High-efficiency fluorescent coordination polymer nanoparticles co-doped with Ce3+/Tb3+ ions for curcumin detection.

Curcumin (Cur) possesses diverse biological and pharmacologic effects. It is widely used as a food additive and therapeutic medicine. A study to determine a sensitive detection method for Cur is necessary and meaningful. In this work, double rare earth ions co-doped fluorescent coordination polymer nanoparticles (CPNPs) were developed for the Cur detection. The CPNPs were synthesized by using adenosine monophosphate (AMP) as bridge ligands via coordination self-assembly with Ce3+ and Tb3+. The AMP-Ce/Tb CPNPs exhibited the characteristic green fluorescence of Tb3+ and had high luminescence efficiency. Under the optimal conditions, the fluorescence intensity of AMP-Ce/Tb CPNPs could be significantly quenched by Cur. The fluorescence quenching extent at λex/λem of 300 nm/544 nm showed a good linear relationship with the Cur concentration in the range of 10 to 1000 nM. The detection limit was as low as 8.0 nM (S/N = 3). This method was successfully applied to the determination of Cur in real samples with satisfactory results. The luminescence mechanism of AMP-Ce/Tb CPNPs and the fluorescence quenching mechanism of the CPNPs by Cur were both examined.

Diphenylalanine Deposition by Dip-Coating from Acidic Solutions: Fibers and Closed Homogeneous Films.

A simple but precisely controllable strategy by molecular assembly that enables the construction of biomaterials is always in the development. Dip-coating deposition of diphenylalanine (FF) onto planar solid substrates from aqueous acidic (acetic, propanoic, formic, and HCl) solutions is studied as a function of the process control parameters (deposition speed, initial concentration of FF and acids, and external gas flow). The results are studied by optical microscopy, AFM, and ellipsometry. For low acidity and low FF concentrations, FF forms microfibers, nanofibers, or stripes of fiber aggregates. For higher acidity and FF concentrations, closed films of FF of remarkably smooth surfaces are found. The thickness of these films can be well-controlled by the FF concentration and the deposition speed and explained by the evaporation regime. These unusual results provide new possibilities to fabricate more abundant structures by a simple strategy and develop a candidate for biological membrane areas.

Surfactant-Assisted Assembly of Dipeptide Forming a Broom-like Structure.

Understanding the influence of surfactants on the assembly of peptides has a considerable practical motivation. In this paper, we systematically study the anionic surfactant-assisted assembly of diphenylalanine (FF). FF forms broom-like structures in a concentration of sodium cholate (NaC) around the CMC, and assembles into linear and unidirectional rods in the presence of low and high surfactant concentrations. FF's improved hydrogen bonding and controlled assembly rates are appropriate for other anionic surfactants. At this stage, the use of FF as the simplest protein consequence can be helpful in the investigation of further protein-surfactant interactions.

Covalent-reaction-induced interfacial assembly to transform doxorubicin into nanophotomedicine with highly enhanced anticancer efficiency.

Herein, we show that a molecular assembly offers tremendous opportunities of affording existing building units with new physicochemical properties, holding promise in wide applications. Herein, we develop a facile covalent assembly using a natural occurring linker, genipin, to efficiently transform a traditional chemo drug, doxorubicin, into a nanophotomedicine. A possible mechanism is proposed, in which doxorubicin reacts with genipin through covalent bonding to produce poorly soluble units, which further form nuclei and mediate the interfacial assembly to generate uniform nanoparticles. Such assembled nanophotomedicine shows remarkably enhanced singlet oxygen generation ability (about 1000 folds), leading to a much higher photodynamic activity. Moreover, this self-carried nanodrug exhibits adjustable size, excellent colloidal stability, high capacity and preferable endocytosis. These favorable features lead to greatly improved anticancer efficiency under light at the same dosage, compared to that of pure doxorubin. We believe this study brings a new dimension to develop advanced drug delivery systems by molecular assembly.

Transformation of Dipeptide-Based Organogels into Chiral Crystals by Cryogenic Treatment.

