Application of anthocyanins as natural dye extracted from Brassica oleracea L. var. capitata f. rubra: dyeing studies of wool and silk fibres

Brassica oleracea L. var. capitata f. rubra (Red Cabbage) dye is composed mainly of natural pigment called anthocyanins used as a natural colourant. Wool and silk fibres were dyed with the aqueous extract obtained from red cabbage. The dyeing process was investigated and the combined effects of dyeing conditions on the colour yield parameter (K/S) were studied. Resulted fastness to wash, rubbing and light of the dyed fabrics were evaluated. Chemical Oxygen Demand (COD) and Biological Oxygen Demand (BOD₅₎ of the residual effluent were measured. Best dyeing conditions were found to be: 50 g/100 mL, pH 2, 60 min and 100 °C, respectively, for the red cabbage weight, pH, dyeing duration and temperature. Good fastnesses properties were found in both cases: for wool and silk fabrics. It was found also that the calculated biodegradability ratio (COD/BOD₅) of the residual bath of dyeing wool and silk with red cabbage extract are lower than 1.5 which means that these baths are biodegradable.     

Occlusion of transition metal ions by new adsorbents synthesized from plant polyphenols and animal fibrous proteins

Removing and collecting heavy and rare metal ions from industrial effluents and waste aqueous solutions are improtant problems. Our previous studies showed that animal fibrous proteins (AFPs) such as hen eggshell membrane, chicken feather (CF), wool, and silk were stable and insoluble proteins and had an excellent ability to bind not only hard (Mn²⁺ and Fe³⁺) but alsosoft (Ag⁺, Au⁺, Pd²⁺, Pt²⁺, and Hg²⁺) acids from aqueous solutions. In this study, we syntheszed some adsorbents for transition (Cr⁶⁺, Mn²⁺, Co²⁺, Ni²⁺, and Cu²⁺) and heavy (Cd²⁺) metalions from AFPs (gelatin, CF, and wool) and plant polyphenols (lignin and tannin) by heating a mixture of AFPs and plant polyphenols under acidic conditions. In batch experiments, pH profile, time dependency, and isotherm analysis were performed to determine binding properties of adsorbents for transition and heavy metal ions. Columnexperiments were also performed to removecopper ion from aqueous solution. The results showed that the new adsorbents were effective for collecting and removing transition and heavy metal ions from aqueous solutions.     

Preparation of gold nanoparticles on eggshell membrane and their biosensing application

A facile green biosynthesis method has been successfully developed to prepare gold nanoparticles (AuNPs) of various core sizes (25 ± 7 nm) using a natural biomaterial, eggshell membrane (ESM) at ambient conditions. In situ synthesis of AuNPs-immobilized ESM is conducted in a simple manner by immersing ESM in a pH 6.0 aqueous solution of HAuCl₄ without adding any reductant. The formation of AuNPs on ESM protein fibers is attributed to the reduction of Au(III) ions to Au(0) by the aldehyde moieties of the natural ESM fibers. Energy dispersive X-ray spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray powder diffraction unambiguously identify the presence of AuNPs on ESM. The effect of pH on the in situ synthesis of AuNPs on ESM has been investigated in detail. The pH of the gold precursor (HAuCl₄) solution can influence the formation rate, dispersion and size of AuNPs on ESM. At pH ≤3.0 and ≥7.0, no AuNPs are observed on ESM while small AuNPs are homogeneously dispersed on ESM at pH 4.0-6.0. The optimal pH for AuNPs formation on ESM is 6.0. AuNPs/ESMs are used to immobilize glucose oxidase (GO_x) for glucose biosensing. AuNPs on ESM can increase the enzyme activity of GO_x. The linear response range of the glucose biosensor is 20 μM to 0.80 mM glucose with a detection limit of 17 μM (S/N = 3). The biosensor has been successfully applied to determine the glucose content in commercial glucose injections. Our work provides a very simple, non-toxic, convenient, and green route to synthesize AuNPs on ESM which is potentially useful in the biosensing field.     

A new biomaterial,hen egg shell membrane,to eliminate heavy metal ion from their dilute waste solution

The egg shell membrane (ESM) is an intricate lattice network of stable and water-insoluble fibers with high surface area. ESM accumulates and eliminates various heavy metal ions from dilute aqueous solution with high affinity and in short contact time, depending on pH and characteristics of the individual ion. Under certain conditions, the level of precious ions, Au, Pt, and Pd accumulation approaches 55, 25, and 22% of dry wt of ESM, respectively. Also uranium uptake 30% of that of ESM. Experiments suggested that ESM is promising to use for the purpose of removal/recovery of metals and water pollution control.     

