Humidity-Regulating Trays: Moisture Absorption Kinetics and Applications for Fresh Produce Packaging

For packaged fresh produce, inappropriate high relative humidity (RH) levels and condensation of water vapour cause premature spoilage. Humidity-regulating trays were developed to solve this issue. They were made from a thermoformed multilayer structure: polyethylene (outside)/foamed hygroscopic ionomer (active layer) with 0 or 12 wt% NaCl/hygroscopic ionomer (sealing layer, inside). Moisture absorption kinetics of the humidity-regulating trays with 0 and 12 wt% NaCl (T-0 and T-12, respectively) was investigated under different RH conditions (76, 86, 96 and 100 %) at 13 °C for 16 days. Additional trays containing 7 g of distilled water were closed with a high barrier lidding film, and the headspace RH was continuously monitored as a function of time. As control, a polypropylene (control-PP) tray was used. Strawberries and tomatoes were used to test capability of the trays to regulate in-package RH. The amount of water absorbed by the T-0 and T-12 trays was 7.6 and 13.2 g, respectively. Active hygroscopic ionomer layer was effective in water vapour absorption, and the integration of NaCl into this active layer increased the water vapour absorption capacity of the tray. The Weibull model adequately described the moisture sorption kinetics of the individual packaging trays as a function of time. The headspace RH of trays covered with a lidding film was found to be 89.8, 99.6 and 100 % in the T-12, T-0 and control-PP trays, respectively. The T-12 trays containing fresh produce best regulated the in-package RH below 97 % and maintained overall quality, but at the expense of slightly higher product weight loss (2–3 wt% for strawberry, 1 wt% for tomatoes) compared to the control-PP trays (0.3–0.6 wt%).     

Bicyclische Oxalamidine – Bausteine für hochsubstituierte 2,2′-Bipyridine und Benzolderivate

Bicyclic Oxalic Amidines as Building Blocks for Highly Substituted 2,2′-Bipyridines and Benzene Derivatives The bis-imidoylchlorides 1 derived from oxalic acid exhibit a high regio- and chemoselectivity. As in the case of 2-picolylamine 2 the acylation with oxalyl chloride furnished the expected open chained oxalic diamides 3a while the imidoylchlorides 1 yield exclusively the new pyrido[1,2-a]-pyrazines 4 . These heterocycles represent readily crystallisable and orange-red coloured compounds with a mesomeric dipolar aromatic substructure. The synthetic value of 4 is based on their easy transformation into highly substituted arenes and hetarenes. Thus, electron deficient dienophiles as dimethyl acetylenedicarboxylate lead to the bipyridines 6 via Hetero-Diels-Alder-Reaction and subsequent 1,5-hydrogen shift. In a complex reaction the derivatives of maleic acid 7a – c yield the bipyridines of type 9 while the new hexasubstituted arenes 10 can be isolated under anaerobic conditions and with an excess of dienophilic component. A x-ray structural determination of 10b shows an alternation of bond lenghts in the benzene ring. This can be considered as a distinct disturbance of aromaticity caused by the arrangement of substituents.     

Diazoverbindungen. 72. (Diazoalkyl)phosphane – Synthese durch elektrophile Diazoalkansubstitution und oxidative Additionsreaktionen am Phosphor

Diazo Compounds. 72. Diazoalkylphosphanes – Synthesis by Electrophilic Diazoalkane Substitution and Oxidative Addition Reactions at Phosphorus Electrophilic diazoalkane substitution of the diazomethyl compounds 1a,b with the chloro phosphanes 2a-o in the presence of lithium diethylamide yields the diazoalkyl phosphanes 3a-z . Oxidative addition of oxygen, sulfur and selenium at phosphorus leads into the series of oxo, thioxo and selenoxo phosphanes having diazoalkyl substituents ( 4a-d, 5a-m and 7a-d ). The silyl group of 5n,o is cleaved by chromatography on aluminium oxide to yield the (diazomethyl)phosphane sulfides 6a,b .     

