Study of the thermal elimination process of sulphinyl-based PPV precursors by solid state NMR

A sensitive protocol to judge the completeness of the elimination reaction for soluble and insoluble conjugated polymers prepared via precursor routes is presented based on UV/vis and ¹H wideline NMR relaxometry in the solid state. Especially the proton spin-lattice decay time in the rotating frame, T_1ρH, has proven to be suitable for an accurate determination of the completeness of the elimination reaction. Especially for long side-chain substituted PPV derivatives, UV/vis seems to be limited due to thermochromic effects. Furthermore, it is shown by solid state ²H wideline NMR spectroscopy that incomplete elimination results in an enhanced polymer backbone chain mobility. Both the completeness of elimination and insight into the molecular dynamics can be of significant importance toward the performance of photovoltaic devices.     

Practical implications of the phase-compositional assessment of lipid-based food products by time-domain NMR

The objective of this work is to determine the solid fat content (SFC) of the fat-oil phase in oil-in-water (O/W) emulsions, i.e., the droplet SFC, using transverse relaxation decay deconvolution (TRDD) analysis. The TRDD NMR experiment classifies protein protons as mobile, semimobile, and nonmobile. Hence, protein contributes more or less to the solid content detected by TRDD as a function of pH, protein content, and protein denaturation. By taking into account the protein contribution to the overall solid content, one can estimate the droplet solid content in O/W emulsions. The SFC can then be deduced if one converts the ingredients' mass fraction into ingredients' proton fraction using the ingredients' proton densities.     

Filtration in hydrophobic media: 2. A triglyceride partition phenomenon as observed by tangential filtration of butter oil

Having demonstrated a partition of a hydrophobic medium (butter oil) under crossflow filtration and having tentatively explained the phenomenon on stereochemical and saturation basis, the molecular partition was studied by tangential filtration. Under specific hydrodynamic conditions, a filtration phenomenon was demonstrated. The solid fat content (SFC) at 20°C of the fractions obtained was investigated accordingly. When the molecular partition takes place, an SFC divergency between the permeate and the retentate is observed. The amplitude of the divergency depends on experimental conditions.     

Optical Determination of Solid Fat Content in Fats and Oils: Effects of Wavelength on Estimated Accuracy

The melting profile of solid fat content (SFC) is a parameter of primary importance for the food industry since it affects many important product characteristics such as stability, physical appearance, spreadability, and sensation in the mouth. Reference techniques to measure SFC in fats and oils include pulsed nuclear magnetic resonance (pNMR) and differential scanning calorimetry (DSC), which are reliable and accurate, but require expensive instrumentation and trained personnel. Herein, the accuracy of a recently proposed optical technique to measure SFC is investigated in terms of peak wavelength of incident radiation. A sensor system featuring an array of seven LEDs with peak wavelength in the visible and NIR range is built, and the results compared with data from DSC. All the wavelengths investigated have high accuracy in SFC estimation, especially at 590 (yellow) and 880 nm (NIR). Practical applications : Quick and easy determination of solid fat content in fats and oils by a simple experimental setup. The technique is based on optical attenuation measurements during a thermal cycle. The technique can be implemented in a measurement instrument for in-situ analysis of solid fat content.     

TAG composition and solid fat content of palm oil, sunflower oil, and palm kernel olein belends before and after chemical interesterification

Modification of the characteristics of palm oil (PO), sunflower oil, and plam kernel olein (PKOo) according to conventional three-component mixture designs was undertaken by a combination of blending and chemical interesterification (CIE) techniques. TAG composition and solid fat content (SFC) profile of the starting blends were analyzed and compared with those of the interesterified blends. Upon CIE, extensive rearrangement of FA among TAG was evident. Concentrations of several TAG were increased, some were decreased, and several new TAG were formed. The resulting changes in TAG profile were reflected in the SFC of the blends. The SFC values of the chemically interesterified blends, except binary blends of PO/PKOo, revealed that they were softer than their respective starting blends. SFC data also indicated that eutectic interaction occurred between PO and PKOo in the starting blends and that this interaction was diminished after CIE.     

