Progress in Practice: The Synergy Derived From Knowing Pedagogy as Well as Chemistry

What is the value that comes from consciously and explicitly linking what we know about chemistry with what we do in the classroom? It is tempting to dismiss this question because we are uncomfortable with the implication that there are times when what we do in the classroom is not informed by our personal understanding of chemistry. Yet instructors of introductory chemistry courses often lack the personal understanding, especially the kind that comes from laboratory experience, for significant parts of the course. An experienced general chemistry instructor, for example, probably understands the practical expectations of teaching this subject better than anyone who has recently graduated with a Ph.D. in physical or inorganic chemistry. Although the merits of this situation are worth reflecting on at another time, a reasonable operational assumption is that a substantial portion of the introductory program is defined by its own existence rather than as an identifiable area of specialization. The general chemistry curriculum is flexible to the degree that it can accommodate a variety of backgrounds in its instructors, yet it is constrained by the historical inertia that has defined it. To a lesser yet still significant extent, beginning instructors of organic chemistry face the same problem when their understanding of more specialized topics (such as the synthesis of heterocyclic compounds, transition metal organometallics, carbohydrate and peptide chemistry) is limited by their inexperience in those areas. Organic chemists might have only studied these topics as a part of their own introductory or intermediate instruction, and the textbook in use could be their primary source of information. Consequently, introductory chemistry instruction is filled with its own “urban myths”, or perhaps they are parables [1] passed down from author to author, about chemical phenomena that may or may not stand up to the scrutiny of contemporary understanding. Sometimes this is by design; for instance, demonstrating some general features about macroscopic properties can be done by using simplifications like the ideal gas assumptions or with the use of concentration instead of activity. Intentional simplifications that use less sophisticated models to explain phenomena at an adequate level of complexity are commonplace (in fact, this is not a bad interpretation of Occam’s Razor as it applies to science in general). This may be analogous to the way our colleagues in physics begin college instruction with Newtonian mechanics, or the way chemists can successfully use valence bond models for molecular structure to do a prodigious amount of chemistry without ever invoking a Hamiltonian operator. Problems can arise, however, whenever an instructor’s depth of understanding of a subject is only marginally different than the simplified version of it. Agassi [2] offers a sobering view on the way some writers of introductory textbooks “mislead the innocent reader” (implying that unwary instructors will sometimes mislead learners). He laments that individuals who ultimately choose science do so in spite of their formal education and he refers to them as “those who survive the injury of the science textbook.”     

Theory of solid-state thermal decomposition reactions

A case is presented to recommend strongly that scientists interested in thermal chemistry should make comprehensive, conscientious, clinical and critical analyses of the strengths and weaknesses of The L??vov Thermochemical Theory (L??vov, Thermal decomposition of solids and melts??new thermochemical approach to the mechanism, kinetics and methodology, Springer, Berlin, 2007), used to interpret the kinetics and mechanisms of reactions that occur on heating. The shortcomings underlying the theory (some originally developed for solid decompositions) currently uncritically accepted in this field are reviewed, and these deficiencies are contrasted with the successes of L??vov??s approach. To promote the use of this alternative theory, features that may have discouraged researchers unfamiliar with its assumptions, methodology and applications are discussed here. A new scientific theory cannot be ignored or discounted without adequate consideration and testing, particularly in a stagnant area of chemistry that lacks guiding principles and unifying concepts. Novel ideas in the literature (L??vov 2007) deserve recognition, critical appraisal and, if possible, exploitation to maintain the progress of scientific research.     

Tutorial: Capillary Electrophoresis

In recent years a number of exciting developments have emerged in the area of scientific computational tools for classroom use. Computer Algebra Systems (CASs), for example, Maple, are at the forefront of this arena. Such tools have been long sought by teachers of physical chemistry, inherently a mathematics intensive subject. With a CAS at hand, students can look forward to taking college science courses, like physical chemistry, without the usual mathematics anxiety. These tools can be used to do numerical and symbolic mathematics including calculus and linear algebra. In addition, they have wonderful graphics capabilities that include three-dimensional plots, contour plots, and animations. This paper describes the implementation of Maple in two junior-level physical chemistry courses. The materials used for beginning workshops are presented here and additional examples of Maples graphic and algebraic capabilities are described.     