Biosorption of actinides from dilute waste actinide solution by egg-shell membrane

Removal of radioactive elements from the effluent and waste aqueous solutions is an important problem. In previous laboratory batch experiments, hen egg-shell membrane (ESM) was stable as an insoluble protein and was very capable of binding heavy metal ions from aqueous solution. Batch laboratory pH profile, time dependency, and capacity experiments were performed to determine the binding of uranium (U) and thorium (Th) to ESM. Batch pH profile experiments indicated that the optimum pH for binding these actinides was approx 6.0 (U) or 3.0 (Th). The adsorption isotherms were developed at pH 5.0 (U) or 3.0 (Th) at 25°C, and the adsorption equilibrium data fitted both Langmuir and Freundlich models. The maximum uptakes by the Langmuir model were about 240 mg U/g and 60 mg Th/g dry weight ESM. In addition, their adsorption capacities increased as salt concentration increased. ESM could also accumulate uranium from dilute aqueous solution by adjusting to the optimum pH. These results showed that ESM was effective for removing actinides from solution and would be useful in filtration technology to remove actinides from aqueous solution. S.-I. Ishikawa is a research fellow at the Japan Society for the Promotion of Science.     

Chemical imaging of corrosion: sum frequency generation imaging microscopy of cyanide on gold at the solid-liquid interface

Sum frequency generation (SFG) imaging is used to monitor, in situ, the reaction of cyanide ions with gold surface. Spatial and chemical variations across the surface are observed as a function of time. The initial period resulted in the formation of linearly bound cyanide to gold, and continuous exposure of gold film to cyanide solution led to the presence of higher-coordinated gold-cyanide complexes. These species were identified by their specific position in the SFG vibrational spectrum (2105, 2140, 2170, and 2225 cm(-1)). The relative amounts of these gold-cyanide species varied across the surface as resolved by SFG microscopy.     

Preconcentration of silver(I), gold(III) and palladium(II) in sea water with p-dimethylaminobenzylidenerhodanine supported on silica gel

A water-insoluble chelating material, p-dimethylaminobenzylidenerhodanine on silica gel (DMABR—SG) is described for preconcentration of trace amounts of silver(I), gold(III) and palladium(II) from water samples. Radioactive tracers (^110mAg and ¹⁹⁵Au) were used to study the behavior of silver and gold; palladium was monitored spectrophotometrically as its 1-(2-pyridylazo)naphthol complex in chloroform. In batch experiments, silver was quantitatively retained on the DMABR—SG at acidities ranging from 1.7 M to pH 5, and gold from 3 M to pH 5; equilibrium was achieved within 1 min for both elements. From sea water, silver ion was completely retained at pH 1.0–6.5 and gold ion at pH 1.0–3.5. In the case of palladium, shaking for about 20 min was required for quantitative retention at pH 1.0–5.0 for aqueous solution and at pH 1.0–7.0 for sea water. The chelating capacity of the DMABR—SG was 23 μmol Ag, 11 μmol Au and 11 μmol Pd per g. Quantitative recovery of silver and gold on DMABR—SG columns from sea water was achieved at higher flow rates (1–2 l h^-1 and 2–3 l h^-1, respectively) than with other chelating resins, e.g., Chelex 100, palladium required slower flow rate (150 ml h^-1). Silver retained on the DMABR—SG column was completely eluted with 20 ml of 2.5% sodium thiosulfate solution but palladium remained on the column. Silver, gold and palladium were quantitatively eluted with 20 ml of 0.1% thiourea in 0.1 M hydrochloric acid.     

Engineering Aqueous Fiber Assembly into Silk‐Elastin‐Like Protein Polymers

Self‐assembled peptide/protein nanofibers are valuable 1D building blocks for creating complex structures with designed properties and functions. It is reported that the self‐assembly of silk‐elastin‐like protein polymers into nanofibers or globular aggregates in aqueous solutions can be modulated by tuning the temperature of the protein solutions, the size of the silk blocks, and the charge of the elastin blocks. A core‐sheath model is proposed for nanofiber formation, with the silk blocks in the cores and the hydrated elastin blocks in the sheaths. The folding of the silk blocks into stable cores—affected by the size of the silk blocks and the charge of the elastin blocks—plays a critical role in the assembly of silk‐elastin nanofibers. Furthermore, enhanced hydrophobic interactions between the elastin blocks at elevated temperatures greatly influence the nanoscale features of silk‐elastin nanofibers.

