An amino-functionalized ordered mesoporous polymer as a fiber coating for solid phase microextraction of phenols prior to GC-MS analysis.

An amino-functionalized ordered mesoporous polymer (OMP-NH2) was synthesized and applied as a fiber coating for solid phase microextraction of polar phenols from environmental samples. The fiber coating was prepared by loading the OMP-NH2 powder onto a stainless steel wire through silicone gel. Combined with GC-MS, the fibers were employed to quantify trace of phenols in water through headspace-SPME. The characterization showed the OMP-NH2 to have a large specific surface area (420 m2 g-1) and good thermal stability (>400 °C). Due to its mesoporous structure and favorable interactions via hydrogen bonding and π stacking interactions with phenols, the sorbent represents a promising candidate for the separation and enrichment of polar phenols. Extraction conditions, such as temperature, extraction time, salt concentration, pH value and desorption time, were fully optimized. Under the optimized conditions, the coating exhibits an enrichment effect that is ~2-10 times better than that of a commercial polyacrylate coating. Figures of merit include (a) low limits of detection (0.05-0.16 ng L-1), (b) wide linear ranges (0.2-10,000 ng L-1), and (c) high enrichment factors (510-2272). The relative standard deviations for one fiber and fiber-to-fiber were in the range of 4.0-6.1% and 4.6-7.4%, respectively. The method was applied to the determination of phenols in water samples and gave satisfactory recoveries between 85.4 and 112.2%. Graphical abstract An amino-functionalized ordered mesoporous polymer (OMP-NH2) was synthesized by a solventless method and applied as headspace solid phase microextraction (HS-SPME) fiber coating for the extraction of polar phenols from the environmental samples.

Generation and Application of Fluorescent Anti-Human ß2-Microglobulin VHHs via Amino Modification.

The functionalization of VHHs enables their application in almost every aspect of biomedical inquiry. Amino modification remains a common strategy for protein functionalization, though is considered to be inferior to site-specific methods and cause protein property changes. In this paper, four anti-ß2M VHHs were selected and modified on the amino group by NHS-Fluo. The impacts of amino modification on these VHHs were drastically different, and among all th examples, the modified NB-1 maintained the original stability, bioactivity and homogeneity of unmodified NB-1. Specific recognition of VHHs targeting ß2M detected by fluorescence imaging explored the possible applications of VHHs. Via this study, we successfully functionalized the anti-ß2M VHHs through amino modification and the results are able to instruct the simple and fast functionalization of VHHs in biomedical researches.

ArgC-Like Digestion: Complementary or Alternative to Tryptic Digestion?

Enzymatic digestion of complex protein samples is often performed by use of multiple proteases to improve protein identification and characterization. Combining trypsin with ArgC is one option to enhance sequence coverage in bottom-up proteomics. However, the low selectivity of this endoprotease derogates from the benefit of the combination. Our approach here is to mimic ArgC digestion by chemically modifying all lysine residues in proteins so that trypsin can only cleave C-terminal to arginine. Four different amine modifications, dimethylation, acetylation, propionylation, and carbethoxylation, were tested, and the protocols were optimized. A nearly complete conversion of the primary amines was achieved for all modifications. Tryptic digestion of Escherichia coli lysate proteins after acylation of lysine residues shows the most significant improvement compared with data received from ArgC digest. After propionylation, 9216 unique peptides identified 1439 proteins, which, compared with a conventional tryptic digestion, represents the identification of 150 additional proteins due to a reasonable reduction of the sample complexity and higher fragmentation efficiencies of the peptides. It is therefore concluded that the Arg-C like digestion should no longer be regarded as a complementary approach but forms a viable and superior alternative to the conventional trypsin digestion.

Selective adsorption of Cu(II) on amino-modified alginate-based aerogel: As a catalyst for the degradation of organic contaminant.

