Pub Date : 2018-01-01Epub Date: 2018-02-13DOI: 10.1007/s00706-018-2147-5
Anna Lisik, Anna Prescha, Levent E Cavlaz, Halina Grajeta, Witold Musiał
Abstract: The atomic absorption spectrometry (AAS) method is one of the most accessible procedures for ferrous ions testing in various compositions including pharmaceutical preparations. The aim of the study was to develop and partially validate analytical method which could be an excellent alternative to the routine procedure performed within dissolution studies. Electric conductivity is simple, fast, and hassle-free method. The samples during dissolution process were measured using conductivity probe in entire dissolution assessment protocol. The conductivity results were compared to data obtained from AAS. The dissolution studies were performed according to modified pharmacopoeial standards, in 900 cm3 of purified water as an acceptor medium, at 37 °C, until the achievement of an equilibrium state for every tested composition. Validity study of the developed method confirmed acceptable linearity of obtained calibration plots (r2 > 0.9553). Linearity at 100% level was found to be 100.59, 97.49, and 94.82, respectively, for drug compositions A, B, and C. Precision results were 100.45, 95.97, and 95.73, respectively, for A, B, and C, with RSD below 2% between all samples in all above mentioned formulations. The drug composition D hindered the proper validation of the method due to the high variability between samples. The method has acceptable performance features for evaluation of three of four solid drug composition containing ferrous ions.
{"title":"The evaluation of alternative method of ferrous ions assessment in pharmaceutical preparations.","authors":"Anna Lisik, Anna Prescha, Levent E Cavlaz, Halina Grajeta, Witold Musiał","doi":"10.1007/s00706-018-2147-5","DOIUrl":"10.1007/s00706-018-2147-5","url":null,"abstract":"<p><strong>Abstract: </strong>The atomic absorption spectrometry (AAS) method is one of the most accessible procedures for ferrous ions testing in various compositions including pharmaceutical preparations. The aim of the study was to develop and partially validate analytical method which could be an excellent alternative to the routine procedure performed within dissolution studies. Electric conductivity is simple, fast, and hassle-free method. The samples during dissolution process were measured using conductivity probe in entire dissolution assessment protocol. The conductivity results were compared to data obtained from AAS. The dissolution studies were performed according to modified pharmacopoeial standards, in 900 cm<sup>3</sup> of purified water as an acceptor medium, at 37 °C, until the achievement of an equilibrium state for every tested composition. Validity study of the developed method confirmed acceptable linearity of obtained calibration plots (<i>r</i><sup>2</sup> > 0.9553). Linearity at 100% level was found to be 100.59, 97.49, and 94.82, respectively, for drug compositions A, B, and C. Precision results were 100.45, 95.97, and 95.73, respectively, for A, B, and C, with RSD below 2% between all samples in all above mentioned formulations. The drug composition D hindered the proper validation of the method due to the high variability between samples. The method has acceptable performance features for evaluation of three of four solid drug composition containing ferrous ions.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 5","pages":"931-937"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-018-2147-5","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36064556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-01-01Epub Date: 2018-08-20DOI: 10.1007/s00706-018-2227-6
Barbara Mirosław, Dmytro Babyuk, Agnieszka Łapczuk-Krygier, Agnieszka Kącka-Zych, Oleg M Demchuk, Radomir Jasiński
Abstract: 5-(Nitromethyl)-3-phenyl-4,5-dihydroisoxazole was obtained as a product of a high-yielding [3 + 2] cycloaddition reaction of in situ-generated benzonitrile N-oxide and 3-nitroprop-1-ene. For the first time, the regiochemistry of this reaction was unambiguously proven by X-ray structural analysis. The quantum-chemical calculation performed at the M06-2X/6-31G(d) (PCM) theoretical level affords a basis for explaining the course of reaction as well as the nature of transition states. Next, further DFT calculations together with spectral data shed light on structural aspects of the product.