Synthesis, reactions, and applications of fluorine-containing multifunctional carbon compounds

The chemistry of compounds containing a carbon atom bearing three or four different labile functional groups has received little attention. These compounds should be of considerable significance in theoretical and synthetic organic chemistry. Among the compounds with multifunctional structures, those having both carbonyl and halogen groups in addition to other heteroatom groups seem especially valuable from a synthetic viewpoint. Their potential use as probes in pure and applied synthetic chemistry has not been exploited, presumably because of structural instability and a paucity of synthetic approaches. Keeping this background in mind, we focused on the synthesis of a new class of multifunctional carbon compounds in which ester carbonyl, halogen, and other heteroatom-derived functional groups are directly attached to the central carbon atom. Fluorine was chosen as the halogen because of the inherent stability of the CF bond and because of the fundamental chemical and biological interest in fluorine-containing compounds. The synthesis, reactions, and some applications of various fluorine-containing multifunctional carbon compounds are described.     

Merging constitutional and motional covalent dynamics in reversible imine formation and exchange processes

The formation and exchange processes of imines of salicylaldehyde, pyridine-2-carboxaldehyde, and benzaldehyde have been studied, showing that the former has features of particular interest for dynamic covalent chemistry, displaying high efficiency and fast rates. The monoimines formed with aliphatic α,ω-diamines display an internal exchange process of self-transimination type, inducing a local motion of either "stepping-in-place" or "single-step" type by bond interchange, whose rate decreases rapidly with the distance of the terminal amino groups. Control of the speed of the process over a wide range may be achieved by substituents, solvent composition, and temperature. These monoimines also undergo intermolecular exchange, thus merging motional and constitutional covalent behavior within the same molecule. With polyamines, the monoimines formed execute internal motions that have been characterized by extensive one-dimensional, two-dimensional, and EXSY proton NMR studies. In particular, with linear polyamines, nondirectional displacement occurs by shifting of the aldehyde residue along the polyamine chain serving as molecular track. Imines thus behave as simple prototypes of systems displaying relative motions of molecular moieties, a subject of high current interest in the investigation of synthetic and biological molecular motors. The motional processes described are of dynamic covalent nature and take place without change in molecular constitution. They thus represent a category of dynamic covalent motions, resulting from reversible covalent bond formation and dissociation. They extend dynamic covalent chemistry into the area of molecular motions. A major further step will be to achieve control of directionality. The results reported here for imines open wide perspectives, together with other chemical groups, for the implementation of such features in multifunctional molecules toward the design of molecular devices presenting a complex combination of motional and constitutional dynamic behaviors.     

A "traceless" Staudinger ligation for the chemoselective synthesis of amide bonds

[reaction: see text] Here we report a novel modification of our previously reported "Staudinger ligation" that generates an amide bond from an azide and a specifically functionalized phosphine. This method for the selective formation of an amide bond, which does not require the orthogonal protection of distal functional groups, should find general utility in synthetic and biological chemistry.     

Catalytic asymmetric carbon-carbon bond-forming reactions in aqueous media

Use of water as a reaction solvent or co-solvent has received much attention in synthetic organic chemistry. Recently, successful examples of catalytic asymmetric carbon-carbon bond formation in aqueous media have been developed. Most of these examples show characteristic features that are realized only in the presence of water. The role of water in these reactions is also discussed here.     

