containing hybrid organogel revealed the presence of both graphene sheets and entangled gel nanofibers. The AFM study indicated the presence of 3 to 4 layers in exfoliated graphene in ODCB and the presence of both graphene nanosheets and the network of gel nanofibers in the hybrid gel system. The rheological investigation suggested that the flow of the hybrid organogel had become more resistant towards the applied angular frequency upon the incorporation of graphene into the organogel. The hybrid gel is about seven times more rigid than that of the native gel.     

Efficient Hydro- and Organogelation by Minimalistic Diketopiperazines Containing a Highly Insoluble Aggregation-Induced,Blue-Shifted Emission Luminophore**

We report the synthesis, gelation abilities and aggregation-induced, blue-shifted emission (AIBSE) properties of two minimalistic diketopiperazine-based gelators. Despite containing a highly insoluble luminophore that makes up more than half of their respective molecular masses, efficient hydrogelation by multiple stimuli for one and efficient organogelation for the other compound are reported. Insights into the aggregation and gelation properties were gained through examination of the photophysical and material properties of selected gels, which are representative of the different modes of gelation. The synthesis of the gelators is highly modular and based on readily available amino acid building blocks, allowing the efficient and rapid diversification of these core structures and fine-tuning of gel properties.     

Green synthesis of silver nanoparticles by using eugenol and evaluation of antimicrobial potential

The importance of green synthesis was revealed with advantages such as: eliminating the use of expensive chemicals; consume less energy; and generate environmentally benign products. With this aim, silver nanoparticles (AgNPs) were synthesized by using isolated eugenol from clove extract. Its antimicrobial potential was determined on three different microorganisms. Clove was extracted and eugenol was isolated from this extract. Green synthesis was performed and an anti‐microbial study was performed. All extraction and isolation analyses were performed by high‐performance liquid chromatography (HPLC); identification and confirmation were achieved using liquid chromatography–mass spectrometry (LC–MS); and scanning electron microscopy was used for characterization. Both HPLC and LC–MS analyses showed that eugenol obtained purely synthesized AgNPs and 20‐25‐nm‐sized and homogeneous shaped particles seen in images. The antimicrobial effects of AgNPs at eight concentrations were determinated against Staphylococcus aureus, Escherichia coli and Candida albicans, and maximum inhibition zone diameters were found as 2.6 cm, 2.4 cm and 1.5 cm, respectively. The results of the antimicrobial study showed that eugenol as a biological material brought higher antimicrobial effect to AgNPs in comparison to the other materials found in the literature.     

Three distinct read-out modes for enzyme activity can operate in a semi-wet supramolecular hydrogel

Assays of hydrolytic enzyme activity, such as of glycosidases and phosphatase, as well as several proteases, using a semi-wet supramolecular hydrogel array composed of a glycosylated amino acetate are described. It has been demonstrated that the microcavity formed by gel fibrils is suitable to immobilize native enzymes without denaturation under semi-wet conditions, and thus the nanofiber has been rationally used as a sensing domain to monitor enzymatic reactions. By using a fluorogenic substrate, reducing the size of the hydrogel can significantly improve the problem of suppressed diffusion within the gel matrix thus making the hydrogel a promising semi-wet matrix for evaluating enzyme activity. Confocal laser scanning microscopy observations have shown that an environmentally sensitive fluorescent probe accumulates in the hydrophobic domain of the gel fiber and emits fluorescence more strongly upon hydrolytic cleavage of the substrate peptides. Not only a simple environmentally sensitive probe but also a FRET (fluorescence resonance energy transfer)-type read-out mode can be devised to analyze the enzymatic hydrolysis-triggered redistribution of the probe between the nanospace and the nanofiber to accomplish a more clearly distinguished enzyme assay. Thus, it is clear that three distinct read-out modes, that is, 1) fluorogenic substrates, 2) substrates bearing an environmentally sensitive probe, or 3) a substrate exhibiting FRET, can operate under the semi-wet hydrogel conditions used in these investigations. In addition, owing to the unique properties of the present supramolecular hydrogel in semi-wet conditions, that is, its phase-segregation properties and dynamics, the supramolecular substrate/enzyme array has successfully been used for high-throughput screening of single and multiple enzymes based on their activity, lysate analysis, and quantitative evaluation of inhibitor potency and selectivity.     

