A facile one-pot protocol for the synthesis of tetrazolyl-tetrahydroisoquinolines via novel domino intramolecular cyclization/Ugi-azide sequence

A facile one-pot, four-component domino reaction between 2-(2-bromoethyl)benzaldehyde, isocyanide, amine, and azide for the synthesis of tetrazolyl-tetrahydroisoquinoline derivatives has been developed. The reaction sequence involves intramolecular replacement of halide by iminium nitrogen followed by Ugi-azide reaction. The reaction is catalyst/additive free and takes place under ambient conditions with short reaction times to furnish products in good to excellent yields.     

高硫煤镜质组热解过程中结构变化及有机硫形态变迁规律研究

用手选富集与离心分离相结合的方法,从两种全硫含量相近的新西兰煤（NXL;S_t,ad=1.84%）和山西煤（SX;S_t,ad=1.80%）中分离出高纯度镜质组。在高纯Ar气氛下,分别制备了300、500、700和1 000 ℃下的镜质组焦。用FT-IR研究了两种镜质组中的脂肪氢、芳香氢随温度的变化,结果表明,SX镜质组中脂肪氢的相对含量较高,在热解过程中活性高于同温度下的NXL镜质组;两种镜质组中的脂肪氢相对含量都随温度升高而降低,温度高于500 ℃时,SX镜质组中脂肪氢相对含量基本不变,当温度高于700 ℃时,NXL镜质组中的脂肪氢相对含量基本保持不变;热解过程芳香氢都表现出先增大后减小的趋势。用XPS研究了镜质组中的有机硫含量及形态随温度的变化,结果表明,SX镜质组中易分解的有机硫化物较多,在300 ℃以下即可分解完全;NXL镜质组中的有机硫化物分解完全在700 ℃左右,两种镜质组中的噻吩类硫的含量都随热解温度的升高而增加,砜类硫的含量随热解温度的升高而降低。     

Rapid analysis of phthalic acid esters in environmental water using fast elution gas chromatography with mass spectrometry and adaptive library spectra

A method for the fast determination of the components in a complex sample by using gas chromatography with mass spectrometry was developed and used for the quantitative analysis of phthalic acid esters in environmental water. In the method, the adaptively corrected mass spectra were used to compensate for the differences between the library spectra and the measured ones in the experiment. The correction was obtained by the iterative transformation of the library spectra using iterative target transformation factor analysis, and the resolution was performed by non‐negative immune algorithm using the corrected spectra. Rapid analysis of 16 phthalic acid esters in water samples was achieved using fast elution gas chromatography with mass spectrometry measurements. The results show that the mass spectra and chromatographic profiles of the phthalic acid esters can be obtained from the overlapping signal of 13 min elution, and accurate quantitative analysis can be obtained. The recoveries of the phthalic acid esters obtained by standard addition are between 90.3 and 107.4%, and the relative standard deviations obtained in repeated measurements are less than 9%.     

In situ single‐crystal to single‐crystal (SCSC) transformation of the one‐dimensional polymer catena‐poly[[diaqua(sulfato)copper(II)]‐μ2‐glycine] into the two‐dimensional polymer poly[μ2‐glycine‐μ4‐sulfato‐copper(II)]

The one‐dimensional coordination polymer catena‐poly[diaqua(sulfato‐κO)copper(II)]‐μ₂‐glycine‐κ²O:O′], [Cu(SO₄)(C₂H₅NO₂)(H₂O)₂]_n, (I), was synthesized by slow evaporation under vacuum of a saturated aqueous equimolar mixture of copper(II) sulfate and glycine. On heating the same blue crystal of this complex to 435 K in an oven, its aspect changed to a very pale blue and crystal structure analysis indicated that it had transformed into the two‐dimensional coordination polymer poly[(μ₂‐glycine‐κ²O:O′)(μ₄‐sulfato‐κ⁴O:O′:O′′:O′′)copper(II)], [Cu(SO₄)(C₂H₅NO₂)]_n, (II). In (I), the Cu^II cation has a pentacoordinate square‐pyramidal coordination environment. It is coordinated by two water molecules and two O atoms of bridging glycine carboxylate groups in the basal plane, and by a sulfate O atom in the apical position. In complex (II), the Cu^II cation has an octahedral coordination environment. It is coordinated by four sulfate O atoms, one of which bridges two Cu^II cations, and two O atoms of bridging glycine carboxylate groups. In the crystal structure of (I), the one‐dimensional polymers, extending along [001], are linked via N—H...O, O—H...O and bifurcated N—H...O,O hydrogen bonds, forming a three‐dimensional framework. In the crystal structure of (II), the two‐dimensional networks are linked via bifurcated N—H...O,O hydrogen bonds involving the sulfate O atoms, forming a three‐dimensional framework. In the crystal structures of both compounds, there are C—H...O hydrogen bonds present, which reinforce the three‐dimensional frameworks.     

