Microstructure design of CTAC:FA and BTAC:FA lamellar gels for optimized rheological performance utilizing automated formulation platform.

OBJECTIVES: The main objective of this paper was to optimize hair conditioner performance through variation of composition utilizing automated cosmetic formulation platform and advanced characterization techniques as well as develop understanding of how performance (wet combing and wet lubrication) of hair conditioner is affected by its rheology (i.e. yield stress) and controlled breakdown of the formulations (dilution). The experimental results show that yield stress greatly impacts rheology, stability and performance of the lamellar gels for hair conditioning. METHODS: All samples were prepared on the Chemspeed Flex Formax. A mechanical rheometer was used to measure bulk viscosity and yield stress in each sample. Dia-stron tensile tester was used to measure the lamellar gels ability to reduce combing force. Potential stronger lamellar gel network formation in the formed lamellar gels potentially leads to higher yield stress exhibited. Viscosity values were also measured after a controlled breakdown (i.e. dilution) of each sample. This was also carried out using a mechanical rheometer. RESULTS: Yield stress of the formulations was engineered through composition variation and was recorded in each system. The highest yield stress value is 251.179 Pa at a BTAC/CA ratio of 6:10, and the lowest yield stress is 50.14 Pa at a BTAC/CA ratio of 6:5. The highest yield stress value is 50.14 Pa at a CTAC/CA ratio of 6:10, and the lowest yield stress is 19.98 Pa at a CTAC/CA ratio of 2:10. The highest overall yield stress values can also be observed in the BTAC/CA system, whereas the CTAC/CA system has relatively lower yield stress values. Dilution of each formulation caused a breakdown in viscosity of each formulation with the formulations with highest yield stress maintaining higher viscosity than the other formulations. The formulations with highest yield stress in each system which also maintains the highest dilution viscosity (6% BTAC/10% CA and 6% CTAC/10% CA) have the best effect on reducing overall combing force, that is from dry hair tress to wet hair tress and after product is rinsed off. At a BTAC/CA system of ratio 6:5, there is an 89% reduction in combing force and a 95% reduction in combing force in the BTAC/CA system of ratio 6:10. At a CTAC/CA system of ratio 2:10, there is a 65% reduction in combing force and a 88% reduction in combing force in the CTAC/CA system of ratio 6:10. A 'conditioned' soft feel was observed on each hair tress as the sample was applied and after it was rinsed off. CONCLUSIONS: The overall performance of the lamellar gels for hair conditioning can be engineered through optimization of the formulation microstructure and formulation microstructure breakdown on dilution.