Determination of solid fat index by fourier transform infrared spectroscopy

A unique and rapid Fourier transform infrared (FTIR) spectroscopic method for the determination of solid fat index (SFI) of fats and oils was developed, which is capable of predicting the SFI profile of a sample in approximately two minutes, without the need for tempering. Hydrogenated soybean oil samples (n=72), pre-analyzed for SFI by dilatometry, were melted and their FTIR spectra acquired using a 25 μm NaCl transmission flow cell maintained at 80°C. Approximately half the samples were used for calibration, with the balance used as validation samples. Partial least squares (PLS) calibrations were developed from selected spectral regions that are associated with thecis, trans, ester linkage and fingerprint regions of the spectrum and related to the dilatometric SFI values obtained at 50, 70, 80, and 92°F. The calibrations were initially optimized and cross-validated by using the “leave one out” approach, with the accuracy and reproducibility of the calibration models assessed by predicting the validation samples. The overall cross validation accuracy of the PLS calibration models was in the order of ±0.71 SFI units over the four temperatures. Week-to-week validation accuracy and reproducibility was determined to be ±0.60 and ±0.38 SFI units, respectively, the reproducibility being within the specifications associated with the dilatometric reference method. To facilitate routine “on-line” FTIR analyses, a Visual Basic program was written to drive the spectrometer, prompt the user to load the sample, calculate, and print the SFI values determined from the PLS calibrations. As structured, the FTIR method has the potential to serve as a viable substitute for the traditional dilatometric SFI method, with the elimination of the tempering step reducing analysis time from hours to minutes. The FTIR approach should also be applicable to the determination of solid fat content if calibrated against solids data obtained by nuclear magnetic resonance.     

The phase composition and molecular motions of plasticized wheat gluten-based biodegradable polymer materials studied by solid-state NMR spectroscopy

The water plasticized wheat gluten (WG) materials were prepared by thermal processing and studied by dynamic mechanical analysis and solid-state NMR spectroscopy. The results indicate that the materials displayed a broad distribution of molecular motions and could be divided into different phases in terms of their mobility above the T_g. The rigid phase mainly consisted of proteins and starch with enhanced interactions between the two components via hydrogen bonding with water molecules. Lipid and water formed the mobile phase, however, lipid molecules were always more mobile than water. The intermediate phase consisted of plasticized starch and proteins (mainly proline and glutamine segments). The whole plasticized WG materials were heterogeneous at a scale of 20-30 nm, but the miscibility between proteins and starch was enhanced via increasing hydrogen bonding interactions with water molecules. Such strong hydrogen bonding acted as adhesion among these multi-components/phases over a wide range of temperature thus resulting in good mechanical properties of the materials. The results demonstrated that solid-state NMR techniques can provide valuable information of quantitative composition of phase structures with different mobility in a multi-component system and the chemical nature of each phase along with the interactions among these components/phases.     

固相萃取-流动注射-化学发光法测定鸡饲料和鸡肉中的氯霉素

基于氯霉素与铬(Ⅵ)的氧化-还原反应所产生的铬(Ⅲ)催化Luminol(鲁米诺)-过氧化氢化学发光体系的研究,样品中氯霉素采用液乙酸乙酯提取,固相萃取净化,结合流动注射技术和化学发光检测,建立了一种高灵敏度的快速测定鸡饲料和鸡肉中氯霉素的新方法。方法线性范围为0.03～5mg/mL和0.04～5μg/mL,方法检出限为0.03mg/kg和0.05μg/kg,平均回收率>75%,RSD为11.2%和15.4%(饲料:2.0mg/kg;鸡肉:0.5μg/kg,n=11)。     

Water balance and pore structure development in cementitious materials in internal curing with modified superabsorbent polymer studied by NMR

In this contribution, the water balance between modified superabsorbent polymer particles of various grain sizes and a hydrating cement matrix is studied both for ordinary and white Portland cements by means of NMR relaxometry. Different approaches for the evaluation of the experimental data are compared: inverse Laplace transforms and several multicomponent fitting models. Both evaluations provide well-comparable results with respect to the overall water quantities absorbed and re-released by the superabsorber. The experimental data indicate fast water uptake within less than 5 min after watering the superabsorber/cement mixture. The re-release of the water begins along with the onset of the hydration reaction and is finished after 1 day for superabsorber powders with a dry grain size below 125 μm and takes about 2 days for larger dry grain size. The water uptake of the superabsorber inside the cement matrix is quantified to about 2250% of its dry weight.     

