In this next of this series of editorials, we look back on papers published in 1924 and 1974 in The Journal of Physical Chemistry, to see what topics were important in physical chemistry in the past and how The Journal of Physical Chemistry grew. In 1924, The Journal of Physical Chemistry published 110 articles, which was over double the number of manuscripts compared to the previous year (43). The articles were published in 12 issues, which appeared at the start of each month. This is a departure from previous years, where only nine issues were published, and the journal was not published over the summer. This schedule stayed in place until 1933, which was the year that S. C. Lind took over as the Editor-in-Chief from the founding editor, W. D. Bancroft. The change in Editor-in-Chief saw a large drop in the number of papers, presumably because many colleagues and friends of Bancroft boycotted the journal. (In 1932, 24 papers were published from Cornell University, Bancroft’s home institution, whereas Cornell only contributed one paper in 1933.) The topics covered in 1924 in The Journal of Physical Chemistry included studies of phase diagrams, the characterization of porous materials, catalysis (and negative catalysis), and super-heated liquids. There were a number of papers on what are now classic freshman chemistry topics, such as equilibrium and solubility, (1) phase diagrams for liquid mixtures, (2,3) and the Joule–Thompson coefficient for helium. (4) The journal also included a study of the size distribution of Ag halide particles in photographic emulsions (an early nanoscience paper!). (5) The authors found that the size distributions were better described by the function y=Ae−k(lnx−a)2$y=A{\mathrm{e}}^{-k{(\ln x-a)}^2}$, rather than a regular Gaussian, which they derived assuming that particle growth is proportional to area. (5) We leave it to the reader to check this. The most cited papers in 1924 were a study of the phase diagram of the sodium metasilicate–silica binary system (cited 73 times) (6) and a paper on super-heating liquids (cited 68 times). (7) In this later work the authors carefully examined how preparation of the glass capiliaries used to contain the liquids affected the results. This included the following procedure: “A long capillary tube bent into a flat spiral was immersed in boiling mercury for an hour while the pressure in the tube was kept down to less than 1 mm. It was then sealed off, cooled, the tip broken off under freshly boiled ether, and the whole cut up into a number of U-tubes.” No mention of the potential hazards associated with boiling mercury were mentioned, which is not considered best practices by modern standards. The most prolific authors in 1924 were the Editor-in-Chief Bancroft with 11 articles (10% of the published papers in the journal that year) and N. R. Dhar from the Chemical Laboratory at the University of Allahabad who published 7 papers, mostly on solution reactions. Bancroft’s papers included very little, if any, new data; they were treatises (formally written essays) on other published materials. Many included large portions of quoted material. One was a treatise with R. P. Allen on metallic luster, with the following goal: “In a previous paper there has been given a discussion of metallic luster chiefly from the view-point of the physicist. In this article it is proposed