OBJECTIF: L'objectif principal de ce document est d'optimiser les performances des après-shampooing grâce à la variation de sa composition en utilisant une plateforme de formulation cosmétique automatisée et des techniques de caractérisation avancées, ainsi qu'en comprenant mieux comment les performances (peignage humide et lubrification humide) de l'après-shampooing sont affectées par sa rhéologie (c.-à-d. limite élastique) et répartition contrôlée des formulations (dilution). Les résultats expérimentaux montrent que la limite d'élasticité a un impact important sur la rhéologie, la stabilité et les performances des gels lamellaires pour le conditionnement des cheveux. MÉTHODÉS: Tous les échantillons ont été préparés sur le Chemspeed Flex Formax. Un rhéomètre mécanique a été utilisé pour mesurer la viscosité en vrac et la limite élastique dans chaque échantillon. Un testeur de traction Dia-stron a été utilisé pour mesurer la capacité des gels lamellaires à réduire la force de peignage. La formation d'un réseau de gel lamellaire potentiellement plus fort dans les gels lamellaires formés conduit potentiellement à une limite d'élasticité plus élevée. Les valeurs de viscosité ont également été mesurées après une dilution de chaque échantillon. Cela a également été réalisé à l'aide d'un rhéomètre mécanique. RÉSULTATS: La limite d'élasticité des formulations a été modifiée par variation de la composition et a été enregistrée dans chaque système. La limite d'élasticité la plus élevée est de 251,179 Pa à un rapport BTAC/CA de 6,10 et la limite d'élasticité la plus basse est 50,14 Pa à un rapport BTAC/CA de 6: 5. La valeur de limite d'élasticité la plus élevée est de 50,14 Pa à un rapport CTAC/CA de 6,10 et la contrainte d'élasticité la plus basse est de 19,98 Pa à un rapport CTAC/CA de 2:10. Les valeurs globales de contrainte d'écoulement les plus élevées peuvent également être observées dans le système BTAC/CA tandis que le système CTAC/CA a des valeurs de contrainte d'écoulement relativement plus faibles. La dilution de chaque formulation a provoqué une dégradation de la viscosité de chaque formulation, les formulations ayant la limite d'élasticité la plus élevée conservant une viscosité plus élevée que les autres formulations. Les formulations avec la limite d'élasticité la plus élevée dans chaque système qui maintient également la viscosité de dilution la plus élevée (6% BTAC/10% CA et 6% CTAC/10% CA) a le meilleur effet sur la réduction de la force de peignage globale, c'est-à-dire des cheveux secs aux cheveux mouillés tressées et après que le produit soit rincé. Dans un système BTAC/CA de rapport 6: 5, il y a une réduction de 89% de la force de peignage et une réduction de 95% de la force de peignage dans le système BTAC/CA de rapport 6:10. Dans un système CTAC/CA de rapport 2:10, il y a une réduction de 65% de la force de peignage et une réduction de 88% de la force de peignage dans le système CTAC/CA de rapport 6:10. Une sensation de douceur a été observée sur chaque tresse lors de l'application de l'échantillon et après le rinçage. CONCLUSION: Les performances globales des gels lamellaires pour le conditionnement des cheveux peuvent être conçues par l'optimisation de la microstructure de formulation et la décomposition de la microstructure de formulation lors de la dilution.

A label-free PFP-based photoelectrochemical biosensor for highly sensitive detection of PARP-1 activity.

Poly(ADP-ribose) polymerase-1 (PARP-1), as an original tumor marker, has aroused wide attention in recent years. However, only a few researches have been done for PARP-1 activity detection because PARP-1 is lack of optical or electrochemical property. In this work, a label-free and high-sensitive photoelectrochemical (PEC) biosensor for PARP-1 activity detection based on poly[9,9-bis(6'-N,N,N-trimethylammonium)hexyl]fluorenylene phenylene (PFP) has been designed. To the best of our knowledge, it is the first time that PEC has been used to monitor PARP-1 activity. PARP-1 were activated under the function of activated dsDNA, as a result, branched polymers of ADP-ribose (PAR) with plentiful negative charge were formed in the presence of nicotinamide adenine dinucleotide (NAD+). Subsequently, positively charged PFP with good photoelectrochemical properties, were absorbed on PAR via electrostatic interaction. High photocurrent was produced under light induction, which was depended on the PARP-1 activity. The biosensor has a wide linear range from 0.01 to 2 U with a detection limit of 0.007 U. The strategy has been applied in breast and ovarian cancer cells to detection PARP-1 activity with approving results, which signifies that it is a promising tool for clinical diagnosis.

Precise Proton Mapping near Ionic Micellar Membranes with Fluorescent Photoinduced-Electron-Transfer Sensors.

One of the challenges for fluorescent sensors is to reduce their target environment size from a micrometer scale, such as biological cells, to a nanometer scale. Proton maps near membranes are of importance in bioenergetics and are the first goal in nanometer-scale analysis with fluorescent sensors. Thirty-three fluorescent photoinduced-electron-transfer pH sensors bearing an environment-sensitive benzofurazan fluorophore and having different hydrophobicity/hydrophilicity and hydrogen-bonding abilities were prepared. These sensors were scattered in nanospaces associated with anionic and cationic micelles as model membranes to indicate proton availability and polarity in local spaces. Gathering the data from the sensors allowed the successful drawing of proton maps near anionic and cationic micelles, in which electrostatic attraction/repulsion of protons by the charged head groups of micelles and dielectric suppression of protons were clearly observed.

Interactions of miltefosine with erythrocyte membrane proteins compared to those of ionic surfactants.