In this study, amino-modified graphene oxide(NGO) was prepared by introducing amino functional groups. Based on the cross-linking between Ca(II) and sodium alginate (SA), associated with dense slit-like pore resulted from the nano-sheet accumulation of NGO and montmorillonite (MMT), composite aerogels (NGM) with stable pore structure were constructed, thus it realized the selective recovery of hydrated copper ions in complex wastewater systems. Raman analysis and density functional theory calculation confirmed the construction of amino-modified defect GO and significantly improved its chemical reactivity, which laid the foundation for the construction of slit pore structure of NGM (SEM can confirm). At the same time, it proposed that the good selective adsorption of Cu(II) on NGM was related to the synergism of strong electrostatic force, ion exchange and complexation based on the characterizations of FT-IR and XPS. In order to realize the value-added utilization of NGM aerogel (NGMC) after adsorbing Cu(II), NGMC was used as a catalyst to degrade organic pollutants in wastewater. Systematic experiments shown that NGMC can degrade organic pollutants with a degradation efficiency >80 %. In summary, NGM had a broad application prospect for selective recovery of Cu(II) from complex wastewater systems without second pollution.

Candesartan Cilexetil Formulations in Mesoporous Silica: Preparation, Enhanced Dissolution In Vitro, and Oral Bioavailability In Vivo.

Candesartan cilexetil (CC) is one of well-tolerated antihypertensive drugs, while its poor solubility and low bioavailability limit its use. Herein, two mesoporous silica (Syloid XDP 3150 and Syloid AL-1 FP) and the corresponding amino-modified products (N-XDP 3150 and N-AL-1 FP) have been selected as the carriers of Candesartan cilexetil to prepare solid dispersion through solvent immersion, and characterized through using powder X-ray diffraction analysis, infrared spectroscopy, differential scanning calorimetry, scanning electron microscopy, and solid-state nuclear magnetic resonance spectroscopy, etc. The state of CC changed from crystalline to amorphous after loading onto the silica carriers, in which no interactions between CC and silica existed. Then, the dissolution behaviors in vitro were studied through using flow-through cell dissolution method. CC-XDP 3150 sample exhibited the most extensive dissolution, and the cumulative release of CC from it was 1.88-fold larger than that of CC. Moreover, the pharmacokinetic results in rats revealed that the relative bioavailability of CC-XDP 3150 and CC-N-XDP 3150 solid dispersions were estimated to be 326 % % and 238 % % in comparison with CC, respectively. Clearly, pore size, pore volume, and surface properties of silica carrier have remarkable effect on loading, dissolution and bioavailability of CC. In brief, this work will provide valuable information in construction of mesoporous silica-based delivery system toward poorly water-soluble drugs.

One-pot solvothermal synthesis of In-doped amino-functionalized UiO-66 Zr-MOFs with enhanced ligand-to-metal charge transfer for efficient visible-light-driven CO2 reduction.

Metal organic frameworks (MOFs) with high porosity and highly tunable physical/chemical properties can serve as heterogeneous catalysts for CO2 photoreduction, but the application is hindered by the large band gap (Eg) and insufficient ligand-to-metal charge transfer (LMCT). In this study, a simple one-pot solvothermal strategy is proposed to prepare an amino-functionalized MOF (aU(Zr/In)) featuring an amino-functionalizing ligand linker and In-doped Zr-oxo clusters, which enables efficient CO2 reduction driven with visible light. The amino functionalization leads to a significant reduction of Eg as well as a charge redistribution of the framework, allowing the absorption of visible light and the efficient separation of photogenerated carriers. Furthermore, the incorporation of In not only promotes the LMCT process by creating oxygen vacancies in Zr-oxo clusters, but also greatly lowers the energy barrier of the intermediates for CO2-to-CO conversion. With the synergistic effects of the amino groups and the In dopants, the optimized aU(Zr/In) exhibits a CO production rate of 37.58 ± 1.06 µmol g-1 h-1, outperforming the isostructural University of Oslo-66- and Material of Institute Lavoisier-125-based photocatalysts. Our work demonstrates the potential of modifying MOFs with ligands and heteroatom dopants in metal-oxo clusters for solar energy conversion.

Amino-terminated SiO2-Al2O3 composite aerogels from fly ash for improved removal of Cu2+ and Pb2+ ions in wastewater: one-pot synthesis, excellent adsorption capacity and mechanism.