{"title":"Regiospecific formation of the nitromethyl-substituted 3-phenyl-4,5-dihydroisoxazole via [3 + 2] cycloaddition.","authors":"Barbara Mirosław, Dmytro Babyuk, Agnieszka Łapczuk-Krygier, Agnieszka Kącka-Zych, Oleg M Demchuk, Radomir Jasiński","doi":"10.1007/s00706-018-2227-6","DOIUrl":"10.1007/s00706-018-2227-6","url":null,"abstract":"<p><strong>Abstract: </strong>5-(Nitromethyl)-3-phenyl-4,5-dihydroisoxazole was obtained as a product of a high-yielding [3 + 2] cycloaddition reaction of in situ-generated benzonitrile <i>N</i>-oxide and 3-nitroprop-1-ene. For the first time, the regiochemistry of this reaction was unambiguously proven by X-ray structural analysis. The quantum-chemical calculation performed at the M06-2X/6-31G(d) (PCM) theoretical level affords a basis for explaining the course of reaction as well as the nature of transition states. Next, further DFT calculations together with spectral data shed light on structural aspects of the product.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 10","pages":"1877-1884"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-018-2227-6","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36510810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-01-01Epub Date: 2018-06-07DOI: 10.1007/s00706-018-2215-x
Joanna Fedorowicz, Jarosław Sączewski
Abstract: This review is aimed to provide extensive survey of quinolones and fluoroquinolones for a variety of applications ranging from metal complexes and nanoparticle development to hybrid conjugates with therapeutic uses. The review covers the literature from the past 10 years with emphasis placed on new applications and mechanisms of pharmacological action of quinolone derivatives. The following are considered: metal complexes, nanoparticles and nanodrugs, polymers, proteins and peptides, NO donors and analogs, anionic compounds, siderophores, phosphonates, and prodrugs with enhanced lipophilicity, phototherapeutics, fluorescent compounds, triazoles, hybrid drugs, bis-quinolones, and other modifications. This review provides a comprehensive resource, summarizing a broad range of important quinolone applications with great utility as a resource concerning both chemical modifications and also novel hybrid bifunctional therapeutic agents.
{"title":"Modifications of quinolones and fluoroquinolones: hybrid compounds and dual-action molecules.","authors":"Joanna Fedorowicz, Jarosław Sączewski","doi":"10.1007/s00706-018-2215-x","DOIUrl":"10.1007/s00706-018-2215-x","url":null,"abstract":"<p><strong>Abstract: </strong>This review is aimed to provide extensive survey of quinolones and fluoroquinolones for a variety of applications ranging from metal complexes and nanoparticle development to hybrid conjugates with therapeutic uses. The review covers the literature from the past 10 years with emphasis placed on new applications and mechanisms of pharmacological action of quinolone derivatives. The following are considered: metal complexes, nanoparticles and nanodrugs, polymers, proteins and peptides, NO donors and analogs, anionic compounds, siderophores, phosphonates, and prodrugs with enhanced lipophilicity, phototherapeutics, fluorescent compounds, triazoles, hybrid drugs, bis-quinolones, and other modifications. This review provides a comprehensive resource, summarizing a broad range of important quinolone applications with great utility as a resource concerning both chemical modifications and also novel hybrid bifunctional therapeutic agents.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 7","pages":"1199-1245"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6006264/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36293485","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-01-01Epub Date: 2017-07-15DOI: 10.1007/s00706-017-2010-0
Christina Gaunersdorfer, Mario Waser
Abstract: Sultones, the cyclic esters of hydroxyl sulfonic acids, are a fascinating class of heterocycles and the recent years have witnessed an increasing interest in these molecules, especially in six-ring δ-sultones. The importance of these compounds is either because of their biological properties themselves or due to their versatility as intermediates in more complex target syntheses. Accordingly, the development of new synthesis methods to access δ-sultones is an important and rewarding task which we wish to highlight in this review.
{"title":"Progress in the synthesis of δ-sultones.","authors":"Christina Gaunersdorfer, Mario Waser","doi":"10.1007/s00706-017-2010-0","DOIUrl":"https://doi.org/10.1007/s00706-017-2010-0","url":null,"abstract":"<p><strong>Abstract: </strong>Sultones, the cyclic esters of hydroxyl sulfonic acids, are a fascinating class of heterocycles and the recent years have witnessed an increasing interest in these molecules, especially in six-ring δ-sultones. The importance of these compounds is either because of their biological properties themselves or due to their versatility as intermediates in more complex target syntheses. Accordingly, the development of new synthesis methods to access δ-sultones is an important and rewarding task which we wish to highlight in this review.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 4","pages":"701-714"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-017-2010-0","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36031580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-01-01Epub Date: 2017-11-28DOI: 10.1007/s00706-017-2083-9
Volkmar Trommer, Fabian Fischer, Marko Hapke
Abstract: The concise synthesis of a novel chiral diyne substrate for the assembly of chiral naphthylpyridines was described and different conditions for the cobalt-catalyzed co-cyclotrimerization with nitriles investigated. The products are novel naphthylpyridines possessing configurationally stable biaryl axes.