For miltefosine (MIL), a zwitterionic alkylphospholipid approved for leishmaniasis treatment, the mechanism of action is not well established. Electron paramagnetic resonance (EPR) spectroscopy has indicated that the interaction of MIL with membrane proteins has similarities to that of ionic surfactants. A general concern about leishmanicides is their high hemolytic potential, so we decided to compare the interactions of MIL and three ionic surfactants with the erythrocyte membrane. Measurements with two different spin labels indicated that the surfactants sodium dodecyl sulfate (SDS, anionic), cetyltrimethylammonium chloride (CTAC, cationic) and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS, zwitterionic) as well as MIL increase the dynamics of erythrocyte membrane proteins in a concentration-dependent manner. SDS produced the smallest increases in protein dynamics and was also the least hemolytic for measurements in PBS and in whole blood. Spin label EPR measurements performed directly in the blood plasma detected increased albumin stiffness caused by 2.5 mM SDS due to electrostatic/hydrophobic interactions. For 10 mM concentrations of the compounds, the EPR spectra showed a fraction of albumin with greater mobility and another with the same as that of the untreated plasma. The zwitterionic compounds MIL and HPS did not present significant differences in this study.

N-Terminus Alkylation of Vancomycin: Ligand Binding Affinity, Antimicrobial Activity, and Site-Specific Nature of Quaternary Trimethylammonium Salt Modification.

A series of vancomycin derivatives alkylated at the N-terminus amine were synthesized, including those that contain quaternary trimethylammonium salts either directly at the terminal amine site or with an intervening three-carbon spacer. The examination of their properties provides important comparisons with a C-terminus trimethylammonium salt modification that we recently found to improve the antimicrobial potency of vancomycin analogues through an added mechanism of action. The N-terminus modifications disclosed herein were well-tolerated, minimally altering model ligand binding affinities (d-Ala-d-Ala) and antimicrobial activity, but did not induce membrane permeabilization that was observed with a similar C-terminus modification. The results indicate that our earlier observations with the C-terminus modification are sensitive to the site as well as structure of the trimethylammonium salt modification and are not simply the result of nonspecific effects derived from introduction of a cationic charge.

Flow-Injection Chemiluminescence Method for Sensitive Determination of Ascorbic Acid in Fruit Juices and Pharmaceutical Samples Using a Luminol-Cetyltrimethylammonium Chloride Reversed Micelle System.

A highly sensitive flow-injection (FI) method was developed for the determination of ascorbic acid using chemiluminescence (CL) based detection. This method involved the following processes: (1) reduction of tetrachloroaurate(III) in hydrochloric acid with ascorbic acid; (2) on-line extraction of the residual Au(III) with rhodamine B from the aqueous hydrochloric acid solution into toluene, followed by the separation of the Au(III)-containing organic phase from the aqueous phase through a microporous Teflon membrane in the flow system; and (3) the measurement of CL produced in a flow cell upon mixing of the extract stream of Au(III) in toluene with luminol in the reversed micellar medium of cetyltrimethylammonium chloride-water in 1-hexanol-cyclohexane, which was injected into a CL reagent stream. In this procedure, a reduction in the CL intensity occurred due to the addition of ascorbic acid to the Au(III) solution. The CL signal of Au(III) decreased with increasing concentration of ascorbic acid in the aqueous sample solution. The proposed procedure allowed the indirect quantitative determination of ascorbic acid in the range of 1.0 × 10-12 to 1.0 × 10-7 M with a correlation coefficient of 0.987 and relative standard deviation of 2.1% (n = 6) at 1.0 × 10-9 M. The proposed FI-CL methodology was successfully applied for quantitative determination of ascorbic acid in fruit juices and pharmaceutical samples.

Gold-chlorophyll a-hybrid nanoparticles and chlorophyll a/cetyltrimethylammonium chloride self-assembled-suprastructures as novel carriers for chlorophyll a delivery in water medium: Photoactivity and photostability.