Evaluating data for atmospheric models, an example: IO + NO2 = IONO2

Data for the title reaction have been fit to the different formalisms used by the NASA and IUPAC data evaluation panels. The data are well represented by either formalism. Reported values for the bond dissociation energy at 0 K, D0(IO-NO2) vary from about 95 to 135 kJ mol(-1), with uncertainty ranges of about 20 kJ mol(-1). Master equation/RRKM methods were employed in an attempt to reconcile these values with the data. This was possible within reasonable bounds and suggests a value in the neighborhood of 150 kJ mol(-1). As always, there are sufficient assumptions and unknowns in such an attempt, that this value is somewhat uncertain, but the true value is not expected to be too far from this result. Thus, it is possible to evaluate data of the type addressed here in a manner reasonably consistent with the basic understanding of pressure dependent rate coefficients for use in atmospheric or other models of "engineering" problems. There are, however, strict limits on our ability to know specific details. It is possible that true anharmonicity corrections that include stretch-bend interactions as well as effects due to averaging rotational contributions could combine to lower this value by as much as 10 kJ mol(-1). In addition collision and energy transfer parameters are somewhat uncertain.     

Heats of hydrogenation of compounds featuring main group elements and with the potential for multiply bonding

Reaction enthalpies are calculated for the hydrogenation reactions of main group hydrides with the potential for multiple bonding, and thus the unsaturated character of these species is determined. In addition to the global minimum structures, which leave in some cases no hope for even a single E-E bond (E=Group 13, 14, or 15 element), calculations are also performed for geometries with maximum potential for multiple bonding. The trends down the groups and the periods are established. Interpretations have to take several factors into account. These factors sometimes work hand in hand but also against each other. We also include in our survey the species [HGaGaH]2- as a free anion and Na2[HGaGaH] as well as their hydrogenation products [H2GaGaH2]2- and Na2[H2GaGaH2]2-. The results show that the presence of the Na+ ions has a significant impact on their chemistry, and thus suggests that they are involved to a large extent in the bonding. Our results indicate that the compounds should be described as cluster compounds.     

Relativistic effects on the electronic structure and volatility of group-8 tetroxides MO4, where M=Ru, Os, and element 108, Hs

The influence of relativistic effects on properties and volatility of the group-8 tetroxides MO4, where M=Ru, Os, and element 108, Hs, was studied on the basis of results of the fully relativistic (four component) and nonrelativistic density functional theory calculations. Relativistic effects were shown to increase bond strengths and decrease bond lengths in these molecules. They are responsible for a decrease in molecular polarizabilities and an increase in ionization potentials. The effects are much stronger in HsO4 than in the lighter congeners. Relativistic effects were also shown to slightly decrease dispersion interaction energies of RuO4, OsO4, and HsO4 with an inert (quartz or silicon nitride) surface, i.e., they increase volatility of these compounds as studied in the "one-atom-at-a-time" gas-phase chromatography experiments. They do, however, not influence the trend in group 8: both relativistically and nonrelativistically, volatility should change as RuO4相似文献   

Recent Progress in Oxo- and Fluorometalate Chemistry

About a quarter of a century ago a review article having almost the same title appeared in this journal^[1]. Since then many hundreds of new fluorides and oxides of metals have been synthesized, and repeatedly subjected to detailed investigation. Why, and to what end are such compounds still studied^[2]? Has our knowledge been not only widened but also deepened? What advances have been made in synthetic chemistry in this sector? Have new ideas led to unforeseen results and have unexpected findings forced the revision of tested concepts? This area of research belongs to solid state chemistry, and in the meantime has become almost unsurveyable even for a committed researcher. In this paper, therefore, an attempt is made to outline any relevant advances that have been made and to present open questions and new aspects using selected examples, mainly from the chemistry of the first row of the transition metal series. Those not directly involved in this area may be surprised to find that even substances with a simple composition are also cited. They might ask whether such compounds mentioned in text books are not already understood. Although it is a widely-held view that such compounds are well known, this is incorrect: Probably no-one has ever prepared a sample of CrF₂ or Na₂O whose composition “adequately” exactly corresponded to the quoted formula^[3]. Typical examples which demonstrate the considerable effort necessary for finally proving what others long ago already assumed to know, can be taken from the area of inorganic chemistry (e.g.: As₂O) as well as from organic chemistry (e.g. C₄[C(CH₃)₃]).     