{"title":"Novel naphthylpyridines from cobalt-catalyzed cyclotrimerization of a chiral diyne.","authors":"Volkmar Trommer, Fabian Fischer, Marko Hapke","doi":"10.1007/s00706-017-2083-9","DOIUrl":"https://doi.org/10.1007/s00706-017-2083-9","url":null,"abstract":"<p><strong>Abstract: </strong>The concise synthesis of a novel chiral diyne substrate for the assembly of chiral naphthylpyridines was described and different conditions for the cobalt-catalyzed co-cyclotrimerization with nitriles investigated. The products are novel naphthylpyridines possessing configurationally stable biaryl axes.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 4","pages":"755-763"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-017-2083-9","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36031582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract: The preparation, structural characterization, luminescence, and catalytic activity of three palladium(II) complexes bearing imino phenoxide ligands are reported. The X-ray studies revealed that the complexes are mononuclear with palladium centres coordinated in a square-planar coordination environment. Two of the complexes are emissive in solution at room temperature. The catalytic activities towards the ring-opening polymerization of rac-lactide (rac-LA) were tested. Polymers with moderate molecular weights and relatively broad dispersity (Ð) were obtained. Kinetic studies revealed that the polymerization followed first-order kinetics.
{"title":"Palladium complexes containing imino phenoxide ligands: synthesis, luminescence, and their use as catalysts for the ring-opening polymerization of <i>rac</i>-lactide.","authors":"Mrinmay Mandal, Manuela List, Ian Teasdale, Günther Redhammer, Debashis Chakraborty, Uwe Monkowius","doi":"10.1007/s00706-017-2119-1","DOIUrl":"10.1007/s00706-017-2119-1","url":null,"abstract":"<p><strong>Abstract: </strong>The preparation, structural characterization, luminescence, and catalytic activity of three palladium(II) complexes bearing imino phenoxide ligands are reported. The X-ray studies revealed that the complexes are mononuclear with palladium centres coordinated in a square-planar coordination environment. Two of the complexes are emissive in solution at room temperature. The catalytic activities towards the ring-opening polymerization of <i>rac</i>-lactide (<i>rac</i>-LA) were tested. Polymers with moderate molecular weights and relatively broad dispersity (<i>Ð</i>) were obtained. Kinetic studies revealed that the polymerization followed first-order kinetics.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 4","pages":"783-790"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5906497/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36031584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-01-01Epub Date: 2018-08-09DOI: 10.1007/s00706-018-2221-z
Hubert Byliński, Tomasz Dymerski, Jacek Gębicki, Jacek Namieśnik
{"title":"Complementary use of GCxGC-TOF-MS and statistics for differentiation of variety in biosolid samples.","authors":"Hubert Byliński, Tomasz Dymerski, Jacek Gębicki, Jacek Namieśnik","doi":"10.1007/s00706-018-2221-z","DOIUrl":"https://doi.org/10.1007/s00706-018-2221-z","url":null,"abstract":"","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 9","pages":"1587-1594"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-018-2221-z","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36455424","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-01-01Epub Date: 2018-08-09DOI: 10.1007/s00706-018-2242-7
Martyna Lubinska-Szczygeł, Dominika Pudlak, Tomasz Dymerski, Jacek Namieśnik
Abstract: Citrus fruits are very popular food products. There are many species and varieties of them. There are also documented cases of some citrus fruits causing a severe allergic reaction. Some species of the citrus fruits, especially hybrid ones show a reduced allergenic effect due to the lack of seeds. There is a need for rapid methods for evaluation of citrus' botanical origin. During research, the headspace of three citrus fruits Citrus Aurantifolia, Citrus japonica, and Citrus × floridana was analysed using electronic nose based on ultrafast gas chromatography and gas chromatography with mass spectrometry. In the paper, two approaches were compared. The usefulness of an electronic nose to control the quality of hybrids was demonstrated. The results obtained during ultrafast gas chromatography analyses were subjected to statistical analysis. Four chemometric methods namely: principal component analysis (PCA), discriminant function analysis (DFA), soft independent modeling of class analogies (SIMCA), statistical quality control (SQC) were used to distinguish between limequat and its parent fruits. Electronic nose combined with chemometrics is a novel analytical tool for hybrid fruits' classification due to their botanical origin. It can supplement established techniques by providing results in a short time and at a low cost.