to take up the subject from the view-point of the psychologist, clearing the way for the next article which will present the subject as the physical chemist sees it.” (8) This was achieved by discussing recent work by psychologists. Apparently Bancroft and Allen were not too impressed: “...Kirschmann’s paper was called to our attention by a professor of psychology as representing the very latest thing in the way of scientific progress in the study of metallic luster. Of course that was an exaggeration; but Kirschmann’s paper never could have been published if anybody had realized how extraordinarily bad it is.” However, the authors did concede that “The mere fact that so much of what Kirschmann says is wrong is not in itself conclusive proof that he is wrong throughout.” This language is also not considered best practices by modern standards when commenting on the work of others. Bancroft was not the only person to write treatises for the journal; Clyde Mason (also from Cornell University) wrote papers on the color of metals during “tempering” (9) and the physics behind blue eyes (10) that were critical reviews of the literature. Mason and Bancroft were very interested in blue colors, and between them, they wrote four articles on this subject in The Journal of Physical Chemistry in 1924. The journal also included a study of the spectrum of furfural, a very strong absorber in the UV and a common component of coffee, by Frederick Getman. (11) Figure 1 shows spectra taken from the paper. The authors state that “The position of the head of the absorption band is ... λ 270 μμ” where the now unconventional “μμ” units denote micro-millimeters. Figure 1. Left: Spectrum of furfural determined by Getman (solid line) and compared to a previous report (dashed line). The frequency units are mm^–1. Right: Spectrograms corresponding to (1) the lamp, (2) 50 mm of solvent, and solutions containing (3) 1:100, (4) 1:1000, (5) 1:10,000, and (6) 1:100,000 parts furfural to solvent. Reprinted with permission from ref (11). Copyright 1924 American Chemical Society. The spectra show almost complete absorption of UV light even at “1 part in 100,000 parts solvent”. The reason for this absorption was not understood, but the author notes: “If it be true, as the advocates of the theory of dynamic isomerism maintain, that no organic compound shows an absorption band unless the possibility of tautomerism exists within the molecule, the existence of selective absorption in furfural might be explained by an isorropic process such as is represented by the following formulas:”This is a complicated way of saying that the molecule is conjugated, with different ways of drawing the double bonds. As in the previous years, the journal also published book reviews primarily written by Bancroft. Both the number and length of the reviews increased over the previous year. The June issue included a review of the book “Everyday Mysteries: Secrets of Science in the Home” by Charles Greeley Abbot which was in a series of books entitled “Young People’s Shelf of Science”. It was written to “present modern views of the several sciences in a comprehensive and attractive form”. Bancroft praised the book, despite a few perceived faults in some of the explanations. He concluded the review by saying “Using aluminum sulphate as fertilizer for blueberries to produce an acid soil was