Dynamic covalent chemistry

Dynamic covalent chemistry relates to chemical reactions carried out reversibly under conditions of equilibrium control. The reversible nature of the reactions introduces the prospects of "error checking" and "proof-reading" into synthetic processes where dynamic covalent chemistry operates. Since the formation of products occurs under thermodynamic control, product distributions depend only on the relative stabilities of the final products. In kinetically controlled reactions, however, it is the free energy differences between the transition states leading to the products that determines their relative proportions. Supramolecular chemistry has had a huge impact on synthesis at two levels: one is noncovalent synthesis, or strict self-assembly, and the other is supramolecular assistance to molecular synthesis, also referred to as self-assembly followed by covalent modification. Noncovalent synthesis has given us access to finite supermolecules and infinite supramolecular arrays. Supramolecular assistance to covalent synthesis has been exploited in the construction of more-complex systems, such as interlocked molecular compounds (for example, catenanes and rotaxanes) as well as container molecules (molecular capsules). The appealing prospect of also synthesizing these types of compounds with complex molecular architectures using reversible covalent bond forming chemistry has led to the development of dynamic covalent chemistry. Historically, dynamic covalent chemistry has played a central role in the development of conformational analysis by opening up the possibility to be able to equilibrate configurational isomers, sometimes with base (for example, esters) and sometimes with acid (for example, acetals). These stereochemical "balancing acts" revealed another major advantage that dynamic covalent chemistry offers the chemist, which is not so easily accessible in the kinetically controlled regime: the ability to re-adjust the product distribution of a reaction, even once the initial products have been formed, by changing the reaction's environment (for example, concentration, temperature, presence or absence of a template). This highly transparent, yet tremendously subtle, characteristic of dynamic covalent chemistry has led to key discoveries in polymer chemistry. In this review, some recent examples where dynamic covalent chemistry has been demonstrated are shown to emphasise the basic concepts of this area of science.     

联二炔囊泡的光致聚合、热致变色及应用

物理化学实验为各大高校本科化学教学的主干实验课程之一。虽然各高校的物理化学实验内容已十分丰富,但仍然缺乏将不同章节知识点融会贯通以及与学科前沿密切联系的综合型实验内容。我们根据南开大学郭东升教授课题组发表的一篇有关联二炔程序性响应检测胆碱酯酶的工作设计了“联二炔囊泡的光致聚合、热致变色及应用”的物理化学实验,涉及到联二炔缔合胶体的制备、联二炔的紫外光致聚合反应和聚联二炔的热致变色,进而显示其在防伪领域的潜在应用价值。希望通过此实验,使学生对物理化学中的缔合胶体、光化学、热力学、动力学等章节有更深一步的贯通性掌握,并了解自组装、光聚合、变色材料和防伪等相关研究领域的前沿动态。     

Isotope effects in liquid water by infrared spectroscopy. IV. No free OH groups in liquid water

The presence of free OH (OH not H-bonded) in bulk water is a key element for the determination of its molecular structure. The OH covalent bond infrared (IR) absorption is highly sensitive to the molecular environment. For this reason, IR spectroscopy is used for the determination of free OH. A workable definition of this is obtained with methanol (MeOH) in hexane where minute quantities of free OH are present. These absorb at 3654?cm(-1) (a 27?cm(-1) redshift from the gas position) with a full width at half height of 35?cm(-1). The IR spectrum of water between room temperature and 95?°C does not display such a band near 3650?cm(-1). This indicates that we do not see, in the IR spectra, the "free" OH group. From this we conclude that it is not present in liquid water at least down to the 1000 ppm level which is the limit of detectivity of our spectrometer. Other spectroscopic considerations of methanol and water in acetonitrile solutions indicate that weak H-bonds are also not present in liquid water.     

The Lewis legacy: the chemical bond--a territory and heartland of chemistry

Is chemistry a science without a territory? I argue that "chemical bonding" has been a traditional chemical territory ever since the chemical community amalgamated in the seventeenth century, and even before. The modern charter of this territory is Gilbert Newton Lewis, who started the "electronic structure revolution in chemistry." As a tribute to Lewis, I describe here three of his key papers from the years 1913, 1916, and 1923, and analyze them. Lewis has defined the quantum unit, the "electron pair bond," for construction of a chemical universe, and in so doing he charted a vast chemical territory and affected most profoundly the mental map of chemistry for generations ahead. Nevertheless, not all is known about the chemical bond" the chemical territory is still teaming with new and exciting problems of in new materials, nanoparticles, quantum dots, metalloenzymes, bonding at surface-vapor interfaces, and so on and so forth.     