The stability of Chlorophyll a in water during prolonged exposure, at room temperature, to a neon lamp has been investigated by means of UV-vis and fluorescence spectroscopies. In addition, the Chlorophyll a (photo)stability evaluation in presence of suitable carriers has been performed in order to investigate its reactivity under the same conditions, for possible and future applications in Antimicrobial Photodynamic Therapy. Cetyltrimethylammonium chloride was chosen to solubilize Chlorophyll a in water. While, cetyltrimethylammonium chloride-capped gold nanoparticles offer a great opportunity because combine the Chlorophyll a action, used as a photosensitizer in Antimicrobial Photodynamic Therapy, with gold nanoparticles effect used in photothermal therapy. Indeed, the latter ones have exhibited an interesting rise of temperature if irradiated with visible light. Overall, both examined systems, cetyltrimethylammonium chloride/Chlorophyll a and gold nanoparticles/Chlorophyll a, were able to induce the Reactive Oxygen Species formation fundamental for a potential application in Antimicrobial Photodynamic Therapy.

Effect of surfactant species and electrophoretic medium composition on the electrophoretic behavior of neutral and water-insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis.

We have recently demonstrated the separation of neutral and water-insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis (NACZE) using a cationic surfactant of cetyltrimethylammonium chloride (CTAC). In this study, eight ionic surfactants were investigated for the separation of four synthetic polymers (polystyrene, polymethylmethacrylates, polybutadiene, and polycarbonate); only three surfactants (CTAC, dimethyldioctadecylammonium bromide, and sodium dodecylsulfate) caused their separation. The order of the interaction between the polymers and the surfactants depended on both the surfactant species and the composition of the electrophoretic medium. Their investigation revealed that the separation is majorly affected by the hydrophobic interactions between the polymers and the ionic surfactants. In addition, the electrophoretic behavior of polycarbonate suggested that electrostatic interaction also affects the selectivity of the polymers.

Alkyl(C16, C18, C22)trimethylammonium-Based Herbicidal Ionic Liquids.

In the framework of this study a synthesis methodology and characterization of long alkyl herbicidal ionic liquids (HILs) based on four commonly used herbicides (2,4-D, MCPA, MCPP, and dicamba) are presented. New HILs were obtained with high efficiency (>95%) using an acid-base reaction between herbicidal acids and hexadecyltrimethylammonium, octadecyltrimethylammonium, and behenyltrimethylammonium hydroxides in alcoholic medium. Among all synthesized salts, only three compounds comprising the MCPP anion were liquids at room temperature. Subsequently, the influence of both the alkyl chain length and the anion structure on their physicochemical properties (thermal decomposition profiles, solubility in 10 representative solvents, surface activity, density, viscosity, and refractive index) was determined. All HILs exhibited high thermal stability as well as surface activity; however, their solubility notably depended on both the length of the carbon chain and the structure of the anion. The herbicidal efficacy of the obtained salts was tested in greenhouse and field experiments. Greenhouse testing performed on common lambsquarters (Chenopodium album L.) and flixweed (Descurainia sophia L.) as test plants indicated that HILs were characterized by similar or higher efficacy compared to commercial herbicides. The results of field trials confirmed the high activity of HILs, particularly those containing phenoxyacids as anions (MCPA, 2,4-D, and MCPP).

Application of TiO2-organobentonite modified by cetyltrimethylammonium chloride photocatalyst and polyaluminum chloride coagulant for pretreatment of aging landfill leachate.

This study investigated the treatment performance for aging leachate containing refractory organic pollutants by TiO2-organobentonite photocatalyst combined with polyaluminum chloride (PAC) coagulant. TiO2 was immobilized on organobentonite granules as a supporter modified by cetyltrimethylammonium chloride (CTAC). The prepared catalysts were characterized by ESEM, FTIR, and XRD analysis, which showed that TiO2-organobentonite catalyst had uniform coating of TiO2 on support. Chemical oxygen demand (COD) and NH3-N removal rates by combination of TiO2-CTAC2.0 photocatalysis and PAC coagulation were evaluated, optimized, and compared to that by either treatment alone, with respect to TiO2-CTAC2.0 dose, photocatalytic contact time, pH, and PAC dose. Furthermore, higher removal rates (COD 80 %; NH3-N 46 %) were achieved by response surface methodology (RSM) when TiO2-CTAC2.0 photocatalysis was followed by PAC coagulation at optimized conditions. The optimized experimental conditions were TiO2-CTAC2.0 dosage of 5.09 g/L, at pH 5.53, photocatalytic contact time for 180 min, and PAC dosage of 1062 mg/L.