new to the reviewer [Bancroft], p. 91, though he ought to have known about it, and even if one does not wish to grow blueberries it is a distinct achievement to grow rhododendrons and laurel really well.” (12) In contrast to 1924, in 1974 The Journal of Physical Chemistry saw a decrease in the number of published papers compared to the previous year (578 in 1974 compared to 672 in 1973). The Editor-in-Chief at the time was Bryce Crawford (University of Minnesota). He was not scientifically active in the 1970s, and it would not be until 1980 when Mostafa El-Sayed become Editor-in-Chief that the article count would start increasing again on a yearly basis by bringing the journal more into the mainstream. (13) The highest cited papers in 1974 were a study of electrical relaxation in molten salts, (14) a study on the heating/cooling rate affecting the glass transition temperature, (15) and a paper by Jortner and co-workers on electron transfer reactions in polar solvents (16) that includes a quantum mechanical description of the polaron modes of the liquid and the vibrational modes associated with ion solvation. These papers are still being actively cited today (Moynihan et al.’s paper on glass transitions received over 30 citations in 2023!). The most prolific author was Harold Scheraga, who published seven papers in 1974, the highest cited being a methods paper for determining intermolecular potentials for CNDO calculations from crystal data. (17) The most popular topic in The Journal of Physical Chemistry in 1974 was studies of radicals and transient species (more than 50 papers). The highest cited of these was a study by Neta and Fessenden on the reactions of hydroxyl radicals with phenol and aniline. (18) In this paper, pulsed radiolysis was used to produce OH radicals, and the products were probed by electron spin resonance (a very popular tool for these types of studies). There were also several highly cited papers on micelles. Tanford published a thermodynamics study of micelle formation which gave predictions for the critical micelle concentration and the micelle size distribution. (19) This paper is still well cited today, including in a recent Perspective article published in the Journal of Physical Chemistry B! (20) Aniansson and Wall published a study of the kinetics of micelle formation. (21) Kerry Thomas and Micheal Grätzel published two micelle papers, one that presented experimental data and analysis of pyrene emission in micelles (22) and another on the fate of photoelectrons produced by photoionization. (23) Micheal Grätzel was a junior researcher at this time, who has since become very well-known for his work in artificial photosynthesis, particularly for dye-sensitized solar cells (the so-called “Grätzel cell”). (24) Theory on micelles also included a Monte Carlo study of micelle formation by Christen and Eicke, (25) which, although not highly cited, includes a wonderful flow diagram for the calculations (see Figure 2). Figure 2. Flowchart for Monte Carlo calculations performed by Christen and Eicke in ref (25). Reprinted with permission from ref (25). Copyright 1974 American Chemical Society. Studies of biomolecules were not well represented in 1974, with only a few papers on proteins and one of these being a study of positron annihilation, which was more about the positrons than the proteins. (26) Several