Graphical abstract:
摘要:柑橘类水果是非常受欢迎的食品。它们有许多种类和变种。也有一些柑橘类水果引起严重过敏反应的记录。某些种类的柑橘类水果,特别是杂交的柑橘类水果,由于缺乏种子,其致敏性降低。目前急需一种快速鉴定柑橘植物来源的方法。在研究中,采用基于超快速气相色谱和气相色谱-质谱联用技术的电子鼻对三种柑橘类水果Aurantifolia、citrus japonica和citrus x floridana的顶空进行了分析。本文对两种方法进行了比较。演示了电子鼻对混合动力汽车质量控制的有效性。在超快气相色谱分析得到的结果进行统计分析。采用主成分分析(PCA)、判别函数分析(DFA)、类类比的软独立建模(SIMCA)和统计质量控制(SQC) 4种化学计量学方法对石灰甜瓜与其亲本果实进行了鉴别。电子鼻与化学计量学相结合是杂交果实分类的一种新的分析工具。它可以通过在短时间内以低成本提供结果来补充现有技术。图形化的简介:
{"title":"Rapid assessment of the authenticity of limequat fruit using the electronic nose and gas chromatography coupled with mass spectrometry.","authors":"Martyna Lubinska-Szczygeł, Dominika Pudlak, Tomasz Dymerski, Jacek Namieśnik","doi":"10.1007/s00706-018-2242-7","DOIUrl":"https://doi.org/10.1007/s00706-018-2242-7","url":null,"abstract":"<p><strong>Abstract: </strong>Citrus fruits are very popular food products. There are many species and varieties of them. There are also documented cases of some citrus fruits causing a severe allergic reaction. Some species of the citrus fruits, especially hybrid ones show a reduced allergenic effect due to the lack of seeds. There is a need for rapid methods for evaluation of citrus' botanical origin. During research, the headspace of three citrus fruits <i>Citrus Aurantifolia, Citrus japonica</i>, and <i>Citrus </i>× <i>floridana</i> was analysed using electronic nose based on ultrafast gas chromatography and gas chromatography with mass spectrometry. In the paper, two approaches were compared. The usefulness of an electronic nose to control the quality of hybrids was demonstrated. The results obtained during ultrafast gas chromatography analyses were subjected to statistical analysis. Four chemometric methods namely: principal component analysis (PCA), discriminant function analysis (DFA), soft independent modeling of class analogies (SIMCA), statistical quality control (SQC) were used to distinguish between limequat and its parent fruits. Electronic nose combined with chemometrics is a novel analytical tool for hybrid fruits' classification due to their botanical origin. It can supplement established techniques by providing results in a short time and at a low cost.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 9","pages":"1605-1614"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-018-2242-7","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36455426","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-01-01Epub Date: 2018-08-09DOI: 10.1007/s00706-018-2229-4
Anna Różańska, Dorota Sieńska, Tomasz Dymerski, Jacek Namieśnik
Abstract: The quality of the fruit is affected by several main ingredients and the aroma plays a fundamental role during the selection of fruit by consumers. In the case where several fruit have similar aromas and only one of them has specific health properties, it is very important to find the differences in the volatile organic compounds (VOCs) composition to distinguish these samples. Such situations are often found for hybrid fruit. Sweetie is a hybrid of grapefruit and pummelo. Sweetie fruit is characterized by high antioxidant potential and a positive effect on human health. The aim of this study was to verify the unique volatile compositional traits of three species of citrus fruit. Proton transfer reaction Time-of-Flight mass spectrometry (PTR-TOF-MS) was utilized to obtain the mass-resolved fingerprints of VOCs. The chemical formula of these VOC masses was tentatively identified. Principal component analysis was performed to evaluate the differences between the groups.