顶空固相微萃取-气相色谱法测定水中1,4-二氯苯

建立顶空固相微萃取(HS-SPME)气相色谱测定水中1,4-二氯苯(1,4-DCB).选择SPME前处理技术,毛细色谱柱分离,ECD检测器检测.最低检出质量浓度为1.88 μg/L;工作曲线相关系数为0.992 2;低、中、高三种浓度加标回收率分别为108％、93.1％、117％,相对标准偏差(n=6)分别为7.09％、6.21％、6.98％.该方法具有较好的灵敏度、精密度和回收率.     

Determination of solid fat content (SFC) of binary fat blends and use of these data to predict SFC of selected ternary fat blends containing low-erucic rapeseed oil

Several oils and fats often used for the industrial preparation of European shortenings were blended in binary systems. The equilibrium (after 48 h at 15°C) solid fat contents (SFC; determined by pulsed NMR spectroscopy) were measured and plotted against blend composition. SFC of the blends resulted from the SFC of each fat for the considered temperature as well as the type of interaction existing between those fats (namely, ideal behavior, monotectic interaction, eutectic interaction, and so on). The type of relationship fitted was dependent on the kind of interaction: Linear relationships were found for total compatibility between fats, and polynomial-type (order 2) relationships were found for fats exhibiting incompatibility. Some corresponding ternary oils and fats blends were also prepared and analyzed. Selected relationships (regression equations of the fitted curves) obtained for binary blends were combined in order to calculate the SFC of the corresponding ternary blends. Experimental values were generally close to predicted ones. The representation of SFC as a function of composition is interesting as it allows one to determine rapidly and easily the type of molecular interaction between two fats and also to determine equations that can be combined to calculate easily the SFC of corresponding ternary blends crystallized in the same way with a good accuracy. The texture (hardness) of several binary and ternary blends was also measured. The combination of the results obtained for SFC with the results obtained for the hardness of binary blends allows the prediction of the hardness of a corresponding ternary blend under the same conditions.     

Melting behavior of blends of milk fat with hydrogenated coconut and cottonseed oils

The melting behavior of milk fat, hydrogenated coconut and cottonseed oils, and blends of these oils was examined by nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). Solid fat profiles showed that the solid fat contents (SFC) of all blends were close to the weighted averages of the oil components at temperatures below 15°C. However, from 15 to 25°C, blends of milk fat with hydrogenated coconut oils exhibited SFC lower than those of the weighted averages of the oil components by up to 10% less solid fat. Also from 25 to 35°C, in blends of milk fat with hydrogenated cottonseed oils, the SFC were lower than the weighted averages of the original fats. DSC measurements gave higher SFC values than those by NMR. DSC analysis showed that the temperatures of crystallization peaks were lower than those of melting peaks for milk fat, hydrogenated coconut oil, and their blends, indicating that there was considerable hysteresis between the melting and cooling curves. The absence of strong eutectic effects in these blends suggested that blends of milk fat with these hydrogenated vegetable oils had compatible polymorphs in their solid phases. This allowed prediction of melting behavior of milk-fat blends with the above oils by simple arithmetic when the SFC of the individual oils and their interaction effects were considered.     

催化裂化油浆固含量测定及组成分析

采用灰分法、过滤法、离心法测量了某重油催化裂化装置外甩油浆的固体颗粒含量,对几种方法在固含量测定方面的结果差异进行对比分析。实验结果表明,离心法测量的固含量约为2850μg/g,介于灰分法和过滤法之间。离心法结果显示,油浆中重组分与细粉颗粒存在较强的吸附作用,分离中能否准确得到焦粉是造成结果差异的主要原因。离心法耦合后续焙烧能够分离获得油浆中一定量的催化剂细粉颗粒,通过激光粒度仪、元素分析仪、XRD、BET、SEM-EDS等手段对分离得到的固体颗粒以及初始FCC催化剂进行了表征。FCC催化剂粒径集中在32～120μm之间,为规则的球形分布,油浆中的固体颗粒呈不规则的块状分布,粒径在0.4～40μm之间,其中催化剂细粉的粒径在1～30μm之间;催化裂化油浆中的固体颗粒组成主要有催化剂细粉、焦粉和碱金属K、Ca、无机盐和金属元素Sb、Fe等。     

Chemical composition and physical properties of soft (tub) margarines sold in Malaysia

Seven samples of domestic and imported Malaysian tub margarines were analyzed for their fatty acid and triglyceride (carbon number) composition, solid fat content, dropping and softening points, crystallization temperature, polymorphic form, color, and textural attributes. Domestic margarines were formulated from palm oil or palm olein and palm kernel oil with a liquid oil but no hydrogenated oils. Two imported products contained hydrogenated palm oil product, which resulted in a high level of β′ crystals, whereas the domestic nonhydrogenated products contained more β than β′ crystals. Crystal habit was related to the fatty acid and triglyceride composition of the high-melting glycerides. Domestic products were firmer in texture, probably because they were formulated to be sold in a tropical climate.     