A novel green template for the synthesis of mesoporous silica

Mesoporous pure silicas and functionalized silica with a narrow pore size distribution centered at 3.8 nm were prepared by a novel template, amphiphilic dendritic polyglycerol. The resulting silica materials were characterized by electron microscopy; nitrogen adsorption; (1)H, (13)C, and (29)Si solid-state cross-polarization magic-angle spinning NMR spectroscopy. It was shown that the template could be completely removed from the pure and functionalized silica in an environmentally friendly way by means of a simple water extraction procedure. Furthermore, it was shown that these materials could be easily functionalized, for example, by employing aminopropyl groups. Thus, a new environmentally friendly pathway to this fascinating class of silica material has been opened.     

Green synthesis of silver nanoparticles using Thymus kotschyanus extract and evaluation of their antioxidant,antibacterial and cytotoxic effects

Present study used ecofriendly, cost efficient and easy method for synthesis of silver nanoparticles (Ag NPs) at the room temperature by Thymus Kotschyanus extract as reducing and capping agent. Various analytical technique including UV–Vis absorption spectroscopy determined presence of Ag NPs in the solution, the functional groups of Thymus Kotschyanus extract in the reduction and capping process of Ag NPs are approved by FT‐IR, crystallinity with the fcc plane approved from the X‐ray diffraction (XRD) pattern, energy dispersive spectroscopy (EDS) determined existence of elements in the sample, surface morphology, diverse shapes and size of present Ag NPs were showed by using scanning electron microscopy (SEM), atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM). Beginning and end destroy temperature of present silver nanoparticles were determined by thermal gravimetric spectroscopy (TGA). In addition, antibacterial, antioxidant and cytotoxicity properties of Ag NPs were studied. Agar disk and agar well diffusion are the methods to determined antibacterial properties of synthesized Ag NPs. Also MIC (Minimum Inhibitory Concentration) and MBC (Minimum Bactericidal Concentration) were recognized by macro broth dilution assay. DPPH free radical scavenging assay was used for antioxidant property and compare to butylated hydroxytoluene (BHT) as standard antioxidant that showed high antioxidant activity more than BHT. Synthesized Ag NPs have great cell viability in a dose depended manner and demonstrate that this method for synthesis silver nanoparticles provided nontoxic. The average diameter of synthesized Ag NPs was about 50–60 nm.     

Molecular structure of agarose chains in thermoreversible hydrogels revealed by means of a fluorescent probe technique

Thermoreversible hydrogels of agarose with both high and low molecular weights were studied by means of a fluorescence probe method using 1‐anilino‐8‐naphthalene sulfonic acid (ANS). The fluorescence spectra of ANS in agarose/water changed markedly with agarose concentration. Analysis of the spectra shows that this change is not due to a shift of the whole spectrum, but that there are two fluorescent components of ANS in addition to the fluorescence peak at 542 nm due to free ANS molecules in water. The fluorescence component at 461 nm is assumed to be from ANS intercalated within either a single 3₁ helix‐form agarose chain or nonpolar region produced by chemical defect, and the fluorescence component between 507 and 522 nm is assumed to be from ANS in aggregated regions of agarose chains having a loose helical structure. There is no doubt that a certain number of water molecules are included in the aggregated region. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 680–688, 2005     

Microwave-assisted synthesis of biofunctional and fluorescent silicon nanoparticles using proteins as hydrophilic ligands

Protective shell: A microwave-assisted method allows rapid production of biofunctional and fluorescent silicon nanoparticles (SiNPs), which can be used for cell labeling. Such SiNPs feature excellent aqueous dispersibility, are strongly fluorescent, storable, photostable, stable at different pH values, and biocompatible. The method opens new avenues for designing multifunctional SiNPs and related silicon nanostructures.     

Green synthesis of silver nanoparticles using green alga (Chlorella vulgaris) and its application for synthesis of quinolines derivatives

Nanoparticles have been used century ago but have regained their importance in recent years being simple, ecofriendly, pollutant free, nontoxic, low-cost approach, and due good atom economy. In this report, we have demonstrated the synthesis of silver nanoparticles using green algae (Chlorella vulgaris) which in turn was used for synthesis of biologically important quinolines. Algal extract was prepared and treated with silver nitrate solution for the synthesis of silver nanoparticles. Synthesized nanoparticles were characterized with the help of analytical tools like UV, FTIR, X-ray, and SEM and used as a catalyst for the synthesis of quinolines.     