papers explored the properties of peptides and amino acids, including a study of the interaction of hydrated electrons with peptide linkages, (27) circular dichroism and IR measurements of the conformations and hydrogen bonding in an alanine derivative, (28) and a flash photolysis study of cysteine. (29) Rosano and co-workers reported on the surface viscosity of bovine serum albumin monolayers, (30) which showed unusual surface pressure effects attributed to folding and unfolding of the protein. This paper was inspired by a visit to the University of Sofia, Bulgaria (made possible by funds from the NSF and the Bulgarian Academy of Sciences) at a time when travel to Eastern Block countries was severely limited. The paper was cited as a highlight of current literature in 1975, (31) which was strangely its only citation at the time of writing this editorial. Future Nobel Prize in Chemistry winner F. Sherwood Rowland also published with The Journal of Physical Chemistry in 1974─one article on the reaction of ¹⁸F atoms with O₂, NO, SO₂, N₂, and CO (32) and a letter to the editor regarding collisions of fluorinated small molecules in the gas phase. (33) He also published a very influential paper in 1974 in Nature with Mario Molina that demonstrated the link between photodissociation of chlorofluorocarbons (freons) and the damage they caused to the ozone layer. (34) This paper was foundational for Rowland and Molina winning the Nobel Prize in Chemistry in 1995 along with Paul J. Crutzen. This Editorial is jointly published in The Journal of Physical Chemistry A/B/C. This article references 34 other publications. This article has not yet been cited by other publications. Figure 1. Left: Spectrum of furfural determined by Getman (solid line) and compared to a previous report (dashed line). The frequency units are mm^–1. Right: Spectrograms corresponding to (1) the lamp, (2) 50 mm of solvent, and solutions containing (3) 1:100, (4) 1:1000, (5) 1:10,000, and (6) 1:100,000 parts furfural to solvent. Reprinted with permission from ref (11). Copyright 1924 American Chemical Society. Figure 2. Flowchart for Monte Carlo calculations performed by Christen and Eicke in ref (25). Reprinted with permission from ref (25). Copyright 1974 American Chemical Society. This article references 34 other publications.

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《物理化学杂志》中的 50 年前和 100 年前─2024 年版

在本系列社论的下一篇中，我们回顾了 1924 年和 1974 年在《物理化学杂志》上发表的论文，了解过去物理化学中哪些主题很重要以及《物理化学杂志》是如何发展的。1924年，《物理化学杂志》发表了110篇文章，比前一年（43篇）增加了一倍多。这些文章共出版 12 期，每月月初出版。这与往年不同，往年只出版了九期，而且该杂志在夏季没有出版。这个时间表一直保留到 1933 年，这一年 SC Lind 从创始编辑 WD Bancroft 手中接任主编。主编更换后，论文数量大幅下降，大概是因为班克罗夫特的许多同事和朋友抵制了该期刊。（1932 年，班克罗夫特的母校康奈尔大学发表了 24 篇论文，而康奈尔大学在 1933 年只发表了一篇论文。）1924 年《物理化学杂志》涵盖的主题包括相图研究、多孔材料表征、催化（和负催化）和过热液体。有许多关于现在经典的新生化学主题的论文，例如平衡和溶解度、(1) 液体混合物的相图、(2,3) 和氦的焦耳-汤普森系数。(4) 该杂志还包括一项关于照相乳剂中卤化银颗粒尺寸分布的研究（一篇早期的纳米科学论文！）。(5) 作者发现该函数可以更好地描述尺寸分布y = A e − k ( lnX-a2​​$y=A{\mathrm{e}}^{-k{(\ln x-a)}^2}$，而不是常规高斯分布，他们假设粒子生长与面积成正比而得出。(5) 我们留给读者检查这一点。1924年被引用最多的论文是一篇关于偏硅酸钠-二氧化硅二元体系相图的研究（被引用73次）（6）和一篇关于过热液体的论文（被引用68次）。(7) 在后来的工作中，作者仔细研究了用于容纳液体的玻璃毛细管的制备如何影响结果。其中包括以下程序：“将一根弯曲成扁平螺旋的长毛细管浸入沸腾的汞中一小时，同时将管内的压力保持在 1 毫米以下。然后将其密封、冷却，在新煮沸的乙醚下将尖端折断，并将整个部件切成许多 U 形管。” 没有提及与沸腾汞相关的潜在危险，按照现代标准，这不被认为是最佳做法。1924 年最多产的作者是主编 Bancroft，发表了 11 篇文章（占当年期刊发表论文的 10%），阿拉哈巴德大学化学实验室的 NR Dhar 发表了 7 篇论文，大部分是关于溶液的反应。班克罗夫特的论文中几乎没有包含任何新数据。它们是关于其他已出版材料的论文（正式撰写的论文）。