A study of molecular adsorption of a cationic surfactant on complex surfaces with atomic force microscopy.

The study of molecular adsorption on solid surfaces is of broad interest. However, so far the study has been restricted to idealized flat smooth rigid surfaces which are rarely the case in real world applications. Here we describe a study of molecular adsorption on a complex surface of the submicron fibers of a fibrous membrane of regenerated cellulose in aqueous media. We use a cationic surfactant, cetyltrimethylammonium chloride (CTAC), as the adsorbing molecule. We study the equilibrium adsorption of CTAC molecules on the same area of the fibers by sequentially immersing the membrane in pure water, 1 mM and then a 20 mM solution of CTAC. Atomic force microscopy (AFM) is applied to study the adsorption. The force-volume mode is used to record the force-deformation curves of the adsorbed molecules on the fiber surface. We suggest a model to separate the forces due to the adsorbed molecules from the elastic deformation of the fiber. Interestingly, knowledge of the surface geometry is not required in this model provided the surface is made of elastically homogeneous material. Different models are investigated to estimate the amount of the adsorbed molecules based on the obtained force curves. The exponential steric repulsion model fits the force data the best. The amount of the adsorbed surfactant molecules and its dependence on the concentration are found to be reasonable compared to the data previously measured by means of Raman scattering done on a flat surface of silica.

New pressure-assisted sweeping on-line preconcentration for highly polar environmentally relevant nitrosamines: Part 2. Cationic and anionic surfactants with zero-flow capillaries.

We recently introduced a pressure-assisted sweeping-reversed migration-EKC (RM-EKC) method for preconcentration of neutral polar N-nitrosamines with low affinity for the micellar phase. The type of surfactant and phase ratio are dominant factors in dictating the magnitude of interactions between analyte and micellar phase, thus four surfactants (anionic and cationic) with a range of functionalities (SDS, ammonium perfluorooctanoate (APFO), bile salts, and cetyltrimethylammonium chloride (CTAC)) were evaluated for sweeping-RM-EKC of highly polar N-nitrosamines. All gave acceptable results for sweeping-RM-EKC when used in high concentrations (≥200 mM) with low EOF. While no single surfactant was superior by all measures, all but the bile salts had useful performance characteristics. APFO showed the narrowest peak widths and highest number of theoretical plates, though two species co-migrated at all concentrations (25-300 mM); SDS and the cationic surfactant CTAC also showed good separation characteristics and could resolve all peaks, but CTAC had wider separation window. Various types of capillaries coated for EOF control were compared for use with anionic and cationic surfactants. A commercial zero-EOF capillary coated with a polymer bearing sulfonic acid functional groups showed superior EOF suppression and reproducibility of migration time with all surfactants.

Amphiphile micelle structures in the protic ionic liquid ethylammonium nitrate and water.

Micelles formed by amphiphiles in a protic ionic liquid (PIL), ethylammonium nitrate (EAN), were investigated using synchrotron small-angle X-ray scattering and contrasted with those that formed in water. The amphiphiles studied were cationic hexadecyltrimethylammonium chloride (CTAC) and hexadecylpyridinium bromide (HDPB) and nonionic poly(oxyethylene) (10) oleyl ether (Brij 97) and Pluronic ethylene oxide-propylene oxide-ethylene oxide block copolymer (P123). The scattering patterns were analyzed using spherical, core-shell, and cylindrical scattering models. The apparent micelle shape and size of the surfactants and the block copolymer in the PIL have been reported. At low amphiphile concentrations (<10 wt %) spherical micelles were preferentially formed for all the amphiphiles in EAN. The micelles formed by the two cationic amphiphiles in EAN and water were similar, though different scattering models were required predominantly due to the ionic nature of EAN. The two nonionic amphiphiles formed micelles with similar core radii in water and in EAN. However, the micelle shells composed of ethylene oxide groups fitted to a significantly thicker layer in water compared to EAN. At high concentrations (>10 wt %) in EAN and water, there was a preference for cylindrical micelles for CTAC, HDPB, and Brij 97; however, the P123 micelles remained spherical.