In this study, by using a sol-gel grafting-atmospheric drying method, amino-terminated SiO2-Al2O3 composite aerogels, namely 3-aminopropyltriethoxysilane (APTES) or 3-(2-amino-ethoxy) propylmethyldimethoxysilane (AEAPMDS) modified SiO2-Al2O3 aerogels (AMSAAs), were synthesized from the fly ash and characterized by field-emission scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy etc.. And the AMSAAs were verified as excellent adsorbents for removing heavy metal ions (Cu2+ and Pb2+ ions) from wastewater. The effects of modification conditions and testing parameters including pH value, adsorbent dose, initial ions concentration, adsorption time and temperature were systematically investigated. Results demonstrated that 0.2 mol/L APTES modified aerogels (0.2APTES-SAAs) possessed the best adsorption properties. Under the optimal pH value of 4.0-6.0 and the adsorbent dose of 0.4-0.6 g/L, the equilibrium adsorption capacities of Cu2+ and Pb2+ ions were as high as 195 mg/g and 500 mg/g within 20-30 min, respectively. The adsorption processes were agreed fairly well with Freundlich isotherm adsorption model and the pseudo-second-order kinetic model, which indicated that the adsorption processes were heterogeneous multilayer adsorption and controlled by the chemical reaction between AMSAAs and heavy metal ions. The obtained adsorption thermodynamic parameters (ΔH°, ΔS° and ΔG°) revealed that the adsorption processes were exothermic and spontaneous with decreased randomness at the solid-liquid interface. The excellent recyclability of as-prepared AMSAAs proved as economically promising adsorbents for practical applications.

Multifunctional modified polylactic acid nanofibrous scaffold incorporating sodium alginate microspheres decorated with strontium and black phosphorus for bone tissue engineering.

Polylactic acid (PLA) nanofibrous scaffolds have received extensive attention in the field of tissue engineering due to their excellent degradability, biocompatibility and the biomimetic extracellular matrix (ECM) topographies. However, the cell affinity and osteogenic activity of PLA scaffolds is not satisfactory because of their intrinsic hydrophobicity, the absence of cell recognition sites and the nucleation sites of the in vivo biomineralization. Furthermore, effective anti-inflammatory activity for the in vivo scaffold could not be ignored, so a strategy to develop a multifunctional PLLA (poly-L-lactic acid) nanofibrous scaffold with improved hydrophilicity, osteoinductivity, excellent near-infrared photothermal-responsive drug release capacity and anti-inflammatory activity via incorporating sodium alginate microspheres decorated with strontium and ibuprofen-loaded black phosphorus (BP + IBU@SA microspheres) into aminated modified PLLA nanofiber network is proposed in this study. Scanning electron microscopy (SEM) observation showed that the BP + IBU@SA microspheres were homogeneously dispersed into the modified PLLA matrix with uniform nanofiber structure and the chemical composition of the as-prepared scaffolds was confirmed by X-ray diffraction analysis (XRD) and elemental mapping. The photothermal property of the scaffolds was assessed under near-infrared (NIR) light irradiation, the results manifested that the entrapment of BP nanosheets endowed PLLA nanofibrous scaffold with significantly high photothermal conversion efficiency and optical cycle stability. Meanwhile, the scaffold also displayed an excellent photothermal-responsive intelligent drug release performance toward Sr2+ and ibuprofen. Moreover, the in vitro studies revealed that the as-developed scaffolds possessed a good biocompatibility for cell adhesion and proliferation and an improved bioactivity to induce apatite formation. All these results indicated the potential of the fabricated scaffolds in tissue engineering applications.

One-step controllable synthesis of amino-modification siloxene for enhanced solar water-splitting.

Novel two-dimensional silicon-based material siloxene has been synthesized handily by a one-step method, which utilizes the characteristics of the topological exfoliation to simplify the process of synthesis and modification. It is worth mentioning that for the first time amino-modified derivative has been investigated. Amino modification can promote the oxidation of siloxene, enlarge the bandgap and extend the carrier lifetime of siloxene. The application of siloxene before and after modification in water-splitting has been investigated. In addition, the superiority of the resultant two-dimensional materials was concisely elaborated, which revealed that owing to more effective photogenerated carriers' separation in amino modification siloxene, hydrogen production could be greatly promoted.

Amino modification enhances reproductive toxicity of nanopolystyrene on gonad development and reproductive capacity in nematode Caenorhabditis elegans.

