Cys Complexes Research Articles

Silver‐Mediated Growth of Chiral Ag/Au‐Cysteine Hybrid Nanospheres with Giant Chiroptical Response

AbstractThe chiral Ag/Au‐cysteine hybrid nanospheres (HNSs) have been prepared by using cysteine (Cys) as an inductive agent via wet chemistry methods. Unlike the case of the dipole approximation, the circular dichroism spectra can be divided into two components: 1) one region associated with the interband absorption enhanced optical activity of structural arrangement of Cys molecules at 200–320 nm; 2) another region corresponding to a ligand‐to‐metal charge transfer mixed with ligand‐to‐metal‐metal charge transfer excitation due to the synergetic interplay of the electrostatic interaction between Cys side chains and the Au(I)⋅⋅⋅Au(I) aurophilic attraction in the Au(I)‐Cys complexes, located at 350–400 nm. The chiroptical response increases dramatically with increasing the concentration of Au from 0.1 to 1.56 × 10−3 m, and subsequently decreases with further increasing the concentration of Au from 3.12 to 12.5 × 10−3 m, which is similar to the sergeants and soldiers effect of chiral polymer materials. Furthermore, the circinate‐like morphology of the alloyed nanospheres is strongly dependent on the presence of Ag and the chiral bimetal HNSs present excellent enantioselective recognition for amino acids in catalytic electrochemical reactions due to the specific activity and chiral active spots.

L-cysteine intercalated layered double hydroxide for highly efficient capture of U(VI) from aqueous solutions

l-cysteine intercalated Mg/Al layered double hydroxide (Cys-LDH) composites were fabricated and applied for treating the U(VI) contaminated wastewater under various conditions. Interaction mechanisms and adsorption properties were investigated by using batch experiments with spectroscopy analysis. The adsorption isotherms and kinetics were fitted perfectly with the Langmuir isotherm and the pseudo-second-order model, respectively. The significant maximum adsorption capacity of Cys-LDH (211.58 mg/g) compared to LDH was attributed to the larger number of functional groups on Cys-LDH. The presence of humic acid (HA) decreased U(VI) elimination on Cys-LDH at high pH but increased U(VI) removal at low pH. Typically, the presence of various anions (such as NO3−, Cl−, ClO4− and SO42−) did not obviously affect U(VI) adsorption on Cys-LDH, while the coexisted CO32− significantly affected U(VI) elimination. The predominate adsorption were determined to be the formation of Cys-U(VI)-Cys complexes with cysteine in the Cys-LDH interlayers. The results demonstrated that the Cys-LDH are promising adsorbents for efficient elimination and extraction of radionuclides in actual environmental contamination management.

Quantum chemical study of the molecular structure of the sodium dodecylsulfate complexes with glycine and cysteine

The quantum chemical modeling of sodium dodecylsulfate (DDSNa) complexes with glycine (Gly) and cysteine (Cys) is carried out at the DFT/B97D level using the Grimme hybrid exchange-correlation functional with a dispersion correction and the 6-311++G(2d,2p) basis set. The structure of the Gly and Cys molecular and zwitterionic forms is examined. The structures and the formation energies of DDSNa…Gly and DDSNa…Cys complexes are determined. The effect of the amino acid structural features on the stability of the complexes they form with DDSNa is analyzed. The NBO analysis of the electron density distribution in the DDSNa molecule is performed.

A specific nanoprobe for cysteine based on nitrogen-rich fluorescent quantum dots combined with Cu2+