Photoinduced iron-cyclopentadienyl (Fe-Cp) bond cleavage reactions and photocontrolled polymerizations of strained [1]ferrocenophanes

Although extensive previous studies have shown that strained [1]ferrocenophanes predominantly undergo ring-opening chemistry at the bridging atom E-cyclopentadienyl (E-Cp) bond, recent reports have highlighted that reactivity at the Fe-Cp bond can also occur, especially on photoactivation. We provide an overview of recent results from our group and those of other researchers. In addition, the development of photocontrolled living polymerizations of sila[1]ferrocenophanes using Fe-Cp bond cleavage chemistry is described.     

Azide-derivatized gold nanorods: functional materials for "click" chemistry

We describe herein the synthesis of functional gold nanorods suitable for carrying out "click" chemistry reactions. Gold nanorods modified with a copolymer containing sulfonate and maleic acid groups have been conjugated to a bifunctional azide molecule (amine-PEG-azide). The maleic acid molecules in the copolymer participate in carbodiimide-mediated amide bond formation with amine groups of the azide linker, whereas the sulfonate groups prevent nanorod aggregation in water. Spectroscopic and zeta-potential measurements have been used to confirm the successful surface modification of the gold nanorods. These azide-functionalized nanorods can carry out chemical reactions based on click chemistry. As a case study, we have demonstrated the "clicking" of azide-nanorods to an acetylene-functionalized enzyme, trypsin, by a copper-catalyzed 1,3-dipolar cycloaddition reaction. The enzyme is not only stable after bioconjugation but is also biologically active, as demonstrated by its digestion of the protein casein. For comparison, the biological activity of trypsin conjugated to gold nanorods by two other commonly used methods (carbodiimide-mediated covalent attachment via amide bond formation and simple electrostatic adsorption) has been studied. The enzyme conjugated by click chemistry demonstrates improved biological activity compared with other forms of bioconjugation. This general and simple approach is easy, specific with higher yields, environmentally benign, and applicable to a wide range of analytes and biomolecules.     

稀土金属有机化学的一个前沿领域:稀土卡宾化学

在过渡金属有机化学中,含过渡金属-主族元素(C,N,P)双键的卡宾配合物化学具有重要地位.它不仅对人们理解过渡金属和主族元素的成键理论很重要,而且这类配合物具有一些很好的、以及特征性的反应和催化性能.在过去的30年中,人们在含稀土金属-主族元素(C,N,P)单键的稀土金属烷基、胺基配合物以及膦基配合物化学研究上取得了很好的进展.稀土卡宾配合物化学是相关研究工作者接下来需要和渴望开拓的一个重要领域.人们在这一方面进行了积极的探索,合成得到了一些稀土桥联卡宾配合物和稀土卡宾配合物的模拟物.虽然它们离稀土金属-主族元素双键的稀土末端卡宾配合物有差距,但可以为稀土末端卡宾配合物的研究提供一些线索.本论文论述了这方面的研究成果,以及最近在稀土末端氮卡宾配合物上的一个突破.     

Copper(II)-catalyzed amidations of alkynyl bromides as a general synthesis of ynamides and Z-enamides. An intramolecular amidation for the synthesis of macrocyclic ynamides

A general and efficient method for the coupling of a wide range of amides with alkynyl bromides is described here. This novel amidation reaction involves a catalytic protocol using copper(II) sulfate-pentahydrate and 1,10-phenanthroline to direct the sp-C-N bond formation, leading to a structurally diverse array of ynamides including macrocyclic ynamides via an intramolecular amidation. Given the surging interest in ynamide chemistry, this atom economical synthesis of ynamides should invoke further attention from the synthetic organic community.