Cu Doping-Induced Transformation from [Ag62S12(SBut)32]2+ to [Ag62−xCuxS12(SBut)32]4+ Nanocluster

The change in the valence state of nanocluster can induce remarkable changes in the properties and structure. However, achieving the valence state changes in nanoclusters is still a challenge. In this work, we use Cu²⁺ as dopant to “oxidize” [Ag₆₂S₁₂(SBu^t)₃₂]²⁺ (4 free electrons) to obtain the new nanocluster: [Ag_62−xCu_xS₁₂(SBu^t)₃₂]⁴⁺ with 2 free electrons. As revealed by its structure, the [Ag_62−xCu_xS₁₂(SBu^t)₃₂]⁴⁺ (x=10∼21) has a similar structure to that of [Ag₆₂S₁₂(SBu^t)₃₂]²⁺ precursor and all the Cu atoms occupy the surface site of nanocluster. It′s worth noting that with the Cu atoms doping, the [Ag_62−xCu_xS₁₂(SBu^t)₃₂]⁴⁺ nanocluster is more stable than [Ag₆₂S₁₂(SBu^t)₃₂]²⁺ at higher temperature and in electrochemical cycle. This result has laid a foundation for the subsequent application and exploration. Overall, this work reveals crystals structure of a new Ag−Cu nanocluster and offers a new insight into the electron reduction/oxidation of nanocluster.     

The Influence of Different Pretreatment Methods on Color and Pigment Change in Beetroot Products

Vegetable processing pomace contains valuable substances such as natural colors that can be reused as functional ingredients. Due to a large amount of water, they are an unstable material. The aim of our research was to assess how the pretreatment method (thermal or nonthermal) affects the properties of powders obtained from beet juice and pomace after the freeze-drying process. The raw material was steamed or sonicated for 10 or 15 min, and then squeezed into juice and pomace. Both squeezed products were freeze-dried. The content of dry substance; L*, a*, and b* color parameters; and the content of betalain pigments were analyzed. Pretreatments increased the proportion of red and yellow in the juices. Steam and ultrasound caused a significant reduction in parameter b* in the dried pomace. A significant increase in betanin in lyophilizates was observed after pretreatment with ultrasound and steam for 15 min. As a result of all experiments, dried juices and pomaces can also be used as a colorant source. However, there is higher potential with pomaces due to their additional internal substances as well as better storage properties. After a few hours, juice was sticky and not ready to use.     

Heavy Metals in Acrylic Color Paints Intended for the School Children Use: A Potential Threat to the Children of Early Age

Heavy metals are the harmful elements, regarded as carcinogens. Nevertheless, owing to their physical and chemical properties, they are still used in the production of several commercial products. Utilization of such products increases the chance for the exposure of heavy metals, some of them are categorized as probable human carcinogens (Group 1) by the International Agency for Research on Cancer. Exposure of heavy metals to school children at early age can result severe life time health issues and high chance of emerging cancer. Thus, we have performed study relating to the presence of heavy metals in acrylic color paints commonly used by the school children. Acrylic paints of different colors were assayed for seven potential heavy metals manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), arsenic (As), cadmium (Cd) and lead (Pb) using microwave digestion and iCAPQ inductively coupled plasma mass spectrometry (ICP-MS) system. The optimized method including paints digestion reagents nitric acid (HNO₃, 65%, 5 mL) and hydrofluoric acid (HF, 40%, 2 mL) have offered excellent method performance with recovery values ranged between 99.33% and 105.67%. The elements were identified in all of the analyzed samples with concentrations ranged from 0.05 to 372.59 µg/g. Cd constitutes the lower percentage (0.05%), whereas Zn constitutes high ratio contribution which was tremendously high (68.33%). Besides, the paints contamination was also color specific, with considerably total heavy metal concentrations found in brunt umber (526.57 µg/g) while scarlet color (12.62 µg/g) contained lower amounts. The outcomes of our investigation highlight the necessity for guidelines addressing the heavy metals in acrylic color paints intended for the school children usage.     