Although amino modified nanopolystyrene could cause toxicity on environmental organisms, the effect of amino modification on nanopolystyrene toxicity is still largely unclear. We here employed Caenorhabditis elegans as an animal model to compare the effects between pristine and amino modified nanopolystyrene particles in inducing reproductive toxicity. Nanopolystyrene (35 nm) could cause the damage on gonad development as indicated by the endpoints of number of total germline cells, length of gonad arm, and relative area of gonad arm. Nanopolystyrene exposure also reduced the reproductive capacity as reflected by the endpoints of brood size and number of fertilized eggs in uterus. Moreover, amino modification enhanced nanopolystyrene toxicity on both the gonad development and the reproductive capacity. Additionally, induction of germline apoptosis and formation of germline DNA damage contributed to the enhancement of nanopolystyrene toxicity in reducing reproductive capacity by amino modification. Our results highlight the potential environmental risk of amino modified nanopolystyrene in inducing reproductive toxicity on gonad development and reproductive capacity of environmental organisms.

Alendronate delivery on amino modified mesoporous bioactive glass scaffolds to enhance bone regeneration in osteoporosis rats.

The regeneration capacity of osteoporotic bones is generally lower than that of normal bones. Nowadays, alendronate (AL) are orally administrated for osteoporosis due to the inhibition of bone resorption. However, systemic administration of AL is characterized by extremely low bioavailability and high toxicity. In this study, the amino-modified mesoporous bioactive glass scaffolds (N-MBGS) were fabricated by a simple powder processing technique as a novel drug-delivery system for AL. The effects of AL on the osteogenic differentiation of bone mesenchymal stem cells derived from ovariectomized rats (rBMSCs-OVX) were first estimated. The loading efficiency and release kinetics of AL on N-MBGS were investigated in vitro and the osteogenesis of AL-loaded N-MBGS in rat calvarial defect model was detected by micro-CT measurements and the histological assay. Our results revealed that proper concentration of AL significantly promoted osteogenic differentiation of rBMSCs-OVX. The amount and delivery rate of AL were greatly improved through amino modification. Additionally, scaffolds with AL showed better bone formation in vivo, especially for the N-MBGS group. Our results suggest that the novel amino-modified MBGS are promising drug-delivery system for osteoporotic bone defect repairing or regeneration. The experimental schematic of the novel amino-modified MBGS as a promising drug-delivery system for osteoporotic bone regeneration.

Superiority of amino-modified chiral mesoporous silica nanoparticles in delivering indometacin.

The present study established indometacin (IMC) delivery system with chiral mesoporous silica nanoparticles (CMSNs) and amino-modified chiral mesoporous silica nanoparticles (Amino-CMSNs) that previously reported as pharmaceutical excipients, and their systemic biological effects, mainly consisting of in vitro drug intestinal permeability, haemolysis assay, in vivo pharmacokinetics, anti-inflammation pharmacodynamics and gastric irritation, were addressed. It turned out that the two IMC delivery systems established by CMSN and Amino-CMSN significantly improved drug intestinal permeability due to the improved drug dissolution caused by conversion of drug crystalline state to amorphous phase. Further, IMC-loaded Amino-CMSN was the superior choice because of its higher dissolution rate. Furthermore, CMSN and Amino-CMSN were safe to be circulated in blood, and Amino-CMSN with significant lower haemolysis ratio than CMSN was better for the minimum haemolytic behaviour. Oral bioavailability and anti-inflammation effect of IMC delivery systems established by CMSN and Amino-CMSN were enhanced compared with IMC, which was attributed to the primary cause of the improvement of IMC dissolution, and Amino-CMSN exhibited better biological effect. As a result of these facts, it is believed that the effective delivery of IMC by Amino-CMSN will provide a new candidate to formulate poorly soluble drugs so as to significantly develop pharmaceutical application.

pH-Sensitive mesoporous silica nanoparticles anticancer prodrugs for sustained release of ursolic acid and the enhanced anti-cancer efficacy for hepatocellular carcinoma cancer.