Amino Acid Based Low‐Molecular‐Weight Ionogels as Efficient Dye‐Adsorbing Agents and Templates for the Synthesis of TiO2 Nanoparticles

The gelation of ionic liquids is attracting significant attention because of its large spectrum of applications across different disciplines. These ‘green solvents’ have been the solution to a number of common problems due to their eco‐friendly features. To expand their applications, the gelation of ionic liquids has been achieved by using amino acid‐based low‐molecular‐weight compounds. Variation of individual segments in the molecular skeleton of the gelators, which comprise the amino acid and the protecting groups at the N and C termini, led to an understanding of the structure–property correlation of the ionogelation process. An aromatic ring containing amino acid‐based molecules protected with a phenyl or cyclohexyl group at the N terminus were efficient in the gelation of ionic liquids. In the case of aliphatic amino acids, gelation was more prominent with a phenyl group as the N‐terminal protecting agent. The probable factors responsible for this supramolecular association of the gelators in ionic liquids have been studied with the help of field‐emission SEM, ¹H NMR, FTIR, and luminescence studies. It is the hydrophilic–lipophilic balance that needs to be optimized for a molecule to induce gelation of the green solvents. Interestingly, to maximize the benefits from using these green solvents, these ionogels have been employed as templates for the synthesis of uniform‐sized TiO₂ nanoparticles (25–30 nm). Furthermore, as a complement to their applications, ionogels serve as efficient adsorbents of both cationic and anionic dyes and were distinctly better relative to their organogel counterparts.     

Green synthesis and antibacterial effects of aqueous colloidal solutions of silver nanoparticles using clove eugenol

Silver nanoparticles were synthesized using clove extract (CE). Scanning transmission electron microscopy (STEM) revealed the morphology of the metallic Ag nanoparticles obtained via the clove extract synthesis (Ag NPs‐CE), which had a uniform distribution and average sizes varying from 10 nm to 100 nm. Fourier transform infra‐red (FTIR) spectroscopy showed that clove eugenol acts as a capping and reducing agent being adsorbed on the surface of Ag NPs‐CE, enabling their reduction from Ag⁺ and preventing their agglomeration. Formation of the Ag⁰ structure is also confirmed in the FTIR spectrum by the presence in the Ag NPs‐CE sample of the –C=O and –C=C vibrations at wavenumbers 1600 and 2915 cm^‐1, respectively. Antibacterial and antifungal tests using three strains of bacteria and one fungi strain showed that the Ag NPs‐CE performed better compared to pure clove extract (CE) sample.     

Flash chemistry: fast chemical synthesis by using microreactors

This concept article provides a brief outline of the concept of flash chemistry for carrying out extremely fast reactions in organic synthesis by using microreactors. Generation of highly reactive species is one of the key elements of flash chemistry. Another important element of flash chemistry is the control of extremely fast reactions to obtain the desired products selectively. Fast reactions are usually highly exothermic, and heat removal is an important factor in controlling such reactions. Heat transfer occurs very rapidly in microreactors by virtue of a large surface area per unit volume, making precise temperature control possible. Fast reactions often involve highly unstable intermediates, which decompose very quickly, making reaction control difficult. The residence time can be greatly reduced in microreactors, and this feature is quite effective in controlling such reactions. For extremely fast reactions, kinetics often cannot be used because of the lack of homogeneity of the reaction environment when they are conducted in conventional reactors such as flasks. Fast mixing using micromixers solves such problems. The concept of flash chemistry has been successfully applied to various organic reactions including a) highly exothermic reactions that are difficult to control in conventional reactors, b) reactions in which a reactive intermediate easily decomposes in conventional reactors, c) reactions in which undesired byproducts are produced in the subsequent reactions in conventional reactors, and d) reactions whose products easily decompose in conventional reactors. The concept of flash chemistry can be also applied to polymer synthesis. Cationic polymerization can be conducted with an excellent level of molecular-weight control and molecular-weight distribution control.     

利用聚(N-异丙基丙烯酰胺-co-丙烯酸)银纳米团簇构建宽pH响应范围的激发比率型荧光探针EI北大核心CSCD

以N-异丙基丙烯酰胺(NIPAM)和丙烯酸(AA)为pH敏感单体,合成聚(N-异丙基丙烯酰胺-co-丙烯酸),并以此作为模板制备了pH敏感的聚(N-异丙基丙烯酰胺-co-丙烯酸)银纳米团簇。结合了时间分辨荧光、透射电镜(TEM)、红外光谱(FT-IR)方法,对团簇的光学性能进行了研究。团簇的荧光对不同的pH具有灵敏的响应。团簇的荧光强度与pH在4.95~11.02的范围内呈线性关系,高pH(11.02)与低pH(4.95)相比,荧光强度降低约62.4%。同时,305 nm与453 nm处荧光激发强度的比值(I;/I;)与pH在5.94~11.02的宽范围内成线性关系,利用该荧光比率可以对pH进行定量检测。