     

Water‐Soluble Polypeptides at Aqueous Interface Produce Extensible Silk‐Like Fiber

A silk‐like extensible poly(α,L ‐amino acid) fiber is created by self‐assembly of poly(α,L ‐lysine) and poly(α,L ‐glutamic acid) at their aqueous solutions' interface. Distinguishing features of the PLL/PLG fiber are the high extensibility and good stretch. Stretching after spinning changes this fiber to a rigid and strong one. The concept and the poly(α,L ‐amino acid) fibers themselves open doors for the production of new protein fibers which are more silk‐ and wool‐like.     

固定化铜离子亲和膜色谱柱吸附血红蛋白的研究

将纤维素滤纸进行碱处理及环氧活化、偶联亚氨基二乙酸、固定化铜离子等处理,并将其装入自制的色谱柱管,制得固定化铜离子亲和膜色谱柱。该柱可用于吸附血红蛋白(hemoglobin,Hb),吸附率可达到90%以上。考察了上样量、pH值、温度、上样速度等因素对固定化铜离子亲和膜吸附Hb的影响。实验结果表明,固定化铜离子亲和膜色谱柱吸附血红蛋白的最佳条件为：室温下实验,缓冲体系的pH值控制在6~8,上样速度0.5~1.0 mL/min,上样量为3.16~7.90 mg/g。     

The extraction of low-concentrations of gold(I) with 198Au as a radiotracer

The solvent extraction of gold from alkaline cyanide solution was studied by using ¹⁹⁸Au as a radiotracer. The influence of several variables on the gold extraction, including the concentration of gold, the molar ratio of extractants to gold(I), the volume percentage of cosolvent and the pH value of the aqueous phase, was investigated. The results indicated that the radioactive tracer technique is a quick, accurate, and convenient tool to investigate the extraction behavior of an element existing in low concentrations. The experimental results indicated that the studied amines, tetradecyldimethylbenzylammonium chloride, N1923 and tri-n-octylamine, could be used as extractants for the recovery of gold from aqueous alkaline cyanide solutions.     

Comparison of extraction methods for the analysis of natural dyes in historical textiles by high-performance liquid chromatography

Different methods for the extraction of Dactylopius coccus Costa, Rubia tinctorum L., Isatis tinctoria L., Reseda luteola L., Curcuma longa L. and Cotinus coggygria Scop. from wool fibres are investigated using high-performance liquid chromatography with diode array detector (HPLC-DAD). The efficiencies of five extraction methods which include the use of HCl (widely used extraction method), citric acid, oxalic acid, TFA and a combination of HCOOH and EDTA are compared on the basis of the (a) number, (b) relative quantities, measured as HPLC peak areas and (c) signal-to-noise ratios (S/N) of the compounds extracted from the wool substrates. Flavonoid glycosides and curcuminoids contained in R. luteola L. and C. longa L., respectively, according to liquid chromatography with mass spectrometry (LC-MS) identifications, are not detected after treating the fibres with HCl. All the other milder methods are successful in extracting these compounds. Experiments are performed using HPLC-DAD to compare the HPLC peak areas and the S/N of the following extracted compounds: indigotin, indirubin, curcumin, demethoxycurcumin, bisdemethoxycurcumin, fisetin, sulfuretin, luteolin, luteolin-7-O-glucoside, apigenin, carminic acid, alizarin, puruprin and rubiadin. It is shown that the TFA method provides overall the best results as it gives elevated extraction yields except for fisetin, luteolin, apigenin and luteolin-7-O-glucoside and highest S/N except for fisetin and luteolin-7-O-glucoside. It is noteworthy that treatment of the fibres with the typical HCl extraction method results overall in very low S/N. The TFA method is selected for further studies, as follows. First, it is applied on silk dyed samples and compared with the HCl method. The same relative differences of the TFA and HCl methods observed for the wool dyed samples are reported for the silk dyed samples too, except for rubiadin, luteolin and apigenin. Thus, in most cases, the nature of the substrate (wool or silk) appears to have negligible effects on the relative difference of the two extraction methods. Second, the selected TFA method is applied to treat wool and silk historical samples extracted from textiles of the Mamluk period, resulting in the identification of several colouring compounds. In all extraction methods mentioned above, DMSO is used to dissolve the dyes, after acid treatment.     