Controlled molecular assembly is an important approach for the synthesis of single-component materials with diverse functions. Unlike traditional heat treatment or solvent modulation, cryogenic treatment at 77 K enabled the tunable transition of a self-assembled diphenylalanine organogel into a hexagonal crystal. Under these conditions, the assembled molecules undergo an internal rearrangement in the solid state to form a well-defined chiral crystal structure. Moreover, these assemblies exhibit enhanced emission. This strategy for the synthesis of single-component supramolecular assemblies can create new functions by manipulating phase transitions.

Synthesis of Peptide-Based Hybrid Nanobelts with Enhanced Color Emission by Heat Treatment or Water Induction.

We demonstrate that an inorganic lanthanide ion (Tb(3+)) or organic dye molecules were encapsulated in situ into diphenylalanine (FF) organogels by a general, simple, and efficient co-assembly process, which generated peptide-based hybrid nanobelts with a range of colored emissions. In the presence of a photosensitizer (salicylic acid), the organogel can serve as an excellent molecular-donor scaffold to investigate FRET to Tb(3+). More importantly, heat treatment or water induction instigated a morphology transition from nanofibers to nanobelts, after which the participation of guest molecules in the FF assembly was promoted and the stability and photoluminescence emission of the composite organogels were enhanced.

Hydrogels as the plant culture substrates: A review.

A class of hydrophilic polymers known as "hydrogels" have extensive water content and three-dimensional crosslinked networks. Since the old period, they have been utilized as plant culture substrates to get around the drawbacks of hydroponics and soil. Numerous hydrogels, particularly polysaccharides with exceptional stability, high clarity, and low cost can be employed as plant substrates. Although numerous novel and functionalized hydrogels might assist in overcoming the drawbacks of conventional media and giving them more functions, the existing hydrogel-based plant growth substrates rarely benefit from the developments of gels in the previous few decades. Prospects include the development of new conduction techniques, the creation of potential new hydrogels, and the functionalization of the hydrogel as plant culture substrates.

CuInS2 quantum dots as a near-infrared fluorescent probe for detecting thrombin in human serum.

This paper describes a novel, simple method for the highly sensitive and selective detection of thrombin using fibrinogen (Fib) and CuInS(2) quantum dots (QDs) as biosensing probes. Water-soluble near-infrared CuInS(2) QDs capped by mercaptopropionic acid (MPA) were directly synthesized by a hydrothermal method. Addition of fibrinogen to the CuInS(2) QDs solution led to the formation of a Fib-CuInS(2) QDs complex through electrostatic interactions and hydrogen bonding, and resulting in the enhancement of photoluminescence (PL) intensity and a red shift of the PL peak. Once thrombin was introduced into the Fib-CuInS(2) QDs system, it catalyzed the polymerization of the free and conjugated fibrinogen species to form insoluble fibrillar fibrin-CuInS(2) QDs agglutinates. After centrifugation, the PL intensity of the supernatants decreased upon increasing the concentration of thrombin. This Fib-CuInS(2) QDs probe provided a highly specific selectivity and a linear detection of thrombin in the range of 6.7 × 10(-11) to 3.9 × 10(-7) mol L(-1) with a detection limit (LOD) of about 8.7 × 10(-12) mol L(-1), and realized the thrombin detection in human serum samples directly. Compared with those obtained by using other nanomaterials and aptamer-based detection methods, this approach provided a lower LOD for thrombin detection. The proposed approach provides a simple and fast-responding procedure, which might hold a promising potential for application in the diagnosis of diseases associated with coagulation abnormalities and cancers.

Controlled-Alignment Patterns of Dipeptide Micro- and Nanofibers.

Ordered assemblies of the peptide diphenylalanine (FF) are produced and deposited on planar substrates. The FF aggregate growth is achieved through precipitation from aqueous ammonia solutions induced by solvent evaporation. The applied dip-coating technique confines the FF assembly growth to a narrow zone near the three-phase contact. The growth was observed online by optical microscopy and was investigated systematically as a function of the process parameters. Depending on the external gas flow (to influence solvent evaporation), the withdrawal speed, the initial FF, and the initial ammonia concentrations, FF forms long, straight, and rigid microfibers and/or shorter, curved nanofibers. Under certain process conditions, the FF fibers can also aggregate into stripes. These can be deposited as large arrays of uniform stripes with regular widths and spacings. Scenarios leading to the various types of fibers and the stripe formation are presented and discussed in view of the experimental findings.