As a new member of the carbon quantum-dot family, fluorescent nitrogen-rich quantum dots (NRQDs) were prepared by a mixed solvothermal method using 2-azidoimidazole and aqueous ammonia as reactants. These NRQDs are rich in nitrogen up to 40.2%, which are endowed with high fluorescence quantum yield, good photostability, water-solubility and favourable biocompatibility. We further explored the use of NRQDs combined with Cu2+ as a nanoprobe for sensing fluorescently of cysteine (Cys) in complex biological samples. In this sensing system, the fluorescence is significantly quenched via energy transfer from NRQDs to Cu2+ for the coordination of amino-containing groups with Cu2+. The strong affinity between Cu 2+ and Cys leads to the formation of Cu2+-Cys complexes and cause the detachment of Cu2+ from the surface of NRQDs, thus the fluorescence of NRQDs recover. This nanoprobe allows analysis of Cys by modulating the switch of the fluorescence of NRQDs with a detection limit of 5.3nM. As expected, the proposed NRQDs-Cu2+complex-based nanoprobes were successfully applied for the determination of Cys in human serum and plasma samples with recoveries ranging from 97.2% to 105.7%. The probe ensemble was also successfully applied to imaging of Cys in living cells with satisfactory results, which shows strong potential for clinical diagnosis.

Effect of l-Cysteine and Transition Metal Ions on Dimethyl Sulfide Oxidation.

During malt kilning, significant amounts of dimethyl sulfide (DMS) oxidize leading to the formation of dimethyl sulfoxide (DMSO), a precursor of DMS during fermentation. Yet, knowledge regarding reaction mechanisms of DMSO formation during malt production is limited. The role of thiols in sulfide oxidation is unclear as they possess sulfoxide reducing ability as well as pro- and antioxidative properties. This study investigated the effects of the thiol l-cysteine (Cys), molecular oxygen, transition metal ions, and EDTA on DMS oxidation in aqueous model solutions. Highest oxidative DMS consumption was observed when Cys was combined with iron(II) (∼12%) and copper(II) (∼40%). Response surface modeling (RSM) revealed that Cys together with copper(II) had a strictly prooxidative effect and no antioxidative behavior was found. Hydrogen peroxide, as generated via autoxidation of Cys-Cu(I)-Cys complexes, was supposed to be the primary DMS oxidant in this work. Based on redox kinetics, potential reaction mechanisms, and their impact on oxidative processes in thermal food processing, such as malt and beer production, are discussed.

Efficient generation of volatile species for cadmium analysis in seafood and rice samples by a modified chemical vapor generation system coupled with atomic fluorescence spectrometry

A vapor generation procedure to determine Cd by atomic fluorescence spectrometry (AFS) has been established. Volatile species of Cd are generated by following reaction of acidified sample containing Fe(II) and l-cysteine (Cys) with sodium tetrahydroborate (NaBH4). The presence of 5mgL−1 Fe(II) and 0.05% m/v Cys improves the efficiency of Cd vapor generation substantially about four-fold compared with conventional thiourea and Co(II) system. Three experiments with different mixing sequences and reaction times are designed to study the reaction mechanism. The results document that the stability of Cd(II)–Cys complexes is better than Cys–THB complexes (THB means NaBH4) while the Cys–THB complexes have more contribution to improve the Cd vapor generation efficiency than Cd(II)–Cys complexes. Meanwhile, the adding of Fe(II) can catalyze the Cd vapor generation. Under the optimized conditions, the detection limit of Cd is 0.012μgL−1; relative standard deviations vary between 0.8% and 5.5% for replicate measurements of the standard solution. In the presence of 0.01% DDTC, Cu(II), Pb(II) and Zn(II) have no significant influence up to 5mgL−1, 10mgL−1and 10mgL−1, respectively. The accuracy of the method is verified through analysis of the certificated reference materials and the proposed method has been applied in the determination of Cd in seafood and rice samples.

Visual detection of Ca(2+) based on aggregation-induced emission of Au(I)-Cys complexes with superb selectivity.

A label-free optical probe was developed for Ca(2+) detection based on the aggregation-induced emission property of Au(i)-thiolate complexes. Upon incubation with Ca(2+), the Au(I)-cysteine complexes rapidly aggregated through Cys-Ca(2+) interaction, resulting in a luminescent emission of the complexes. The label-free probe was low cost, simple in design and fast in response.