{"title":"Analysis of volatile fraction of sweetie (<i>Citrus maxima </i>×<i> Citrus paradisi</i>) and its parent fruit using proton transfer reaction mass spectrometry.","authors":"Anna Różańska, Dorota Sieńska, Tomasz Dymerski, Jacek Namieśnik","doi":"10.1007/s00706-018-2229-4","DOIUrl":"https://doi.org/10.1007/s00706-018-2229-4","url":null,"abstract":"<p><strong>Abstract: </strong>The quality of the fruit is affected by several main ingredients and the aroma plays a fundamental role during the selection of fruit by consumers. In the case where several fruit have similar aromas and only one of them has specific health properties, it is very important to find the differences in the volatile organic compounds (VOCs) composition to distinguish these samples. Such situations are often found for hybrid fruit. Sweetie is a hybrid of grapefruit and pummelo. Sweetie fruit is characterized by high antioxidant potential and a positive effect on human health. The aim of this study was to verify the unique volatile compositional traits of three species of citrus fruit. Proton transfer reaction Time-of-Flight mass spectrometry (PTR-TOF-MS) was utilized to obtain the mass-resolved fingerprints of VOCs. The chemical formula of these VOC masses was tentatively identified. Principal component analysis was performed to evaluate the differences between the groups.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 9","pages":"1629-1634"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-018-2229-4","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36455428","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-01-01Epub Date: 2018-01-25DOI: 10.1007/s00706-017-2117-3
Ernst Gamsjäger, Manfred Wiessner
Abstract: Thermodynamic data of various crystalline solids are assessed from low temperature heat capacity measurements, i.e., from almost absolute zero to 300 K by means of semi-empirical models. Previous studies frequently present fit functions with a large amount of coefficients resulting in almost perfect agreement with experimental data. It is, however, pointed out in this work that special care is required to avoid overfitting. Apart from anomalies like phase transformations, it is likely that data from calorimetric measurements can be fitted by a relatively simple Debye-Einstein integral with sufficient precision. Thereby, reliable values for the heat capacities, standard enthalpies, and standard entropies at T = 298.15 K are obtained. Standard thermodynamic functions of various compounds strongly differing in the number of atoms in the formula unit can be derived from this fitting procedure and are compared to the results of previous fitting procedures. The residuals are of course larger when the Debye-Einstein integral is applied instead of using a high number of fit coefficients or connected splines, but the semi-empiric fit coefficients keep their meaning with respect to physics. It is suggested to use the Debye-Einstein integral fit as a standard method to describe heat capacities in the range between 0 and 300 K so that the derived thermodynamic functions are obtained on the same theory-related semi-empiric basis. Additional fitting is recommended when a precise description for data at ultra-low temperatures (0-20 K) is requested.
{"title":"Low temperature heat capacities and thermodynamic functions described by Debye-Einstein integrals.","authors":"Ernst Gamsjäger, Manfred Wiessner","doi":"10.1007/s00706-017-2117-3","DOIUrl":"https://doi.org/10.1007/s00706-017-2117-3","url":null,"abstract":"<p><strong>Abstract: </strong>Thermodynamic data of various crystalline solids are assessed from low temperature heat capacity measurements, i.e., from almost absolute zero to 300 K by means of semi-empirical models. Previous studies frequently present fit functions with a large amount of coefficients resulting in almost perfect agreement with experimental data. It is, however, pointed out in this work that special care is required to avoid overfitting. Apart from anomalies like phase transformations, it is likely that data from calorimetric measurements can be fitted by a relatively simple Debye-Einstein integral with sufficient precision. Thereby, reliable values for the heat capacities, standard enthalpies, and standard entropies at <i>T</i> = 298.15 K are obtained. Standard thermodynamic functions of various compounds strongly differing in the number of atoms in the formula unit can be derived from this fitting procedure and are compared to the results of previous fitting procedures. The residuals are of course larger when the Debye-Einstein integral is applied instead of using a high number of fit coefficients or connected splines, but the semi-empiric fit coefficients keep their meaning with respect to physics. It is suggested to use the Debye-Einstein integral fit as a standard method to describe heat capacities in the range between 0 and 300 K so that the derived thermodynamic functions are obtained on the same theory-related semi-empiric basis. Additional fitting is recommended when a precise description for data at ultra-low temperatures (0-20 K) is requested.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 2","pages":"357-368"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-017-2117-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"35876773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}