Interaction of bovine serum albumin (BSA) with novel gemini surfactants studied by synchrotron radiation scattering (SR-SAXS), circular dichroism (CD), and nuclear magnetic resonance (NMR).

The interaction of three dicationic (gemini) surfactants-3,3'-[1,6-(2,5-dioxahexane)]bis(1-dodecylimidazolium) chloride (oxyC2), 3,3'-[1,16-(2,15-dioxahexadecane)]bis(1-dodecylimidazolium) chloride (oxyC12), and 1,4-bis(butane)imidazole-1-yl-3-dodecylimidazolium chloride (C4)--with bovine serum albumin (BSA) has been studied by the use of small-angle X-ray scattering (SAXS), circular dichroism (CD), and (1)H nuclear magnetic resonance diffusometry. The results of CD studies show that the conformation of BSA was changed dramatically in the presence of all studied surfactants. The greater decrease (from 56 to 24%) in the α-helical structure of BSA was observed for oxyC2 surfactant. The radii of gyration estimated from SAXS data varied between 3 and 26 nm for the BSA/oxyC2 and BSA/oxyC12 systems. The hydrodynamic radius of the BSA/surfactant system estimated from NMR diffusometry varies between 5 and 11 nm for BSA/oxyC2 and 5 and 8 nm for BSA/oxyC12.

MoS2 nanocrystals confined in a DNA matrix exhibiting energy transfer.

We report the wet chemical synthesis of MoS2 nanocrystals (NCs), a transition-metal dichalcogenide, using DNA as a host matrix. As evidenced from transmission electron microscopy (TEM), the NCs are highly crystalline, with an average diameter of ~5 nm. Ultraviolet-visible (UV-vis) absorption studies along with band gap calculations confirm that NCs are in quantum confinement. A prominent red shift of the optical absorption bands has been observed upon formation of the thin film using hexadecyltrimethylammonium chloride (CTAC), i.e., in the case of MoS2@DNA-CTAC. In the thin film, strong electron-phonon coupling arises because of the resonance effect, which is reflected from the emergence of intense first-, second-, and third-order Raman peaks, whenever excited with the 488 nm line. We have established that our as-synthesized MoS2 NCs quench the fluorescence of a well-known DNA minor groove binding probe, Hoechst 33258. Unprecedented fluorescence quenching (94%) of donor (Hoechst 33258) emission and efficient energy transfer (89%) between Hoechst 33258 and MoS2 NCs (acceptor) are obtained. The donor-acceptor distance of these conjugates has been described by a Förster resonance energy transfer (FRET)-based model. Furthermore, employing a statistical method, we have estimated the probability of the distance distribution between the donor and acceptor. We believe that the study described herein may enable substantial advances in fields of optoelectronics, photovoltaics, catalysis, and many others.

Enthalpic signature of methonium desolvation revealed in a synthetic host-guest system based on cucurbit[7]uril.

Methonium (N(+)Me3) is an organic cation widely distributed in biological systems. As an organic cation, the binding of methonium to protein receptors requires the removal of a positive charge from water. The appearance of methonium in biological transmitters and receptors seems at odds with the large unfavorable desolvation free energy reported for tetramethylammonium (TMA(+)), a frequently utilized surrogate of methonium. Here, we report an experimental system that facilitates incremental internalization of methonium within the molecular cavity of cucurbit[7]uril (CB[7]). Using a combination of experimental and computational studies, we show that the transfer of methonium from bulk water (partially solvated methonium state) to the CB[7] cavity (mostly desolvated methonium state) is accompanied by a remarkably small desolvation enthalpy of just 0.5 ± 0.3 kcal·mol(-1), a value significantly less endothermic than those values suggested from gas-phase model studies. Our results are in accord with neutron scattering measurements that suggest methonium produces only a minimal perturbation in the bulk water structure, which highlights the limitations of gas-phase models. More surprisingly, the incremental withdrawal of the methonium surface from water produces a nonmonotonic response in desolvation enthalpy. A partially desolvated state exists, in which a portion of the methonium group remains exposed to solvent. This structure incurs an increased enthalpic penalty of ~3 kcal·mol(-1) compared to other solvation states. We attribute this observation to the pre-encapsulation dewetting of the methonium surface. Together, our results offer a rationale for the wide distribution of methonium in a biological context and suggest limitations to computational estimates of binding affinities based on simple parametrization of solvent-accessible surface area.