FTIR, XAS, and XRD study of cadmium complexes with l-cysteine

Cysteine (cys) plays a vital role in the detoxification of cadmium (Cd), but the coordination of this metal to cys is not well understood, although extensively studied. In this investigation, our results showed that the ratio Cd:cys 1:2 precipitate as a amorphous white powder, the Cd:cys 1:4 provided for a viscous liquid without precipitating, while the Cd:cys 1:6 resulted in long, clear, needle-like crystals. FTIR and XAS analysis indicated that cys was coordinated to Cd through S ligands on the cys. EXAFS of the Cd:cys products showed small differences in the coordination environment. The complex from Cd:cys 1:2 reaction displayed two different Cd–S interactions at 2.69 and 2.54Å, each consisting of two neighboring atoms. The complex from the Cd:cys 1:4 reaction showed four equally distant Cd–S interactions at 2.47Å. The comples from the Cd:cys 1:6 reaction exhibited a Cd–S interaction of four S ligands at approximately 2.54Å. All the Cd:cys complexes had a tetrahedral arrangement of S ligands around the central Cd atom. The XRD demonstrated that the Cd:cys 1:2 and 1:4 reaction products were amorphous and no diffraction peaks were observed. However, the Cd:cys 1:6 reaction product showed strong diffraction peaks, crystallizing into a monoclinic unit cell (C2/C).

The structural and bonding evolution in cysteine–gold cluster complexes

The bonding characteristics in cysteine-gold cluster complexes represented by thiolate (Au(n)·Cys(S) (n = 1, 3, 5, 7)) and thiol (Au(n)·Cys(SH) (n = 2, 4, 6, 8)) is investigated by density functional theory with 6-31G(d,p) and Lanl2DZ hybrid basis sets. The complexes exhibit very different bonding characteristic between these two forms. In the Au(n)·Cys(S) complexes, the charge transfers from gold clusters to sulfur atoms. The number of S-Au bonds in the Au(n)·Cys(S) complexes evolves from one to two when n is greater than three. For n equals three, i.e. Au(3)·Cys(S), its ground state only has one S-Au bond. While the only S-Au bond in Au(1)·Cys(S) is mainly covalent, the nature of the S-Au bond in other thiolates is featured with the combination of covalent and donor-acceptor interactions. In particular, one stable isomer of Au(3)·Cys(S) with two S-Au bonds, which is 2 kcal mol(-1) higher in energy than the corresponding ground state, consists of one covalent and one donor-acceptor S-Au bond explicitly. Moreover, the localized three center two electron bonds are formed within the Au clusters, which facilitates the formation of the two S-Au bonds in Au(5)·Cys(S) and Au(7)·Cys(S) complexes. In the Au(n)·Cys(SH) complexes, the donor-acceptor interaction prevails in the Au-SH bond by transferring lone pair electrons from the sulfur atom to the adjacent gold atom. Interestingly, the orbital with much more 6s-component in Au(4)·Cys(SH) enhances the donor-acceptor bonding character, thus yields the strongest bonding among all the Au(n)·Cys(SH) complexes studied in this paper. In general, the bonding strength between gold clusters and cysteine is positively correlated with the S-Au overlap-weighted bond order, but negatively correlated with the S-Au bond length. Lastly, the covalent and donor-acceptor S-Au bond strength is computed to be 48 and 18 kcal mol(-1), respectively.

Aqueous Phase Synthesized CdSe Magic-Sized Clusters: Solution Composition Dependence of Adsorption Layer Structure

We report dispersion solution composition dependence of the adsorption layer structure and the physical and optical properties of aqueous phase-synthesized semiconductor nanoparticles (NPs). We synthesized cysteine (Cys)-capped CdSe NPs with well-defined core structures, dispersed them in a series of aqueous solutions with different compositions, and then investigated their adsorption layer structure and physical and optical properties. Each CdSe NP consisted of a (CdSe)33 or (CdSe)34 magic-sized cluster (d - 1.45 nm) core, a ligand-Cys shell, and an adsorption layer. The dispersion solution composition strongly affected the adsorption layer structure of the CdSe NPs. The solution with a composition close to that of the as-prepared solution stabilized the physical and optical properties of the NPs. The solution with a composition different from that of the as-prepared solution, however, resulted in large changes in their adsorption layer structure and thus their physical and optical properties. The solution composed of neutral or weakly charged Cys and Cd-Cys complexes led to the adsorption layer with low charge density and that destabilized the NPs. The solution containing only neutral or weakly charged forms of Cys, without Cd-Cys complexes, was favorable to the formation of a thick adsorption layer with low charge density and that destabilized the NPs. The amount of adsorbed Cys in the adsorption layer depended on the dispersion solution composition. However, the amount of adsorbed Cd-Cys complexes in the adsorption layer was almost constant regardless of the dispersion solution composition.