Alizarin Red S as a colored agent for the extraction-photometric and color measurement determination of some local anesthetic organic compounds

The possibility has been considered for using 1,2-dihydroxyantraquinonone-3-sulfoacid (Alizarin Red S, ARS) as a colored agent for the determination of organic bases as of their ion associates. Spectrophotometric and colorimetric properties of the ion associates of cetyltrimethylammonium bromide and local anesthetics Novocaine and Lidocaine with ARS have been studied in aqueous solutions at pH 2–6; the optimal conditions for the formation of ion associates have been determined and the extraction mechanism has been revealed. Calibration curve equations have been obtained for the dependences of the absorbance of extracts and back extracts of organic bases in aqueous and organic phases, as well as the chromaticity functions (CF) of the ion associates on the concentration of the organic bases in aqueous and organic phases. Molar absorption coefficients and CF of the considered ion associates have been determined. The advantages of the color measurement over spectrophotometry for the determination of molar absorption coefficients and CF have been demonstrated. An application of the developed procedure has been proposed.     

Structure and microporous formation of cellulose/silk fibroin blend membranes: Part II. Effect of post-treatment by alkali

Blend membranes (RCF1) were prepared from mixture solution of cellulose and silk fibroin (SF) in cuoxam by coagulating with acetone–acetic acid (4:1 by volume). The blend membranes were subjected to post-treatment with 10% NaOH aqueous solution, and their structure and properties were characterized by FT-IR, X-ray diffraction, DSC, SEM and DMTA. In previous work, cellulose/SF blend membranes (RCF2) prepared by coagulating with 10% NaOH aqueous solution formed a microporous structure, in which the SF as a pore former was almost completely removed from the membrane. However, when the blend membranes RCF1 were immersed in 10% NaOH aqueous solution for post-treatment, a strong hydrogen bonding between cellulose and SF inhibited the removal of SF. Although alkali is a good solvent for SF, the blend membranes RCF1 such obtained from cellulose and SF were alkali resistant. The crystallinity and the mean pore size of the blend membranes slightly decreased with increasing post-treatment time. This work provided a cellulose/silk blend membrane, which can be used under alkaline medium.     

Picomolar Detection of Melamine Using Molecularly Imprinted Polymer‐Based Electrochemical Sensors Prepared by UV‐Graft Photopolymerization

Molecularly imprinted polymer (MIP) films of melamine were prepared by photopolymerization of vinylic monomers on diazonium‐modified gold electrodes. The gold‐grafted MIPs are specific and selective for melamine in either organic or aqueous media. The interferent molecules cyromazine and cyanuric acid were not recognized by the MIPs. The limit of detection was as low as 1.75×10^?12 mol L^?1 at S/N=3. Efficiency of melamine rebinding is related to the solubility parameter of the organic solvent or pH and ionic strength of the aqueous medium. It is concluded that diazonium salts permit to design robust electrochemical MIP sensors.     

Production,Partial Characterization,and Use of a Red Biochrome Produced by <Emphasis Type="Italic">Serratia sakuensis</Emphasis> subsp. nov Strain KRED for Dyeing Natural Fibers

We have described a novel red biochrome, 514 Da in size, produced by solid-state cultivation of a bacterial isolate obtained from garden soil. The growth requirements of the isolate, the chemical characteristics of the biochrome produced, and the application of the biochrome in dying of silk, wool, and cotton fabrics have been studied. The biochrome obtained after 52 h of incubation and having a λ _max of 535 nm was used for dyeing the fabrics. We found that silk, wool, and cotton fabrics dyed with this new natural red compound have high color strength values and dye uptake along with good color fastness as well as antibacterial activity.     