许多内容包含大部分引用的材料。其中一篇是 RP Allen 撰写的关于金属光泽的论文，其目标如下：“在之前的一篇论文中，主要从物理学家的角度对金属光泽进行了讨论。在这篇文章中，建议从心理学家的角度来讨论这个主题，为下一篇文章扫清道路，下一篇文章将以物理化学家的视角来呈现这个主题。” (8) 这是通过讨论心理学家最近的工作来实现的。显然，班克罗夫特和艾伦并没有太印象深刻：“……一位心理学教授引起了我们对科施曼论文的注意，因为它代表了金属光泽研究中科学进展的最新进展。当然，这是夸张的说法。但如果有人意识到基尔施曼的论文有多么糟糕，它就永远不可能发表。” 然而，作者确实承认，“基尔什曼所说的很多内容都是错误的，这一事实本身并不能证明他自始至终都是错误的。” 在评论他人的工作时，按照现代标准，这种语言也不被视为最佳实践。班克罗夫特并不是唯一一个为该杂志撰写论文的人。克莱德·梅森（同样来自康奈尔大学）撰写了关于“回火”过程中金属颜色的论文 (9) 以及蓝眼睛背后的物理原理 (10)，这些论文是对文献的批判性评论。梅森和班克罗夫特对蓝色非常感兴趣，他们在《物理化学杂志》上就此主题撰写了四篇文章1924 年。该杂志还收录了 Frederick Getman 对糠醛光谱的研究，糠醛是一种很强的紫外线吸收剂，也是咖啡的常见成分。(11) 图 1 显示了从纸上获取的光谱。作者指出，“吸收带头部的位置是…… λ 270 μμ ”，其中现在非常规的“ μμ ”单位表示微毫米。图 1. 左：Getman 测定的糠醛谱（实线）并与之前的报告（虚线）进行比较。频率单位为 mm ^–1。右图：对应于 (1) 灯、(2) 50 mm 溶剂以及含有 (3) 1:100、(4) 1:1000、(5) 1:10,000 和 (6) 1:100,000 的溶液的光谱图部分糠醛转化为溶剂。经参考文献 (11) 许可转载。版权所有 1924 美国化学会。光谱显示，即使在“100,000 份溶剂中的 1 份”中，紫外线也几乎被完全吸收。这种吸收的原因尚不清楚，但作者指出：“如果真如动态异构理论的倡导者所坚持的那样，除非分子内存在互变异构的可能性，否则任何有机化合物都不会显示出吸收带，那么糠醛中选择性吸收的存在可以通过等向过程来解释，如下式所示：“这是一种复杂的方式来表示分子是共轭的，具有不同的绘制双键的方式。与前几年一样，该杂志还发表了主要由班克罗夫特撰写的书评。审稿数量和篇幅均较上年有所增加。六月号包括对查尔斯·格里利·阿博特（Charles Greeley Abbot）所著的《日常之谜：家庭科学的秘密》一书的评论，该书属于题为“年轻人的科学书架”的系列书籍。它的写作目的是“以全面且有吸引力的形式呈现多种科学的现代观点”。班克罗夫特赞扬了这本书，尽管其中一些解释存在一些明显的错误。他在总结评论时说：“使用硫酸铝作为蓝莓肥料来生产酸性土壤对于评论者 [Bancroft] 来说是新鲜事，第 17 页。91，虽然他应该知道这一点，即使一个人不想种蓝莓，但能把杜鹃花和月桂树种得很好也是一项了不起的成就。” (12) 与1924年相比，1974年《物理化学杂志》与上年相比，发表论文数量有所减少（1974 年为 578 篇，1973 年为 672 篇）。当时的主编是布莱斯·克劳福德（Bryce Crawford）（明尼苏达大学）。他在 20 世纪 70 年代在科学上并不活跃，直到 1980 年 Mostafa El-Sayed 成为主编，文章数量才开始逐年增加，使该期刊更多地融入主流。(13) 1974 年被引用次数最多的论文是一项关于熔盐中电弛豫的研究，(14) 一项关于加热/冷却速率影响玻璃化转变温度的研究，(15) 以及 Jortner 及其同事关于电子的论文极性溶剂中的转移反应 (16)，包括液体极化子模式和与离子溶剂化相关的振动模式的量子力学描述。这些论文至今仍被积极引用（Moynihan 等人关于玻璃化转变的论文在 2023 年获得了超过 30 次引用！）。最多产的作者是 Harold Scheraga，他在 1974 年发表了 7 篇论文，其中被引用次数最多的是一篇用于根据晶体数据计算 CNDO 计算分子间势的方法论文。(17) 1974年《物理化学杂志》最热门的话题是自由基和瞬态物种的研究（超过50篇论文）。其中被引用最多的是 Neta 和 Fessenden 关于羟基自由基与苯酚和苯胺反应的研究。(18) 在本文中，脉冲辐射解用于产生 OH 自由基，并通过电子自旋共振（此类研究中非常流行的工具）探测产物。还有几篇关于胶束的论文被高度引用。坦福德发表了胶束形成的热力学研究，预测了临界胶束浓度和胶束尺寸分布。(19) 这篇论文至今仍被广泛引用，包括最近发表在《Journal of Physical Chemistry B》上的一篇 Perspective 文章！(20) Aniansson 和 Wall 发表了一项关于胶束形成动力学的研究。(21) Kerry Thomas 和 Micheal Grätzel 发表了两篇胶束论文，其中一篇介绍了胶束中芘发射的实验数据和分析 (22)，另一篇介绍了光电离产生的光电子的命运。(23) Micheal Grätzel 当时是一名初级研究员，此后他因其在人工光合作用方面的工作而闻名，特别是在染料敏化太阳能电池（所谓的“Grätzel 电池”）方面。(24) 胶束理论还包括 Christen 和 Eicke 对胶束形成的蒙特卡洛研究，(25) 尽管引用次数不多，但其中包括一个精彩的计算流程图（见图 2）。图 2. Christen 和 Eicke 在参考文献 (25) 中执行的蒙特卡罗计算流程图。经参考文献 (25) 许可转载。版权所有 1974 美国化学会。1974 年，生物分子的研究还没有得到很好的体现，只有几篇关于蛋白质的论文，其中一篇是正电子湮灭的研究，更多的是关于正电子而不是蛋白质。(26) 几篇论文探讨了肽和氨基酸的特性，包括水合电子与肽键相互作用的研究，(27) 丙氨酸衍生物中构象和氢键的圆二色性和红外测量，(28) 和半胱氨酸的闪光光解研究。(29) Rosano 和同事报告了牛血清白蛋白单层的表面粘度，(30) 显示出由于蛋白质折叠和展开而产生的不寻常的表面压力效应。本文的灵感来自于对保加利亚索非亚大学的访问（由美国国家科学基金会和保加利亚科学院资助），当时前往东部地区国家的旅行受到严重限制。这篇论文在 1975 年被引用为当前文献的亮点，(31) 奇怪的是，这是撰写这篇社论时唯一引用的论文。未来的诺贝尔化学奖获得者 F. Sherwood Rowland 也于 1974 年在《物理化学杂志》上发表了一篇关于^{18 个}F 原子与 O ₂、NO、SO ₂、N ₂和 CO反应的文章(32) 和一封信给编辑关于气相氟化小分子碰撞的信息。(33) 1974 年，他还与马里奥·莫利纳 (Mario Molina) 在《自然》杂志上发表了一篇非常有影响力的论文，证明了氯氟碳化合物（氟利昂）的光解作用与它们对臭氧层造成的破坏之间的联系。(34) 这篇论文为 Rowland 和 Molina 与 Paul J. Crutzen 一起荣获 1995 年诺贝尔化学奖奠定了基础。本社论联合发表于《物理化学杂志 A / B / C》。本文引用了 34 篇其他出版物。这篇文章尚未被其他出版物引用。图 1. 左：Getman 测定的糠醛谱（实线）并与之前的报告（虚线）进行比较。频率单位为 mm ^–1。右图：对应于 (1) 灯、(2) 50 mm 溶剂以及含有 (3) 1:100、(4) 1:1000、(5) 1:10,000 和 (6) 1:100,000 的溶液的光谱图部分糠醛转化为溶剂。经参考文献 (11) 许可转载。版权所有 1924 美国化学会。图 2. Christen 和 Eicke 在参考文献 (25) 中执行的蒙特卡罗计算流程图。经参考文献 (25) 许可转载。版权所有 1974 美国化学会。本文引用了 34 篇其他出版物。