NMR Molecular Dynamic and Thermal Analysis Studies of Amescla Resin

Two polyethylene (PE) samples (named BF and ES) were blended with 5% organoclay by melt processing at different shear rates. X-ray diffraction (XRD) showed that the organoclay was incorporated into the PE matrices. From the results it was determined that the level of intercalation was very similar for both systems. The knowledge of molecular dynamics of PE nanocomposites is very important since it depends on the clay dispersion. Thus, the objective of this work was to employ a new technique to understand changes in the molecular mobility for these systems. The samples were characterized by proton nuclear spin-lattice relaxation time (T₁H), which is measured in a low-field NMR spectrometer. The influence of the samples' preparation was evaluated through the relaxation data. For polyethylene resins, two values of relaxation parameter were found and they were attributed to mobile region (low value) and rigid region (high value). These values change after nanocomposite formation, confirming the changes in the resin matrix after organoclay was incorporated.     

Feasibility Study on the Determination of the Solid Fat Content of Fats Using Temperature‐Modulated Optical Refractometry

The solid fat content (SFC) at different temperatures is an important characteristic of fat phases because it correlates to functionality in product applications. Consequently, this characteristic is also used to specify fat compositions in trade. Of three methods applicable, pulsed nuclear magnetic resonance (pMNR) is predominantly applied. Dilatometry and differential scanning calorimetry (DSC) find much less application. Handling with glass vials and high equipment costs make the search for alternatives to pNMR a useful endeavor. Optical refractometry is evaluated with respect to its potential to determine SFC values. Since refractometry is in the first place not suited for suspensions the positive results found are surprising. Applying temperature modulated optical refractometry (TMOR), isothermal optical refractometry with a superimposed temperature undulation yields repeatable results that are highly comparable to pNMR data. For the system studied (palm oil, coconut oil, partially hydrogenated palm oil), TMOR clearly outperforms DSC when pNMR is considered the method of reference. The key finding that refractive index is suitable to determine properties of suspensions is accompanied by the indications that refractometry has the potential to enable competitive methods within the fat technology. Practical Applications: The observation that refractometry can deliver quantitative data on fat suspensions enables the development of an array of new analytical methods. Next to SFC values and melting point, studies on the characterization of polymorphism can be envisioned. Since the device is robust and affordable, it could be in product development and quality control.     

Relationship between slip melting point and pulsed NMR data of palm kernel oil

A quantitative relationship between slip melting point (SMP) of palm kernel oil and pulsed nuclear magnetic resonance (NMR) data was established. Regression analysis on the SMP and solid fat content (SFC) data by NMR afforded the following relationship: SMP (°C) = 0.03278 X (SFC 10) + 0.1458 X (SFC 20) + 19.1738 where SFC 10 was the solid fat content (%) at 10°C and SFC 20 was the solid fat content (%) at 20°C. The coefficient of multiple correlation was 0.87871. The equation was tested with 12 samples of crude and refined palm kernel oil. SMPs as determined indirectly by NMR correlated well with the conventional open capillary tube results (r = 0.99998). The maximum difference observed was 0.3°C. The correlation can be applied usefully for quality control.     

固相萃取-高效液相色谱法测定化妆品中的丙烯酰胺

建立了保湿防晒系列化妆品中丙烯酰胺含量的高效液相色谱测定方法.采用丙酮超声提取样品中的待测物,提取液经浓缩吹干后用水溶解,经固相萃取小柱净化后用反相高效液相色谱法测定.丙烯酰胺在0.01 mg/L～5.0 mg/L与对应峰面积呈良好线性关系(R=0.999 5).在添加量为0.05 mg/kg,0.50 mg/kg和1.00 mg/kg时,平均回收率在81.3%～83.8%,变异系数在2.3%～3.0%,方法检出限为0.05 mg/kg.结果表明,该法操作简便、灵敏、准确,适用于化妆品中丙烯酰胺含量的测定.