Radikalreaktionen an N-Heterocyclen. XI [1] Reaktionen von 3-Methyl-pyrazolin-5-onen mit Phenoxyl-Radikalen

Free Radical Reactions of N-Heterocyclic Compounds. XI. Reaction of 3-Methyl-pyrazolin-5-ones with Phenoxy Radicals Pyrazolin-5-ones ( 3a–i ) were oxidized with 2,4,6-trisubstituted phenoxy radicals ( 2a–d ) to the corresponding radicals ( 4a–i ), which dimerised or combined with phenoxy radical ( 2a ) depending on the R¹- and R⁴-substituents in ( 3 ). In the case of 3-methyl-1-phenyl-pyrazolin-5-one ( 3f ) the primary radical combination products were not found, but the corresponding quinone methide ( 17 ) and the o-phenol derivative ( 18 ) were isolated. Products and yields have been investigated as a function of mol ratio substrate: oxidant and solvent. The radical combination products ( 7–10 ) could de-tertbutylated in the presence of aluminium chloride or in the presence of trifluoroarcetic acid, forming heterocyclic substituted phenols ( 21 ) and ( 22 ).     

Testing the Precision Initiation Couplers

It is possible to properly test a Precision Initiation Coupler (PIC) for its detonation profile and the rotational symmetry of its detonation wave using the Multi-Streak and/or Flash-Gap-Technique both with central linear streak line and circle streak which is comprised of dots for better evaluation.     

Native Liquid Chromatography and Mass Spectrometry to Structurally and Functionally Characterize Endo-Xylanase Proteoforms

Xylanases are of great value in various industries, including paper, food, and biorefinery. Due to their biotechnological production, these enzymes can contain a variety of post-translational modifications, which may have a profound effect on protein function. Understanding the structure–function relationship can guide the development of products with optimal performance. We have developed a workflow for the structural and functional characterization of an endo-1,4-β-xylanase (ENDO-I) produced by Aspergillus niger with and without applying thermal stress. This workflow relies on orthogonal native separation techniques to resolve proteoforms. Mass spectrometry and activity assays of separated proteoforms permitted the establishment of structure–function relationships. The separation conditions were focus on balancing efficient separation and protein functionality. We employed size exclusion chromatography (SEC) to separate ENDO-I from other co-expressed proteins. Charge variants were investigated with ion exchange chromatography (IEX) and revealed the presence of low abundant glycated variants in the temperature-stressed material. To obtain better insights into the effect on glycation on function, we enriched for these species using boronate affinity chromatography (BAC). The activity measurements showed lower activity of glycated species compared to the non-modified enzyme. Altogether, this workflow allowed in-depth structural and functional characterization of ENDO-I proteoforms.     

3- Instead of 4-helix formation in a de novo designed protein in solution revealed by small-angle X-ray scattering

De novo design and chemical synthesis of proteins and their mimics are central approaches for understanding protein folding and accessing proteins with novel functions. We have previously described carbohydrates as templates for the assembly of artificial proteins, so-called carboproteins. Here, we describe the preparation and structural studies of three alpha-helical bundle carboproteins, which were assembled from three different carbohydrate templates and one amphiphilic hexadecapeptide sequence. This heptad repeat peptide sequence has been reported to lead to 4-alpha-helix formation. The low resolution solution structures of the three carboproteins were analyzed by means of small-angle X-ray scattering (SAXS) and synchrotron radiation circular dichroism (SRCD). The ab initio SAXS data analysis revealed that all three carboproteins adopted an unexpected 3+1-helix folding topology in solution, while the free peptide formed a 3-helix bundle. This finding is consistent with the calculated alpha-helicities based on the SRCD data, which are 72 and 68 % for two of the carboproteins. The choice of template did not affect the overall folding topology (that is for the 3+1 helix bundle) the template did have a noticeable impact on the solution structure. This was particularly evident when comparing 4-helix carboprotein monomers with the 2x2-helix carboprotein dimer as the latter adopted a more compact conformation. Furthermore, the clear conformational differences observed between the two 4-helix (3+1) carboproteins based on D-altropyranoside and D-galactopyranoside support the notion that folding is affected by the template, and subtle variations in template distance-geometry design may be exploited to control the solution fold. In addition, the SRCD data show that template assembly significantly increases thermostability.