Highly charged cyanine fluorophores for trafficking scaffold degradation.

Biodegradable scaffolds have been extensively used in the field of tissue engineering and regenerative medicine. However, noninvasive monitoring of in vivo scaffold degradation is still lacking. In order to develop a real-time trafficking technique, a series of meso-brominated near-infrared (NIR) fluorophores were synthesized and conjugated to biodegradable gelatin scaffolds. Since the pentamethine cyanine core is highly lipophilic, the side chain of each fluorophore was modified with either quaternary ammonium salts or sulfonate groups. The physicochemical properties such as lipophilicity and net charge of fluorophores played a key role in the fate of NIR-conjugated scaffolds in vivo after biodegradation. The positively charged fluorophore-conjugated scaffold fragments were found in salivary glands, lymph nodes, and most of the hepatobiliary excretion route. However, halogenated fluorophores intensively accumulated into lymph nodes and the liver. Interestingly, balanced-charged gelatin scaffolds were degraded into urine in a short period of time. These results demonstrate that the noninvasive optical imaging using NIR fluorophores can be useful for the translation of biodegradable scaffolds into the clinic.

Near-infrared lipophilic fluorophores for tracing tissue growth.

Longitudinal monitoring of cell migration, division and differentiation is of paramount importance in cell-based medical treatment. However, currently available optical techniques for tracing cell growth and tissue development are limited in applications due to genetic modification, toxicity and inaccurate detection when utilizing the visible spectrum. We have developed lipophilic near-infrared (NIR) fluorophores with high optical properties and a low background signal that allows longitudinal monitoring of cell proliferation and differentiation. Intracellular labeling efficacy was highly dependent on the physicochemical properties of fluorophores such as lipophilicity, charge, polar surface area and rotational bonds. Among the series of NIR cyanine fluorophores, ESNF 13 showed high solubility in aqueous buffer, high membrane penetration, low cytotoxicity and a long-term signal maintainability with a high signal intensity. This study will guide tissue engineers in designing long-term cell trafficking agents with better physicochemical and optical properties.

Short-range interactions between surfactants, silica species and EDTA4- salt during self-assembly of siliceous mesoporous molecular sieve: a UV Raman study.

The effects of surfactants, counterions and additive salts on the formation of siliceous mesoporous molecular sieves during self-assembly process were investigated by UV Raman spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. The surfactant molecules experience the rearrangement after adding the silica species and adjusting the pH value. The obvious change of the Raman bands related to the surfactants supports a cooperative interaction between surfactant and inorganic species during self-assembly process. The addition of EDTANa(4) to the system induces the interaction between the COO(-) groups of EDTA(4-) and silanol groups of silica and a strong interaction between the EDTA(4-) and the N(+)(CH(3))(3) groups of the surfactant. The above interactions may be the main reason for the salt effect. The new information from the change of the chemical bonds allows for a further analysis to the interactions of different salts between surfactants and silica species at molecular level.

Combination of two chromophores: synthesis and PDT application of porphyrin-pentamethinium conjugate.

A general method for the synthesis of a novel porphyrin with pentamethine periphery substitution is described. The combination of two chromophoric systems, a porphyrin macrocycle and a polymethine moiety was achieved by transformation of tetrapyridyl porphyrin. The synthetic strategy included conversion of the tetrapyridyl porphyrin to its corresponding 2,4-dinitrophenylpyridinuim salt, which was subsequently converted to tetrakis(meso-pentamethinium salt) on the porphyrin core. This novel porphyrin exhibited PDT properties as manifested by the induction of apoptosis in the myeloid cell line HL-60 and the effective reduction of amelanotic melanoma in nude mice.