Effect of gold nanoparticles on the fluorescence excitation spectrum of α-fetoprotein: local environment dependent fluorescence quenching

The effect of colloid gold nanoparticles (AuNPs) on the fluorescence excitation spectrum of α-fetoprotein (AFP) has been investigated experimentally. The excitation spectral peaks of AFP with low concentration from 0.01 ng ml(-1) to 12 ng ml(-1) increase monotonically with increasing of AFP concentration. When some gold colloids were added to the AFP solution, the excitation peak at 285 nm decreases distinctly. By comparing the excitation peak intensity of AFP solution with gold colloids and without gold colloids at different AFP concentrations, the quenching effect from gold nanoparticle was more effective at lower AFP concentration. So the range of concentration from 0.01 ng ml(-1) to 0.09 ng ml(-1) will be the potential range of applications because of the higher sensitivity. The physical origin based on local field effect was investigated to illuminate this local environment dependent fluorescence quenching. The changing extent of quenching with different AFP concentrations can be attributed to the nonlinear decreasing of the local field factor of gold nanoparticles as a function of environmental dielectric constant.     

Quantitative method for analysis of tobacco‐specific N‐nitrosamines in mainstream cigarette smoke by using heart‐cutting two‐dimensional liquid chromatography with tandem mass spectrometry

A heart‐cutting two dimensional liquid chromatography coupled with tandem mass spectrometry method was developed for the analysis of tobacco‐specific N‐nitrosamines (TSNAs) at low concentration level in Virginia‐type cigarette smoke. A strong cation exchange column was utilized for the first dimensional separation, which effectively removed acidic and neutral components in the smoke, followed by a reversed phase liquid chromatography coupled with tandem mass spectrometric analysis. To capture components of the TSNAs in the effluent on the trapping column, a compensating pump was applied for online dilution and pH adjustment during the period of the TSNAs fraction transferring and enrichment. Highly sensitive determination of the TSNAs in mainstream cigarette smoke was achieved by isotope deuterated internal standards under the multiple reaction monitoring mode. Compared with traditional methodologies, the method was almost no matrix interference. Limits of quantity for the TSNAs were within 0.027–0.094 ng/mL, and the results showed good reproducibility and accuracy. Finally, the new method was applied for analysis of the Kentucky reference cigarettes and the results agreed well with joint experiments of Cooperation Centre for Scientific Research Relative to Tobacco.     

Removal of Co(II) from aqueous solution by using hydroxyapatite

Herein, hydroxyapatite (HAP) was prepared by aqueous precipitation technique and was characterized by using FT-IR and XRD to determine its chemical functional groups and micro-structure. The removal of cobalt from aqueous solution to HAP was studied by batch technique as a function of various environmental parameters such as contact time, pH, ionic strength, foreign ions, fulvic acid (FA), and temperature under ambient conditions. The results indicated that the sorption of Co(II) on HAP was strongly dependent on pH and ionic strength. The presence of FA enhanced the sorption of Co(II) on HAP at low pH, whereas reduced Co(II) sorption on HAP at high pH. The Langmuir, Freundlich and D-R models were used to simulate the sorption isotherms at three different temperatures of 303.15, 323.15 and 343.15 K. The thermodynamic parameters (ΔH°, ΔS° and ΔG°) calculated from the temperature dependent sorption isotherms indicated that the sorption process of Co(II) on HAP was spontaneous and endothermic. The sorption of Co(II) was dominated by outer-sphere surface complexation and ion exchange at low pH, whereas inner-sphere surface complexation or surface precipitation was the main sorption mechanism at high pH values. The results suggest that the HAP is a suitable material in the preconcentration and solidification of Co(II) from large volumes of aqueous solutions.     

Disposable Amperometric A-fetoprotein Immunosensor Based on the Biocompatible Silk Protein Membranes-Modified Indium Tin Oxide Electrodes

A simple and disposable electrochemical immunosensor for detection of 68 kDa alpha-fetoprotein (AFP) was fabricated based on films of silk fibroin protein membrane (SFPM)/Prussian blue (PB)/deposition of gold nanoparticles (DpAu). First, DpAu and PB were electrochemically deposited successively on the surface of indium tin oxide (ITO) electrode. Then, SFPM with excellent biocompatibility was modified on the surface of PB/DpAu/ITO. The SFPM could form a stable matrix on the electrode surface for the deposition of immunoactive agents. More importantly, the SFPM could prevent the possible leakage of electron mediator and enhance the stability of immunosensor. Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to characterize the assembly process of the modified electrode. The linear range of the proposed immunosensor extended from 1.0 to 200.0 ng/mL for detection of AFP with a detection limit of 0.6 ng/mL. Moreover, the CV test demonstrated the immunosensor exhibited acceptable reproducibility and stability. This composite membrane could be applied for the detection of different biomarkers, diagnosis, and monitoring of carcinoma.

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