Aqueous phase-synthesized small CdSe quantum dots: adsorption layer structure and strong band-edge and surface trap emission

We synthesized, in aqueous solution at room temperature, small water-soluble CdSe quantum dots (QDs) with strong photoluminescence (PL) and then correlated the PL with their adsorption layer structure. For synthesizing the QDs, their initial synthesis condition was controlled to form small Cd-containing species capable of passivating dangling bonds on the CdSe core surface. Each CdSe QD (d ~ 2.5 nm) consisted of a CdSe core (d ~ 2.1 nm), a cysteine (cys)-ligand shell, and an adsorption layer composed of Cd–cys complexes (mainly CdL(-H)−, cys ≡ H2L), cys (as L2−), Cd(OH)2, and CdOx (x ≥ 1). Our CdSe QDs showed strong blue band-edge PL as well as strong green surface trap PL. Their PL quantum yield (QY) of ~18% was unexpectedly high, considering their extremely small core size and their absence of any wide-bandgap inorganic shell. We attributed the QY to their adsorption layer species. The small weakly charged Cd–cys complex and the small neutral cadmium oxides in the adsorption layer could relatively readily diffuse into the unprotected surface sites on the core. These wide-bandgap species coalesced selectively on the unprotected surface sites with minimal spatial disturbance to the preexisting surface Cd-ligand coordination, and passivated them effectively. These decreased nonradiative recombination of the excitons significantly and thus led to the unexpectedly high QYs.

Chemical Vapor Generation of Arsane in the Presence of l-Cysteine. Mechanistic Studies and Their Analytical Feedback

The complex reactivity of the system As-AH-RSH-THB (As=As(III), As(V); AH=HCl, HClO4, CH3COOH; RSH=L-cysteine (Cys); THB=NaBH4) was investigated using continuous flow (CF) hydride generation (HG) coupled either with atomic absorption (AAS) or atomic fluorescence spectrometry (AFS). AsH3 generation was examined in the presence of Cys by varying acidity and the type of acid, the mixing sequence, and the reaction time of reagents. The strong depression of arsane generation, which is typically observed in the range of acidity of 0.2-2 M HCl, can be addressed to the low reaction rate of thiol-borane, hydroboron complexes, or both toward those As(III) substrates that are formed in the same reaction environment. The simultaneous presence of Cys-borane and As(III)-Cys species is at the origin of the gap of the arsane generation efficiency in the 0.2-2 M HCl acidity range. The selective formation of Cys-borane complexes, which are formed faster than As(III)-thiol complexes, can be achieved by a careful choice of the mixing sequence of the reagents. The simultaneous mixing of sample, Cys, and THB is able to reduce substantially the gap of the arsane generation efficiency in the 0.2-2 M HCl acidity range. These properties were employed to implement a simple method for selective determination of As(III) in samples containing inorganic arsenic: (i) Total inorganic arsenic is determined by sample treatment with 0.2 M Cys for 30 min, acidity 0.1 M HCl, followed by CF-HG-AFS; (ii) As(III) is selectively determined in 0.005 M CH3COOH in the presence of Cys using a chemifold setup allowing the simultaneous mixing of sample, 0.2 M Cys and 0.1 M THB. The selectivity, measured from the ratio between the slopes of calibration graphs As(III)/As(V), is 220. The interference effects of Cu(II), Fe(III), Ni(II), Co(II), Ag(I), Pd(II), and Pt(IV) can be kept under control using the simultaneous mixing of all the reagents. The tolerance toward the interferences was almost the same as that obtained by allowing the formation of As(III)-Cys complexes (offline sample pretreatment with Cys for 30 min). The method was tested with the application to the natural waters and mineral well waters analysis employing CF-HG-AFS.