Ursolic acid (UA) as a nature product exhibits good anti-cancer activity, low toxicity, and good liver protection features. However, the low-solubility and poor bioavailability restrict its further clinical application. To overcome this problem, a pH-sensitive prodrug delivery system (UA@MSN-UA) that incorporated acid-sensitive linkage between drug and silica-based mesoporous nanosphere (MSN) was successfully designed and synthesized. The physicochemical properties of the UA@MSN-UA nanoparticles were investigated for shape, particle size, zeta potential, nitrogen adsorption-desorption and infrared (IR) spectroscopy. The nanoparticles were further evaluated for in vitro cytotoxicity, including proliferation inhibition, cell cycle distribution and apoptotic effects against human hepatocellular carcinoma HepG2 cells. The TEM image showed that the size of synthesized MSN nanoparticle was a near-spherical shape with ~100nm diameter. In vitro cytotoxicity testing demonstrated that UA@MSN-UA nanoparticles prodrug exhibited higher proliferation inhibition, cell cycle arrest at the G2/M phase and significantly caused the early and late apoptosis in HepG2 cells, which would be contributed to high loading capacity, high cellular uptake and sustained release of UA. Overall, the UA-modified MSN prodrug delivery system can be a promising drug carrier for improving the bioavailability of UA, and further enhance its anti-cancer efficacy.

Comparison of bare and amino modified mesoporous silica@poly(ethyleneimine)s xerogel as indomethacin carrier: Superiority of amino modification.

The purpose of this study was to facilely develop amino modified mesoporous silica xerogel synthesized using biomimetic method (B-AMSX) and to investigate its potential ability to be a drug carrier for loading poorly water-soluble drug indomethacin (IMC). For comparison, mesoporous silica xerogel without amino modification (B-MSX) was also synthesized using the same method. The changes of characteristics before and after IMC loading were systemically studied using fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS) and nitrogen adsorption/desorption analysis. The results showed that B-MSX and B-AMSX were spherical nanoparticles with mesoporous structure. Compared with B-MSX, IMC loading capacity of B-AMSX was higher because more drug molecules can be loaded through stronger hydrogen bonding force. DSC and SAXS analysis confirmed the amorphous state of IMC after being loaded into B-MSX and B-AMSX. The in vitro drug release study revealed that B-MSX and B-AMSX improved IMC release significantly, and B-AMSX released IMC a little faster than B-MSX because of larger pore diameter of IMC-AMSX. B-MSX and B-AMSX degraded gradually in dissolution medium evidenced by color reaction and absorbance value, and B-AMSX degraded slower than B-MSX due to amino modification. In conclusion, B-AMSX with superiority of higher loading capacity and enhanced dissolution release can be considered to be a good candidate as drug carrier for IMC.

Highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste with amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent.

Amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent was used as a novel sorbent to highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste in the presence of Fe(II). These hot-dip galvanizing pickling waste mainly contain ZnCl2 and FeCl2 in aqueous HCl media. The properties of this magnetic adsorbent were examined by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), infrared spectrometer (FT-IR) and BET surface area measurements. Various factors influencing the adsorption of Zn(II) ion such as initial concentration of metal ions, the amount of adsorbent, pH value of the solutions, the concentration of coexisting iron ion were investigated by batch experiments. The results indicated that the adsorption equilibrium data obeyed the Freundlich model with maximum adsorption capacities for Zn(II) to 169.5mg/g. The maximum adsorption occurred at pH 5±0.1 and Fe(II) interferences had no obvious influence. This work provides a potential and unique technique for zinc ion removal from hot-dip galvanizing pickling waste.

Amino modification of biochar for enhanced adsorption of copper ions from synthetic wastewater.

Biochar was modified as a high efficient and selective absorbent for copper ions (Cu(II)) by nitration and reduction. Results of X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) analyses indicated that the amino groups were chemically bound to the functional groups on the biochar surface. Kinetics, thermal dynamics, and adsorption and desorption of Cu(II) in fixed-bed were investigated. The results demonstrated that the amino-modified biochar exhibited excellent adsorption performance for Cu(II). The adsorption capacity and bed volume of the modified biochar are five- and eight- folds of the pristine biochar, respectively. The Cu(II) combined with the amino groups through strong complexation based on the comparison of XPS and ATR-FTIR analyses before and after adsorption, which endows it with the high pH stability and ion selectivity.