Characterization of Food Packaging Films with Blackcurrant Fruit Waste as a Source of Antioxidant and Color Sensing Intelligent Material

Chitosan and pectin films were enriched with blackcurrant pomace powder (10 and 20% (w/w)), as bio-based material, to minimize food production losses and to increase the functional properties of produced films aimed at food coatings and wrappers. Water vapor permeability of active films increased up to 25%, moisture content for 27% in pectin-based ones, but water solubility was not significantly modified. Mechanical properties (tensile strength, elongation at break and Young’s modulus) were mainly decreased due to the residual insoluble particles present in blackcurrant waste. FTIR analysis showed no significant changes between the film samples. The degradation temperatures, determined by DSC, were reduced by 18 °C for chitosan-based samples and of 32 °C lower for the pectin-based samples with blackcurrant powder, indicating a disturbance in polymer stability. The antioxidant activity of active films was increased up to 30-fold. Lightness and redness of dry films significantly changed depending on the polymer type. Significant color changes, especially in chitosan film formulations, were observed after exposure to different pH buffers. This effect is further explored in formulations that were used as color change indicators for intelligent biopackaging.     

Probiotic Yoghurts with Sea Buckthorn,Elderberry, and Sloe Fruit Purees

Elderberries, sea buckthorn, and sloe berries are fruits of wild-grown bushes, valued in folk medicine for their health-promoting properties but still rarely applied in food. The aim of the present study was to produce probiotic yoghurts with a 10% addition of sweetened purees prepared from elderberries (EPY), sea buckthorn (SBPY), and sloe berries (SPY) and to assess their chemical composition, acidity, content of polyphenols and anthocyanins, ferric reducing antioxidant power (FRAP) and antiradical power (ARP), level of starter microbiota, concentration of acetaldehyde and diacetyl, syneresis, instrumentally measured color and texture parameters, and sensory acceptance. The results were compared to those obtained for plain probiotic yoghurt (PPY) and the changes tracked during 1 month of cold storage at 2 week intervals. The addition of elderberry and sloe berries significantly increased the antioxidant capacity of probiotic yoghurts, probably due to a high content of polyphenols, especially anthocyanins. However, anthocyanins were more stable in the EPY when compared to the SPY. All yoghurt treatments were characterized by good sensory quality and viability of starter microorganisms, including probiotic strains during cold storage. Elderberries promoted the evolution of diacetyl in yoghurts during storage and, together with sloe berries, produced increased syneresis and the greatest changes in color profile compared to PPY.     

Effect of Filtrated Osmotic Solution Based on Concentrated Chokeberry Juice and Mint Extract on the Drying Kinetics,Energy Consumption and Physicochemical Properties of Dried Apples

Background: Filtration of osmotic solution affects selective penetration during osmotic dehydration (OD), and after drying is finished, this can influence the chemical composition of the material, which is also modified by OD. Methods: Osmotic dehydration was carried out in filtrated and non-filtrated concentrated chokeberry juice with the addition of mint infusion. Then, this underwent convective drying, vacuum-microwave drying and combined convective pre-drying, followed by vacuum-microwave finishing drying. Drying kinetics were presented and mathematical models were selected. The specific energy consumption for each drying method was calculated and the energy efficiency was determined. Results and Discussion: The study revealed that filtration of osmotic solution did not have significant effect on drying kinetics; however, it affected selective penetration during OD. The highest specific energy consumption was obtained for the samples treated by convective drying (CD) (around 170 kJ·g⁻¹ fresh weight (fw)) and the lowest for the samples treated by vacuum-microwave drying (VMD) (around 30 kJ·g⁻¹ fw), which is due to the differences in the time of drying and when these methods are applied. Conclusions: Filtration of the osmotic solution can be used to obtain the desired material after drying and the VMD method is the most appropriate considering both phenolic acid content and the energy aspect of drying.