Highly sensitive detection of dopamine based on gold nanoflowers enhanced-Tb(III) fluorescence.

We developed a trace level detection method for dopamine (DA) based on the metal-enhanced fluorescence (MEF) effect of gold nanoflowers (AuNFs). AuNFs prepared were excellent enhancement fluorescence substrates due to their unique morphology with rich edges and sharp quoins. DA was the target analyte and also as a bridge reagent that could regulate the distance between AuNFs and Tb3+. The characteristic fluorescence of Tb3+ was enhanced significantly through the synergistic effect between the luminescence sensitized by DA and the MEF caused by AuNFs. Under the optimum experimental conditions, the fluorescence intensity of Tb3+ at 545 nm demonstrated very significant sensing ability against DA concentration and showed a good linear relationship in the range of 0.80-300 nM and the limit of detection was 0.21 nM (S/N = 3). The proposed method was also validated in serum samples and the dopamine hydrochloride injection samples with satisfactory results.

Co-assembled gold nanorod@tripeptide core-shell nanospheres for aqueous Hg2+ removal.

The construction of peptide and metal nanoparticles hybrid is attractive to explore their synergistic properties and applications extensively. However, it remains a challenge to fabricate a well-defined and size-controllable short peptide/Au nanoparticles hybrid. Here, we report a facile and flexible co-assembly strategy for the construction of tripeptide coated Au nanorods (AuNRs). The tripeptide (Phe-Phe-Cys, FFC) grows via covalently crosslinking to form spheres. The size of the core@shell nanospheres can be controlled by modulating the amount or size of AuNRs. Especially, the concentration of AuNRs fixes the amount of seeds, which further affect the local concentration of FFC on the surface of AuNRs seed, leading to a narrower diameter of hybrid compared to FFC spheres. Moreover, owing to their synergistic effects, this hybrid exhibits a good adsorption capacity of Hg2+ from aqueous solutions by electrostatic interaction and forming into Au/Hg amalgam. This strategy could be extended to the fabrication of other biomolecules and metal nanoparticle hybrids with diverse functions.

Unidirectional Branching Growth of Dipeptide Single Crystals for Remote Light Multiplication and Collection.

Herein, we report on the unidirectional branched assembly of diphenylalanine dipeptide through a one-step rapid evaporation process. Large numbers of crystalline tubular branches with smooth surfaces are developed from a hexagonal solid microrod mimicking a "Christmas tree". Density functional theory suggests the formation of tubular diphenylalanine aggregates with cis isomers. The diphenylalanine branched assembly shows good optical waveguide properties that can transmit light homogeneously along the crystal fibers as well as harvest light from the tips of branches to the microrod terminals. These findings hold importance in the development of bioinspired optical fibers for information transmission in a microscale.

Facile Co-Assembly of a Dipeptide-Based Organogel toward Efficient Triplet-Triplet Annihilation Photonic Upconversion.

By one-step molecular co-assembly, a diphenylalanine-based photonic upconversion organogel was constructed within 20 seconds. Impressively, such an assembled system exhibits green-to-blue triplet-triplet annihilation upconversion with a relative quantum yield of 12 % even under ambient conditions.

Gelatin-Assisted Synthesis of Vaterite Nanoparticles with Higher Surface Area and Porosity as Anticancer Drug Containers In Vitro.

The fabrication of porous vaterite nanoparticles with improved stability in aqueous solution and higher surface area is still a challenge. Here, inspired by the formation of mesoporous silica nanoparticles, we have taken gelatin as a "surfactant" to assist in the formation of vaterite nanoparticles and help create pores on their surface due to the distinct solubility and molecular morphology of gelatin in different solutions. The formation mechanism of vaterite nanoparticles and pores was investigated in detail, indicating that the existence of gelatin has a crucial effect on the formation of vaterite nanoparticles and their stability. Meanwhile, the elution of gelatin from vaterite nanoparticles via washing with hot water accounts for their higher surface area. Their application as an anticancer drug (doxorubicin) carrier after folic acid treatment was also investigated. These nanoparticles have advantages for drug release due to their pH-sensitive structure and also have enhanced cytotoxicity toward cancer cells due to the folic acid modification.